DE2342933C2 - Process for the production of a zeolite catalyst and use of the catalyst produced by this process for the catalytic conversion of hydrocarbons - Google Patents

Description

-0.05 7 "} - 30 <Ρη, ο < -0.05 Γ + 70

Fulfills.

2. Use of the catalyst prepared according to claim 1 for catalytic conversion and especially for hydro-splitting hydrocarbons.

of a catalyst by applying one or more catalytically active components to a zeolite having a composition, expressed in moles of the oxides, 0.7 to 1.2 Na ₂ O · Al 2 O 3 · 4.7 to 5.3 SiO ₂ · χ H ₂ O, in which χ is at most 12 and preferably 3 to 9, and the powder X-ray diffraction diagram given in Table A, in which at least some of the sodium ions contained in it are replaced by hydrogen and / or ammonium ions or by calcium or rare earth metal ions, so that the Zeolite has a sodium content of less than 1 wt Heat treatment in the atmosphere surrounding the material maintains a partial pressure of water vapor (Ph ₁ Q in m t 'g column) as a function of the temperature of the material (T in "C) n becomes the condition in the temperature range from 100 ° C to the final temperature of the heat treatment

- 0.05 Γ + 30 <Ρηλ ^ -0.05 Τ + 70

Fulfills.

Surprisingly, it has been shown that when carrying out the first heat treatment under the specified conditions with respect to the water vapor partial pressure, the following, if applicable further heat treatments under other conditions can be carried out without this the high catalyst activity achievable according to the invention is adversely affected.

35 Table A

From DE-OS 20 58 908 a method for producing a catalyst is known, according to which one or more catalytically active components are applied to a zeolite which has a composition expressed in moles of the oxides of 0.7 to 1.2 Na ₂ O Al ₂ O) · 4.7 to 5.3 SiO ₂ · χ H ₂ O, where χ is at most 12 and preferably 3 to 9 and the zeolite has the powder X-ray diffraction diagram given in Table A below. In addition, at least some of the sodium ions contained in the zeolite are replaced by hydrogen and / or ammonium ions or by calcium or rare earth metal ions, so that its sodium content is less than 1 percent by weight. In the known process, the product is subjected to heat treatment one or more times in the course of its production up to final temperatures of 400 to 550 ° C. and is then kept at this temperature.

The zeolite used as the carrier material (hereinafter referred to as KSOL) has a uniform pore diameter of about 0.5 nm producible catalysts are particularly suitable for the selective hydrocracking of straight-chain hydrocarbons, which are present in mixtures with branched-chain and cyclic hydrocarbons,

It has now been found that the selectivity of these catalysts can be significantly improved, if during the heat treatment (s) a certain temperature is dependent on the temperature used Wasserdampfpärtiäldftick is maintained-

The method according to the invention for the production of radiation / C u-Ki? I
2 Θ

Wavelength 0.15405 nm
Relative intensity

7.15-7.95 M. W. 8.80- 9.80 S. 12.70 13.10 M. 15.00-17.00 VS 17.55-17.95 M. 19.60-20.20 VS 20.40-21.60 M. 22.15 22.75 S. 25.80 26.20 VS 27.20 28.80 29.90 30.50 1 'I " 3! /. OO 30.80 V S 30.25 31.05 31.30 31.90 M. M. 34.40 34.80 50 ^ 50 91 in the Θ = the Bragg angle VS = very strong, S = strong, M = medium strength, W = weak, and

65

The starting zeolite has special adsorption properties, who reveal themselves in the fact that he

after dehydration at 240 ⁰ C under vacuum for one at 100 ° C and a hydrocarbon pressure of 40 mmHg measured n-hexane adsorption of at least 0.25 mmol / g and a ratio of mmol / g of adsorbed η-hexane to mmol / g absorbed 2,3-dimethylbutane of at least 8.

The method according to the invention is preferably carried out in such a way that during the heating of the material in the temperature range from 100 ° C. to the final temperature, the condition ΔΡ _α2 ο / ΔΤ <0 is met, in which Δ Τ a small temperature rise of the material during heating and <dPn. o mean the corresponding change in the water vapor partial pressure of the atmosphere surrounding the material. In addition, in the method according to the invention, the water vapor partial pressure of the atmosphere surrounding the material is preferably reduced by 10 to 20 mm of mercury if temperatures of 275 to 325 ° C. are reached when the material is heated to the final temperature. Furthermore, the water vapor partial pressure of the atmosphere surrounding the material is preferably reduced by 35 to 50 mm of mercury when the material is heated to a temperature of 200 ° C. and by 10 to 20 mm of mercury when temperatures of 275 to 325 ° C. are reached.

As a zeolite KSOL carrier material for the invention Catalysts produced are preferably a zeolite KSO! with an n-hexane adsorption of at least 0.40 mmol / g and in particular at least 0.75 mmol / g after dehydration in vacuo 240 ° C and measured at a hydrocarbon pressure of 40 mm mercury column and a temperature of 100 ° C used.

The material as a carrier fo ^r the present invention produced catalysts ver <-? Ndete zeolite Ksol is preferably obtained by a procedure as is described in DE-OS 20 58 908th

In the preparation of the catalyst according to the invention, at least some of the in the zeolite KSOl existing sodium ions are replaced by other cations. As a carrier material for the invention Catalysts produced, a zeolite KSOl is preferably used, the sodium content of which less than 0.05 weight percent has been decreased. The sodium ions can expediently from the zeolite KSOl can be removed by treating the zeolite one or more times with an aqueous. Heated solution containing ammonium ions. When replacing at least a portion of the sodium ions performed by other cations in several stages using one or more heat / wipe treatments care must be taken that during the first heat treatment of the material the the aforementioned relationship between the water vapor partial pressure of the atmosphere surrounding the material and the temperature of the material is met.

Particularly favorable results are obtained if the zeolite is used three times from the following stages subject to existing treatment:

(a) Lrhiuen the zeolite with an aqueous ammonium ion containing solution,

(b) filtering off the zeolite,

(c) washing the zeolite and drying after the third treatment.

Equally very favorable results are obtained when the zeolite is twice or three times the aforementioned three-stage treatment, then the heat treatment according to the invention and then subjected again, two or three times to the above three-stage treatment and finally is dried.

For the selective hydrocracking of straight-chain in light hydrocarbon fractions containing paraffins by means of the prepared according to the invention Catalyst can be both a precious metal of the flu

ίο VIII of the Periodic Table, such as one or more Non-noble metals containing catalysts can be used. Catalysts, their catalytically active Metal component consists of a noble metal of group VIII, generally contain 0.05 to 5 Güwichtsteile and preferably 0.1 to 2 parts by weight of the noble metal per 100 parts by weight of the carrier material. Particularly suitable noble metals of group VIII des Periodic table of the elements are platinum, palladium and ruthenium. Catalysts, their catalytically active Metal components consist of one or more non-ferrous metals, generally contain 0.1 to 35 parts by weight and preferably 0.1 to 15 Parts by weight of this metal per 100 parts by weight of carrier material. Particularly suitable non-precious metals are nickel, cobalt and the rare earth metals. Suitable combinations of non-precious metals are Combinations of nickel with calcium and combinations of nickel with rare earth metals.

The application of the metals to the zeolite KSOl

J ₀ can be prepared by means of one of the known methods commonly used, such as by means of impregnation, percolation, impregnation with the formation of a slurry. Ion exchange and competitive ion exchange.

After the metals have been applied to the carrier material, the material is dried and then subjected to a heat treatment. If this is the first heat treatment, the aas catalytic material is subjected, d. H. if

_If no heat treatment has been applied during the replacement of at least some of the sodium ions of the zeolite by other cations, care must be taken to ensure that the aforementioned relationships between the water vapor partial dn ;; the atmosphere surrounding the material and the temperature of the material are fulfilled.

The heat treatments used in the preparation of the catalyst according to the invention who preferably in an oxygen-containing gas carried out. Air is eminently suitable as the oxygen-containing gas. The aforementioned heat treatment lungi_n are preferably down to a final tempera door of at least 450 ° C.

In addition to the production of a catalyst from a zeolite KSOl support material, the present invention also relates to the use of the catalyst produced in this way for converting hydrocarbons and, in particular, for hydrocracking

of hydrocarbons, the catalysts are preferably used in their sulfidic form-

The selective hydrocracking of straight-chain paraffins using the invention

Catalysts prepared can suitably be used at temperatures from 300 to 500 ° C and pressures from 5 to 100 bears to be carried out. The Räürreströmungsgeschieber can have 1 to 201 feed per liter

Catalyst per hour, and 1 to 10 moles of hydrogen can be used per mole of feed. The process is preferably carried out at temperatures of 350 to 450 ^° C., pressures of 10 to 50 bar and a hydrogen / feed molar ratio of 2 to 8 s

The examples illustrate the invention.

Manufacture of Zeolite KSOl

A commercially available silicon dioxide-aluminum oxide cleavage catalyst with the following properties is used as the starting material for the production of zeolite ι ο KSOL
Water content: 15.3 percent by weight
Aluminum content or sodium content, based on the dry substance: 12.8 or <0.5 percent by weight,
Surface area and pore volume after calcining at 600 ° C.: 658 m ² / g and 0.75 ml / g, respectively.

A mixture of the molar composition Na ₂ O 4 · Al ₂ O _{3 to} 11.2 SiO ₂ ■ 150 H ₂ O is successful forming under stirring _M adding a solution of 8 kg of sodium hydroxide in 18.75 kg of water to a mixture of 24 82 kg of the above-mentioned cleavage catalyst and 41.6 kg of water are prepared. The entire mixture is refluxed for 12 hours with stirring >=> After the reaction mixture has cooled, the zeolite is filtered off with water until the pH of the filtrate is below 10 and dried at 120 ⁰ C

The zeolite KSOl (Zeolite I) has the following properties:

An X-ray diffraction pattern (powder diagram) of the zeolite essentially corresponding to the values listed in Table B. The chemical composition 1.12 Na ₂ O ■ Al ₂ O ₃ · 5.03 SiO ₂ · 4.70 H ₂ O. The following adsorption behavior (after dehydration in vacuo at 240 ° C) at a hydrocarbon pressure of 40 mm of mercury and a temperature of 100 ⁰ C: adsorption of n-hexane 0.84 mmol / g and of 23-DimethyIbutan 0.06 mmol / g. A reverberation is

mmol / g adsorbed n-hexane

4'y

mmol / g adsorbed u-Κί / 2,3-Di me thy! Butane reflection Table B. radiation (/. nm wavelength and 15405 nm 2 β Relative 1.17 intensity B. 0.95 (On / / "1 B. D 7.55 0.686 M) SII 9.30 0.553 26th VVB. D. 12.90 0.499 W. SlI 16.00 0.445 48 SII 17.75 0.423 100 *) VB 19.90 0.396 4h SH 21.00 0.342 250 SH 22.45 0.318 42 VVB ₁ D 26.00 0.296 62 SlI 28.00 0.294 88 VB, D 30.20 0.291 D. 30.40 0.283 Depreciation SfI 30.65 464 31.60

30th

35 radiation:
2 (·)

ti. 11 m

Wavelength 0.15405 nm

Relative intensity (H) O // ")

reflection

34.60
38.30
39.20
39.40
42.70
43.50
47.80
50.65
53.40
54.35
54.98
56.0O

61.4 (1

0.259
0.235
0.230
0.229
0.212
0.208
0.190
0.180
0.171
0.169
0.167
0.164
0.151

SH

SH

SH

SH

SH

SH

SH

SH

SH

SH

SH

*! / _i; =! niensitii! de -.tirl .ι,
diffraction pattern.

1 I jn / elriievinn in the x-ray

The letters used in Table B to describe the reflection mean: SH = sharp; D = diffuse; B = broad; VB = very broad; WB = extremely wide; Θ = Bragg angle and d = lattice plane spacing.

Removal of some of the sodium ions from the KSOl zeolite

An NH ₄ VH ⁺ -ZeOlUh-KSOl is prepared as follows from the Na ⁺ -zeolite KS01 (zeolite I) which has been obtained in the aforementioned manner. The zeolite is subjected to three treatments comprising the following successive steps:

(a) Boiling the zeolite for 1 hour with a 1 omolar NH ₄ NO ₃ solution,

(b) filtering off the zeolite, and

(c) washing the zeolite with water.

After the third treatment the zeolite at 120 ⁰ C is dried, the thus prepared NH ₄ ⁺ VH--ZeOIiIh Ksol (zeolite II) comprises a substantially to the values listed in Table A corresponding X-ray diffraction pattern (powder diffraction) on.

example 1

^{An amount of the NHWH +} -7poliths-KS01 (zeolite II) prepared in the manner described above corresponding to 750 g of dry substance is mixed with 1850 ml of an 0.1 molar NH4NOi solution and the pH of the mixture is adjusted to 7 with concentrated ammonia. A solution of 96.5 g of Ni (NO ₃ ) Z in a mixture of 200 g of 25% ammonium hydroxide and 1850 ml of an 0.1 molar NH 3 NO solution is added to this mixture with stirring. . After the addition, the mixture is stirred at 50 ° C. for a further 24 hours.

temperature 350 ⁰ C pressure 35 bar Space velocity 21 l-i h- ' Hydrogen / feed Molar ratio 8th

The results of the hydrocracking tests are summarized in Table C in which the activity of the catalysts is expressed as the difference in octane number (zlROZo) between the C ₅ "fraction of the product and the Ci * fraction of the feed.

Tabel C. Water vapor partial pressure of the during the Activity of Kata- Air, mm Hg column Heat treatment Catalyst lyser while from 300 to 500 C. (A ROZ ₀ ) No the heat and during the treatment Maintenance from 20 to a temperature 300 ( from 500'C 30th 20th 50 15th 7.6 1 50 45 7.4 2 50 3 6.8 3 50 5 6.1 4th 50 50 2.6 A. 50 20th 4.7 B. 50 20th 4.5 C. 20th 200 3.5 D. '.Of) 4.8 L. 200 3.0 F.

10

After filtering off and washing with water, the solid material is ^{dried at 120 °} C. for 12 hours. The powder is pressed into tablets and then ground into particles with a size of 0.177 to 0.548 mm. This material is converted into 14 catalysts (1 to 4 and A to K) containing 2 g of nickel per 100 g of support material by heating the material samples in air at a rate of 2.3 ° C./min. first from room temperature to 300 ⁰ C and 300 ⁰ C to a final temperature of 500 ⁰ C for 3 hours and then maintaining this final temperature of the samples prepared. During this heat treatment, the partial pressure of water vapor shown in Table C is applied.

The catalysts prepared in the manner described above are used for selective hydrocracking straight-chain paraffins in a hydrocarbon mixture that is produced by isomerizing a light gas oil fraction has been obtained

The Cs * fraction of that used as a feed Isomer has an unleaded octane number (RON) of 79.1. The catalysts are sulfidic in their Shape used. The conversion of the catalysts into the sulfidic form is achieved by adding under Reaction conditions of 1500 mg of sulfur per kg of feed in the form of tert-butyl mercaptan Infeed carried out during the first two hours of the hydrocracking test The conditions under which the hydrocracking experiments are carried out are listed below:

35 KaIa-

lyser

WasserdaninTparlialdfuck the
Air, mm Hg column

during the

derllil / e-flilre treatment
treatment from 3 (X) to 5ÜU c
from 2 (1 to and during the
300 (maintenance

a temperature

of 500 (

Activity of the Kalalysalof

U ROZ ₀ )

G 100 100 3.5

H 150 150 4.2

J 20 100 2.2

K 40 100 4.0

Notes on Table C
Ot The catalysts 1 to 4 s: r; the catalysts produced according to the invention. In their manufacture, the condition was:

- 0.05 T + 30 <Phkj <- 0.05 T + 70,

which is referred to as the "inventive criterion" in the examples below, is fulfilled.

The catalysts A to K are catalysts not produced according to the invention. she were included in the table for reasons of comparison. The criterion according to the invention has not been met in their production. A comparison of the Activities of the catalysts 1 to 4 and the catalysts A to K shows that the catalysts 1 to 4 have a much higher activity.

Example 2

Four catalysts on a zeolite KSOL carrier material are made as follows:

_{Samples of an NH 4} ⁺ / H + zeolite KS01 (zeolite II) prepared in the manner described above are in air at a rate of 23 ° C / min. heating said starting from room temperature, and initially to 300 ° C, then heated from 300 ° C to the final temperature of 450 ⁰ C and finally the sample holding for 2 hours at the final temperature of 450 ⁰ C. The samples are then subjected to the same manner as above in the production of the NH ₄ ⁺ / H ⁺ -zeolite KS01 (zeolite II) from Na + -zeolite KSOl (zeolite I) carried out three treatments with NH4NO3. ^{Nicke 1} is then applied to the samples in the same way as described in Example 1. Four catalysts (5, 6, L and M) containing 2 g of nickel per 100 g of support material are converted from the material obtained by heating the material in air a speed of 23 ° C / min. produced with heating initially from room temperature to 300 ^° C. and then from 300 ^° C. to the final temperature of 500 ^° C. and finally keeping the samples at the final temperature of 500 ^{° C. for 2 hours.} The partial pressure of water vapor in the air maintained during the two heat treatments is given in Table D.

The catalysts prepared in the aforementioned manner are used for the selective hydrocracking of straight-chain paraffins in a hydrocarbon mixture uses this when isomerizing a

ίο

Light gasoline fraction has been obtained. The Hydrospaitungsversuche are with the same feed and under the same conditions as in Example 1

Table D.

described carried out. The results of the hydrocracking experiments are summarized in Table D below.

catalyst Water vapor partial pressure of the air, ram I Ig ^ column when heating 300 second ilitz treatment to 500 C and b. on Activity of No. to 500 C and b. on when heated when heated from 300 keep right the Catalyst right halls of from 20 to Temperature of 500 C (A ROZ ₀ ) first l-strand treatment Temperature of 500 C " 300 C 30th when heated 30th 5 from 20 to 30th 50 5 300 C 5 5 3ö 5 5 5 8.0 6th 50 5Ü 7.8 L. 50 0 M. 5 ö 5

Notes on Table D

The catalysts 5 and 6 are catalysts produced according to the invention. In the Production of catalyst 5 is the inventive criterion for both the first and the second Heat treatment has been met. In the production of catalyst 6, the criterion according to the invention is was only fulfilled during the first, but not during the second heat treatment.

The catalysts L and M are not produced according to the invention. she have been included in the table for reasons of comparison In the preparation of catalyst L, the inventive criterion is neither in the first nor in the second heat treatment. In the preparation of catalyst M, this is according to the invention Criterion was met in the second, but not in the first heat treatment. A comparison of the activities of the catalysts shows that the conditions under which the first Heat treatment of the material is crucial for the activity of the finished catalyst are. A comparison of the activities of the catalysts 5 and 6 shows on the one hand that when carrying out the first heat treatment of the material under the conditions according to the invention with a finished catalyst high activity is obtained and that a subsequent heat treatment under different conditions does not adversely affect this high activity. A comparison of the activities of catalysts L and M shows, on the other hand, that when the first heat treatment of the material is carried out under conditions not according to the invention Conditions a finished catalyst with low activity is obtained and that a later one Heat treatment carried out according to the invention does not lead to an improvement in this low activity.

Claims (1)

Patent claims: 1. A process for producing a catalyst by applying one or more catalytically active components to a zeolite with a composition, expressed in mols of the oxides, 0.7 to 1.2 Na ₂ O · Al ₁ Oj · 4.7 to 5.3 SiO ₃ ■ χ H ₂ O, where χ is at most 12 and preferably 3 to 9, and the powder X-ray diffraction diagram given in Table A, in which at least some of the sodium ions contained in it by hydrogen and / or ammonium ions or by calcium or Rare earth metal ions are replaced, so that the zeolite has a sodium content of less than 1% by weight, and one or more times π heat treatment of the product in the course of the process to final temperatures of 400 to 550 ° C and subsequent holding at this temperature , characterized in that at least during the first heat treatment in the atmosphere surrounding the material, a water vapor partial pressure fPmo in mm Hg column) as a function of the temperature of the material (T i n ⁰ C) is maintained, the condition in the temperature range from 100 ⁰ C to the end temperature of the heat treatment