A MET-DD OF PRODUCING A ZEOLITE BETA HYDROCARBON CONVERSION CATALYST

This invention relates to a method of producing a zeolite beta-containing hydrocarbon conversion catalyst of improved stability and, in particular, improved stability to hydrothermal deactivation. Zeolite beta is a known zeolite which has been shown to possess activity for hydrocarbon conversion and which has a number of interesting and useful properties. As disclosed in U.S. Patent No. 4,419,220, zeolite beta has been found to possess activity for paraffin isomerization in the presence of aromatic components in hydrocarbon feeds such as gas oils and this property may be exploited in the production of low pour point, isoparaffinic products such as jet fuels, other middle distillates and lubricants of high viscosity index and low pour point. European Patent Publication No. 94827 discloses a process in which heavy oils are simultaneously subjected to hydrocracking and dewaxing using a catalyst based on zeolite beta which also contains a hydrogenation component. The process is able to effect a bulk conversion of the oil while, at the same time, yielding a low pour point product. The ability of zeolite beta to isomerize paraffins may also be exploited in the production of gasolines by catalytic cracking, either in fluid bed (FCC) or moving, gravitating bed (TCC) catalytic cracking processes. European Patent Publication No. 186,446 discloses a catalytic cracking process employing a mixture of zeolite beta and a faujasite cracking catalyst for the production of gasoline of improved octane and of improved low pour point distillates by catalytic cracking processes.

In spite of its interesting and useful properties, zeolite beta still presents some problems in practical utilization. One of these is its hydrothermal stability. For catalytic cracking, in

particular, the zeolite cracking catalyst must withstand very severe deactivating conditions in the regenerator where the cracking catalyst is oxidatively regenerated with an oxygen-containing regeneration gas. During the regeneration process, the coke which accumulates on the catalyst is burned to form carbon monoxide and carbon dioxide together with water which is formed from the hydrogen content of the coke and from the hydrocarbons entrained with the catalyst. Under the high temperatures prevailing in the regenerator, the water is present as steam and produces a severe deactivating effect on the zeolite, which can result in the loss of crystallinity, activity and selectivity. It is therefore desirable to improve the stability of zeolite beta containing hydrocarbon conversion catalysts, especially for use in catalytic cracking processes. It has now been found that hydrocarbon conversion catalysts based on zeolite beta may be improved, particularly in their hydrothermal stability, by compositing the catalysts with a compound containing a complex metal cation, preferably a hydroxychloride complex of aluminum. In addition to possessing hydrothermal stability the catalysts also exhibit improved physical strength.

According to the present invention there is provided a method of producing hydrocarbon conversion catalyst comprising treating zeolite beta with hydroxychloride of aluminum.

The preferred hydroxychloride complexes are aluminum hydroxychloride itself and hydroxychloride complexes of aluminum and zirconium.

In addition to zeolite beta the present hydrocarbon conversion catalysts may also contain other active components including, in particular, other zeolites, especially large pore size zeolites such as the faujasites, especially ultrastabilized Y zeolite (USY), and ZSM-20, and intermediate pore size zeolites such as ZSM-5 and ZSM-11. The catalysts are preferably made by compositing the zeolite beta together with any other zeolite components in a matrix which may be either a synthetic oxide matrix such as silica, alumina or silica-alumina or a clay matrix.

The present hydrocarbon conversion catalysts contain zeolite beta as an active hydrocarbon conversion component. Zeolite beta is a known zeolite and is described in U.S. Patent No. 3,308,069 and RE 28,341. Zeolite beta may be synthesized with relatively high silica:alumina ratios, for example, in excess of 100:1 and it is possible to achieve even higher ratios by thermal treatments including steaming and acid extraction, and in this way it is possible to make highly siliceous forms of the zeolite with silicaralu ina ratios ranging from the lowest ratio at which the zeolite may be synthesized up to 100:1, 1,000:1, 30,000:1 or even higher. Although these forms of the zeolite would be capable of being used in the present process, the fact that catalytic cracking requires the catalyst to possess a relatively high degree of acidity, generally implies that the more acidic materials, with silica:alumina ratios from 15:1 to 150:1 will be preferred, with ratios from 30:1 to 70:1 being particularly preferred. Because zeolite beta may be synthesized relatively easily with silica:alumina ratios of this magnitude, the zeolite may generally be used in its as-synthesized form, following calcination to remove the organic cations used in its preparation. It is generally preferred not to incorporate substantial amounts of alkali or alkaline earth metal cations into the zeolite, as disclosed in U.S. Patent No. 4,411,770, because these will generally decrease the acidity of the material. If lower acidity should be desired, however, this is preferably achieved by using zeolite forms of higher silica:alumina ratio rather than by adding alkali or alkaline earth metal cations to counter the acidity, because the more highly siliceous forms of the zeolite tend to be more resistant to hydrothermal degradation. Acid extraction is a preferred method of dealuminization either on its own or with preliminary steaming; dealuminized catalysts made in this way have been found to have improved liquid product (gasoline/distillate) selectivity.

The acidic functionality of the zeolite at the time that it is used as fresh catalyst, is typically in excess of 0.1, as measured by the alpha activity test, with preferred alpha activities being in the range of from 1 to 500 or even higher, and more commonly in the range of 5 to 100. The method of determining alpha values is described in U.S. Patent No. 4,016,218 and in J. Catalysis, VI, 278-287 (1966). However, the initial alpha value will be relatively rapidly degraded in a commercial catalytic cracking unit because the catalyst passes repeatedly through steam stripping legs to remove occluded hydrocarbons and in the regeneration process, a considerable amount of water vapor is released by the combustion of the hydrocarbonaceous coke which is deposited on the zeolite. Under these conditions, aluminum tends to be removed from the framework of the zeolite, decreasing its inherent acidic functionality.

Zeolite beta may be synthesized with trivalent framework atoms other than aluminum to form, for example, borosilicates, boroaluminosilicates, gallosilicates or galloaluminosilicate structural isotypes. These structural isotypes are considered to constitute forms of zeolite beta, the term zeolite beta being used in this specification to refer to materials of ordered crystalline structure possessing the characteristic X-ray diffraction of zeolite beta. The zeolite may be partially exchanged with certain cations in order to improve hydrothermal stability, including rare earths and Group IB metals.

The catalyst may also contain other catalytically active components, especially zeolites which may be either of the large pore size, intermediate pore size or small pore size. Small pore size zeolites are exemplified by zeolite A and erionite. Intermediate pore size zeolites are exemplified by zeolites ZSM-5,

ZSM-11, ZSM-12, ZS -22, ZSM-23 and ZSM-35. These zeolites are disclosed, respectively, in U.S. Patents Nos. 3,702,886 and RE 29,949 (ZSM-5), 3,709,979 (ZSM-11), 3,832,449 (ZSM-12), 4,076,342 (ZSM-23) and 4,016,245 (ZSM-35). Large pore size zeolites are

characterised by a structure which includes a twelve-membered ring system and are exemplified by the faujasite zeolites such as zeolite

X, zeolite Y and the various forms of zeolite Y including rare earth Y (REY) and ultrastabilized Y (USY) and of these, ultrastabilized Y 5 is particularly preferred because of its hydrothermal stability.

USY is a known zeolite and is described, for example, in US Patents Nos . 3,293 , 192 and 3 ,449,070. Other large pore size zeolites which may be composited with zeolite beta include zeolite ZSM-4, ZSM-18 and ZSM-20. These zeolites are described respectively in U.S. 10 Patents Nos . 3 , 923 , 639; 3 , 950 , 496 and 3 ,972 , 983.

In order to improve the physical strength of the catalysts, the zeolite beta, either on its own or combined with another catalytically active ingredient as described above , is formulated with a matrix or binder in order to improve its crush strength and 15 attrition res istance. The zeolite will therefore generally be incorporated in a clay or other matrix material such as a synthetic metal oxide, especially silica, alumina, silica-alumina, magnesia or a combination of such oxides. Other metal oxides such as silica -magnesia, silica-zirconia, silica-thoria, silica-beryllia, 20 silica-titania or ternary compositions such as silica-alumina- thoria, silica-alumina-zirconia, silica -alumina -magnesia and silia-magnesia-zirconia may also be used. Certain clays may also be used as binder materials, especially acid-treated clays which have superior activity. The zeolite beta together with any other 25 catalytically active zeolite may be composited with the binder material in a conventional manner to produce the final matrixed catalyst. If a synthetic metal oxide such as alumina or silica or silica-alumina is used as the matrix , the zeolite component may be co-gelled with the matrix components or alternatively, a pre-formed

30 zeolite may be added to a gel of the matrix prior to drying. Clays may suitably be composited with the zeolite component by slurrying the zeolite with the clay, followed by homogenisation of the slurry and spray drying of the mixture to produce the final matrixed catalyst. Naturally occurring clays which can be composited with

the modified zeolite include those of the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.

The relative proportions of zeolite and inorganic matrix may vary widely with the zeolite content ranging from between 1 to 99 percent by weight and more usually in the range of 5 to 80 percent by weight of the composite.

The dried catalyst may be subjected to various activation treatments including ion exchange, e.g., to reduce sodium content or to introduce other desired cationic species such as rare earths and generally, ammonium exchange will be employed to bring the zeolite component or components into their active hydrogen forms.

Calcination will normally precede any cation exchange treatment in order to remove organic directing agents used in the synthesis of the zeolite.

The catalysts according to the present invention are stabilized by treatment wth a hydroxychloride of aluminum which is added to the zeolite and any matrix material used to form the finished catalyst. Thus, in the uncalcined state the catalysts contain the zeolite beta together with any other catalytic components, the matrix material (if used) and the aluminum hydroxychloride. On calcination, the aluminum compound will usually be converted to some other form, usually the oxide, which is dispersed through the catalyst and which produces the desired stabilising effect.

The stabilizing compound employed may be aluminum hydroxy chloride itself or may contain other elements, such as zirconium. One preferred mixed metal complex is aluminum zirconium hydroxy chloride Al,Zr(OH)gCl. which is preferably used in the form of a reaction product of the mixed metal complex with an equimolar proportion of an organic complexing agent such as glycine.

The amount of the stabilizing aluminum employed is generally from 1 to 25, preferably 2 to 10, weight percent of the zeolite content of the catalyst.

The stabilizing component may be mixed with the zeolite component of the catalyst and any binders at any suitable stage in the manufacture of the catalyst, for example, by slurrying with the zeolite and binder prior to homogenization and drying. Alternatively, the stabilizer could be added to a gel of the binder containing added zeolite. The normal treatments carried out after drying of the catalyst such as calcination followed by ammonium and other cation exchange may take place in the normal way.

The catalysts containing the aluminum hydroxychloride complexes exhibit improved physical strength together with improved hydrothermal stability and in addition, exhibit higher activity in catalytic cracking operations. It has been observed that the octane number of gasoline produced by catalytic cracking using the present stabilized catalysts may be higher than that of cracked gasolines produced by conventional catalyst compositing techniques. The improved resistance to hydrothermal deactivation is also a value in other processes, especially a hydroprocessing applications such as hydrocracking, isomerization, dewaxing, alkylation, hydration and the like.

The invention will now be more particularly described with reference to the following Examples. Example 1

A zeolite beta catalyst containing 25. zeolite beta in a matrix of 25% alumina/501 clay and containing aluminum hydroxychloride [Al ₂ (0H)pCl] was prepared by mixing the aluminum hydroxychloride with clay and zeolite beta to form a slurry which was then homogenized and spray dried. After spray drying the catalyst was mildly calcined at 1000°F (540°C) for one hour and subsequently ammonium and rare earth exchanged. This catalyst is referred to below as Catalyst A.

A comparable zeolite beta catalyst containing 25 wt.% zeolite beta in a matrix of 45.3% silica/3.4% alumina/26.3% clay was prepared by the conventional hydrogel technique in which the zeolite and the clay are dispersed in a hydrogel of the silica and alumina matrix components after which the mixture is homogenized and spray dried. After spray drying the catalyst was ammonium and rare earth exchanged to form a catalyst referred to as Catalyst B.

Both catalysts were steam deactivated (10 hours, 1450°F (790°C), 45% steam, 55% air atmospheric pressure), and then evaluated it for their cracking activity in a fixed fluidized bed reactor at 960°F (515°C) using a sour heavy gas oil feed.

The properties of the two catalysts are set out in Table 1 below, while Table 2 shows the results achieved from the cracking experiment. As shown in Table 2, Catalyst A showed a higher activity and higher gasoline octane number than did Catalyst B, indicating that the former had a greater hydrothermal stability. The physical properties of the catalyst show that the overall physical properties of Catalyst A are superior to those of Catalyst B although the mild calcination may have contributed partly to the low attrition index for Catalyst A; it is doubtful that a similar treatment would have resulted in a low attrition index for Catalyst B.

Table 1

Properties of Zeolite Beta Catalysts

Catalyst A Catalyst B

Attrition Index 4 43 (Fresh sample)

Pore Volume, cc/g 0.39 0.36

Packed Density, g/cc 0.72 0.65

Table 2

Catalytic Cracking on Zeolite Beta FCC Catalysts

Catalyst

Treatment: Hours 10.0 10.0

Temperature, ^> F(°C) 1450(790) 1450(790) % Steam 45 45

Cat/Oil 5.00 5.00

WHSV 12.00 12.00

Reaction Temperature, ³ F(°C) 960(515) 960(515)

Conversion, % wt. 59.3 37.9

Conversion, % vol. 61.2 39.6

C5+ Gasoline, % vol. 38.1 29.9

C5+ Gasoline, % wt. 31.4 24.0

Total C4, % vol. 17.9 9.4

Dry Gas, % wt. 10.0 5.8

Coke, % wt. 6.48 2.03

C-On-Cat, Final, wt. 1.10 0.35

N-C5, % vol. 0.4 0.2

1-C5, % vol. 2.0 0.9

C5=, % vol. 5.6 3.3

N-C4. vol. 1.3 0.6

N-C4 , % wt. 0.8 0.4

I-C4 , % vol. 5.4 2.4

I-C4 , % wt. 3.3 1.4

C4=, % vol. 11.1 6.4

C4=, % wt. 7.3 4.2

C3, % vol. 2.5 1.2

C3, % t. 1.4 0.7

C3=, % vol. 9.7 5.5

C3=, % t. 5.5 3.1

C2, % t. 0.8 0.5

C2=, % wt. 0.5 0.4

Cl, % t. 0.8 0.4

H2, % t. 0.13 0.07

H2S, % wt. 0.97 0.62

Hydrogen Factor 69 58

Recovery, % wt. 94.0 95.6

Alkylate, % vol. 34.8 19.9

C5+ Gasoline+Alkylate, vol. 72.8 49.0 Outside 1-C4, % vol. 18.0 11.1 R 0 N +0, Raw Gasoline 93.3 91.5 M 0 N +0, Raw Gasoline 0.0 0.0 R 0 N +0, C5+ Gasoline 92.8 91.0 RON+0, C5+ Gasoline+Alkylate 93.5 92.3

LF0 wt. 33.0 40.9

HFO wt. 7.7 21.2

G + D, % wt 64.3 64.9

Example 2 Zeolite beta (75g) was slurried with 1500ml deionised water and 50g aluminum chlorhydrate, charged to an autoclave and stirred for 30 min. The mixture was then heated to 180°F (82°C) and held for two hours at this temperature. The mixture was discharged from the autoclave and the catalyst recovered by filtration, washing with water and drying. The resulting catalyst was identified as Catalyst C.

In a similar manner, zeolite beta (lOOg) was slurried with 1500ml deionized water and 25g aluminum chlorhydrate and the mixture held at 160°F (71°C) for one hour in an autoclave. The resulting catalyst is identified as Catalyst D.

Another catalyst was prepared by slurrying zeolite beta (lOOg) with 20g _v£Cl ₂ in 1200 milliliters deionized water followed by mixing for one hour after which 25g aluminum chlorhydrate was added. The mixture was then held at 160°F (71°C) for two hours in an autoclave. The resulting catalyst was identified as Catalyst E.

Zeolite beta (200g) was slurried in 1200 ml. water and 200g of mixed rare earth (lanthanum/cerium) chlorides added as a 60% wt./wt. solution REC1,6H ₂ 0. The mixture was held at 180°F (82°C) for two hours in an autoclave before formulating into catalyst. The finished catalyst was designated Catalyst F.

In a similar manner, the following catalysts were prepared using the described materials and slurrying them in water as described above: (Catalyst G): Zeolite beta (507g), REC1 ₃ solution (50g), aluminum chlorhydrate (50g), 180°F two hours.

(Catalyst H): Zeolite beta (75g), 20% TiCl ₃ solution (20g), aluminum chlorhydrate (50g), room temperature one hour.

(Catalyst I): Zeolite beta (50g) TiCl ₃ (50g), room temperature.

(Catalyst J): Zeolite beta (30g) ZrOCl ₂ ^* 8H ₂ 0 (20g), room temperature (ion exchange reaction).

(Catalyst K): Zeolite beta (80g) MgCl ₂ (16g), room temperature, one hour.

(Catalyst L): Zeolite beta (150g), zirconium aluminum chlorhydrate/glycerine complex (500g), 180°F(82°C) two hours.

(Catalyst M): Zeolite beta (250g), aluminum chlorhydrate (lOOg), 260°F(127°C), 20 hours. (Catalyst N): Zeolite beta (150g), U0 ₂ N0 ₃ 2 6H ₂ 0

(50g) 180°F, 1 hour (ion exchange).

(Catalyst 0): Zeolite beta (lOOg), aluminum chlorhydrate (50g), 160°F(71°C) 20 hours.

The initial alpha values (after calcination) of Catalysts C-0 are given in Table 3 below together with the alpha values of these catalysts before and after steaming. Two steaming treatments were used as follows.

Treatment S - 1000°F (540°C), 2 hours, 0 psig (100 kPa abs.)

Treatment S-, _^ - 1200°F (650°C), 4 hours, 0 psig (100 kPa abs. )

Table 3 also shows the surface areas of the catalyst before and after these treatments.

Table 3 Catalyst Hydrothermal Stability

Surface Area Alpha m^.g.-l

Catalyst Calcined Steamed(S) Steamed(Si) Calcined Steamed(S) Steamed(S ^* ι)

C 508 458 404 261 91 13

D 556 487 — 301 19 8

E 553 472 421 267 125 11

F 603 — — 213 85 3 I

G I

540 482 426 338 104 14 I—'

H 589 522 — 285 91 7 t*o

I

I I

575 — — 227 66 5

J 563 -— 96 54 4

97 L 585 ___. 464 242 _._._. 23

M 521 — — 307 86 12

N 620 — 361 96 8

0 — — 322 88 13

Exaπrple 3 A fluid cracking catalyst comprising 15% wt% of zeolite beta and 10 wt. % of ultrastable Y, (USY) were supported on a silica-alumina-clay matrix was prepared as follows. A zeolite slurry was prepared by mixing 800 g. of Kaopaque (trade mark) clay ( 87.32% solids) first with 3387 g. of aluminum chlorhydrate ( 24%

A1 ₂ 0 ₃ ) for 15 minutes and then with 3110 g. of ball-milled (25.72% solids) zeolite beta and 1964.3 g. of ball-milled USY ( 27.15% solids) for 30 minutes. In a separate vessel, a matrix slurry was prepared by mixing 750 g. of Kaopaque (trade mark) clay with 28 ,760 g . of water and 6038 g . of sodium silicate solution,

(Q-brand (trade mark) , 28.9% Si0 ₂ ) , neutralizing with 574 g. of concentrated sulfuric acid ( 96.3% H-^SO^) , mixing with 770 g. of aluminum sulfate solution ( 20% A1 ₂ 0, over a period of 30 minutes, adjusting the pH to 4.3 , and mixing for an additional 30 minutes. The zeolite slurry was blended with the matrix slurry and stirred for 30 minutes. The mixture was filtered, reslurried with water to contain 10.1% solids, homogenized and spray-dried. The catalyst was exchanged with ammonium nitrate solution and then with rare-earths chloride solution, and finally dried at 250°F (121°C) . Before FCC evaluation, the catalyst was steam -deactivated at 1450 °F

( 790°C) for 10 hours in an atmosphere of 45% steam and 55% air to simulate catalyst aging in a commercial FCC unit. This catalyst is designated as Catalyst P.

For comparison, a fluid catalyst containing 25% zeolite beta alone in a similar matrix was prepared, and is designated as

Catalyst Q. Two catalysts that contain USY only, one in an Al ₂ 0,/clay matrix and the other in Si0 ₂ /Al ₂ 0,/clay matrix , were also provided for comparison. They are designated as Catalyst R and Catalyst S, respectively. The chemical and physical properties of these catalysts are shown in Table 4 below.

Table 4

Chemical Composit :ion and Physical Propelrties of FCC Catalysts

Catalyst P Zeolite, wt.% 5 R

Beta 15 25 0 0

USY 10 0 25 20

Matrix, wt.%

Si0 ₂ 32.6 32.6 0 48.3

A1 ₂ 0 ₃ 17.4 17.4 25 3.7

Clay 25 25 50 28

Physical PropertitϊS Surface Area, m' 7g 144 124 159 109

Pore Volume, cc _> 'g 0.31 0.25 0.24 0.20

Packed Density, g/cc 0.75 0.81 0.78 0.88 Attrition Index 16 24 5

The cracking activity of these catalysts was evaluated in a fixed -fluidi zed bed reactor at 350°C(960°F) using sour heavy gas oil (SHGO) with 1.0 minute on-stream. The properties of the chargestock are shown in Table 5. The activity is compared at a constant catalyst-to-oil ratio of 4, as shown in Table 6 , while ths product selectivity is compared at a constant conversion of 65 vol%, as shown in Table 7.

Table 5

5

10 Bromine Number 3.9 CCR, wt % 0.29 Sulfur, wt% 2.37 Hydrogen, wt% 12.50 Nitrogen, Total, ppmw 700

15 Nitrogen, Basic , ppmw 341 Molecular Weight 343 Nickel, ppm 0.18 Vanadium, ppm 0.65 Iron, ppm 4.1

20 Copper, ppm 0.10

Distillation (D1160) °F( °C)

IBP (Initial Boiling Point) 471 (244)

5% vol. 592 (311)

10% 647 (342)

25 20% 699 (371) 30% 733 (389) 40% 766 (408) 50% 798 (426) 60% 827 (442)

30 70% 862 (461) 80% 901 (483) 90% 947 (508) 95 986 ( 530)

Composition, wt %

35 Paraffins 19.9

Naphthenes 27.0

Aromatics 53.2

Table 6

Cracking Activity, Constant Cat/Oil

40 Catalyst P £ R

Catalyst/Oil, wt/wt 4 4 4 4

Conversion, vol. % 65.1 50, .6 71.8 59.6

C5+ Gasoline, vol. % 47.7 37, .2 56.4 50.3

Total C4' s, vol. % 16.2 12. .8 15.6 12.5

45 Dry Gas, wt% 9.7 7, .0 9.1 6.3

Coke, wt% 3.5 2, .5 4.8 2.2

RON+0 , C5+ Gasoline 91. 1 92. .5 90.3 89.7

G+D , vol% 77.4 73, .2 82.0 80.2

G+] A, vol% 109.2 100, .1 107.4 102.8

Table 7 Estimated Product Distribution 65% Constant Conversion

Catalyst P Q R S

Conversion, vol. % 65 65 65 ^~ 65

C5+ Gasoline, vol. % 47.7 39.9 52.2 47.2

Total C4's, vol. % 16.7 20.4 14.6 14.9

Dry Gas, wt. % 9.5 12.2 7.4 7.9

Coke, wt.% 3.5 4.0 3.5 2.8

R0N+0, C5+ Gasoline 91.4 92.9 90.3 89.5

G+D, vol.% 77.3 69.1 82.9 74.8

G+D+A, vol.% 109.0 111.1 107.7 102.0

The results indicate that Catalyst P has an activity equivalent to the USY alone catalysts (R and S) , but much greater than the zeolite beta along catalyst (Q) . Higher gasoline octane quality and higher total liquid (G+D+A) yield are observed for

Catalyst P, compared to Catalyst R and Catalyst S. A catalyst with 25% USY alone in a similar matrix as Catalyst P is expected to have a cracking activity and product selectivity between those of Catalyst R and Catalyst S. However, the zeolite beta/USY composite catalyst prepared by the disclosed method is expected to have a better overall FCC performance.