DE1297792B - Process for the catalytic cracking of a hydrocarbon oil - Google Patents

Description

The invention relates to a process for normal aliphatic hydrocarbons catalytic cracking of a hydrocarbon oil at the expense of cracking the other components Production of hydrocarbons with lower boiling points of the feed material happens, so that in the total area in the presence of a catalyst, which results in an even poorer yield of gasoline optionally base exchanged aluminosilicate of 5 would be achieved.

Has a defined pore size. In the USA.-Patent 2 971903 is a ver

The cracking of hydrocarbons for production to improve the quality of hydrocarbons of lower-boiling hydrocarbons, in particular, in which hydrocarbons are described in especially those in the engine fuel area of a conversion zone at elevated temperatures boiling, has a special technical meaning. io with a crystalline metal aluminosilicate catalyst are numerous catalysts for the catalytic gate, the uniform pore openings between approximately Cracking of hydrocarbons has been described 6 and has about 15 angstrom units and the the, including those based on AIu, the only conversion catalyst in the conversion minosilicates, which is often referred to as zeolites is the treatment zone, are brought into contact will. 15 and an improved quality hydrocarbon

Those using different types of catalysts substance product with a molecular weight that is not catalytic cracking processes carried out are higher than that of the former hydrocarbon a number of requirements which are mediums.

there is still only a compromise between kata- In the known method, sodium-

lytic activity, catalytic selectivity, maxi- 20 aluminosilicates and their base exchange forms, Mal yield of gasoline, maximum efficiency - with metal ions replacing part of the sodium, speed of the system per unit of time, octane number or quality can be used. The metal aluminosilicate catalyst of the gasoline obtained or the amount of gate formed, however, in the known method Coke. In view of the multitude of complex single conversion catalyst in the conversion reactions, that accompany a cracking process, it is 35 lungszone.

has not been practically possible, however, to a catalyst according to the known method

To arrive at the entrance of a certain desired does not solve the problem all in the hydrocarbon reactions completely allowed and at the same time other constituents contained in the raw material Completely excludes reactions. To take advantage of cracking.

There is a general view of cracking going on. 30 In Chemical and Engineering News, March 1962, with known technical catalysts at see below, p. 52ff., is a molecular sieve in the form of a new one different relative reaction rates for synthetic mordenites are described. This aluminum variety Hydrocarbon species, this minosilicate can be in the sodium form or in a Velocities generally exist in the hydrogen form below and is through a high Order marked in terms of the ease of the Krak- 35 silicon-aluminum ratio. Incision lose weight: especially the hydrogen form can be used for carbon

1. alkyl aromatic compounds, especially with hydrogen conversions, e.g. B cracking Dehydra alkyl groups of two or more carbon ^tlsleren> isomerization and Alkyheren used atoms to dealkylated cracking products; will. ,,,,, · t_ ·. ■,

2 naphthenes ⁴ ° The molecular sieve described is only m limited

3 ^# Isoaliphaterr ^tem scope effective as a catalyst. For example

4 normal aliphatics ^{, there is no s} P ^ezmscn selective effect for the Krak-

of paraffins. The one in the publication

In the case of cracking processes carried out to date, information was provided about catalytic effects a relatively large proportion of the feed 45 or exchange with other cations are related and of reaction intermediates and not on application of a product having a pore exploited, as it is essentially insignificant in diameter of about 10 angstrom units. Tending amount of desired products from nor- The object of the invention is in particular the sheep paint aliphatic hydrocarbons receive a process for catalytic cracking became. Conventional working methods with reverse recovery of hydrocarbon oils by means of a catalyst, Can lead to the cracking of normal of the majority of the components of the feed aliphatic Hydrocarbons occurring material, as well as the known technical Difficulties do not solve satisfactorily because catalysts, cracks and also the property has many of the others in the recycle feed, normal aliphatic paraffins rolled into one keep connections more often stronger from the cat- 55 to crack higher extent than before, analyzers are attacked as the normal ali- The method according to the invention is thereby phatic hydrocarbons, the cracking of which is characterized by a catalyst consisting of a is desirable. Mixture of

The problem of cracking normal aliphatic. . _A,. ... . "

Hydrocarbons cannot be produced by using 60 ^a > ^eme ^ aluminosilicate with a pore size of a catalyst which for this particular is less than 7 Angstrom units and

Hydrocarbon class is specifically selective, solved b) a cracking catalyst more generally effective. The input material for a technical ability, possibly incorporated into a porous one Cracking plant is made up of a wide variety of carbon matrix that is used. Hydrogen together, including aromatics, 65

acyclic compounds, alicyclic compounds, According to a preferred embodiment of the

Olefins, cycloolefins or cycloparaffins, and the invention uses a catalyst in which any selectivity towards the cracking of component b) from an aluminosilicate with

a pore size of more than 8 angstrom units.

The catalysts to be used according to the invention catalyze the cracking of normal paraffins, while at the same time cracking the other components of a conventional one Effecting a feed stream to produce gasoline; this increases the performance of the Reaction system increased.

Component a) consists in the mixture to be used as a catalyst according to the invention of an aluminosilicate with a pore size of less than 7 angstrom units, preferably between 5 and 6.8 Angstrom units, while the other component b) from the catalyst is more general Effectiveness, d. H. a catalyst, the general activity for cracking the possesses various types of hydrocarbons that occur in technical gas oil. Presumably be by using an aluminosilicate with a pore size of less than 7 angstrom units as Component a) only normal aliphatic hydrocarbons selectively from mixtures of these hydrocarbons with other compounds let into the catalyst and become usable products cracked.

The term "pore size" used here refers to the apparent pore size in difference to the crystallographic pore diameter. The apparent pore size can be defined as the largest critical dimension of the molecular species that of the aluminosilicate in question adsorbed under normal conditions. The largest critical dimension corresponds to the diameter of the smallest cylinder, which is a model of the molecule, which one using the best available values of bond distances, bond angles and van der Waals radii are constructed, records. The crystallographic pore diameter is the free diameter of the associated silicate ring in the zeolite structure as calculated from the X-ray diffraction analysis; the apparent Pore size for a given aluminosilicate is always larger than the crystallographic pore diameter.

If a catalyst component b) is chosen which gives a relatively high amount of coke, but for production either good gasoline yields or gasoline with a high octane rating is suitable the association with the catalyst component b), which is specific to normal aliphatic paraffins is directed to less coke formation as aliphatics are cracked into useful products. From the foregoing it can be seen that the invention has become a very essential and decisive one Progress in the crack field leads to the need for compromise made in the Selecting a cracking catalyst has heretofore been inevitable, is essentially eliminated.

Another important technical advantage of the method according to the invention is that it gives a refinery a high degree of adaptability or flexibility, both with regard to the type as well as the yields of the products obtained from the plant. It is known, that the most favorable product distribution for a period of time does not necessarily mean the most advantageous product distribution for another period. For example, heating oil consumption is high in winter larger than in summer, so that a plant that uses a given amount of fuel oil per unit volume of feedstock continuously generated, is not appropriate. The method according to the invention opens to refineries a new way of modifying the products received from the plant, simply by controlling the The extent to which normal aliphatic hydrocarbons are cracked.

The general activity catalyst component b) comprises a variety of materials which can be either homogeneous or heterogeneous. The most common cracking catalyst component of general activity includes solids such as acid treated clays, dried inorganic oxide gels and gelatinous precipitates of alumina, silica, zirconia, magnesia, thorium oxide, titania, boron oxide, and combinations of these oxides with each other and with other components, e.g. B. silicon dioxide-aluminum oxide, silicon dioxide-magnesium oxide, silicon dioxide-zirconium oxide, silicon dioxide-boron oxide, silicon dioxide-titanium oxide, fluorides or fluoroborates on silicon dioxide-aluminum oxide or aluminum oxide carriers. The conventional solid cracking catalysts listed above generally have an effective pore diameter within the range of 30 to 10,000 angstrom units, and they also have a porosity of at least 0.05 cm ³ / g, and usually between 0.1 and about 1.0 cm ³ / g on.

A preferred embodiment of the invention lies in the use of a catalyst Aluminosilicate with a pore size of more than 8 angstrom units as component b), d. H. as Catalyst of general effectiveness.

The aluminosilicates contained in the catalysts to be used according to the invention have a crystalline and / or cryptocrystalline structure and essentially consist of a solid three-dimensional network of SiO ₄ and AlO ₄ tetrahedra, in which the tetrahedra are cross-linked by a proportion of oxygen atoms are; the ratio of the total aluminum and silicon atoms to the oxygen atoms is 1: 2. In their hydrated form, the aluminosilicates can be represented by the following formula:

MjO: Al ₂ O ₃ : w SiO ₂ : y H ₂ O,

M denotes at least one ion of positive valence which balances the electrovalence of the tetrahedron, η denotes the valence of the ion, w are the moles of SiO ₂ and y are the moles of H ₂ O. The ions of positive valence can be one or more of a number are formed by metal ions, hydrogen ions and ammonium ions, depending on whether the aluminosilicate is produced synthetically or occurs naturally. The ions of positive valence as well as silicon, aluminum and oxygen are arranged in the aluminosilicates in the form of a crystalline salt in a specific and constant crystalline pattern. The structure contains a large number of small cavities which are interconnected by a number of even smaller holes or channels. These cavities and channels are exactly uniform in size.

Aluminosilicates with a pore size of less than 7 angstrom units and preferably 5 to

6.8 Angstrom units are known in the art useful aluminosilicates include and include a variety of substances, chabazite, gmelinite, clinoptilolite, erionite (offretite), both natural and synthetic. Examples are the zeolites A, T and the zeolites oc, ZK-4 and ZK-5.

Zeolite ZK-4 can be represented by the following molar ratios of the oxides:

0.1 to 0.3 R: 0.7 to 1.0 M ₁ O: Al ₂ O ₃ : 2.5 to 4.0 SiO ₂ : y H ₂ O,

herein, R is a member selected from the group consisting of methyl 3.5 to 5.5. In the synthesized form, zeoammonium oxide, hydrogen oxide and their mixtures contain primarily sodium cations and can co-exist with one another, M is a metal cation of the valency represented by the following unit cell formula «, and y is any value of approximately:

Na _7.5 ± ₂ H ₂ ± 0.5 [9 ± 2 AlO ₂ · 15 dz 2 SiO ₂ ].

Zeolite ZK-4 can be prepared by containing 15 ammonium ions and preparing an aqueous solution composition which, in terms of has, in terms of molar ratios of oxides, oxides, Na ₂ O, Al ₂ O ₃ , SiO ₂ , H ₂ O and tetramethyl- which falls into the following ranges:

SiO ₂ / Al _a O ₃ 2.5 to 11,

Na ₂ O

0.5 to 2.5,

Na ₂ O + [(CHg) ₄ N] ₂ O

25 to 50,

H ₂ O

Na ₂ O + [(CHa) ₄ N] ₂ O

Na ₂ O + [(CHs) ₄ N] ₂ O
SiO ₂

Ibis 2,

the mixture is then washed at a temperature of about 30 until the pH of the feet

100 to 12O ⁰ C kept until the crystals formed the washing liquid essentially with the

are, and then the crystals are matched by the mother of the wash water, and then

I eye severed. The crystal material is dried.

Zeolite κ can be represented in molar ratios of the oxides as follows:

0.2 to 0.4 R: 0.6 to 0.8 M ₂ O: Al ₂ O ₃ : 4.0 to 6.0 SiO ₂ : y H ₂ O,

herein, R is a member selected from the group made from methyl, with the exception that the molar ratio

ammonium oxide, hydrogen oxide and mixtures thereof from silicon dioxide to aluminum oxide at least

gen, M is a metal cation of valence n, 20: 1, the molar ratio of [(CH ₃ ) ₄ N] ₂ O to Na ₂ O

and y are the moles of H ₂ O. about 10: 1 and the formation temperature about 60 to

Α is zeolite ZK-4 is in a manner similar to zeolite 90 ⁰ C.

Zeolite ZK-5 can be represented by the following composition in terms of molar ratios of the oxides will:

0.3 to 0.7 RpO: 0.3 to 0.7 M ₂ 0: 1 Al ₂ O ₃ : 4.0 to 6.0 SiO ₂ -JH ₂ O,

m η

Here R denotes a nitrogen-containing cation, the 50 zeolite ZK-5 can be prepared by preparing an aqueous solution from an N, N'-dimethyltriethylenediammonium ion _{, which comes as the oxide Na 2} O, or mixtures of this cation with water-Al ₂ O ₃ , SiO ₂ , H ₂ O and N, N'-Dimethyltriethylendistoff, and m is its valence; M is a metal containing ammonium ions and a composition η is its valence, and y is any value, expressed as molar ratios of the oxides, from about 6 to about 10. 55 which falls within the following ranges:

SiO _a / Al ₂ O ₃ from about 2.5 to 15,

from about 0.1 to 2.5,

Na ₂ O

Na ₂ O + C ₈ H ₁₈ N ₂ O

H ₂ O
Na ₂ O + C ₈ H ₁₈ N ₂ O

Na ₂ O + C ₈ H ₁₈ N ₂ O SiO ₂

from about 25 to 50, from about 1 to 2,

the mixture is kept at a temperature of about 90 to 120 ^° C. until the crystals are formed, and then the crystals are separated off from the mother liquor.

7 8

The crystal material is then washed to an extent of less than 0.25 equivalents and

until the pH of the washing liquid flowing off is preferably less than 0.1 equivalent per gram atom

essentially the same as that of the wash water - aluminum can be present are essentially

correct, and then dried. did not borrow other metallic cations with the

Aluminosilicates with a pore size greater than 5 resulting acidic aluminosilicate combined, A

as 8 angstrom units are also known and effective treatment with the gaseous or

include both natural and synthetic liquid medium to achieve the appropriate

Materials, e.g. B. the zeolites 1OX, 13X, Y, L, acidic aluminosilicates will vary with the duration of the

Faujasite. Treatment and the temperature at which this

The majority of the aluminosilicates come habit- io is led to change. Elevated temperatures tend to be borrowed naturally or is in the form of their alkali used to increase the speed of treatment, or alkaline earth salts produced synthetically, but while the duration of the same is reversed to that In general, the invention also includes the concentration of hydrogen ions or ammonium of acidic aluminosilicates, acid-metal ions in the medium changes. Generally it can be said Aluminosilicates and metal aluminosilicates. 15 that the temperatures used in

Acid aluminosilicates are those compositions from below the surrounding room temperature, in which essentially all originally ratur (24 ° C) up to temperatures below the metallic decomposition temperature of the aluminosilicate present in an aluminosilicate. Cations by protons or proton generator After the treatment, the treated aluminum can be replaced are. so silicate should be washed with water, preferably

For the production of the aluminosilicates and those with distilled or deionized water until the Finished catalysts will be used within the scope of the invention- draining wash water has a pH value of wash dung no protection claimed. has water, d. H. between about 5 and 8. The AIu-

These catalysts are made by drying minosilicate and then treating it by means of a precursor of the aluminosilicate with a water-heating medium in an inert atmosphere at temperatures which activates a source of water in the range of about 204 to 815 ° C, wherein substance ions or ammonium ions convertible into hydrogen ions, if such are present, an ion, e.g. B. ammonium ions contains. The pH will suffer conversion to hydrogen ions.
of the gaseous or liquid medium can be analyzed for its metal ion content according to known methods, depending on the precursor 30. The analysis of the aluminosilicate and its atomic arrangement also includes an examination of the flux silicon and aluminum. If the aluminosilicate-containing washing liquid for cations which, as a resultant material, have an atomic ratio of silicon to aluminum obtained from the treatment in the washing liquid is at least greater than about 3.0, the liquid may become liquid.

or gaseous medium hydrogen ions, ammo-35 The procedure used practically for the treatment of the aluminonium ions or a mixture thereof containing the silicate can be carried out in a pH in the range of less than 1.0 to batchwise or continuous process below up to a pH -Value of about 12.0 equivalent atmospheric, sub-atmospheric, or over-being. Within these limits are the pH values to be carried out at atmospheric pressure. One for media containing an ammonium ion, solution of the hydrogen ions and / or ammonium in the range from 4.0 to 12.0 and preferably between ions in the form of a molten material, one having a pH of 4.5 and 8.5. For media containing steam or an aqueous or non-aqueous hydrogen ion, the pH values in the solution can be slowly passed through a fixed bed of the aluminosilicate range from less than 1.0 up to about 7.0. If desired, a hydrothermal treatment, and preferably within the range of 3 to 45, or equivalent up to 6.0. When the atomic ratio of the aluminosilicate non-aqueous polar solution silicate treatment greater than about 1.4 and less than about 3.0 average are made by using the aluminum, the pH values for the gaseous or minosilicate and medium are closed liquid media containing hydrogen ions, introduces vessel which is maintained under autogenous pressure in the range of 3.8 to 7.0 and preferably within 50. Similarly, treatments can be performed at a pH range of 4.0 to 6.0. When ammonium turns which include melt or vapor ions, either alone or in phase contact, provided that the combination with hydrogen ions, the melting point or the evaporation temperature of the pH values are in the range of 4.5 to 12.0 and preferred acid or ammonium compound among the range within the limits of 4.5 to 8.5. If 55 is the settling temperature of the aluminosilicate,
the aluminosilicate material can have an atomic ratio of various acidic compounds with silicon to aluminum less than about 3.0, ease of use as a source of hydrogen ions, a medium which includes both inorganic and ammonium ions is preferably used. also include organic acids.

When carrying out the treatment with the 60 Typical inorganic acids that are used

gaseous or liquid medium which can be given are e.g. B. hydrochloric acid, hypochlorous acid,

applied method of contacting a chloroplatinic acid, sulfuric acid, sulphurous acid,

Precursor of the aluminosilicate with the desired hydrosulfuric acid, peroxydisulfonic acid (H ₂ S ₂ O ₈ ),

Medium up to such a point in time when peroxymonosulphuric acid (H ₂ SO ₆ ), dithionic acid

metal- 65 (H ₂ S ₂ O ₆ ), sulfamic acid (H ₂ NSO ₃ H), amidodisulfone-

cations by non-metallic ions positive acid [NH (SO ₃ H) ₂ ], chlorosulfuric acid, thiocyanate

tive valence are replaced. With the exception of acidic, hyposulphurous acid (H ₂ S ₂ O ₄ ), pyrosulfur

Alkali cations, which as impurities up to an acid (H ₂ S ₂ O ₇ ), thiosulfuric acid (H ₂ S ₂ O ₃ ), nitro

9 10

sulfonic acid (HSO ₃ · NO), hydroxylamine disulfonic acid cation. These aluminosilicates can be treated by treating [(HSO ₃ ) ₂ NOH] ₃ nitric acid, nitrous acid, under- ning a precursor of the aluminosilicate with the pre-nitrous acid, carbonic acid. The gaseous or liquid described below Typical organic acids which are used in the media, ie a medium which is used at least one implementation of the invention, include a metal salt, and a medium which contains the monocarboxylic acids, dicarboxylic acids and polyhydrogen ion or a hydrogen ion former carboxylic acids, these can be made more aliphatic, containing aromas. The precursor to be aluminotic or cycloaliphatic in nature. Silicates can be treated with a medium. Yet another class of useful compounds which contains a hydrogen ion followed by a fertilizer are ammonium compounds, which can be found in a medium which contains a metal cation, or vice versa. Furthermore, the acid-metal aluminosilicate can be subjected to contact with a gaseous or the aluminosilicate by temperatures below the decomposition temperature. liquid medium that has both a metallic cation. B. ammonium 15 contains ion formers, are prepared,
chloride, ammonium bromide, ammonium iodide, am- The catalysts used in accordance with the invention, monium carbonate, ammonium bicarbonate, ammo- are produced simply by mechanically mixing the two components together. The ammonium dithiocarbonate, ammonium peroxysulphate, catalysts used according to the invention can be ammonium acetate, ammonium tungstate, ammonium in the form of a powdery mixture in a nium hydroxide, ammonium molybdate, ammonium reactor of the fluidized bed type, by simply using sesquicarbonate, ammonium chloroplumbate, the two components Ammonium dithionate, ammonium fluoride, mixed and ground into powder form. Alternatively, ammonium gallate, ammonium nitrate, ammonium mi- the composition of the aluminosilicate and trit, ammonium formate, ammonium propionate, am- 25 the cracking catalyst pelletized, cast, molded monium butyrate, ammonium valerate, ammonium lac- or otherwise into pieces of the desired size, ammonium oxalonate, Ammo and shape are formed, e.g. into rods, balls, nium palmitate, ammonium tartrate. Still other Am pellets; however, it is preferred that any of these monium compounds which can be used are pieces of particles of both components together, tetraalkyl and tetraaryl ammonium salts, e.g. B. 30 is set.

Tetramethylammonium hydroxide and trimethylam- A preferred embodiment of the invention

monium hydroxide. Other compounds which can be used lie in the use of an aluminosilicate as genes are nitrogen bases, ζ. B. guanidine, pyridine, cracking catalyst using a porous Quinoline. Matrix as a binding agent for it. The preferred class

Similarly, metal aluminosilicates 35 of catalysts are therefore comprised of an aluminosilicate by treating an aluminosilicate precursor with a pore size of 5 to 6.8 Angstrom units with a gaseous or liquid medium that and an aluminosilicate with a pore size greater than a salt of the desired metal or the desired as 8 angstrom units, which in such quantities Contains metals. Conditions combined with a porous matrix, manifold metal compounds with 40 can be dispersed in it or in some other way intimately softened as a source of metallic cations are mixed that the resulting product 1 to Find use, this includes both inorganic 95 percent by weight and preferably 2 to 80 gelatin as well as organic salts of the metals the weight percent of the aluminosilicates in the finished Karaly groups to VIII of the periodic table. Typical sator includes. It can be seen that not both Salts that can be used are, for. B. 45 aluminosilicates mixed with the same matrix Chlorides, bromides, iodides, carbonates, bicarbonates, must, but that many matrix materials include sulfates, Acetates, benzoates, citrates, fluorides, nitrates, can find a twist; however, be preferred Nitrites, formates, propionates, butyrates, valerates, both aluminosilicates with the same matrix particle Lactates, malonates, oxalates, palmitates, hydroxides, combined.

Tartrates. The only restriction on the 50 The term "porous matrix" includes inorganic used special metal salt or the special and organic compounds with which their metal salts used consists in that they combine the aluminosilicates, disperse them or in anin the medium in which they are used, which can be intimately mixed, whereby must be sufficiently soluble to make the necessary the matrix can be active or inactive. It is a first-class metal ion transition to surrender. The preferred 55 borrowed the porosity of that used as the matrix Salts are the chlorides, nitrates, acetates and sulfates. Compositions either of the particular material Typical metals whose salts are used by their own or by mechanical or chemical application can, are z. B. silver, calcium, platinum, beryllium, agents can be introduced. Typical matrix materials Barium, magnesium, manganese, zinc, aluminum that can find use include metals and Zircon, chromium, iron, nickel, cobalt, cerium, lanthanum, 60 their alloys, sintered metals and sintered Yttrium, samarium, neodymium, gadolinium, praseodymium, glass, asbestos, silicon carbide aggregates, pumice stone, Europium, terbium, dysprosium, holmium, erbium, firebrick, diatomaceous earth, activated carbon, orga-ytterbium and lutetium. niche resins, e.g. polyepoxides, polyamides, polyesters,

Another class of aluminosilicates used in vinyl resins, phenolic resins, amino resins, melamines, The acidic acrylic resins, alkyd resins, epoxy resins and inorganic metal aluminosilicates which can be used in the invention are used. These aluminosilicates form oxide gels. These matrix materials hold either a hydrogen ion or a water- the inorganic oxide gels because of their superiority material ion formers as well as at least one metallic porosity, abrasion resistance and stability under

11 12

Reaction conditions, especially under such conditions to precipitate the corresponding oxide. The silica

Reaction conditions such as those used in the cracking of the content to be used according to the invention

Gas oil occur, particularly preferred. Silicon-containing catalysts to be considered

The compositions comprising an inorganic gel matrix are generally within the range

Contain oxide gel, according to various metho- 5 from 55 to 100 percent by weight, so that the metal

which are produced, the aluminosilicates having an oxide content in the range from 0 to 45%. Low

a particle size less than 40 microns, pre-amounts of promoters or other materials that

preferably within the range of 1 to 10 microns that may be present in the composition

crushed and intimately with an inorganic oxide - e.g. cerium, chromium, cobalt, tungsten, uranium, platinum,

gel, while the latter in an io lead, zinc, calcium, magnesium, barium, lithium,

water-containing state, e.g. in the form of a nickel and its compounds, as well as silicon

Hydrosoles, Hydrogeles, Wet Gelatinous Low-Dioxide, Aluminum Oxide, Silica-Aluminum

blow or a mixture thereof. Fine oxide or other silicon-containing oxide combinations can be used

Partial aluminosilicates directly with a silicon as fines in amounts ranging from 0.5 to

containing gel are mixed, which by hydrolyte 15 40 percent by weight, based on the finished cat-

Sizing a basic solution of alkali silicate with a lysator.

an acid, e.g. B. hydrochloric acid, sulfuric acid, acetic acid, the porous matrix can also have been formed from a half. The mixing of the three composite or plastic clay minerals can be made in any desired manner. The aluminosilicate can be incorporated into the clay, for example in a ball mill or in other 20, simply by mixing the two components together Kneading devices. The combined and the mixture to the desired shape aluminosilicates can also be processed in a hydrosol. Suitable clays are e.g. B. attapulgite, dispersed by reacting an alkali kaolin, sepiolite, polygarskite, kaolinite, plastic silicate with an acid or an alkaline Koagu ball clay, bentonite, montmorillonite, mit, chlorite.
lubricant has been obtained. The hydrosol is then solidified in bulk to form a hydrogel, powdered metals, e.g. aluminum, stainless which is then dried and broken into pieces of desired steel and powder of refractory oxides, shape, or by conventional e.g. which have a very low internal spray drying method or by a pore volume. Preferably, these nozzles have essentially no immiscible suspending medium dispersed by themselves in a bath of oil or other aqueous materials for their own catalytic activity.

wa spherically shaped "pearl" catalyst particles The catalyst can work in an inert atmosphere

as described in U.S. Pat. No. 2,384,946 in the vicinity of the

are described. The menden temperature obtained in this way can be precalcined

However, silicon-containing gel comprising aluminosilicate is also initially used during use in

washed free of soluble salts and then calcined after the conversion process. in the

dried and / or calcined, as desired, generally the catalyst is at one temperature

will. dried between about 65 and 316 ° C and thereafter

Similarly, the aluminosilicates can be incorporated into an oxide containing aluminum in air or an inert atmosphere of nitrogen. Such 40 helium, exhaust gas or another inert gas in gels and water-containing oxides are known and temperatures in the range from about 260 to 815 ⁰ C can be produced, for example, by adding ammonium hydroxide, ammonium carbonate to one or more for periods in the range from 1 to 48 hours calcined. It can be seen that the alumino-aluminum salt, for example aluminum chloride, aluminum silicate, can also be calcined in a sufficient amount of oxide gel before being incorporated into the inorganic sulfate, aluminum nitrate. It is further substituted to form aluminum hydroxide, which is evident when the aluminosilicate or the aluminosilicate is dried to aluminum oxide. The silicate not in the manner indicated above, aluminosilicate, can be incorporated into the aluminum-containing oxide before incorporation into a matrix with the gases, while the latter must be treated in the form of a liquid or hydrosol, hydrogel, wet gelatinous base, but that they must also occurs during or after the impact or water-containing oxide. Incorporation into the matrix can be dealt with.

The inorganic oxide gel can also be made from a

There are multiple gels that contain a predominant amount of that catalysts with improved selectivity and

Silicon dioxide in connection with one or more other favorable properties for certain carbon

rer metals or their oxides from group 55 hydrogen conversions, e.g. gas oil cracking,

IB, II, III, IV, V, VI, VII and VIII of the period are obtained when using the catalyst one

systems includes. It is particularly preferable to subject multiple mild steam treatments to

gels of silicon dioxide with metal oxides of the groups elevated temperatures of about 427 to 815 ° C

IIA, III and IVA of the periodic table, especially and preferably at temperatures of about 538

where the metal oxide is made from a rare earth oxide, 60 to 760 ° C. Treatment can

Magnesium oxide, aluminum oxide, zirconium oxide, titanium in an atmosphere of 100% water vapor or

oxide, beryllium oxide, thorium oxide or combina- tion in an atmosphere consisting of water vapor and one

of which there is. The production of multiple gas essentially inert to the aluminosilicate

gelening is known and generally comprises either a consists, is carried out. The steam treatment creates

separate precipitation or a method of working with mixed 65 obviously favorable properties in the aluminum

Precipitation in which a suitable salt of the metal oxide silicate compositions and can be before, after or

is added to an alkali silicate and an acid is carried out in place of calcination,

or base, as required, is added to the particle size of each component that is

13 14

form the catalyst is not narrowly wise 1.8 and more appropriate at least critical and can range from 1 to 200 microns 2.0.

vary, if the same particle sizes within the Preference are given to catalysts in which both

Ranging from 1 to 100 microns are preferred. Aluminosilicates to the same class, e.g. both It should also be noted that the individual composites 5 metal aluminosilicates, or to different classes, The catalyst does not have the same particle size - e.g., a metal aluminosilicate and an acid aluminosilicate must have, and in fact it will be pre-silicate, belong and in the same matrix or in admits that they have different particle sizes as different matrix materials are dispersed, e.g. This results in a rapid separation of the catalyst - an aluminosilicate into silicon dioxide-aluminum oxide components is possible. The catalyst mixture io and the other in silica-zirconia. may be in the form of separate particles. Cracking processes according to the invention may be in

or the mixture may ringertem, atmospheric, or are überatmosphäriworden so that any large particles small schem pressure are carried out in the form of components temperatures of about 204-704 ⁰ C under vervorliegen, the finely ground, mixed and pelletized. The catalyst contains particles of both components. 15 can be in the form of roughly spherical particles or

The exact proportions of pearls used, which are arranged in a resting bed, the one component to the other in the or in the fluidized bed, to the continuously catalyzer is also not added to the catalyst in narrow areas and continuously from the catalyst critical and can be removed over an extremely wide range. Particularly effective be changed. However, it has been found that for ao cracking processes can be achieved if the catalyst most purposes the weight ratio of the to achieve the particular advantages of the working aluminosylate with a pore size smaller than those with a moving bed, e.g. the »Thermoforals 7 angstrom units for the cracking component catalytic cracking process «, as well as in cracking process in the range from 1:10 up to 10: 1 and preferred with a fluidized bed is used, can range from 1: 4 to 4: 1. There is another embodiment of the invention

In the context of the above-described alumino in the process implementation using silicates that were used for the production of a catalyst, the elemental metal or metal according to the invention Catalysts physically form a porous compound in the inner sorption areas of the Matrix, cracking catalysts have been found to have a pore size greater than this that certain aluminosilicates lead to superior results than 8 angstrom units and / or the aluminosilicates nits result if they are used for catalytic cracking with a pore size of less than 7 angstroms Gas oil can be used. First of all, each should contain deposited in units. They are different the composition incorporated aluminosilicate working methods for the introduction of elemental at least 0.5 to 1.0 and more preferably 0.8 to metal in the interior sorption regions of Alumino-1.0 Total equivalents of exchangeable cations 35 silicates known, and these working methods umje Contains gram atom of aluminum. It would capture the reduction of at least a portion of the found that aluminosilicates with a high degree of metallic cations associated with the aluminosilicate exchangeable cations are combined with superior results by any suitable reducing process bring. Second, it is preferred that only medium, e.g. lithium aluminum hydride, hydrogen, a limited amount of alkali metal cations with the 40 carbon monoxide, hydrazine, lithium borohydride, sodium aluminosilicates are united because the presence of trium borohydride, boranes, metallic lithium, sodium of alkali metals tends to be the most catalytic and potassium. The method, at least part of the Depressing or limiting properties; metallic cations to the elemental metal Reducing the activity of the material usually increases, which is particularly beneficial for those who are losing weight Content of alkali metal cations. 45 separation of elemental copper, silver, cadmium, It is accordingly preferred that the aluminosilicates mercury, thallium, tin, lead, iron, cobalt and no more than 0.25 equivalents of alkali metal nickel within the internal sorption areas of the cations per gram atom of aluminum and especially composition.

preferably not more than 0.15 equivalents of alkali. Yet another method of deposition

contain metal cations per gram atom of aluminum. 50 of elemental metal in the inner sorption

What are the metal areas of the cracking catalyst that are combined with the aluminosilicate and have a pore size As far as cations are concerned, cations are generally three out of more than 8 angstrom units and / or des valent metals are most preferred, followed by aluminosilicate with a pore size less than Divalent metal cations; least 7 angstrom units are required to evaporate the Monovalent metal cations are preferred. Of the 55 desired metals in an inert gas with trivalent ones Metal cations are most strongly following the passage of the metal vapor containing Rare earth metal cations, either alone or as a gas through the desired substance. Mixtures of rare earth metal cations are preferred. Other methods of depositing elementary

Furthermore, it is particularly preferred if metals in the inner sorption areas are particularly at least some protons or proton formers are effective with 60 ders when materials with comparable Aluminosilicate are combined. Acid-metal-wise large pore size should be treated in such a way that Aluminosilicates or, in particular, acid-rare earths comprise a treatment with a gaseous one Aluminosilicates in which the metal is 40 to 85% of the total or liquid decomposable compound Equivalents are used as catalysts of metal, followed by a reduction in the decomposed gates preferred. 65 borrowed connection to the elementary metal.

Furthermore, it is preferred if either one of this procedure comprises a dehydration of the or both aluminosilicates have an atomic ratio of catalyst followed by a bare through silicon to aluminum of at least 1.5, preferential passage of the decomposable compounds through a bed

of the catalyst until at least some of the compound enters the inner sorption areas of the catalyst entry. The reduction of the gaseous or liquid decomposable compound can be expedient and conveniently done simply by the action of heat or chemical means, as in the individual is desired. Examples of decomposing compounds that can find use are including carbonyls, carbonyl hydrides, acetylacetonate complexes of the particular metal, reducible Halides, e.g. chromium hexacarbonyl, bistolulylchromium, nickel carbonyl, cobalt carbonyl, iron carbonyl, Iron carbonyl hydride, cobalt carbonyl hydride, molybdenum carbonyl, tungsten carbonyl, manganese carbonyl, Copper acetylacetonate, silver acetylacetonate, gold acetylacetonate, reducible halides and Nitrates, e.g. those of platinum, palladium, selenium, tellurium, copper, silver and gold. In a similar way Halogen acids, e.g. chloroplatinic acid, chloropalladic acid, can also be used. so

Another method of incorporating elemental metals into the internal sorption areas of the solid The cracking catalyst and / or the aluminosilicate is the desired material with a metal amine complex treat and then reduce the amine complex to the elemental metal to obtain. Although it is not critical which particular metal amine complex is used, Such complexes of platinum, palladium, rubidium, osmium, iridium and rhodium are particularly advantageous. The working methods for the deposition of elemental metal in the internal absorption areas of Compounds are known and disclosed in U.S. Patents 3,013,982, 3,013,983, 3,013,984, 3,013,985, 3,013,986, 3,013,987 and 3,013,988.

Although the invention above in particular in connection with the various modifications the preferred embodiment has been described, i.e. the use of a fixed or heterogeneous Material as cracking catalyst of general effectiveness, the process according to the invention is as above has been shown to be applicable in the same way when homogeneous substances are used as catalysts general effectiveness. Homogeneous cracking catalysts are known, and Typical representatives of such materials include, for example, aluminum chloride, aluminum fluoride, ferric chloride, Zinc chloride, stannous chloride, zirconium chloride, sulfuric acid, hydrochloric acid, hydrofluoric acid, tetraethyl lead, Carbon tetrachloride, various halogenated esters, e.g. brominated esters, as well as iodine and chlorine.

The high catalytic activities achieved by the catalysts produced are illustrated below in connection with the cracking of typical hydrocarbons. In the examples below, various reference catalysts were used to demonstrate specific advantages, as well as a reference catalyst comprised of conventional "pearl" type silica-alumina cracking catalysts. The silicon dioxide-aluminum oxide catalyst contained about 10 percent by weight Al ₂ O ₃ and the remainder SiO ₂ . In some cases it also contained a trace amount of Cr ₂ O ₃ , ie about 0.15 percent by weight.

The selectivity of the catalysts according to the invention is further illustrated by their ability to inhibit conversion of a Mid-Continent gas oil having a boiling range 232-510 ° C in gasoline to catalyze an end point of 21O ⁰ C. Vapors of the gas oil are passed through the catalyst at temperatures of 468 or 482 ° C. and essentially atmospheric pressure at a feed rate of 1.5 to 8.0 volumes of liquid oil per volume of catalyst per hour. The method of investigating the catalysts used according to the invention consisted in comparing the various product yields obtained with such catalysts with the yields of the same products obtained from different reference catalysts at the same conversion level and the same temperature. The term "Δ advantage" used in the examples below means the yields obtained from the catalyst used in accordance with the invention minus the yields obtained from the conventional silica-alumina catalysts described above. In each of the tests shown in the examples, the catalysts were pre-calcined prior to their investigation as cracking catalysts at about 538 ⁰ C.

The following embodiments illustrate the implementation of the invention.

Examples 1 to 28 illustrate various specific catalysts that can be used in the process according to of the invention are useful. In any case, all proportions are based on weight.

Examples 29 through 51 detail preparation methods for some of the following listed catalysts and give comparative values for cracking with various others known catalysts.

at > 8 angstrom units % <7 angstrom units 5A % matrix no % game material 80 material Gmelinite 20th material no 1 Silica-alumina 90 ZK-4 10 no 2 Silica-alumina 70 ZK-5 30th McNamee tone 3 Silica-magnesia 50 Rare Earth A 25th no 25th 4th Silica-Zirconia 85 Zeolite tx 15th no 5 Silica-titania 75 Rare Earth A 25th no 6th Silica-alumina 75 Rare Earth A 25th no 7th Silica-alumina 90 Chabazit 10 no 8th Silica-magnesia 85 5A 15th no 9 Alumina-boron oxide 85 15th 10 13 X

909 525/428

- · 13X Continuation of the table <7 angstrom units 5A % matrix % at > 8 angstrom units Lanthanum 13X material Acid-5 A 10 material 80 games material Zeolite L:; .; % SE-Chabazit 10 Silica-alumina 75 11 Acid-L 10 Mn-gmelinite 15th Silica-alumina 12th Ce-Y 15th Ca-Chabazite 50 no 13th SE 13 X 85 Nickel to 5 A. 10 no 75 14th Ni-Y ': 50 SE-Acid-A 10 Silicon dioxide 80 15th Be-X 15th Acid Chabazite 12th Aluminum Oxide-Boron Oxide 70 16 SE acid 13X 10 SE acid 5A 10 Silicon dioxide-aluminum oxide 75 17th SE-Mg-13X 18th Li-Chabazite 5 Silica-alumina 85 18th SE-Acid-13X 15th SE acid mordenite 10 Silica-alumina 75 19th 10 5 Silicon dioxide 75 20th Acid-Y 15th Acid mordenite Silica-alumina 10 21 SE-acid-Y 10 SE-A 10 McNamee tone 75 Acid-Y SE-A 5 Silica-alumina 85 22nd SE-Acid-X '. 15th SE-Acid-A 10 McNamee tone 80 23 Acid-Y 10 Silver on erionite 40 McNamee tone 24 Acid faujasite 10 Acid erionite 10 no 75 25th 60 (Offretit) 10 Silica-alumina 75 26th Acid-Y + 13 X 15th SE-5A Silicon dioxide 27 15th 10 75 Silica-alumina 28 15th

Example 29

10 parts by weight of a synthetic crystalline aluminosilicate identified as zeolite 13X was dispersed in 90 parts by weight of a silica-alumina matrix composed of 94% by weight SiO ₂ and 6% by weight Al ₂ O ₃ to thereby form a pearl hydrogel. The resulting beads were then treated twice with an aqueous solution containing 2% by weight of a mixture of rare earth chlorides (as hexahydrates), each time for 4 hours at room temperature, followed by treatment with a 1% aqueous solution of ammonium chloride for 24 hours consecutive hours. The aluminosilicate was then washed with water until the effluent wash fluid was substantially free of chloride ions and then dried for 24 hours at 648 ⁰ C with water vapor at 1.05 kg / cm ² treated; a catalyst was obtained which had a rare earth content of 7.42 percent by weight, determined as rare earth oxides.

The table below shows the conversion achieved with the above catalyst as well Compare to a conventional silica-alumina cracking catalyst in a study for the cracking of gas oil at 482 ° C:

Conversion, volume percent 64.2

zd advantage (C ₁ + gasoline), volume percent .. +5.6

Octane _(C5 + gasoline) 97.2

Zl advantage octane _(C5 + gasoline) - 1.6

From the table above it can be seen that the one made by the procedure of this example Catalyst made 5.6 volume percent more gasoline than a conventional silica-alumina cracking catalyst, that this increase in gasoline yield was at the expense of the octane number; namely, the octane number was the one obtained Gasoline 1.6 points lower than the octane number obtained in connection with silica-alumina Gasoline.

Example 30

Another catalyst was prepared in substantially the same manner as in Example 29 with except that an aluminosilicate with a

Pore size less than 7 angstrom units was incorporated into the catalyst composition. The exact procedure for preparing the catalyst was as follows: 10 parts by weight of the synthetic crystalline aluminosilicate identified as zeolite 13 X and 5 parts by weight of a synthetic crystalline aluminosilicate identified as zeolite 4A were dispersed in 85 parts by weight of the silica-alumina matrix, which consists of 94 percent by weight SiO ₂ and 6 weight percent Al ₂ O ₃ to form a bead hydrogel. The resulting beads were then treated with a 2 weight percent aqueous solution of a mixture of rare earth chloride hexahydrates for 16 hours of contact at room temperature, followed by treatment with a 1 weight percent aqueous solution of ammonium chloride for 24 consecutive hours at room temperature. The aluminosilicate was then washed with water until the effluent wash fluid was substantially free of chloride ions and then dried for 24 hours at 648 ⁰ C with water vapor at 1.05 kg / cm ² treated; The result was a catalyst with a rare earth content, determined as rare earth oxides, of 5.91 percent by weight and a sodium content of 0.01 percent by weight.

The table below shows the cracking values of the catalyst when it was tested for cracking of gas oil at 482 ° C and comparative values with a conventional silica-alumina cracking catalyst:

Conversion, volume percent 60.0

Zl advantage (C ₁ + gasoline), volume percent .. +5.2

19 2 ©

Octane number (C ₅ + gasoline) 98.1 crystalline aluminosilicates and 10 parts by weight

zl-advantage octane number (C ₈ + gasoline) -0.7 roner McNamee clay were in 75 ^{parts by weight}

a silica-alumina matrix composed of

From the table above, it can be seen that 94 weight percent SiO ₂ and 6 weight percent Al ₈ O ₃ consisted of the addition of a 5 pore size aluminosilicate, dispersed to form a pearl hydrogel, less than 7 angstrom units to a gasoline The resulting composition was 16 hours of generation in essentially the same amount that was kept with a 2 weight percent aqueous solution as treated with the catalyst according to Example 29 of rare earth chloride hexahydrates (A + 5.6 compared to Λ + 5.2 ), followed by a treatment with a weight-based, but with a significantly higher octane-io percent aqueous solution of ammonium chloride, namely 98.1 instead of 97.2. It is therefore 24 consecutive hours. The aluminosilicate can be seen that the incorporation of a silicate was then washed with water until the aluminosilicate, which is selective for the cracking of normal paraffins in the outflowing wash liquid, essentially no more chloride ions, was dried and the was removed inherent lack of the catalyst 15 then 24 hours at 648 ⁰ C with steam at according to Example 29 with respect to the octane number, which treated ^{to 1.05 kg / cm a;} it became a catalyst with its ability to produce higher gasoline yields based on a rare earth content, determined as rare earth yields. oxyde, of 3.02 percent by weight and a sodium

. . obtained content of 0.1 percent by weight.

B e 1 s ρ 1 e 1 Jl _{ao The} following table shows the cracking values of the

A catalyst was essentially the catalyst in the investigation for cracking

Prepared in the same way as in Example 30, with that of gas oil at 482 ° C:

Exception that a somewhat crude McNamee tone is also

was set; this illustrates that cracking values

the matrix also consists of more than one component 25 conversion, volume percent 59.5

can exist. The exact way in which the air flow rate is

Position of this catalyst was as follows: 10 weight- v / v / hour 4

parts of a synthetic gasoline identified as zeolite 13 X, 10 RVP, volume percent 50.8

crystalline aluminosilicate and 5 parts by weight of an excess of C ₄ , volume percent 12.0

synthetic crystalline 30 C ₅ + gasoline identified as zeolite 4A, volume percent 48.6

Aluminosilicate was in 10 parts by weight of total raw C ₄ , volume percent 14.2

McNamee clay and 75 parts by weight silica dry gas, weight percent 5.9

Aluminum oxide, which consists of 94 weight percent SiO ₂ coke, weight percent 2.2

and 6 weight percent Al ₂ O ₃ consisted, dispersed, H ₂ , weight percent 0.04

to form a pearl hydrogel. The resulting 35 λ ν * i

Pearl hydrogel was used for 16 hours with a 2-weight advantage

percent aqueous solution of a mixture of gasoline, 10 RVP, percent by volume +6.8

Treated rare earth chloride hexahydrates, followed by excess C ₄ , percent by volume - 1.5

by treatment with a lgewichtsprozentigen C ₅ + gasoline, volume percent +6.6

aqueous solution of ammonium chloride over 24 to 40 total C ₄ , percent by volume - 1.3

consecutive hours. The aluminosilicate became drying gas, weight percent - 1.4

then washed with water until in the outflowing coke, percent by weight - 2.2

Washing liquid essentially no chloride ions Octane number of the gasoline obtained 96.9

were included, dried and then 24 hours

at 648 ⁰ C with water vapor at 1.05 kg / cm ² behan- 45 From the above table it is evident that

delt; it resulted in a catalyst with a rare use of sodium mordenite in the cata-

Soil content, determined as rare earth oxides, from the sator composition of this example to a higher

6.44 percent by weight and a sodium content of ren yield of C ₅ + gasoline than in Example 29

0.1 percent by weight. led to essentially the same

The table below shows the cracking values of the 50 octane number, namely 96.9 compared to 97.2.

Catalyst in the investigation for cracking _,. . ,.,

of gas oil at 482 ⁰ C: 33 Beisptel

,, ", 10 parts by weight of a zeolite 13 X identifi-

Conversion, 65.5% by volume of _{adorned synthetic} crystalline aluminosilicate,

Zl advantage (C ₅ + gasoline), percent by volume. + 7.0 ₅₅ 5 parts by weight of one identified as Chabazite

Octane number (C ₅ + gasoline) 97.7 crystalline aluminosilicate and 10 parts by weight

raw McNamee clay was made in 75 parts by weight

From the table above it can be seen that a silica-alumina matrix dispersed catalyst of this example not only yawed a product which consisted of 94 percent by weight SiO ₂ and 6 higher octane number than that of Example 29 gave 60 percent Al ₂ O ₃ Pearl hydrogel to (97.7 versus 97.2) but also to form a. The resulting beads pearl was led higher yield of gasoline, as is apparent, the aqueous from the 16 hours with a 2 weight percent Zl advantage for C ₅ + gasoline. Solution of rare earth chloride hexahydrates loading. . is, followed by a 24-hour continuous J3 e ι s ρ ι e 1 32 _6g treatment with a 1 weight percent aqueous 10 parts by weight of a zeolite 13 X identified solution of ammonium chloride. The aluminosilicate, synthetic crystalline aluminosilicate, 5 Ge was then washed with water until essentially no flowing wash liquor identified as sodium mordenite in the major part of it

21 22

Chloride ions were more, dried and then Example 36 hours at 648 ⁰ C with steam at 1.05 atm

treated; a catalyst was obtained which is 100% ^eme s commercially available silica

a rare earth content, determined as the rare earth magnesium oxide were added to a 24-hour Behandoxyde, from 5.5 percent by weight and a sodium 5 lung at 648 ⁰ C with water vapor at 1.05 kg / cm ²

content of 0.1 percent by weight. subjected and then to the cracking of gas oil

The table below shows the cracking values of the at 482 ° C with the following results under catalyst in the investigation for cracking looks for:

of gas oil at 482 ° C: conversion, volume percent 62.7

¹⁰ zl advantage (C ₅ + gasoline), volume percent .. +8.3 cracking cetane number values (C ₅ + gasoline) 94.0

Conversion, volume percentage 60.5

Space flow velocity, example 37

BeSn ^ 0RVP, ^d Volümprozeni &quot; . '. \ '.'. '.'. '. ^{Xfi 1} ^ 10 parts by weight of one identified as zeolite 4A

Excess C ₄ , volume percent 11.9 synthetic crystalline aluminosilica s, which with

C ₆ + gasoline, VohmiprWt 48 4 «f« * ^G * f ^{sch v} _T ^{on rare} , ^ne * earth chlorides

Total C volume percent 14 4 holding aqueous solution had been treated,

Dry gas, weight percent ''.'.'.'.'.'.'.'.'.'. 6J ™ ^den f. ⁹⁰ parts by weight of the commercially available

Coke weight percent 21 ^ao silica-magnesia incorporated, and the

w A »« ,; _rt i, tc ^^^ _O tit nni ^s i ^cn resulting composition was 20 hours

H ₂ , percent by weight 0.04 ^ _{water vapor at atmos} p _häfisch e _m pressure and

662 ° C treated. The catalyst was studied for the Δ benefit cracking of gas oil at 482 ° C and it

Gasoline, 10 RVP, volume percent +6.2 as the following results were obtained:

Excess C ₄ , volume percent -2.0 conversion, volume percent 66.4

C ₅ + gasoline, volume percent +5.8 J advantage (C ₅ + gasoline), volume percent .. +7.5

Total C _4, volume percent cetane -1.5 (C ₅ + gasoline) 95.0

Dry gas, percent by weight - 0.8

Coke, percent by weight - 2.5 3 ° From the table above it can be seen that

Octane number of gasoline 97.3 the addition of the aluminosilicate with a pore size

less than 7 angstrom units to an increase

Example 34 increased a whole octane number in the obtained

Product performed as compared to the results for the 100% silica-alumina consisting of Example 36.

from 90 percent by weight SiO ₂ and 10 percent by weight Example 38

Al ₂ O ₃ , were used to crack gas oil at 482 ° C

and atmospheric pressure. The one identified as Y zeolite at 10 parts by weight

Results obtained from gas oil cracking are after- synthetic crystalline aluminosilicate have been used in

listed standing: 40 90 parts by weight of a silicon dioxide-aluminum

_XT " _T. , ^, "., Oxide matrix dispersed, consisting of 94 percent by weight

Conversion, percent by volume 51.3 ^ _{and fi percent by weight A1} Q ₃ consisted of a

_{To form} ^a 0.6 _{Perl enh drogel> The sicll erge} b _e hands Pearl octane _(C5 + gasoline) 98.8 _hydroge ^ ^ _{6 hours u} ^ - ^ -Vorteil _(C5 + gasoline) volume percent .. _{a 2 weight pro} .

_... ", 45 percent aqueous solution of rare earth chloride

ΰ e 1 s ρ 1 e 1 J3 hexahydrates, followed by a treatment

The procedure according to Example 34 was repeated with a 1 percent strength by weight aqueous. solution

except that 25 parts by weight of any synthetic crystalline hour identified as zeolite 4A of ammonium chloride over 24 consecutive hours. The aluminosilicate was then dried with water, aluminosilicate washed with a rare earth chloride 50 until the aqueous solution containing the effluent wash water containing substantially no chloride ions and the resulting catalyst was treated, and then for 48 hours at 648 ⁰ C composition was treated in the same way as in with water vapor at 1.05 kg / cm ^a; it

Example 34 steamed. resulted in a catalyst with a rare earth

On examination of the above catalyst 55 content, determined as rare earth oxides, of 4.79 ge

for cracking gas oil at 482 ° C became the weight percent.

The following results are obtained: _TT ,, · ,, 1 ^ -.

Conversion, volume percent 64.2

Conversion, percent by volume 49.7 £ " ^Vorte ?, ⁽ & ⁺ - ^Β ™ ^Ζ ™ \ percent by volume ... +8.7

ZI advantage (C ₅ + gasoline), volume percent .. +2.3 60 octane _(C5 + gasoline) 96.0

Octane _(C5 + gasoline) 98.4 _. . ,,.

Example 39

From the table above, it can be seen that 10 parts by weight of one identified as Y zeolite

the addition of an aluminosilicate with a pore size synthetic crystalline aluminosilicate and 5 gel

from less than 7 angstrom units to essentially 65 parts by weight of a syn-

With the same octane number of gasoline, synthetic crystalline aluminosilicate, both with

but with a rare earth chloride hexahydrate containing almost 3 percent by volume

Increase in the yield. Solution had been treated, and 10 weight

23 24

parts of raw McNamee clay were calcined in 75 parts by weight and then for 24 hours at 648 ° C and parts of a silica-alumina matrix, 1.05 kg / cm ² steamed to a catalyst to the 94 _{parts by weight of SiO 2} and 6 parts by weight of Al ₂ O ₃ obtained.

dispersed to form a pearl hydrogel. The catalyst was then used for cracking

The resulting composition was then tested on gas oil at 482 ° C, which was followed by twelve contacts with a 1.4 weight percent result were obtained:

term aqueous solution of ammonium sulfate treated conversion, percent by volume 49.3

delt with each contact a period of 2 hours J.Vorteil (C ₅ + gasoline), ... +6.2 volume percent

would have. The catalyst was then octane number (C ₆ + gasoline) 97.8 with water

washed until the draining washing liquid in the io

It can be seen from the table above that

Sulphate ions was dried and then the use of an aluminosilicate with a ^{pore size of less than 7 angstrom units treated with water vapor at 648 ° C and 1.05 kg / cm 2} to delt a catalyst with a sodium content of a 1.2 volume percent increase the amount of 0.3 percent by weight. 15 obtained gasoline at about the same or even

The above catalyst was then led to the higher octane number.
Cracking of gas oil at 482 ° C with the after-. .

investigated the following results: Example 42

Conversion, volume percent 63.0. ¹⁰ parts by weight of a zeolite 13X identifi-

J-advantage _(C5 + gasoline), volume percent ... + 8.9 ^ao f *? " synthetic crystalline aluminosilicate and

Octane number (C ₅ + gasoline) 96.6 ⁵ parts by weight of one identified as zeolite 4A

synthetic crystalline aluminosilicate have been used in

From the table above it can be seen that 85 parts by weight of a silicon dioxide-aluminum are dispersed by the addition of an aluminosilicate with a pore oxide matrix which consisted of 94 percent by weight of less than 7 angstrom units of 35 SiO ₂ and 6 percent by weight of Al ₂ O ₃ , to form a generation of gasoline in essentially the same bead hydrogel. The resulting beads yield as with the catalyst according to Example 38 were then carried out with a 2 weight percent water, but at a higher octane number. igen solution of rare earth chlorides over 24

consecutive hours at room temperature

Example 40 treated 3 °. The aluminosilicate was then washed with water

washed up in the draining wash water

10 parts by weight of a Y zeolite as chloride ions identified substantially more were synthetic crystalline aluminosilicate were treated in dried, and then 24 hours at 648 ⁰ C with 90 parts by weight of a silica-aluminum steam at 1.05 kg / cm ^2; an oxide matrix consisting of 94 percent by weight of a rare earth catalyst, be-SiO ₂ and 6 percent by weight of Al ₂ O ₃ was dispersed to form a rare earth oxide of 11.0 percent by weight pearl hydrogel. The resulting percentages and a sodium content of 0.04% were then obtained in three contacts with the composition. .

a 1 percent strength by weight aqueous solution of Example

Ammonium chloride treated, each contact 40 10 parts by weight of a zeolite 13 X identified for 16 hours, followed by nine ornamental synthetic crystalline aluminosilicate, 5 Ge contacts for 2 hours each with the same parts by weight of a solution identified as sodium mordenite. The aluminosilicate was then washed with water and crystalline aluminosilicate 10 parts by weight until the effluent wash liquor in the crude McNamee clay was 75 parts by weight essentially free of chloride ions, dried 45 a silica-alumina matrix, and then dispersed with steam at 648 for 30 hours ° C yawed, which treated 94 weight percent SiO ₂ and 6 Ge and 1.05 kg / cm ² to a catalyst weight percent Al ₂ O ₃ to form a pearl hydrogel with a sodium content of 0.27 weight percent. The resulting pearl hydrogel was obtained. with a 2 weight percent aqueous solution of

The above catalyst was then used for the 50 rare earth chloride hexahydrates over 24 on-cracking examined of gas oil at 482 ° C; which treated the other hours at room temperature Results are in the delt below. The aluminosilicate was then washed with water Table listed: washed up in the draining wash water

",. , _ _{Λ n} were essentially no more chloride ions,

Conversion, percent by volume ⁵ ^ ₅₅ dried and then 24 hours at 648 ° C with

J benefit (Q + gasoline) volume percent ... +5.0 _{water vapor at} i _{) 05} kg / cm ² treated; it was

Octane number (C ₆ + gasoline) 97.7 _{dn catalyst with a} rare earth content,

. . j is correct as rare earth oxides, of 11.2 weight

Example 41 percent and a sodium content of 0.2 weight

10 parts by weight of one obtained by exchanging the Na- 60 percent,
trium form of zeolite Y with an NH ₄ C1 solution Example 44

produced acid zeolite Y, 10 parts by weight of one

Rare earth zeolite A, which by treating 10 parts by weight of a zeolite 13 X identifi-

of synthetic crystalline synthetic crystalline aluminosilicate identified as zeolite 4 A, 5 modified aluminosilicate with a rare earth 65 parts by weight of a crystal chloride solution identified as zeolite 5 A, and 80 gel aluminosilicate and 10 parts by weight crude weight parts crude McNamee - Clay were mixed together - McNamee clay were mixed in 75 ^{parts by weight of a, dried, pelletized, 10 hours at 538 0} C silicon dioxide-aluminum oxide matrix, which consists of 94 parts

1,237,792

25 26

weight percent SiO ₂ and 6 weight percent Al ₂ O ₃ which consisted of both rare earth cations and dispersed to form a pearl hydrogel. Contains hydrogen ions combined with it. The resulting bead hydrogel was treated for 16 hours of applicability of the above catalyst to a 2 weight percent aqueous solution of fluidized bed cracking processes, rare earth chloride hexahydrates, followed by spray-drying of the material following a conventional half-counter of treatment with a 1 weight percent electricity method. in the air with an aqueous solution of ammonium chloride above 24 427 ^° C. at the top of the dryer in opposite consecutive hours at room temperature. Direction to the flow of the catalyst slurry was turned - The aluminosilicate was then passed with water. After the spray drying, the washing was recovered until there was in the outflowing washing liquid 10 product at the bottom of the dryer at about 149 to essentially no more chloride ions, 177 ^° C .; it was treated with a catalyst of the dried and then 24 hours at 648 ⁰ C with the required particle size for use in steam at 1.05 kg / cm ^2; it resulted in fluidized bed cracking, a rare earth content catalyst. .

determined as rare earth oxides, of 5.51 weight- 15 B e 1 s ρ 1 e 1 48

percent and a sodium content of 0.4 weight- The catalyst according to Example 47 was pelle-

percent. and graded to 4 to 10 meshes, 10 hours

B ice ο ie 1 45 ^ ^e * 538 ° C and then calcined for 24 hours at 648 ⁰ C.

treated with steam at 1.05 kg / cm ^2.

10 parts by weight of a 20 identified as Zeolite Y. The table below shows the cracking values synthetic crystalline aluminosilicate, 5% by weight of the catalyst in the investigation for the octopus parts a crystalline kung of gas oil identified as Zeolite4A at 482 ° C.

Aluminosilicate and 10 parts by weight of crude McNamee conversion, 52.9 percent by volume

Clay was made in 75 parts by weight of a silica J-Advantage (C ₅ '+ gasoline), percent by volume ... + 6 ^ 5

Dispersed aluminum oxide matrix, which consists of 94 Ge 25 octane number (C ₅ + gasoline) 96.4

weight percent SiO ₂ and 6 weight percent Al ₂ O ₃

duration; a pearl hydrogel was formed. The example 49

resulting composition was 16 hours 10 parts by weight of a zeolite 13 X identifi-

treated with a 2 weight percent aqueous solution of fancy synthetic crystalline aluminosilicate, 5 Ge rare earth chloride hexahydrates, followed by 30 parts by weight of a synthetic identified as zeolite A from a treatment with a 1 weight percent table crystalline aluminosilicate and 10 weight aqueous solution of ammonium chloride over 24 parts of crude McNamee clay were in 75 weight consecutive hours. The aluminosilicate split silicon dioxide-aluminum oxide with an additive was then washed with water until essentially no chlorine was dispersed in the washing liquid _{containing 94% SiO 2} and 6% Al ₂ O _3. The above composition was dried and then formed into a bead hydrogel by the conventional beading method for 24 hours by the conventional beading method treated at 648 ° C with water vapor at 1.05 kg / cm ² , and the result was a rare earth catalyst The pearls were brought into contact for 16 hours with a 2 weight content, determined as rare earth oxides, of 5.1 percent by weight aqueous solution of rare earth weight percent and a sodium content of 0.08 percent by weight chloride hexahydrate, followed by weight percent. of a 24 hour continuous touch

. · _Ι 4ί: ^w ith ^emer lprozentigen aqueous solution of ammonium

Example 4onium chloride. The aluminosilicate was then with

Washed 10 parts by weight of a water identified as Zeolite Y until the outflowing washing liquid had been treated with synthetic crystalline aluminosilicate, which was essentially free of chloride ions at 45 speed, and solutions of rare earth chloride hexahydrates and then sprayed ammonium chloride in the same manner as in Example 47 , and 5 dried. The spray-dried particles were pelletized by weight of a crystal identified as 5A zeolite, sized to 4/10 mesh, heated for 10 hours in linen aluminosilicate in 85 parts by weight of air at 538 ° C and then dispersed for 24 hours in crude McNamee clay and a total of 50,648 ° C treated with steam at 1.05 kg / cm ² , mixed and pelletized to 4/10 mesh. The table below shows the cracking values

The resulting composition was then tested for 24 hours in the investigation of the catalyst for the Krakat 648 ° C with steam at 1.05 kg / cm ² treatment of gas oil at 482 ° C.

delt, wherein a catalyst having a rare earth _Umwan dlung, 61.0 percent by volume

content, determined as rare earth oxides of 1 8 Ge 55 ^ advantage (Q + gasoline), volume percentage ... +6.5

weight percent and pmem sodium content of 0.39 Ge Octane number (C ₅ + gasoline) 98.6

weight percent was obtained.

_. -i / IT protruding from ^ ^s details can be seen that

Example 4 / ^ ₆ Incorporation of an aluminosilicate with a

7.5 parts by weight of a zeolite 13 X identifi- 60 pore size of less than 7 angstrom units

adorned synthetic crystalline aluminosilicate was found to have improved catalytic performance that with one containing rare earth cations, like that of one with 2.2 units higher Solution treated and then in 77.5 parts by weight of the octane number when it was obtained in Example 48, a silicon dioxide-aluminum oxide matrix emerges dispersed.

yaws, the 15 parts by weight of silica-aluminum 65 Beisoiel50

Oxyd fines contained. The resulting composite

The composition was then treated with an ammonium sulfate. It became a silica-zirconia hydrogel

solution treated to obtain an aluminosilicate prepared by adding soluble alkali silicate with a

acidic zirconium sulfate solution at pH 8.0. The hydrogel was then treated for 24 hours at 93 ⁰ C with a lgewichtsprozentigen sulfuric acid solution, followed by treatment with a 2gewichtsprozentigen aqueous solution of ammonium chloride for 24 consecutive hours. The hydrogel was then dried at 132 ° C. for 20 hours, calcined at 538 ° C. for 10 hours, and then treated with steam at atmospheric pressure at 662 ° C. for 20 hours.

The above silica-zirconia catalyst (90 weight percent _SiO2 and 10 weight percent ZrO ₂₎ was then tested for the cracking of gas oil at 482 ⁰ C, whereby the following results were obtained:

Conversion, volume percent 54.6

J advantage (C ₆ + gasoline), ... +3.3 volume percent

Octane _(C5 + gasoline) 97.5

Zl advantage (coke), percent by weight - 1.1 _M

Example 51

A catalyst composition was prepared by adding 44.7 parts by weight of a rare earth aluminosilicate having a pore size less than 7 angstrom units to 2340.0 parts by weight of the silica-zirconia hydrogel prepared by the procedure of Example 50. To the mixture 100 parts by weight of water were added and the whole mass was mixed into a slurry, which was introduced into a dryer of HO ⁰ C and dried for 20 hours. The composition was then calcined for 10 hours at 538 ⁰ C and treated for 20 hours at 662 ⁰ C at atmospheric pressure. The composition of the catalyst at this point was 90 percent by weight of silicon dioxide-zirconium oxide (90-10) and 10 percent by weight of rare earth zeolite A.

The above catalyst was then evaluated for the cracking of gas oil at 482 ⁰ C, whereby the following results were obtained:

Conversion, percent by volume 55.9

Δ -Vorteil (C ₅ + gasoline), ... +4.6 volume percent

Octane _(C5 + gasoline) 97.5

Δ benefit (coke), weight percent - 2.1

From the table above it can be seen that the addition of an aluminosilicate with a pore size from less than 7 angstrom units to producing approximately 1.3 units more gasoline in Combined with the production of about 1 unit less coke at the same octane number.

Some of the terms used in the preceding explanations are defined below:

Zeolite 13 X: sodium form of synthetic faujasite X; described in U.S. Patent 882 244.

Zeolite 5A: calcium form of zeolite A; described in U.S. Patent 2,882,243.

Zeolite 4A: sodium form of zeolite A; described in U.S. Patent 2,882,243.

Zeolite Y: form of synthetic faujasite: described in Belgian patent 617 598. Unless a particular cation and / or the term "acid" or "acidic" is used to denote a Zeolite is preceded, it means that at least a part of the originally with the zeolite combined cations by other metal cations and / or hydrogen ions or precursors thereof are replaced.

Octane number: determined according to ASTM method D-908; usually simply referred to as research octane number (+ 3 cm ³ tetraethyl lead [TEL]).

The rare earth chloride solution used in the examples had the following composition:

Weight percent

Cerium (as CeO ₂ ) 48

Lanthanum (as La ₂ O ₃ ) 24

Praseodymium (as Pr ₆ O ₁₁ ) 5

Neodymium (as Nd ₂ O ₃ ) 17

Samarium (as Sm ₂ O ₃ ) 3

Gadolinium (as Gd ₂ O ₃ ) 2

Other rare earth oxides 0.8

Claims (2)

Patent claims: 1. Method for the catalytic cracking of a Hydrocarbon oil for the production of hydrocarbons with a lower boiling range in the presence of a catalyst which is an optionally base-exchanged aluminosilicate of defined Has pore size, characterized in that a catalyst consists of a mixture of a) an aluminosilicate with a pore size of less than 7 angstrom units and b) a cracking catalyst of general activity, optionally incorporated into a porous one Matrix, is used. 2. The method according to claim 1, characterized in that a catalyst is used, in which component b) consists of an aluminosilicate with a pore size of more than 8 angstrom units consists.