CA1331863C

CA1331863C - Petroleum catalysts

Info

Publication number: CA1331863C
Application number: CA000573073A
Authority: CA
Inventors: Andrew Paul Chapple
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1987-07-30
Filing date: 1988-07-26
Publication date: 1994-09-06
Anticipated expiration: 2011-09-06
Also published as: EP0303372A1; ZA885529B; ATE63569T1; EP0303372B1; DE3862828D1; AU600843B2; AU2002488A; GB8718108D0

Abstract

ABSTRACT
Hycarbon feedstock containing nickel is subjected to a catalytic cracking process using a catalyst comprising zeolite, matrix and mixed oxide. The mixed oxide is selected from calcium, strontium and barium tin oxides and mixtures thereof.

Description

1 - R.3033 Title: PETROLEUM CATALYSTS

Field of the invention:

:~ 5 The invention relates to cracking catalysts and to catalytic cracking, which is a major refinery process for the conversion of hydrocarbons to lower boiling fractions.
More specifically, the invention relates to an improved process for cracking nickel containing feedstocks by using these catalysts.

: Back~round to the invention:

Catalysts containing crystalline zeolites dispersed in.an inorganic oxide matrix have been used for the catalytic cracking of petroleum-derived feedstocks for many years. During this time, it has been widely recognised in the industry that certain contaminants ~notably vanadium, nickel, and iron), initially dissolved .' ' ~ .'.
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r 1 3 3 1 8 6 3 - 2 - R.3033 or dispersed in the hydrocarbon feedstock, are deposited on the catalyst during the catalytic cracking process, and the accumulated deposits lead to undesirable changes in the activity and selectivity of the thus contaminated catalysts. Typically, the harmful effects noted have been increased yields of coke and hydrogen, a phenomenon ascribed to the action of the deposited metals as centres of dehydrogenation.

These problems have become more acute as refiners have faced the need to process heavier feedstocks which contain increased amounts of the metal contaminants, and various strategies have been employed to alleviate the deleterious effects and facilitate smooth running of catalytic cracking units. These approaches have included (1) more frequent replenishment of the circulating catalyst inventory;

(2) withdrawal of the regenerated catalyst and treatment with various chemicals to passivate the metals; - --(3) changes in the design or operation of the catalytic cracker to reduce the poisoning activity of the contaminant metals;
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(4) addition to the feedstock of compounds of elements such as antimony, tin, barium, manganese, germanium and bismuth. Examples of these are found in the patent specifications US 4238362, US 4101417, GB 1598289, US 4377494, US 4367136 and US 3977963.

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~,'. . . - ' ' , `' F"` : ; -~ 1331863 _ 3 _ R.3033 General description of the invention:

The present invention provides a catalyst composition comprising a i) crystalline zeolite, ii) a matrix material, and iii) certain crystalline mixed oxides, derived from the heavier alkaline earth elements (calcium, strontium, barium) and tin, which oxides have themselves no harmful effects on the catalytic properties but are present in amounts sufficient to passivate the dehydrogenation properties of the contaminent nickel.

Accordingly, the present invention provides a catalyst composition comprising i) a crystalline zeolite, ii) a matrix material and iii) a mixed oxide selected from lS calcium, strontium and barium tin oxides and mixtures thereof.
The mixed oxides include hydroxy stannates.

The crystalline zeolite component of the present invention, which is usually present in the range from about 5% to about 40~ by weight, may generally be described as a crystalline, three dimensional, stable structure enclosing cavities of molecular dimensions.
Most zeolites are based on aluminosilicate frameworks, the aluminium and silicon atoms being tetrahedrally coordinated by oxygen atoms. However, for the purposes of our invention we include as ~zeolites" similar materials in which atoms of other elements are present in the framework, such as boron, gallium, germanium, chromium, , ~iron, and phosphorus. Further we include materials such ~-30 as pillared interlayered clays (~PILCSn) ~ which have many --of the catalytically valuable characteristics of the aluminosilicate zeolites. We also include all modifications to the 2bove materials, whether obtained by ion-exchange, impregnation, hydrothermal or chemical treatments.

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--` 1331863 _ 4 _ R. 3033 Zeolites which can be employed in the catalysts and processes of this invention can be natural or synthetic in origin. These naturally occurring zeolites include gmelinite, chabazite, dachiardite, clinoptilolite, faujasite, heulandite, analcite, levynite, erionite, sodalite, canorinite, mepheline, lazurite, scolecite, natiolite, offretite, mesolite, mordenite, brewsterite, fevierite, and the like. Suitable synthetic zeolites are zeolites A,B,E,F,H,J,L,Q,T,W,X,Y,Z, alpha, beta, omega, the EU types, the Fu types, the Nu types, the 2K types, the ZSM types, the ALPO types, the SAPO types, the L2 series, and other similar materials will be obvious. The effective pore size of the synthetic zeolites are preferably between 0.6 and 1.5 nanometers, and the preferred zeolites are those with the faujasite framework and silica/alumina ratios >3, thus including synthetic zeolite Y and the various form of Y which have been made more siliceous by chemical, hydrothermal or thermal treatments.
In a preferred embodiment of the invention, the zeolite is converted to a form which is most applicable for catalytic cracking. In general this involves a sequence of ion-exchange and calcination treatments to introduce acid groups into the zeolite, stabilise the structure, and remove alkali metal cations. The prefered method of achieving this end, well known in the art, is to exchange the zeolite with solutions containing ammonium ions and/or rare earth ions (either a pure rare earth compound or a mixture).
'' t Such treatment can be carried out either on the zeolite before it is incorporated in the catalyst, or on the finished catalyst containing the zeolite, it can be carried out on a filter press, filter table, or filter belt, or by slurrying the zeolite/catalyst in a tank.

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_ 5 _ R.3033 The matrix into which the zeolite is incorporated can have a wide range of compositions. Suitable components include: naturally occurring or synthetic clays, including kaolin, halloysite and montmorillonite;
inorganic oxide gels, including binary gels such as silica, silica-alumina, silica-zirconia, silica-magnesia, aluminium phosphates, or ternary combinations such as silica-magnesia-alumina; and crystalline inorganic oxides such as silica, alumina, titania, zirconia.
Suitable mixed oxides for use as component (iii) are:

CaSnO3 BaSnO3 Ca2SnO4 Ba2SnO4 CaSn(OH)6 BaSn(OH)6 SrSnO3 Sr2SnO4 Sr3Sn207 SrSn(OH)6 The mixed oxide additive is a discrete component of the final catalyst, and is readily identifiable in the fresh catalyst by x-ray diffraction analysis. These materials are insoluble, and are not decomposed into their component oxides over a wide range of thermal and hydrothermal treatments, and, as such are readily identifiable in hydrothermally deactivated catalyst samples. Preferably the mixed oxide is present at a level of least about 0.1% by weight of the catalyst and up to about 20% by weight.
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The chemical form of the additive is central to determininq the concentration in which it is used in the ~
35 catalyst composition, or indeed its method of ~ -incorporation into the catalyst formulation.

\ 1331863 - 6 - R.3033 The additives of this invention can be prepared by various processe~; for example, by calcination of intimate mixtures of the oxides or carbonates of the component elements, in the appropriate molar quantities, or by 5 coprecipitation, or metathesis of salts of the appropriate elements.

Conventional catalyst processinq procedures encompass a wide range of pH conditions, typically pH 3 to pH 10, 10 and require that any additives be resistant to such environments without themselves being decomposed, or resulting in changes in the properties of other catalyst components. The effect of additives not resistant to such environments can be to render the catalyst processing 15 procedure inoperable, or to adversely affect both the physical and catalytic properties of the finished catalyst.

As the form of the additives of the present invention 20 are insoluble and inert to any catalyst processing procedures, the catalysts containing these additives may r be prepared by any of the conventional methods used for the manufacture of FCC catalysts. For example, catalyst may be prepared by making an inorganic oxide sol at pH 3 ~`~ 25 and adding to this, aqueous slurries of the other catalyst - components including zeolite and alkaline earth additive.
; The homogenised slurry can then be spray dried to produce catalyst microspheres, and washed free of soluble salts using for example aqueous ammonium sulphate and water.

The catalyst compositions of this invention are employed in the cracking of nickel containing heavy hydrocarbon feedstocks, to produce gasoline, and light distillate fraction. Typical feedstocks would have an 35 average boiling point greater than 316C, and include such materials as gas oils, and residual oils.

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-' 1331863 _ 7 _ R.3033 Because the catalysts of this invention are effective in cracking processes even when contaminated with nickel to levels in excess of 2000 ppm, these catalysts can be used to process feedstocks containing significantly higher concentrations of nickel than those employed in conventional catalytic cracking operations.

These catalysts may be employed in any catalytic cracking process capable of operating with conventional microsphere fluid catalysts.

Specific description of the invention The following examples illustrate the advantages of the invention. However, it i5 not intended that the invention be limited to the specific examples given.

ExamPle 1 (comparative) - -A catalyst was prepared by combining together lOOg A1203 400g Xaolin, and 270g of CREHY (calcined Rare ` Earth/Ammonium exchanged zeolite Y), in 289Sg of a silica sol (8~ SiO2 w/w) at pH 3.2, to provide a homogeneous ~ -slurry. The slurry was then spray-dried to form catalyst microspheres with an average particle size of about 60 microns.

The spray-dried catalyst was then washed with deionized water, 0.2SM ammonium sulphate, and finally deionized water, until the conductivity of the filtrate fell below 1 milli-mho. The washed catalyst was then dried at 100C (Catalyst A). -A

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- 8 - R.3033 Example 2 A catalyst was prepared by combining together lOOg A1203, 276g Kaolin, 124g SrSnO3, and 270g of CREHY, in 2875g of a silica sol ~8% SiO2 w/w) at pH 3.2, to provide a homogeneous slurry. The slurry was then spray-dried to form catalyst microspheres with an average particle size of about 60 microns.

The spray-dried catalyst was then washed with deionized water, 0.25M ammonium sulphate, and finally deionized water, until the conductivity of the filtrate fell below 1 milli-mho. The washed catalyst was then dried at 100C (Catalyst B).
Example 3 -A catalyst was prepared by combining together lOOg A1203, 300g Kaolin, lOOg CaSnO3, and 270g of CREHY in 2875g of a silica sol (8~ SiO2 w/w) at pH 3.2, to provide a homogeneous slurry. The slurry was then spray-dried to form catalyst microspheres with an average particle size of about 60 microns.

The spray-dried catalyst was then washed with deionized water, 0.25M ammonium sulphate, and finally deionized water, until the conductivity of the filtrate fell below 1 milli-mho. The washed catalyst was then dried at 100C (Catalyst C).
Example 4 A sample of catalyst of example 1, previously thermally treated to 538C for 2 hr, was impregnated with 5000 ppm nickel according to the following procedure.

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_ g _ R.3033 50g of the thermally treated catalyst was slurried in 50 ml of a solution of 1.67g nickel naphthenate in xylene in a rotary evaporator. The slurry was allowed to fully mix for 30 min at room temperature with constant agitation. The slurry was then dried under vacuum to yield the nickel impregnated catalyst.

The impregnated catalyst was finally calcined at 538C for 2 hr (Catalyst D).
ExamPle 5 50g of c:atalyst of example 2, thermally treated to 538C for 2 hr, was impregnated with 5000 ppm nickel using the procedure detailed in example 4. (Catalyst E).

ExamPle 6 50g of catalyst of example 3, thermally treated to 20 538C for 2 hr, was impregnated with 5000 ppm nickel using the procedure detailed in example 4. (Catalyst F).
The above catalysts (A-F) were evaluated in a microactivity test (MAT) unit. Prior to testing, the catalyst samples were thermally treated at 538C for 3 hrs, and then deactivated in steam at atmospheric pressure, at a temperature of 788C for a period of 5 hrs.

The cracking conditions used for the MAT were:-, 30 Reactor temperature ......................... 482C
Weight Hourly Space Velocity ~WHSV) ........ 16.0 Catalyst:Oil ................................ 3.0 :
The gasoil feedstock in these tests was charactericed as -35 follows:- ~

-`` 1331863 - 10 - R.3033 Sulphur, wt% ................................ 0.47 Nitrogen, wt% ............................... 0.11 Conradson Carbon, wt% ....................... 0.26 Aniline point, ...................... 89.6C

Distillation (F) Initial Boiling Point ...................... .630 10% off at 760 mmHg ...................... 741 30% off at 760 mmHg ...................... 797 50% off at 760 mmHg ...................... 842 70% off at 760 mmHg ...................... 887 90% off at 760 mmHg ...................... 964 Final Boiling Point ........................ 1038 Specific Gravity (g/cc) was 0.907 4; i~' E.. `.- `

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J ~ ' ' - 11 - R.3033 CATALYST A D B E C F

Mixed Oxide none none SrSn03 SrSn03 CaSn03 CaSn03 Additive ppm Ni 0 5000 5000 5000 Conversion . :
(wt%) 59.3 55.0 56.1 50.7 55.5 53.4 Gasoline (wt%) 44.7 38.6 43.0 36.6 41.3 37.6 R.-Coke :-: :
(wt%) 2.34 4.79 2.47 4.46 3.33 5.13 ' -.` ~. ::
Hydrogen (wt%) 0.05 0.53 0.05 0.38 0.09 0.33 ~: K.Coke = Coke/(Conversion/(100-Conversion)).
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These results demonstrate the presence of the strontium - -and calcium stannate reduce the dehydrogenation activity , ibrought about by nickel contamination.

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_ ~331863 - 12 - R.3033 Example 7 A zeolite based (CREHY) spray-dried catalyst was prepared containing CaSn(OH)6 (1.1% w/w as CaO). This catalyst was impregr,ated with nickel, and deactivated under an atmospheric of steam in an equivalent manner to that described in the preceding examples. The catalytic performance of this sample (Catalyst G) was measured by MAT, and compared to an equivalent catalyst formulation 10 containing no hydroxy stannate component (catalyst H). , The results of these tests are shown in table lI. -~' Table II

Catalyst G Catalyst H
' Nickel loading (ppm) 5000 5000 Deactivation (C/hr) 788/5 788/5 Conversion (wt%)57.0 54.5 Gasoline (wt%) 39.6 38.3 Hydrogen (wt%) 0.50 0.63 ;~ Coke (wt%) 6.65 6.19 This demonstrates the effectiveness of calcium hydroxystannate in reducing the dehydrogenation activity of contaminent nickel.

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Claims

1. A method of cracking nickel contaminated hydrocarbon feedstocks wherein the feestock is contacted with a catalyst composition comprising:-i) a crystalline zeolite, ii) a matrix material, and iii) a mixed oxide selected from calcium, strontium and barium tin oxides and mixtures thereof.

2. A method according to claim 1 wherein the catalyst composition is contaminated with nickel at a level in excess of 2000 ppm.

3. A method according to claim 1 or 2 wherein the catalyst composition comprises from about 5% to about 40%
by weight zeolite.

4. A method according to claim 1 or 2 wherein the catalyst composition comprises from about 0.1% to about 20%
by weight of mixed oxide.