DE1417651A1 - Catalyst for the conversion of hydrocarbons - Google Patents

Description

Kr / Sch / e.g. 2/2/1

Ä 38 645 IVe / 23'1 »

Catalyst for the conversion of hydrocarbons

'; xstzsssi era «esa

The invention "relates to a hydrocarbon reforming catalyst, which consists of a physical mixture of aluminum oxide, on which platinum is deposited, and oaloined Silica-alumina.

Bs is already a silica-alumina-hydrocarbon reforming catalyst known from an OemiBoii by a receptive! carrier on which a metal hydrogenation catalyst is precipitated, and a silica-ion earth cracking component consists ^ -,

In addition, a Kraok catalyst was noted »the sioh from a mechanical mixture of an inert carrier » loaded with a platinum group metal, and one acidic cleavage component from silicon dioxide and aluminum oxide composed ·.

Finally, a hydrocarbon cracking process was proposed, that uses a catalyst made of a porous inert support material with small amounts of a

ORIGINAL

(AM. 7 S (Abi.g No. 1 Sati 3 des Alter / ftfiseea,

Metal of the platinum group is loaded, and an acidic Kraok component, such as silicon dioxide-aluminum oxide, "consists. ■ - ■. · '·

Although these catalysts have a high activity and a relatively long service life, they have to be regenerated from time to time. It has been found that, for example, the aforementioned silica-ionic earth hydrocarbon reforming catalyst usually no longer has its original activity after regeneration. If it is then possible to bring it back to its "original" activity, it falls off more rapidly. After two or three regeneration processes, the rate of decline in activity is so great that the catalyst can no longer be used. It is : so impossible to pass the catalyst through To bring regeneration neither to its original activity nor to its initial stability. The other state-of-the-art catalysts behave in the same way »

With the help of these reforming catalysts, hydrocarbons with a high ootane number ~. By increasing Motorization, the required amount of high-octane gasoline is increasing from year to year. This need requires reforming processes in which, with increased throughput, hydrocarbons remain constant if possible high octane number can be obtained. These tough demands on the catalytic converters made it necessary to meet them

80 380 2/0 5 24 bad original

to regenerate more and more often. "

'' Frequent 'regeneration is necessary even if

these Eeforaierungskatalysatoren for the isomerization of with .Vsubstituents of low molecular weight alkylated ben-

• zole are used. In order to be economical in this Palle

·

work, it is necessary that practically the equilibrium _: amounts of the isomers are generated. To meet this requirement

"Sufficient, it is necessary," with the previously "known platinum-containing Catalysts low pressures and long contact times

• 'apply. "Under these conditions the catalysts had to \

can be regenerated again and again in a short time. \

There is therefore a need for a catalyst that is well [

can regenerate, which after regeneration has its original " k

.Recovered existing ability, catalytic reforming,]

- and catalytic isomerization reactions' to activate and \

• which, even after a series of regeneration treatments, always regains its original activity and stability ·

The catalyst according to the invention for the conversion of hydrocarbons, which consists of a physical mixture of alumina on which platinum is deposited and calcined silica-alumina ■ consists, the aluminum oxide with the deposited on it

( 809802/0524

Platinum is about 10-90 $> the weight of the finished catalyst and the platinum on the aluminum oxide is between about 0.1 to 2.5% by weight of the finished catalyst, while the silicon dioxide - aluminum oxide has an aluminum oxide content between 7 and 50 $ and which is characterized in that at least one manganese compound, such as the oxide, sulfide or sulfate, is deposited on the silicon dioxide-aluminum oxide, the manganese of the manganese compound in an amount of 0.25 to 1.0 weight by weight Silica-alumina is present.

The catalyst of the invention is generally in the form used by "pellets, rods, extrusions and the like;"

1 * 0

809302/0524

Although other Hsrirbellun ^ sverfahren, c> Ngew _a RIDT be. , can the following procedure has proved particularly suitable and therefore büvoraugt ₉ to all the benefits of achieving "Here, the platinum isolated on asu Aluniniumo ^ dteilohea dejected and da-iach this platinum-alumina Bostandfeeil physically with the Hei Ionon from Siliciumdiosyd- A mixed, on which the manganese compound had been beaten separately _e Using this method iv, a catalyst is obtained which is composed of? The processing of very large quantities of organic substances can be used, since, when it is exhausted after a period of use, it has been regenerated while dividing practically its original quality and stability and in this way for recycling. ending lierseotellt v? ii * do Bie catalysts & qt invention, while many G-ebrauehskreisläxtfe with subsequent Eoge- nerierunc Trer ^ ends are ·

The Almsiniumojiydbe stood part on which, the platinum deposited i.Tu, can be any or any. Mixtures of the commercially available aluminum oxides, such as s _o B _e % -aluminium oxide, γ-1αΐ2ΐη1ιΐΜ033ΓΑ and η -aluminium oxide ^. riiiyd.rat or the iJ- $ rihyarat are precipitated, the Aiuffiiniumoxyae converted during the subsequent Erliitsung to convert the platinum compound to metallic platinum in one of the types of aluminum osmosis listed above

809 80 2/0 5 24 BAD ORIGINAL

werdeno These AlumirrLumoxyde and their _. Conversions are in the publications H ₀ C.-Stumpf, A ₀ G »Kusseil, J ₀ Wp lifewsoiae and · C .IvI ₀ Sucker," üheraial {Transformations of Aluminas are Alumina Hydrates "in Industrial and Engineering Chemistry, Volume 42, p ₀ 1398 ff ... (1950) and by Allen S. Russell and Ciforman Cochran, "Surface Areas of Heated Alumina Hydrates"} in Industrial and Engineering Chemistry, Volume 42, S ₀ 1336 ff. (1950) described «,

The platinum can be deposited on the aluminum oxide gel or on the aluminum oxide after drying and calcination from an aqueous solution of any platinum compound. ydroxyd _? Platinhexamsiino- ) hydro ^ yd, _{Platinhexannuinoohlorid t} Ohloroplatinic acid, Platin-IV-

Chloride, ammonium chloroplatinate and similar platinum-containing solutions are precipitated * '.

After the aluminum oxide has been brought into contact with the solution of the platinum pre-binding agent, any excess solution present is removed and the aluminum oxide is dried. corresponding to known customary methods · The amount of metallic platinum deposited on the support can vary in the range from about 0.1% by weight to 2.5% by weight, based on the weight of the finished catalyst. The amount of platinum should preferably between about 0.25 wt * - #> and 1.0 ßew _o ~ $ ₉ based on the finished.

80 93 02/0 5 24

II 1 1 w -

The silica-aluminum o ^ d cracking component of the catalyst consists presumably of ßinem handoloubliclxon culcinierten Siliciumdiosqjrd-alumina cracking catalyst, which is between;

see ψ / ο and 50 wt »- # contains aluminum osside, the sest au3]

• Siliciuaidioxyd consists «, The commercially available caloinierte, synthe- j

table silica alumina cracking catalysts containing 12% 1

■ to 30 percent, ""# Aluminiumosryd contain and dia currently being \

the petroleum industry used in cracking processes are used to j Production of the catalysts described here is particularly suitable <

The Silioiuradioxyd-Aluiüiniumoj ^ -d-Srackbestigteir can either from a fresh. manufactured cracking catalyst or it can consist of a catalyst whose activity has changed ο The activity of a Eraskkatalysator is according to a distillate-plus-loss scale (D + L) - 1 scale, according to the "procedure von Eirkhimer et al « ₉ " A Bench i. Scale iDest Method for Evaluating Cracking Catalysts ", Proceedings \ of the American Petroleum Instittfs, Division of" Refining, Volume 27, \ (III) So 90 (19 ^ -7), according to the D * If - Akti- \ vity measurement method according to Birkhimer et al., it is possible to have a theoretical maximum of 100 at D + L. But is in general \ my maximum D + L ¥ ert for a fresh synthetic Si i

liciuudioxyd-Aluminumo ^ iyd-Krackkatal ^ sator in the area between j

ι SO and 95ο In spite of this, a number of other methods for measuring the | catalytic cracking activity of a synthotic
The presence of alumina cracking catalysts, which have been described in the literature, becomes a D + L answer in these methods, in far lower terms for a fresh silicon dici ^ yd-.

BATH ORIGINAL

8008C2. 0524

IT I / U

applied, which are usually on the order of 4-5 Ms 65 » ä ^e according to the special test. Accordingly, when a D + L scale with a practical maximum activity of 90 Ms 95 is listed, the method of Biirklrhaer was used.

A number of procedures. to change the cracking activity ■ of silicon dioxide-Al ^^ πliniumoaίyd - ΣrackkataIysatoren has been described; however, is the preferred method. für.-the catalysts according to the invention the treatment of ßiliciumdioxyd-Aluxainiumoxyd-Kat & lysators with steam at 2emperatureit between 371 ° C and 760 ⁰ C (700 ⁰ F ⁰ P and 14-00), and "was with bridges ranging from Atr · Atmospheric pressure up to pressures between 10 and 100 kg / cm and for a sufficient period of time to reach the estimated extent of change. -

Process for the production of Siliciumdioxyd'-Aluiainiuiaosydv Cracking catalysts have been widely published and it has been since the exact process of preparation of the cracking catalyst In fact, it is not critical to the procedures involved not discussed *

- I.

It has been found that the most suitable cracking constituent used in the similar production of the carbon monoxide catalysts according to the invention should have an activity in the range from 30 D-HD to 95 35 + Ti, measured according to the method of BLrkhiner et al .li'alls been the catalyst in the Keforsnierung of Kohlenwa.sserstoffmischunsen ₉ which paraffins, cycloparaffins and aromatic compounds entholten used Soll. ₉ • the range should preferably be between 4-0 D + I * and 80 D + L. If

809802/9524 BADORLGiNAL

the 'catalyst "is intended to be applied to dor isomerization of alkylated benzenes, vnLe example, the Sylolen and ethylbenzene, the preferred range liogt gwisohen 55 B + I" un & 95 DKL.

Aqueous solutions of water-soluble salts, such as manganese, have usually been applied to the water-soluble salts of manganese for the deposition of the manganese on the gi? . Jonnon, soliöron, the chloride, sulfate, sulfate, acetate, Eonsoai;, formula, xactate -and similar salts. _For Bach the relationship between the silicon and aluminum space and the water-soluble manganese alumina solution, the silicon dioxide-aluminum-aluminum oxide is separated from the solution, any excess solution is removed and the silicon dioxide-aluminum oxide is dried,

the Xertifja catalyst by pelleting the dry. Siliciuia! Äio ^ d-AliiiainitLsiox7d -! Reilchcii ₉ which are pre-prepared with a manganese compound, in combination with the platinum-aluminum oxide cords ₉ it is not necessary that the aluminum-aluminum-impregnated silicon dioxide-impregnated silicon dioxide is carried out ^ to calcine, although it is preferred to calcine before pelletizing. ! However, if the catalyst is prepared by pressing the Misc iung from Hon SilioiuBidiosyd-Aluminiumosyd-Teilohen ₉ which are iiapragniert with the Hanganverbindung, un ^ from the platinum AlumiiainiuEiO2Q ^r d ~ particles hex-provided v / ground s: oll, it is necessary , first the HajügszL-connection into an insoluble connection line, eg into the insoluble Qxyü. by calendering or into the water-insoluble suIfidform. The last conversion can be achieved inden the Siliciumdio: q7d ~ aluminumo ^ d - 2partchen with a manganese sulfate or chloride solution and then mixed with

ORIGINAL

809802/0524

? f treated to da.s Kangan in the SuI-

fidform au transfer. Das'mit Hangan-impregne ^ rto silicon dioxide-

Aluminum oxide is then dried »The calcination for |! |

Production of a water-insoluble oxide-or the use If-

of hydrogen sulfide to the sts silting deg water-insoluble. yy £

Sulphide is necessary because the presence of yoni & eioni water walls || f

rend of the squeezing is necessary and consequently the · man- -; ■■ £

gan if the llangan compound is in the form of a soluble salt

would be present, driving the extrusion process to the platinum aluminum; jp

miniuraoxyd component part could wander «It was found that; ·; _. '

In terms of activity, manganese is poison to flotin; weicui a _o B "J

as small an amount as 0.5 wt .- ^ manganese with a platinum χ

Aluaiiniumoxyd-ICata.lysator is mixed, the activity decreases; · /

of the catalytic converter to such an extent _? that the Octsnwert ....

of the reformed product \ is 5 to 6 values lower than \ [

the one, of a product, ?? elches with the same platinum cataly— -)}

sator, which, however, was not poisoned with manganese, manufactured U

wasο ■. . F.

If manganese sala is acetate, benzoate, pormate or lactate \

is used, it is assumed that after calcination with j- "_;

Air this salt practically completely in the water-insoluble Oxyd ι

are convicted. If the chloride is used, it is assumed-] ·

men that the Mun.gan- also transferred overvid.egend into the oxide.

Itft, although small amounts of chloride solidify after air calcination; ·

can be provided. If the üuifat ζην impregnation I-

¥ / ends, only a (part of the sulphate in the oxide at the j

Air calcination transferred, v / above with the residue of the manganese in the \

80980 2/052 ^ BAD ORIGINAL

3? Önn of the sulfide or the unreacted sulfate is present

It has also been found that when the catalyst is through Pelletizing the ingredients is prepared, each of the foregoing listed salts can be used »because the pelletie— tion is carried out in the absence of free water, which, if present, would cause the manganese to migrate ο If the catalyst is manufactured by the extrusion process, It turned out to be necessary to deposit manganese in the form of a silicon oxide-aluminum oxide deposited water-insoluble "compound to use, accordingly it is necessary for the AuspreSverfahron, a salt such as the acetate, berizocyt, formate or io.ctat to use which leads to the insoluble Mangsmosiydvcalciniort can be "or aas insoluble gul- fid from eggs sulfate or chloride to produce as it was described «. - *

The amount of the manganese pre-bond deposited on the silicon dioxide-aluminum oxide can be between 0.25% by weight and. 1.0 GeW ₀ -Yes Mcngan, based on <?. & S Gowicht des Siliciumdi'oxyd-iiluminiuno ^ cyds cheated. Preferably, the length of long-term bond, expressed as manganese, should be in the range of 0.55% by weight - ^P A bin 0.75 _{% by weight 0} - 5 dos of silicon dioxide-aluminum oxide.

Although the Mochanisia from the 'interaction between the ilanganverbindunr-; and your. Silica-alumina oxide, compare the The fflieorie is established that the Kang £ ui reacts with any free silicon dioxide so that the ßiliciuiadioxyd not lüit dom Γ latin from the platinum AluniniuEidos Catalyst can react, causing the catalyst

50 9302/05 ^ BADORlGfNAL

—I I # V »wr

would be desactivated. In this way, the manganese increases by. I.

GB ia.it deo. free silicon dioxide reacts, the segoneration sta-; '

bilicity of the catalyst Sinigo indications for this theory me- ■);

the chemical analysis of the catalytic reu found after the I-rf charge. 3. & 1 the analyzed samples quickly

that carry the Mailgan compound, the mixture is pelleted and then the pelleted egg-smeared ■ the calcination are subjected to the platinum in the metallic state on the AluiDiniumosqj-d and the -Hcii55nsi3ULz on your. Siliciumdioi ^ 'd-Aluiainiujaos.yd in da.s Οτεγϋ or other ■' V ^ rb'Jjtidunsen. au transfer »as described -was. At einia especially bevorsugtüa.

80 9802/0 5 24 BAD ORIGINAL

ren Ms au 27 Gew - # des ses.amten Ilangrans koaiplosr with the Sili ~ f.

connected so that they are in 5Q% ir, er nitric acid insoluble v / aron. In practice it turns out that less than 0.25 Gow _o - # - Manganese is insufficiently sinö, uri with the free silicon dioside j; to react and aof this way oine desactivation of the platinum ·; ]

- ■ j;

to lose, "whereas more than 100 % manganese neutralize the acidic places of the silicon dioxide-aluminum cssrds and thereby destroy their favorable management.

Sin preferred method for Herstollung of the catalysts is that the aluminum oxide particles ö.es "is on which platinum is deposited, particles of und.die Siliciuiadiosyd-Aluminiuta.O2 ^ 7d ETIT the deposited thereon Mansamrerbindung are calcined separately and then the mixture of the calcined Particle is pelletized. If desired, however, after the deposition and Tx ^ ooknunssstä s the dipping from aluminum

carry,
., which form the platinum compound with the particles of silicon

Getting caught after the platinum on the aliin & niumcccrjrd has drained off. ^ Ert Trorden 7rar.aa and the particles have been dried, these
Ssilchcn loit the silicon diol-AlijmiMipmozijd-Teilcherj., On which manganese acetate, bcnzoate, formate or lactate is deposited
ivurdo, mixed and the IPe lichen ealciniort sur making the
Siö-3.o; 3.noxyds. Dieso! Psilcb-ensiiccliiin ^ ■ '■ rf.rd in the presence of .troiea
Water squeezed out, dried and calcined in order to convert the platinum into the metallic additive _{or the like}

Calcining is done with air temperatures in areas
-between 57O ° G and 600 ⁰ C. (700 ⁰ F and 1100 ⁰ F) 'applied during
be 0 ⁰ C (400 ° and 1000 ⁰ S ¹⁾ ngowandt ^ "könnon * · periods between 1 to 6 hours are sufficient - see 200 ⁰ O ^ _.and: yeaperivcuren in the reduction of the platinum lait TTaeserßtoff zv / i! around. the pia- ". tin in the metallic state zn i; bsrfiiiLron ₀ " Similar conditions of the Oslciniej? ians ja with air can be applied in the case of the silicon dioxide di aluminum with the manganese salt then deposited on it. - ';

It has been found that in order to achieve the best results j the Sinaelbostandteile before Felletieren or pressing in

the Fox'm of finely divided powders should be available »preferential,

vreioe in 5'orsi of powders, dio through a sieve with a washing. "

number each approx. ⁶ of 57 ^ (So · 60 Ti..G ₀ Ütmdard ßiüve) and at least - to 'όΟ / ί through a üiob with ^ inor mesh number of "1600 (Uo _o 100

US ₀ Standard oiove) can be given »· * ^:

t the catalyst the corresponding dej? Invention desired Possesses transformation and regeneration properties,

809802/0524

"I 4 Ί / D

should represent aluminumosqyabestsn & cBil and the deposited on it
Fiatin in the Bex'eich between, about 10 / 'j to 90 Gow »->'> of the finished.
Catalyst botr & gon. JTal'ls dor catalyst mainly for
If sea trout is needed, cLio bcvcraugteüte Suse
aung recovered, \ votm. the weight of the AluainiuDiCxyd-Pla
. partly in the range between about - <■% '»to 8;» C-ew. ~ Fi dos manufacture
Ο if any catalyst mainly for the isomerization of alkyl benzene, 3 * B * -solchen, the 8 to 10 carbon atoms ia; Own molecule, use? is to be, it is preferred that the aluminum ossryd platia;. Component iia range between 25? - 'to 80 Gev /.- νό of the finished. , Catalyst is present »■ '■'.>:

The hydrocarbons, - which under the ending dv? Catalytic _'{: catalysts according to the invention dor' may be reformed, are those j-

those in the petrol-krosia area and preferably in the petrol area - - \, ■ boiling »In general, such a fraction has an original . sudden boiling point within the range of about 10 G
up to 32 ° G (50 ° F to 90 °?) and an end point in general from "!; about 19C ⁰ O to 220 ° ö (375 ° Ms 4-25 ° F) and can be used with the invention according to catalysts treated vez & QiLo In sölehaa 'ITralctionen "]; are present as hydrocarbons paraffins, cycloparaffins and aromatic yorbonds _o - ·

The reforming of these hydrocarbons is

chen Bödine ^ ingen carried out, i. at temperatures in the range

from 500 to 540 ⁰ C (600 ° Ms 1000 °?), preferably from 370 ° to

5-'4-O ⁰ O (700 ° to 1000 ⁰ P), at pressures from 3.5 to 70 k ^ / ern ² (50 j:

up to 1000 pounds per square inch) with hourly ilüssi & teife room J ■ ■ <,; * »* J;

809802 / G524 BAD QRK3INAL,.

speeds between 0.5 to 2.0 volumes of hydrogen QS volume of catalyst per hour, preferably 0.75 to fish 2.0 volume;] e volume per hour and hydrogen at low ratios to hydrocarbon between 5 to 15, preferably between 7.5 "to 10.0. - -

Among the alkylated carbonated hydrocarbons, which are un- £

ter · Application _dor% crfindungsgeiuäßen catalysts iaonerisiert |

the methyl- or iLthy! -substituted Ben-. |

zolkohlemvass only off e 3s.it 8 big 10 ICarbon & toriion iia molecule,% £ ■

■ • - ■ such as 3. the Ϊφ-Ιοΐο, Xthylbenaol, the rJethyläthylbonzole, the iüri— | f

. methj'lbenacle and the diethjclben brine. ■ · I ".

The Isomorisiörunjj these Zohlenv / AssorGtorfe using Ii 'dor inventionsGstiiri- ϋ: · η ICutrAlyoatorcn vrircl in G-ogeirwart von We.ssor- -f • stoff with! Teiüporaturcia In Usroich 0. 5 * Ci ⁰ C; ^? i ■ (700 ° to 1000 ⁰ P) ₄ at Prüafcen sv ^ clicn 3.5 and 35 ku / cm ² (50 to r 5OO pounds per 3cfaa.r0 iixch) and init Sauffi £;. GSGhwindiGlceiten ΖΛ-iisohen 0.5 to 6.0 "VcluiB-on flusci ^ ^ jo he Köhlcnv'asserstoffbcischicküJis ^Vo-:; Lunen catalyst ^ e hour and with riclverhältninson V / aoserGtoff Γ

to Eohlenivaiicerstofi * in the area> Avi see 1: 1 to 20: 1 durch-sexMihrt «, -. Steven more before?: Urrb be condin ^ un- ^ er., 'Vobsi Te: ^ ρ er .-. Tür en zv7i 4? -7 ° C am A-SP ⁰ C (800 ° bif = 900 ⁰ S ¹ ) , Dr'Acfce swißcTicn 7.0 to 17.6 ) fv / cu ^ti ~ CiOO bi? ? 50 '7101133.C ¹ P per sc- u ^ re ir: .ch). Zi ^ ün ^ SoOhwindigkci zv-d shert ^ jO to 5 »° volume flüs.'si ^ sr TCohlanv / a ^ sorstoffbcschiklcung ^ e VoDiiiion Ko.-tslj ^ oto ^ js BtM.nde and nolcre reserves of hydrogen to carbon swrlnclion 3: 1 to 12: 1 an ^ ev / taidt • become. . . -

BATH ORIGINAL

809302.0524

.

To measure the. Activity and Stability or Lifetime '| fc

of the various enen according to the method according to the invention. l |

Various tests were carried out on the catalysts produced. ! ??

At the. Standard endurance and activity tests are dio in \ §.

Pillenforia present catalysts broken up and the Eroktion, -v / olche on a sieve with an Ilasohensahl per cm of 20 (Hr.-1Ö U # So Standard ßieve) aux'remains, but through a sieve

free steel of about 2.5 ^z r cm (1-izich). inner diameter with a Q; hermoeleia3nt ₃ which is attached exactly concentrically over the entire length of the catalyst bed, given a permian. . 'Devoniaa: Naphtha- from West Texas having-the following characteristics:. ■ '. ASiEM distillation "•. ^ Over point 84? C (1SJ ⁰ F)

■ 10% point. 99.3 ⁰ Ci (211 ° F)

- Point

Octane number

■ (ASOM method D900) 48.0 -

■ % sulfur 0.070

^ API G-e \? Icht at 15 »Ö ° C -

. .., 0 ⁰ F 57.8 °, ^

v / was over the catalyst xo with a gas velocity of 3 liquid volunen ^ e volume of catalyst per hour under a water

fuel pressure of 35 ₅ 2 kg / cm (500 psig), a 10: 1 ratio of hydrogen to hydrocarbon and a temperature of 516 ° C (960 ° P) cm inlet and outlet of the catalyst bed, which is passed through the ihoriaoelesent in the ! ThermoalementröhrQ determined v.mrde, directed. 809 80 2/0 5 24

with a mesh number of 5 goes (IVr ₀ 8 US Standard Sieve), ver— §

applies .. A sample of 75 ial f / ird in e3, n reaction vessel made of rust-> |

• It is known that .that platinum-containing catalysts according to the type of the invention both have an activity with respect to. Hydrogenation and one activity "have dehydration regarding the Kydrio- ^ is approximately activity important to eino 7erkokaung dos catalyst;.. Through unsaturated reactive intermediates, dio v / ohrcnd the Eoh.lenwasßer * stofiTuawaiidliin3srQaktionen be made to comparable beware. ran in the catalytic ormierung, one of the wich.-: tigsten reactions in the dehydrogenation uter cycloparaffins, whereby '.. aromatic compounds obtained verdaji. The .JTydrierungs-Denydrierungsaktivität of Eatal ^ crystallizer iot when 2.B. the Bescaickungsaaterial s a large proportion of ethyl · contains important in Isonerisierung the alkylated benzenes of the type described here, ₉ /. benzene, said material converted by the hydrogenation activity of the Katalyaators in iitliylcyclohexan v; ill _ö Sin iüeil of Athylcyclohejcans is / andelt by Isoiaerislerungsrsaktionen 2.u Dimethylcyclohe ^ anen un ^ ev, which are dehydrated again to form eL'cr vorschiodenea ^ FIO isomeric _o!

The dehydration reaction is highly endothermic, τοη v / elcher ^: -, In fact, the Yorliegendeh! Tent use was made of a very sensitive method for the determination of the .dohydration: activity of the catalyst by measuring the temperature of the catalyst bed at -trifferonon reactive dehydrogenation Pmikten over its entire length to devoted because of the fall, the temperature of Xatalysatorbettes at Onea gexTisson distance below dos intake point below the Einlaßteiaperatur from _o llewi the Behydrisrungsreaktimn rider abväxts in the catalyst bed, the nearing completion, the Mrmeverlust due to the reaction from compensated by the heat output of the furnace, which is the

80 980 2/0 5 24 _BAD ORIGINAL

Ticncgcfäß surrounds, so that the Ssiaperatur of the catalyst bed again rises until the temperature at the outlet of the catalyst bed is reached again the same, the inlet temperature is β the at this one Temperature "Profile" measured the lowest temperature known as the "rainimale Bed temperature "stated is a very significant one An indication of the activity of the catalyst and the extent to which this temperature has been reduced is a very sensitive indication for the extent of the "loss of catalyst or activity. ·.

In the case of the aeia tea, visr significant results are obtained can be expressed numerically, obtained These are:

(a) Mo octane urspriinglichen product ,, the while reaping dor? A Hours Botrieb receive v / ground.

(b) The original minimum bed temperature, measured after 2½ hours of operation.

(c) The rate of change in the product's oatane number over time, expressed as the decrease in octane number per day ₀

(d) The rate of change of the minimum bed temperature, expressed as degrees per day

This stage: life and activity test is continued for 10 to 14 days, or at least long enough to give any reasonable indication of the rate of decrease in the octane number and the rate of increase; the minimum bed temperature "If a catalyst .-" has a high activity and a high 'stability,' i.e. a long life, the octane number of the original products is high, the original minimum bed temperature is low, the Abf ^ !! speed _; the octane number of the product per tap; is niodrig and the rate of increase of the minimum Bott-Toiapatur per Suj is also nicdi. ·! ^ · «'.ί.Λνΐ; ε ^ ^: - ■ -: .- ·: = 8Ό9802 / 0524 BAD ORIGINAL

In a modified activity test, the catalyst manufactured and -quietly in the same way as in the standard Leberisdausi ^ and activity test dealt with the expectation that the Test approach is only carried out for 24 hours. The minimum bed temperature is measured after 2 hours and again after 24 hours and the number of get the product obtained in 24 hours certainly. '

In your regeneration process, the catalyst is subjected to seven successive "coking-itegeneration cycles, in order to reproduce the deactivation effects " in an accelerated laboratory process, as is obtained under actual factory conditions when the catalyst is used for successive periods der.Heformi © rung with subsequent regeneration after ^ edar heating period is used _o This regeneration process. is carried out as follows: A distillation fraction of a Permian-Devonian Sohiumaterial from "West-iPsxas- with the following properties: ivSTni distillation

45 ⁰ C (11C ⁰ F) 70 ⁰ C (158 ⁰ F) 82 ⁰ C (180 ⁰ F) 97 ° C. (206 ⁰ F) 128 ⁰ C (262 ⁰ F) 168 ° C

uberpunkt S ^C A 10 0 sr 20 Ά Ln
σ > U / j V
CVJ 80 % CD OO 90 % cn O 95 % CO End point Residue

266 ⁰ C (510 ⁰ F) 2G6 ° C

95 »5 ^C / ' ^J
r.5 ii BAD ORIGINAW

ii

/ ΟΟΊ \

üfc! in a cesection vessel with an inner ■. diameter

■■■. ■ V ^C :

from. about 2, ^ 4- C2i (one inch) introduced. The catalyst is

Contact with water erotoff for two hours at 10 ° C

mrcde over .50 g of catalyst with a particle size such as

that he goes through c-in GIeL lait a stitch number js cm of 5,

(Ko «0 f.Se Standard. Sieve), but on a sieve a> with a Παρ

echen number each of 20 (ITo. 12 TJoG ₀ Standard Sieve) is retained, passed «, This catalyst vd.rd in the form of a - j ·

(95O °]?) 'For an hour there is nitrogen at 566 °

Flushed then värd the "Distillatl'rsJrblon over the catalyst; V

tor at 566 ⁰ C (105O ⁰ P) hit a speed of 2 al ^ e Έ ± - U

nute for 12 Mnuten passed "Since hydrogen exists Icein k

, The catalyst during this treatment with coke comparable "ß is

unreiniffb "following the -12 minutes Beströiaungszeifc v / ill · [

the Katslys9 gate with nitrogen at a pitch of 76 ¹ ^ l \ -

3 "e skin for 39 minutes through ^ espü3.t, with a" mixture of s

Air at a speed of 160 ml ^ a minute and by Stick- J.

fabric bol einoj? Speed of 640 ml per minute during one ji

Gesoiatzeit of 304- minutes for the air-nitrogen mixture comparable f

burns and finally the catalyst with nitrogen with ■ ;.

a G-eschwindigkeit of ^ <o ^ e nl minute for five minutes' h

This represents: a cracking and sagging cycle and -this cycle is -filled through six more times, so that a total of seven cycles have been prepared. Ifech dem. seventh circular · race, however, the catalyst ialt air at a rate of ⁷ ml per 8Co liinuto v / rlhrond four hours fired _o "

809 8 C 2/0 5 24 BAD ORIGINAL

In order to determine the usefulness of the catalysts according to the invention, a part of a freshly prepared catalyst was subjected to the standard service life and activity test. Another part of the same catalyst was fed to the regeneration process and this part of the catalyst was subjected to the regeneration process standard lifetime and Aktivitittstewt subject. the "in" and the default lifetime. Aktivitrtstost iriit thine. fx'isoLen portion of the catalyst results obtained vnirden then fait en & dtirch the default lifetime and activity test mit.dsm catalyst ₉ 'of the subjected to the regeneration process T, ^r ci \ Ten, the results obtained compared

In some cases, the fresh catalyst was also subjected to the riocifying alitivity test ιόΛ another rope of the analyzer from the regeneration supplier The results obtained after regeneration were compared * "This latter method was preferred because it does not require the extremely long test times required by the standard life and activity test, but in the same way as to the 1% acb ^w / ice of the" regeneration stability of the catalyst is useful *. .

So that the tested. Catalysts comparable to one another niKd, ^ ux'de a uniform method of catalyst production an ^ ev / andt _o Bino sample of v \ -Aluininiusiü ^ -d siit a surface of about 45C qm Je Orasa., Which by the previous to

BAD ORIGINAL

"8098Q2 / 0524

I / DO I }

-V

guided adsorption method was bestiasmt and with such Rope-sized that the total kenge through a sieve with a number of meshes Every cm of 576 goes and at least 80% of it goes through oin

Sieve with a length of 1600 per cn (ITo.60 TJ.So Standard Sieve and Έο <, 100 FS ₀ Standard Sieve) was made by intimate contact with a solution of chloroplatinic acid using 0.4-5 ml of chloroplatinic acid solution each Grams of activated aluminum iride impregnated. At this concentration of the platinum solution, the platinum consistency obtained, based on the G-3- *

«■ ■ ■ weight of aluminum oxide, C, 69 & pw .-% _e . Times the impregnation was dried finally calcined with air in an oven at 566 ⁰ C (105O ⁰ F) for 3 hours _v to Ghlorplatinsäure to überfüliren f the impregnated alumina in an oven boi about 100 0 (212 ⁰ I) and in Platinnetall. Since a partial agglomeration of the epidemics occurs during the impregnation, the

Catalyst, again through a Sieli with. a number of stitches per cm of 576 (itfOo60 U.S. Standard Sieve). to the agglomerates to remove"

The silicon dioxide / aluminum oxide content was reduced by steam treatment. Activity carried out by, the DM-Hert bostiomt v; urö-e ₉ dessktivi-srto a. fresh commercial cracking catalyst containing 15 Cre ^ r .-% alumini u & axyä and 87 & ew <> - # SiliciuEdio3qrd _s vmrdo sit; Steam at a temperature of 566 ° C (105Q ⁰ 2?) And a Dampfdz-aek of. Treated 1.7 kg / cm (10 psig) for 18 hours so that the catalyst activity obtained was 75 D + L, as measured by the method of Birkhimer et al. This material, in the form of a finely divided powder

\ * ί £ * ΤΓ - ^ ^k ' BAD ORIGINAL

80.9802 / 0524

with about the same particle size as the aluminum oxide, -tjs was then ait an aqueous solution of manganese sulfate using a C ^ -5 ιίΙ solution per grain of silicon dioxide-aluminum oxide> | ϊ and of such a concentration that after drying on; ^! ; .-

the silicon dioside-aluminum oxide the desired G-evrichtsproaont- '■ &

quantity! "angan was deposited, contacted the impregnated silicon ^

Dioxyd ~ Alurainiumox3 ^r d was in an oven at about 100 Q (212 ⁰ IQ ₁ φ

while getrocioiet and with air at 566 ⁰ C (1050 ⁰ F) droi .stunden "^

in eiiioaL Of on calcinierto ₍ ! i%

Eight parts by weight of the platinisiertoii -. Vluniniumoxjrds \ rorden ^

daiin 'with sxvei parts by weight of the GiIi- ', ψ;

ciuriidioxyd ~ Aluminiu32o: v3i "d thoroughly premixed, The 2u, oarar.i3nsetsung ^ J.

was made using a conventional Ctokes pelletizing machine.-Vt

Pelleted The Ka- ''; - ■ manufactured according to the sou ancestors

talysatoron contained on the aluminiUEio ^ d 0.55 ^ platinum, based "; - .;

on the Gcwic'at the completed iLatalysatorSo ^v -

, -. US the following tests result in the superiority χ

the catalyst on- according to the invention for the conversion ν

Preferred and specific by Zohlcnwassarstoffeno -cie positions

Audfä] Irun; 3for £ ien the Jirfindung of which However sslbstverBt ^ nd ^orbitals:; -_ not borrowed is bcochrunkt it.

Tin K. .talys-.tor v / is manufactured according to the previous dom ν · ι · .iV3fehrten Einheitsverfαiircn with the deviation that the "■ Gilioiumuiou ^ yd-Aluiiiniutioxyd not iuit cin ^ r Llangansalalösusig

c;.! a; i: .irt v / uräo, soacQ i: airic lLoi ^ riV ^ r ^ indiing on cozi Giliciu ^ i—
ojrvJ .-. '"l: .." - lniu'ic-jC "i" i νοιΊΛ; ¹ ;. Dlczcx !! ^. ^ ...! ./ ■. "jator, dor liit ^li Z ^u ^^ > -

BAOOfflQiNAL

8 09 802 ^ 052A -

ι- —ι ι # w ν *

given v / ird and the 0.55 ge \ ir .-; j platinum, "especially on the weight £

of the finished catalyst contained, and the previously known Kaf

catalytic converters, the Eegoncrlerun ^ s procedure was under- ■ $

worfeiT and then the modified activity test _o The results of these tests are summarized in Table I <,. '£

■ " . -F

Example 2 -. '%.

Four catalysts are used in accordance with the standard procedure .

Ren manufactured using manganese sulfate solutions for £

Impx'regnation of Siliciuadiosgrd-Alurainiuiaoxyds- To manufacture J *

deo with "IIA" designated first catalyst was the Kon- ' fU

zontration of the manganese sulfate solution such a value that a #

/. . "■" ■■. A.

Equivalent of 0.25 wt .-?> Manganese, based on the weight of the Si- β

liciumdio ^ cyd-AluminiuHoxyds was deposited _o the Llangansulf at—. Jf

concentration of the to laprägniexnins des Sileiumdio ^ -d-Aluirtinium- - ^

oxide of the a \ 7eiten catalyst "IIB" used solution \ -mrde 'Ά

so. regulated that the ilouivalcnt of 0.5 wt. % Manganese., bezo- γ.

enough & uT the weight of the silica-aluininiuiaos ^ rds deposited i '||

vnirde. The Mangsnsulfc \ tlconzontration. the one used to impregnate the ^

Biliciumdioxyd-Alimini unosQrdG the third and fourth Katalysä- \ χ

toro ¹¹ IIC "and" HD ", ended / ended solutions i?

that the equivalent of 0.75 wt. TJ>, where 1.0 wt _. :

on the weight of the silica-aluminum oxide etbgela-: - · '

gort irordGe These catalysts -.before the icosenerierungav ahren .-; ·

and then subjected to nodifiaiertön activity test "V

and in case cios second catalyst ■ ^ · ¹¹ IIB "viurde to the regeneration · -; rierunfjaverf also ätanüard-lifetime and activity ■ tast caigeschlocsöno watches The results of these experiments are in iDcbol-.

lc I listed

80 9 802/05 24 BAD

IH I / DÜ'I

Iqj / cia (30 psig) was treated «, then a TTang Q, 5 Gewi: -; j Manganese, bezoson '"on"läas'"' Siiiciuiidio .-: qsrd --'-

Example T ,, «. . ■ - ^

iniumbsryd "-iiiit a" D4 * L— ^ UcWi ¹ VitÄt- νοϊϊ 75 ^ ver * ·>

"U ¹ UTdO ₁ became" © in SiliciltüäMibi ^ d ^ Xluiaisiät ^ \ f

sort - j ι?

at 566 C for 18 pts. under a pressure of steam from | ff

, deposited iin ilatälysstor &quot; IllX ^ir * was ^ by. Calcining at an ienpöratur of .599 ^ 175O ⁰ F ")""f the other catalyst" 1113 "according to" the Ctandardmetliode calcinier-fc \ 7urdG, d _o h <, at 566 C ₀ ΤάΛι (ifcii from jedösi These Satr.lysatoren Tsrurde dom standard-service life- "and 'Alctivi- ^ tr.tststGt and the modified _41rfcitätstest unterrorl'eh and £

Another rope made of.-springs, this catalytic converter was given to the Hege « Y-. nerierun ^ cverfahron and .enseliließend both the modified ψ

Activity test as well as the standard life and activity test under test ₀ The results of these tests are shown in Table I

^; Eeiapiel V, ■ ^ - ■■ · --—

An Eatalycator ¹ IlT "vairde corresponds to the standard method using a v / üßi ^ i ^ eii .. solution of ilanganciilorid for the IttprEtSniertfjar; des Siliciuradioi ^ rd-iiluminiuiaoxyds.-iierstell the concentration of the, hangoncliloridlos that, on the DilioiuadiQ ^ d-Aluminum oxide ü _s 5 Grew © -yk Manganese, -believed u on the weight of the Oil Dios ^ d-Aluuiiiuia Oxyds, were deposited * i) iec & r.

- \ 26 -

and then subjected to the modified activity test The results of these "experiments are shown in Table I."

A. The rope of the Sil · iciuadio2ς7d-AluBliniumo: ς7d ~ ICracKk: ataiτsators of a D + L- ¥ ert of 60 silted up to the HOrStClIuJa ₁ J dos catalyst "TIIS" was treated with a manganese acetate solution "of such a concentration and in such an amount, that "after drying at 11O ⁰ O (230 ⁰ F) and after Oalcinieruhg · for - three hours at 566 C 0.5 Gevr" - % manganese, based on the weight of the silicon dioxide-aluminum oxide, atif the Siliciumioxyd-Aluniniumo2ς5Γd deposited in the form of the water-insoluble oxide

.., A sample of troitnaelgetrockaetem aluminum hydrate pulyer., ^ G

which contained 0.6 wt

Impräi ^^ _ older: the Aluminiuiao ^ on the _one: &

Chloroplatinic acid solution and hydrogen sulphide get "Pas -... _: ........ j ||

Platinized aluminum hydride powder was correspondingly dosed in y-j

the TJ.So patent publication 2 S3S 444 described Terfahren hergo- .. Jj-

represents and.-..- contained 57.28 Gevr »- $ solids, what by boiling. ■ £

on Ί10O ⁰ O during SWEi \ hours bentisniit v / urdee, The Aluminiumoxyd'- V, trihydrat-Geha.lt of Alusiiniuaoxydteils of Pulve3 s was 75 Ggw? "- ^ ΐ,

ψβ, α by analysis by means of X-ray ^{diffusion with at 110 0} C (250 ⁰ I?). \ -i

found dried samples \ 7urde ₀ 1395 _r g this platini-> • wobbled-Aluminiumosydhydrat powder was thoroughly mixed with 200 g -. of the Monganozyd as described above; - Siliciuadio3cyd ~

Aluffiiniuiaoxyd -JPulvers gssünd-liok poured and 260 nil water - _; au of liischuns added _t where further mixed thoroughly \? _o urde The IiIischung was by a mold of 1 ₉ 19 mm (1/16 inch)

80 980 2/0 5 24 bad o _RIG , _NA L ' ΐ

ItI / WJ

on a 5 »08 cm (2-incli) Welding Engineers Ärasiliaiy extruder (Hodell 2010) with the formation of Auspreßstüekea iron 1.19 "

ZM 6.35 && ■ length (1/16 inch to 1/4 ineli) spread out «, Bas strand— \

pressed material was get3 at about 110 ⁰ O (23O ^ö 2r)? Qc met! and?

at 482 ⁰ C (900 ° I ^? ) calcined with air. This Üitaijsator became |

subject to the blessing procedure and aaasckiBend the ao-]

differentiated activity test The xrgebolsss of these ¥ requests are?

summarized in table I'«- ι

When comparing the aiifgofüJiirteia, Ssstergobnisse, ι

with the preservation in the examples beßehrlöb-QBöii catalysts)

ten times, it should be noted that only no! e! e catalysts _? |

T / elche after the Begene, rieruno; both a bearish iDiisimal Batt- "j

Beaperature as well as a * high oktonsalil after 24 hours "with dea. J Modified Alitivity Test aufwoii.-oa,

Eigonschaitan ontsprecjiend der Zaelstsllimg of the "33? iTi3id" ins on v / ei - sen. In the same VTeiae with the Siiszide ^ rd -! «el
Activity test only such catalyst 021.5 irelelie both, a low
ge rate of increase in Ktiaixialöa Eett- ^ eay> eratur je
As well as a low totality of the decrease in the octane number, "useful Gbv / oM. The liistiegsgöccinvindis—
lcoit dex 'üiniEalen Bött- £' oäiperatur, the eich, caireli 'Versioicli the
ü * enj; Gratur after av / ei Gtuiiden rait of the X * o £ i £ ji; 3?; itii2? aacli 24 ßundon
results, an approach for the I: er; onQrieri23asssti: l3ilität ~ of the Z
ojLtor-G itjtj lot clio xUiivjoratux'liöho üer- iiinia.c.le2i Satt-iiOj-.per
after 24 ritv.iicl :: n vcn r; röJ? .Gror Γοΰοιινίύΐ ^ at the SoErteili ^ is der

809802 / OB24

I : O? Abelle_ ^ ^?

,. '"· Ilinimalo Γ-ott- Octrjj- Anstiog waste ''

(1 'Petit- Tin' -uf £ H - ^ - "-" »β C (I ¹ '^ zoli"^;' der κι- dor ^:

conditions lioiusaiozyd- ^: ΐΐΕοϊΐ after. after "niaalcn Oe tan-Aluminiunioiqfd -2 hours» 24 3td. 24 ßtd.Bett- sahl ^v .. · .- ·.. Torso *. $ o 2ag;

·. '. - ή ο 'ί'ηρ; ■

I (after lie- ■; · no ■ ■ \ 430 485 97.0 '"■

- ■ * ■ (896). (901) t

1IA (riO.cli So-

) 0.25 4? 9 482 ", 97- _? P

(3 93) (099) ■

113 (according to Hg- 0.5 465 470 97.9 0.20? Σ 0.27 ^v

g _S no2; ierur.fs). - (870) (878). ■ (0 ~ " ¹

HO (after. "Qo-0.75 ■ 471 472.5 97.0

) (800) (883). -. ..

HD (nacli. 2e-1.0 470 472 95.0

i) - (878) ^:. (882)

II ± i _r '(before Ee- ■ · 1

conerioruns) 0.5 475.5 476 95.5 0.055 0 0.09 ί

(877) (878) 0.10 ^ !? 1

IIIA (after Se- 0.5 463.5 476 '94.3 0.233 ^ 0 -0.16 |

ΙΪΙΒ (before lic- 0.5 '466 466.5 95.5 0.222 ° C 0.08 f

). · (87Ο) (871) 0.40 P ' \

III3 (according to Ke- 0.5 471 474 94.5 0.494 ° C 0.26}

Conoricruii; ·;) (GOO) (005), ■ 0.89 5 ¹ j

IT (nac · Hq- 0.5 -472 472.5 97.7 - ·?

conor-iei-u.ns) (882) (883)

Y (nacii Rs- 0.5 471 471 94.4 I.

^) (380) (030) '^> ·

Clear Ccta: azaiii, genesaannacii AGiSI method D-908 ■

In advance of the obtained results

of the Katc.Iysotors "I" with the at Verr / endiuis'.dor Hätalysatorca. '"113" or ^tr IIG "erar.ltenen Dr-c; cbnisscn revenge shows that it is not-] v: oi: .C-'1q ict, eino LlanscnTorOincron ^ · aui dea Silica

8 0 9 8 0 2/0524 "BAD ORfGINAL

j.

deposit ,, oinon catalyst · un regenerated is _s to obtain * Ss should be noted 'disß, although the cetane number of the products zrtit these catalysts is practically the same, "bed catalyst ^li I" the minimum bed i'euperetur very high is, ^{honoring the catalysts!:} I1B "and" HQ "the miainyxlo Bott-Ee ^ temperature rises a cut word ·" Due to the height of the minimum bed temperature of the ■ catalyst ^! '1 ^I! the dehydrogenation reaction is so low that this catalyst cannot be used in practice. .

A comparison of the catalysts ¹¹ IIA "and" I "shows that the Congo of Manganese should not be less than 0.25 Ge \ i _o -% aui'v-iron, since iCatnlync.tor" Ilil "only one Slightly improved ice making stability compared to catalyst "I", which has a manganese deposited on the silicon dioside - aluminum oxide; hato - '■ "■

! ■ ice comparison of the edt of the catalysts "3" and ^1: l "Iö" er-L: \ ltcncn iir-gcbnicne v / ird £ it tgo stalls that the amount of Lanrvans ■ ;. on the Giliciuadioir5 ^r d-Aluiiinium "; yd should not be greater than 0.7>9'-' , where 0.5 / i is a particularly preferred term"Katalyaa-.'; gate "113" results in a l'rodulct \ ^r on a low oc tanz eal, from which .; o I find that the Zangan should not be present at a height above 1.0 fre-Wo-% ""

The Verto ± for the Xat-ülysafcorön "ΙΪΙΛ" and "11X3" soi / von,. '.. dali I-'ansan, uüim es ia bovorsu ^ tc-n ü Reich used v; ird _s ICatalys-toron lait au.cnohra.ena good resonance stability results, moreover results from the, v / erten- these liatiilys- 'toxOii, daf; the activity dec Gilioiutadio ^ -d-Alominiumo ^ ds varies

BATH ORIGINAL

"8098C2 / 0524 -

/ DOI

. i

can be and that the Oalciniexnmcstojaperatur varies who & on
can without. the inability of the catalysts in
is significantly adversely affected »

The \ 7erto at catalyst "IT" show that en & era Ksngs
likewise v / ie the sulphate for the deposition of the hangan compound on dea
Siliciundio ^ y'd-Aluminiuia.o: -cyd can be used. ·

^Ji us do cakes for catalyst "T" shows that a loading · A ferred Auüführuncjsform of the invention, according to which dio together * gedetzten compositions are prepared by pressing, a Hege-- 'j nerierunßsstabilität ex'gibt, with those of catalysts, l

τ the dux'ch pellet! exning were made, yergleichb'-ar is ο - ■%

Example 6. · ;;

A l'eil of the catalyst '"ΪΙΒ" became another fortress:;

under; v ^; ox ⁿ fen _? uia its activity ■ and stability with regard to the ■. * ■

formation after regeneration under subsequent strict ·; ^;

Heforiaierungsbodinsungon to bostiimion. ; ^: _;

ΰοΐ this l'ost was the at the standard lifespan - and i Aktivitlitstoüt © inpj-oßctate apparatus-used. As with the standard «| Lebsncaauer- and activity test ^; urdo which are in pill form-> do catalyzer crushed and the traction, which on a standard ■ «

ρ ■. i

Sieve with an Ilaschensahl per cm ~ of 20- (iio ₀ 12 U.3 _o standard öieve)

■ remained behind, but by a standard cieb from a liasciienaahl ■■ '.

each about ^ of 5 (So ₀ 3 IJ ₀ S ₀ Standard Gievo) went, uses «A: -

Sample of 75 nl was packed in the eeclrfcicnscefäß and the "; · Perraian-Bevonian liaphtha 'from 7 / 3st-To3cas ·, which is standard at doa.

Lifespan 'and activity test was used-3, was used on the 1.

Catalyst with a rate of one volume of liquid

809802/0524 B * ^D

per Yolimen catalyst per hour under a. VraBserstoff pressure of 36.2 kg / cm '"(500 püig), a molarun ratio of hydrogen to hydrocarbon of 5» 1 -and oinci · von'51S temperature ⁰ C (960 ⁰ I ¹⁾ at the inlet and outlet of the catalyst bed, it The K'aphtha was passed over the catalyst for 24 hours and was during this period due to the low ratio of hydrogen to coke to hydrocarbon. "Catalyst deposited © The catalyst was deposited after 24 hours at iitHOsphiirendrucIs starting at 39.9 ⁰ O (75O ⁰ F) using nitrogen at 0, ^ 66 Ώ? (20 cubic feet) ^ e lidnute, geaiociit lät ¹ 0.028 m ' ⁵ ( one cubic foot) of air, Eaclidem regenerated the noble coalition, the temperature would be increased to 482 ⁰ C (900 °! · ') and after the combustion had ceased, the air would rise again

3
nit der ü-asckv / ii.die.kcii; voü 0, C2Ü Ii £ o I'4nU "fee. ee & tciGGrt up to a üer-t of 0.283 i * (ton cubic feet) ^ e l -."'inute<, Venn, die Lufvgescnuindir ^ ieit thear Tert öx-rcicht had boi den. - Call conducted on external l'edin gunmen, was heard with the nitrogen supply cuf and the catalyst in air during "four otuiiden burned" the

tor -.vurde α ·; -ηη with Gtickctoff durch ^ eblasen and zixr Durchnit d & n ITaphtlia under the Voracr ^ ohond on led 2z-

n back'ljrrxrLt. This · Λαΐ \ 1 "; during five KreisHlufCsii riederjiolt and after the fifth Eo ^ onoriorun · ;; rrarö.c the ICr-.tal: rs ^ .tcr dom" tondrjrd-Iiebencidauer- und. Subject to activity testing. ITacli 24 hours clieoer Ts, ^ conditions s-icte dac rrodalzt oino Oct ;; nsaiil vcn 94.8 and a nir-irar.lo rntt-'I'orLn-eratur of 468, ^ "G (875 ° -). 3ci rnendirjun: - des ^ ontoa -vurdo fc ^ t-ontollt, eic ·: üi ..: - i; ini ::: -: lc. ^ r-tt-C-Gii-oratur-, je C: .- ™ u: i 0.5G ⁰ C (0,

rise · and di _:>

Cot- scJil j "? ^ CZ around 0.22 Lbfi-.il. T-Lr ^ o l ^ obmsüc äai [j

äai [j.c: i,

80; 9802 / OB9i

his ursprüngliche- activity and stability regenerated vrerdon can no.ch.deui he had lost this auchs during Gebx * and that these F ^ ^ senerierun sfühzGkeit during a number of .Kreisläufen maintained v; ith _e

Ex iel 7

A sample of fresh handolr / usualoa. Erackkatalsrsator, der et * / 7a 13 Geu «- ^ Aluaiiniurioiivc ¹ and 87. & οΐτ _ο -> ί .oiliciuadiozyd. . contained, treated with steam at a temperature of 566 ° C and 1.7 kg / ca (10 psig) vapor pressure for 15 hours, so that the activity of the catalyst increased to a D + L value of 75 humiliated. rurdo, determined after the demonstrations ■ by Birlchiiner et al. This partially desG £ ti * fourth catal ^ aator i; ur was divided in the I-'orm einos fCiin I ^ l \ ^r Gr3, dan-totally / through a Straidärd sieve of a Ka.3ca.enzaiii a's cm ^ of 576 (ITo.60 TJ ₀ G ₀ Standard ß5.ove) and zv. Kinde et ens- 80Γ ·> by a standard biob of an ITacchen number ^ e approx. ² of 1600 (i7o _o 1C0 US _e 3tandard ßieve) s ⁱⁿ G »n with a v such an amount brought into contact that after drying at 110 ⁰ G (23O ⁰ F) and galvanizing in air wiriireöb. three ötxviidcn at 555 ° C 0.5 Ge ^ .- fi Itc-nccia, boso ~ en on the Siliciumdiosjd-AlfXiiriiu2.o: ->'d, -on the ■ Oiliciundic ^ rfd-Aluniniunoxyd in Fora _:

\ of the water-insoluble oxide were deposited.

line trobe of troEnielgetroclrnetom Ali ^ iiniunos.ydli.ydrat-Pulvor ₉ - • clciiec 0.785 Gcr /.-% riatin, r.uf G-lüh ^ oT.'icIitßbasis, contained, vror-00 by -Ir ^ rUc ^ isruns 'ü.os' AluniniuHozrfdh ^ drafbreies üit .Chlorwl'-tin.T. "iur-olönun:; - y2id Schwofol ', väß3cratoff received» Tj: \ s platinicicr-to Aluiiiniü ^'. hjdrat-.i'ü.l ^ ror τ-urdo entoprocb.e.nd dr-s. in the UOS ₀ -

8098C2 / 0S24 _{BAD 0RIG (NAL}

Contained 6 - '; -, 70 G-ct7 «- # Psatctoffo', which is indicated by" Srhitsen n.uf 593 ° C (1100 °? ·) Ehrend sirei St and on foctsoatellt v; urde _o Der Alyniniuao ^ dtrihydr ^ .t ^ eh'ilt dos Γ-ulvorj amount etiTa 75 G-ov / e-7 ', v / as by I? c- * ntcoadlir.frrl-: vionacincilyso nn l> oi 110 ⁰ G (230 ^ο : ϊΓ) fjc ben festgfiGtöllt T.'urdo, 775 g of dLosoo platinum varieties Pulvors ivurdan nit 5 ^ 0 · 3 <3.os - ^ on ^. ~ nc ^ cj / d - Giliciu'öq O3 ^ 7cl-rulvers, Lox'ge -stell, wia Vorlicrsciisnd described, ^ rüncili vorid.sent imä ^ζ ! · 80. Nl ITasssr su der Lliscrrang zuopeben, ■ xvoboi \ voi— torhin {rrüjialicci gorniscnt -v; urdo „Bio Mischujia · vmv & o by oino Posa of 1.19 hot (1 / 16 inch) on c-inor fötroxii ^ press to picture in ^ by l-rciistückön τοπ. 1.19 '^ s. To 6.55 s ^ long (1/16 inch te 1/4 ± xioh.y G.ur . £ Gproscht <> Bas ausfrcpreiitd material was calcined at etv / a 11G ^V G ctnct and at 4S2 ° C (9Ou ⁰ F) in air,; Dcr fex-ti ^ a .vi7or consisted of otv / a ^ loiclisn weights doc p -lrti-

nisierton Aiur, iiirasio: cydbo3tcaidteij.s and des J-Iansanox7d-

Silicon dioxide

Siocer "JCatalysäfcor vrox-de aur iGOusrisior'ang by aly .iroanrLcct ^ n TColilcm / rsserctoffon under Vorwonduns a portion of 75 ccri in G-5: vcnv. '. O.rt by Uasserstcff untex ⁷ den in Scholle II o.ufr; - presented LDdin ^ un ^ en \ -? 3r'.aet. The composition \ lc-r 22- ■ ε chi el-run -; ^ and the "Suscsinienoetzun. ^ -ior obtained products are also in Table II rdt f -uif ^ f; jjc; £ ün.en. The gev / ichtsmäQi ^ e same for don Vsrsiich la.r; at et-va 100 Γΰ _# ■ "

ZIn woitoror Eaüalvcatör ^ arde. corresponding to the in example 7 an ^ ii ^ nitoa i-.letho.du iiox- ^ ostollt; -: it der Auniiahaö, diß die Lcnrjv: dos riatij'iLJ cuf du ^. AlUiiiniuuo :: 7d 0,0 Ccwo- ', ^ was, the ulatinioiorto

Λ. '8 0 98C2 / 0B24 ·' copy

BAD ORIQ _INAL

Ί. * Π / DO I

67 _} 55 G-ov /.- Vö contained solids and

that the Aluiiiniinaoxydtrihydrat-u-ci.iu.lt dos powder »about 77 G-ev; .- fj

-oxytL-i 55 ^ 0 C this "pl & fcinisiorten Aliiidtl ^ l

With 3720 g of the as in Deisxjiol 7 hcr ^ oütelteii!.!, - m ^ a

^ d-AluiainiuBio ^ -d-Jrulvo ^ iii thoroughly vej-iaischt and u'o.sser to the Uiscliunß 'under furtgeoetatoia thorough eii added "The Liischun ^" is pressed, dried in "Geispicl 7 calciniort. The finished catalyst contained about equal parts by weight of platinum-grade aluminum: oaiiiiur.io3q7 "d"bostaii'iteils and dos I; Iansanox / d-3iliciuia0.iojqy'd-AluiairLiriioxyd - BostanäteilSo This catalyst was also used for the Xsoiäeri, vjassonerstoffen- vjassonerstoffen- ! d'5tΌ Si ö Tectbedinguiison and composition of feed and products siiiii Ia jL-cibellö Il Jill ^ oi ^jiu: bo Di ₁ U fjSTViCiltaiu'ißlo ^ ^ ö'l iüli "* weight was at deJLaem attempt above falln otva 100 ^l / y _o

The catalyst was then expired in the first series (7

Ilroislclufe) and again for his Isoaierisicrungsalrtrivitüt using the same Oeschiclcung wio for the Soat des fresh iLvbir.lysCvtora tested Also dioce ulrgebnio.se are in iabclle XI listed »

BATH

8098 0 2/0 5 24 ■

Table II

conditions

supply

Example 7

Ice cream cone 8

'Comperatur,

Pressure, irs

psi-3

koit "(liquid kitln

ICataljsator per hour

ouch

5 850

13.3 175

1.67

Kohlennas α only £ 8.5 [analyzer

fresh

454 850

13.3 175

1.18

9.0

850

13.3 175

1.17

10.2

BAD ORlQINAL

8 0 93C2 / G52

56

Table II (continued) Example? geis-oiel 8

Zussnnensetung .

Beschik- Products Boscliilt— knns G-3 weight reduction weight proaont vrichtsder Bo- present delivery • no loss "calculated

Products, GG

of the Boschickung, no fore-pleasure calculated

catalyst

fresh

regenerated

^C 4 ⁿ 10

z-Qm holocular

0.17

0.10 0.50 0.84 0.64

2.59 1.13

0.14 0.05 0.20 0.12 '0.24 0.25 0.50 0.42 0.55 0.51

0.60

C _r + 'Cyclopa- 0, 93 _p - , 46 2 , 37 ■ 0.5 , 1.79 1.35 refined by.
IiOIlG X'32i iiolö— 1, 12th , 92 ' 1 , 35 c, 7 1.62 2.01 benzene Allied Ben-
sola, ILoloku-
XtJLL qJ w ο ~ - 1 ^ ~ WV ^, 25, 11 . 2 , 45 1.2 2.18 2.48 - 1'oluene Alkylated Bgη-
brine, 2IolGku-
larG'07 / o ^ 154 0, ^ 7, 10 1 , 65. .0.4 1.60 : 2.01 ill! - liortG "Bsn
solo j lioleku— 7, 67 • 0 , 32 0.0 0.41 0.60 ** ■ i. Iiy ^ L 0 GZx2 0 JL 15th 83 , 72 96.1 39.84 S9.54 o-olylene 97 12th , 22 22.8 18.76 17.63 iL-Zjlol 31 19th , 17th 4.2. 15.15 15.11 p-xylene 18th 40 , 67 53.5 58.23 59.20 19th 16 , 66 15.3 17.65 17.35

From the above 'vertca. It turns out that it is p-cylene

dor dioGcs laoiioro roL.ru. (I3oispiol 7) ₅

isn odsr that ο-ΖΙ ^ ΙοΙ cxlz oinor 80 38C2 / G52A

BATH

o-xylene is absent, due to isomerization using the inventive Catalyst can produce · (Example 8) β Example 8 shows also that the catalysts according to the invention several times without loss their isomerization activity can be regenerated, since the achieved product tax yield after the regeneration is practically the same is like the yield obtained with the fresh catalyst

From the examples it can be seen that the catalysts according to the Srfindtms for the isomerization of hydrocarbons and for dio & formation of hydrocarbons <ijej. such procedures that operate under conditions in which the catalyst is periodic must be regenerated, are very valuable «From these examples also shows that the unique regenerative ability of the Catalysts according to the invention result from the deposition of a Kan- '. gan compound on a silica-alumina component results when this union with a component made of platinum on , 'Aluminum oxide is combined'

Of course there are numerous. Variants of these embodiments, possible without departing from the scope of the invention * .. _,

- BAD ORIGINAL

Claims (2)

Claim mwmsämmmmmasa Catalyst for the conversion of hydrocarbons from a physical mixture of aluminum oxide on which platinum is deposited, and from calcium oxide aluminum oxide, the total oxide with the platinum deposited on it being about 10 to 90 $ of the weight of the finished catalyst and the platinum on the aluminum oxide is between 0 ₉ 1 to £ 3 Göw »~ £ of the finished catalyst, while the silicon = dio3cyä-AluDEiiniU! Doa: yä has an aluminum oxide content between 7 $> to 50 Ji« as a result » _v lchnet that otindestfine ein® Hanganverblndusig9 as the oxide, sulfide, or optionally sulfate "if it was considered to deposit the sulfate of manganese Hanganverbindung", 1st deposited on the Sillelustöioxyd ^ Aluaiiniuiaoxyä, wherein the Hangan the Hanganverbindung in an amount of from 0.25 to 1 "0 weight" of the silica-aluminum oxide is present. Documents (Art .; £ l Para. 2 No. 1 sow 3 of the amendment flow, y. 4th 80G8G2 / C5 24