DE2044630C - Process for producing a catalyst and its use - Google Patents

Description

From the German Auslegesdirift 1151082 is a Process for the preparation of halogen-containing catalysts by incorporating a platinum group metal and of germanium in porous inorganic oxide carriers through precipitation of the active components or by soaking with an impregnating solution and then drying, deinating and optionally Known to reduce. As is known, the catalysts obtained in this way can be used for reforming of hydrocarbons or for other hydrocarbon conversion processes will.

It is also known that in such hydrocarbon conversion processes, high molecular weight solid or semi-solid carbonaceous deposits form on the catalyst which adversely affect catalyst activity. The object of the invention was therefore to induce the production of new catalysts which are less sensitive to such carbon-containing deposits and which have increased activity, selectivity and / or stability compared to known catalysts. During reforming, the cetane number of the product is a measure of the AkttvMt UBd and the C _s + yield is a measure of the selectivity. The slower the AMvMt and selectivity of a catalyst deteriorated, the more stable it can be regarded as »

The appropriate process for the production of a halogen-containing catalyst by incorporating 0.01 to 2 percent by weight of a platinum group metal and 0.01 to 5 percent by weight of Ge, calculated as the element and based on the weight of the finished catalyst, in a porous inorganic oxide carrier Precipitation of the active. Components or by soaking with an impregnating solution and then drying, calcining and

For reducing, if necessary, it is characterized in that the catalyst is additionally given from 0.1 to 5 percent by weight Tin, calculated as an element and based on the weight of the finished catalyst, incorporated and after drying Q ^ to 10 stalls

is oafciaiert at 371 bbS93 ° € m loft.

Above all, these catalysts have a high Activity and thus a lower sensitivity to carbonaceous deposits in comparison with known catalysis

3 doors of this type that contain no tin. You can can be used for various hydrocarbon conversion processes, such as for Isomerization, Hydroisomeristeren, Dehydricrcn, Desulfurization, Nitrogen removal, hydrogenation, alkylation,

• 3 dealkylation, hydrodealkylation, transalkylation, cyclization, Dehydrocycling, cracking, hydrocracking or polymerize. In particular, the catalysts are for reforming hydrocarbons and for the coal produced during reforming

Hydrogen conversion reactions suitable.

According to a preferred embodiment of the process according to the invention, 0.05 to 1 percent by weight of platinum, 0.05 to 2 percent by weight of germanium and 0.1 to 1 percent by weight are added to the catalyst

Tin and 0.5 to 1.5 weight percent halogen.

The porous inorganic oxide support used in the preparation of the catalyst expediently has an internal surface area of about 25 to 500 m 2 / g, preferably about 100 to 50 mVg. a bulk density of about 0.3 to 0.7 g / cm ', an average pore diameter of about 20 to 300 Å and a pore volume of about 0.1 to 1 ml / g. It can consist of alumina, titanium dioxide, zirconium oxide, chromium oxide, zinc oxide, magnesia, thorium oxide, boron oxide or combinations thereof. The oxide carrier used is preferably alumina, which may optionally contain other of the inorganic oxides mentioned, such as silica, zirconium oxide or magnesia, the crystalline alumina forms such as y-, ψ

jo and Α-alumina are preferred. y-clay in the form spherical particles with a relatively small diameter, such as 1.6 mm, a bulk density of 0.5 g / cm *, a pore volume of about 0.4 ml / g and a surface area of about 175 mVg

SS proved particularly useful. Instead of the spherical shape However, the alumina carrier can also, for example, be in the form of pills, extruded powders or B & itzen granules. The Platingrup ^ ennietall des The catalyst is preferably platinum »although it is too

te palladium, ruthenium, osmium ode * iridium can be. Preferably, these platelet metals are generally incorporated around the catalyst in an amount of about % to 1% by weight, either in the fat or in the elemental metal

6a in the Fortneffler compound, like tine oxide »sulphide halide. When impregnating with an impregnating solution, it is expedient to use a scale ^L "of chloroplethic acid, AmtnotiiumchloipläÜ ·

Bromoplatinic acid, platinum dichloride or dinitro- 1 percent by weight 23ns. This canoe also like * opiate, palladium chloride, paaladiurachloride - the other metal constituents by precipitation or or palladium nitrate generally takes place in nozzles soaking with an impregnation agent incorporated ; Soak the catalyst with the platinum spp. In the former case it is expedient to use the metal compound after calcining, a water-soluble Zranveraindtmg on one S alumina hydrosol, Loss of the valuable platinum group metal to become like 25nn (fl} - or ZimipV> iialbgenid zo, after which the avoid. Mixture with acidic medium, as carried out

The G can also drip into the catalyst in an oil bath; is transmitted. After in the form of metal or chemical calcining, the oxide carrier contains alumina bond, such as ines oxide, sulfide, halide Oxy- ίο- ZJnn (H> oxide.

chloiids or aluminates. The best results are obtained in the case of the impregnation period, if the Ger- lehe decomposable zinc compound, such as Snn (II) -bromanium in the catalyst in an oxidizing agent, tin (13) chloride, Zum (n) -cMoridpentanydrat, above that of the elementary metal is present, tin (TV> cidoridtetnUiydrate, 25nn (IV> cbloridtrihy preferably in the oxidation level +4. The preferably, 23nn (TV) -cbloriddiamine, tin (rV) -trichloridetriches amount of gsrmanium is 0.05 to 2 Weight foromid, ZumQJfyanoin & t, IxanQJfy-fhioud, ZännCIV) percent, calculated as an element and based on the üaond, Zwn (W} -} oOia, tin (Tv> suffat or Zänn (IV> weight of the finished catalyst. When incorporated tartrate The chlorides are particularly suitable because they introduce the germanium into the oxide carrier by precipitation at the same time halogen in the catalysts, it is expedient to add a μ The tin can also be used simultaneously with the other water-soluble germanium compounds, such as genoa - Metal components in an impregnation solution to the nium tetrachtorid. When incorporated by impregnation, oxide carriers are incorporated, preferably one with an impregnation solution is used. Impregnation solution is used, the chloroplatinic acid, moderately acidic aqueous solutions of a germanium hydrochloric acid, ZUm (II) - oder_ tin (IV) chloride and compound, such as Germanium tetrachloride, germanium as Gennanium tetrachloride dissolved in ethanol contains difluoride, germanium tetrafluoride, germanium diiodide

or germanium monosulfide. Particularly preferred is nium and tin, calculated as elements in which an impregnation solution, the Ger catalyst dissolved in chlorine water, is appropriately about 0.15 to 4 percent by weight of gemanium metal or germanium dissolved in ethanol, preferably about 0.3 to 2 percent by weight of tetrachloride contains. A particularly uniform 30 percent by weight, based on the weight of the finished incorporation of the germanium into the porous an- catalyst. The atomic ratio of the organic oxide carrier is achieved by keeping the tin to platinum nipple metal conveniently at about 0.2: 1 to 3: 1 and the germanium atomic ratio of 1 to 7 and keeping the impregnating solution at about 0.2: 1 to 3: 1 substantially to platinum group metal at about 0.25: 1 to about 6: 1. borrowed a larger volume than that of the 33 Examples of favorable catalyst compositions to be impregnated, diluted oxide support. Appropriately, the volume is as follows, the inorganic ratio of impregnation solution to oxide carrier in the case of min oxide carrier made of alumina with 0.5 to 1.5 weight at least 1.5: 1 and preferably about 2: 1 to 10: 1 . cent halogen content and the following Also it is favorable for this purpose, relatively long weight percentages are calculated as an element. Drinking times, we in the range from about one quarter to one hour, 40
apply.

Halogen contains that obtained according to the invention
Catalyst expediently in an amount of 0.1 to
10.0 percent by weight, especially in an amount of
0.1 to 2.5 and preferably in an amount of 0.5 45
up to 1.5 ° / β · This halogen preferably consists of fluorine
or chlorine, which in an unknown manner to the
Oxide carriers are bound. The halogen can be in
be fed to any of the process stages,
for example as an aqueous solution of hydrofluoric acid, 5 »
Hydrochloric acid or hydrobromic acid, and it can The catalyst is generally 2 to 24 hours

are fed to the catalyst during impregnation with the above-mentioned impregnating solutions at about 93 to 316 ° C. Hydrochloric acid oxide form. This can also be used to produce the an-SS. By using an organic calcine oxide carrier, alumina dehydrosolation air, which halogen or a halogen compound already contains halogen which contains the desired one, can at least partially cover the halogen content during the halogenation. Set at Ver * Calcihterung in the desired height, the Katäly- inventively prepared crinkle It is particularly suitable for this purpose, in the last Tdl catalysts for reforming contain them zweckmatUg -fe 4-calcination in the Calcinierungsluft a 6twa 0.1 to 2.5 Öewiehtepröäiettt in Grazing as a moiver ratio of H ₁ O to HCl of about 20; 1 to isomerization or high cracking catalytic converter, useful to set 100: 1.

moderately 1 to 5 weight ptoaftt fMflgMu After the oilcination, the catalyst wifd before *

The tin can be practically pure and dry for the zügswetse prepared according to the invention Catalyst also in the form of the metal ödet * s Sassetstett with less than J & Volumerteppm MiO A chemical compound such as an oxide, sulfide, is reduced. This reduction takes place favorably ffätogeaids or Ostychlörids are incorporated. This is approximately 0.5 to 10 hours at a time preferred The amount of tin is about 0.1 to a temperature of about 425 to 650 ° C to

catalyst Gnnsmum Weight percent t platinum No. 0.25 tin 0.75 1 0.2 0.25 0.375 2 0.3 0.3 0.375 3 0.2 0.2 0.5 4th 0.5 0.5 0.25 5 0.1 0.5 0.375 6th 0.1

2 04 * 630 Y %

■ * ■ ■ «-

component prafcäscli to the elementary state to Έψ at about 53S ⁰ C, a weak overdiuct:

leduziexen, during the rS ernianfomh c ^ aB ^ p ?! in and one flow velocity of the WassirstQffi /

This re-spur remains through fie. Ka ^ flysatorteflehen correspond to ^ V ^: -

, production can be carried out directly in the ZTisq imnwftgng using an hourly gas space velocity of about -

Catalyst manufacture o «i« r in connection with 5 720 were treated. The duration of this Vonsduk

The duration of the catalytic converter in the de-foaling stage lasted about an hour.

. one? Other procedures may be denied. Example 2

Preferably the reduced catalyst

After treatment with a mixture of water, in order to compare the catalyst with a substance with hydrogen sulfide or piedennolaren according to the state of the art, mercaptans were additionally 0.05 US 0.5 weight percent as follows: Sulfur sulfide as an element and based on the gMchskaftOysator, a catalyst obtained according to the German AusGewicht des Feigen Katsdysater, incorporated Zweck- fegesdkrift 1151082, this is done with a mixture of .10 moles, which uses 0.375 percent by weight platinum, 0, 25 Ge-Wesser substance per MoI hydrogen sulfide in a weight percent germanium and 0.8S by weight of the temperature range from "10 fcwa Hs 593 ⁰ C, preferably chlorine on a y-contained TaneHteträger
under practically anhydrous conditions. The catalyst obtained according to Example 1 and

the comparative catalyst were then separately one

S e i s D i e 1 1 «° test under heavy loads,

to their relative activity and selectivity for the

A catalyst according to the invention was prepared in such a way as to determine the reforming of a Berizinbescbiekuni: First, an alumina was used in all tests, the same charge carrier in the form of 1.5 mm balls after the mixture, the characteristics of which are in the process of U.S. Patent 2,620,314, see Table I below. The experimental procedure An aluminum hydroxyl chloride sol was carried out under practically anhydrous conditions; the dissolution of practically pure aluminum flakes the only significant source of water was those made in hydrochloric acid solution, then hexa- 5.9 ppm by weight water was added to the feed,
methylentetramine added to the sol, the obtained

Solution by dripping into an oil bath with formation of 30 _ ....
of balls as aluminum hydrogel for gelation laoeie
brought, the obtained particles were aged analysis of heavy Kuwait naphtha
and washed and finally dried and calci-,, ",",. "_
ned to form spherical particles of γ-alumina with about specific gravity (15.6 / 15.6 C) ... 0.7374 0.3 weight percent combined chlorine. 35 Initial boiling point in C 85

Germanium tetrachloride was dissolved in ethanol. 10% boiling point in C 96 An aqueous solution of 50% boiling point in C 124 was separated from this Chloroplaic acid, tin (IV> chloride and hydrochloric acid at- 9 °% boiling point in ° C 161

prepares. Then the two solutions intimately reached their end boiling point at ⁰ C 182

mixed and for impregnation of γ-alumina particles 40 sulfur weight ppm 0.5

used in such amounts that a finished nitrogen in ppm by weight is 0.1

Mass with 0.2 percent by weight Ge, 0.375 percent by weight aromatics in percent by volume 8 Found percent Sn and 0.375% Pt. To an equal paraffins in volume percent 71

shaped distribution of the meta-constituents in the naphthene in percent by volume 21

To ensure the whole support material, the «water in ppm were 5.9

Carrier particles for the impregnation solution with constant octane number F-I clear 40.0 Stirring added. The solution volume was about

twice as large as that of the carrier particles. The im- The trial consisted of six periods of each

pragnierlösung was with the carrier about 6 hours following start-up time with lOstündiger test "Vt hour at a temperature of about 21 ⁰ C in 5" period at constant temperature, while the maintained contact. The temperature of the (^ + - reformate product was collected. The impregnation ^{solution was increased to about 107 °} C. and the excess solution was evaporated in a reforming plant from Labo excess solution for about one hour using a catalyst. The dry particles obtained The holding reaction vessel of a hydrogen separator was then calcined in an air atmosphere at a temperature zone, a butane removal column, suitable heating, of about 496 ° C for about 1 hour.
stream, the H ₁ O and HCl in a molar ratio of a hydrogen cycle stream and the feed

about 40: 1 containing, for 4 hours at 524 ° C were mixed and heated and downwardly through the filters it to the Halögengehält the Katälysatotteilcheft einrn- m the catalyst as a fixed underlying layer. containing reaction vessel passed. From the ground

The parts were then analyzed and revealed that an effluent stream was withdrawn calculated as elements, about 0.375 percent by weight cooled about 13 ° C And passed to the separation zone, Platinum, about 0.5% ytrium, about 0.3% tin and in which a hydrogen-rich gas phase differs from a about 0.85% chlorine. The catalyst liquid phase was then trenjhfe. Part of the gas phase Particles of a dry condensation treatment were washed through a washer with sodium with large undergo by being passed with a practically clean surface, and the practically anhydrous Hydrogen flow with less than 20 volumetric ppm of hydrogen flow was returned to the activation vessel *

guided. The excess over the need to maintain the operating pressure was considered to be excess; Separator gas obtained. The liquid phase from the Trennzone- was withdrawn therefrom and passed to Butanentfernerkölonne, 'wherein _v is taken off the light ends amJKopf · "and a C ₅ + -' Reformätstrom obtained as bottom product ^ - was.

The applied in this experiment conditions were as follows: A constant temperature of about 517 ° C for the first three periods, and then a constant temperature of about 536 ⁰ C during the last three periods, a liquid hourly space velocity of 3.0, a pressure at the reactor outlet of 7.8 at and a molar ratio of hydrogen to hydrocarbon at the reactor inlet of 10: 1. This two temperature experiment is designed to quickly and effectively provide two points on the octane yield curve for the catalysts in question.

The octane numbers of the separate trials are for each operating period in Table II along with the Listed reactor inlet temperature and the excess of separator gas.

Table II

Catalyst according to German Auslegeschrift 1151 082 with 0.375 percent by weight Pt, 0.25 percent by weight Ge and 0.85 weight percent Cl

Attempt ι - Reactor· Excess of Octane number period. 2 inlet temperature Spearator gas clear F-I - 3. ⁰ C m »/ m ^l 4th "517 268 96.3 5 517 265 95.1 6th . 517 262 95.0 536 304 '98, 6 536 294 98.5 536 292 98.2

Catalyst according to the invention with 0.375 percent by weight Pt, 0.2 percent by weight Ge, 0.3 percent by weight Sn and 0.85 weight percent Q

1 517 277 97.5 2 517 - 97.2 3 517 271 96.5 4th 536 301 99.4 5 536 294 98.9 6th 536 283 98.1

Since, as stated above, the octane number is a measure of the activity and the excess of separator gas as is a MaO for the selectivity, results from the above table that the catalyst prepared according to the invention with practically the same selectivity possessed increased activity over the prior art catalyst.

Claims (4)

2 §4 # §30 Sponsorship Loan: L · method znr producing a halogen-containing catalyst by ISnarbeiten tob% 01 to! Weight percent of a platinum group metal Tmd 0.01 _ ins 5 percent by weight of germanium calculated KSS element and based the weight avf of the finished catalyst in a porous inorganic Cbddtzäger by precipitation of the active components or shower soaking with an impregnation solution and subsequent drying, calcining and optionally reducing, characterized in that an additional 0.01 to 5 percent by weight of tin, calculated as an element and based on the weight of the finished catalyst, is incorporated into the catalyst and after drying O ₁ S for 10 hours at 371 to 593 "C ia calanated air. 2. The method according to claim 1, characterized in that the catalyst 0.05 to 1 percent by weight of platinum, 0.05 to 2 percent by weight Germanium, 0.1 to 1 percent by weight tin and 0.5 to 14 percent by weight halogen are incorporated. 3. The method according to claim 1 and 2, characterized in that the reduced catalyst by treatment with a mixture of hydrogen with hydrogen sulfide or low molecular weight mercaptans in addition 0.05 to 0.5 weight percent sulfur, calculated as the element and based on the weight of the finished Catalyst, incorporated. 4. Use of a catalyst prepared according to claim 1 to 3 for reforming Hydrocarbons.