NL8301731A - CATALYST AND CATALYST CARRIER, METHOD FOR THE PREPARATION THEREOF, AND METHOD FOR CRACKING HYDROCARBONS USING THIS CATALYST. - Google Patents

Description

* ». *

Catalyst and Catalyst Support, Process for Their Preparation, and Process for Cracking Hydrocarbons Using This Catalyst.

The present invention relates to the preparation of catalytic materials, more particularly to the preparation of dense, hard, particulate hydrocarbon conversion catalysts comprising acid-reacted metakaolin.

Hydrocarbon conversion catalysts, such as fluid cracking catalysts (FCC), are often manufactured by spray-drying aqueous suspensions of catalytically active zeolites and matrix-forming components, such as inorganic oxide gels and / or clays. The resulting catalysts consist of small particles (microspheres) in which the zeolite crystals are distributed by a matrix of catalytically relatively inactive gel or sol binder and clay.

Clay, especially kaolin, has been found to form a particularly suitable FCC catalyst component due to its reasonable price and availability.

The prior art describes the preparation of clay-based hydrocarbon conversion catalysts that have been heat and / or chemically treated to obtain the desired characteristics.

US Patent 2,485,626 describes the preparation of clay-based cracking catalyst in which kaolin clay is subjected to heat treatment and reaction with acid to remove aluminum oxide from the clay structure. The acid-reacted clay is stripped of soluble components by washing and formed into catalyst particles.

U.S. Patent 3,406,124 describes a process for the preparation of catalysts containing crystalline aluminosilicate zeolites dispersed in a matrix of inorganic oxide. The matrix contains a clay component that is leached with acid to remove some of the alumina from the clay structure in the form of soluble aluminum salts. The soluble aluminum-5 salts are precipitated as aluminum hydroxide.

Although the literature describes the preparation of hydrocarbon conversion catalysts, which may consist of or contain heat / chemically treated clays, such as fired / acid-treated kaolin, the refining industry is constantly looking for inexpensive catalysts of acceptable of activity and selectivity, combined with substantial physical strength and abrasion resistance.

Therefore, an object of the present invention is to provide improved catalyst materials.

Another object is to provide hydrocarbon conversion catalysts that are hard, dense and relatively inexpensive to manufacture.

Yet another object is to provide highly active, cost effective FCC catalysts comprising chemically / thermally modified kaolin which can be used in the catalytic cracking of a wide variety of hydrocarbon feedstocks.

Another object is to provide inexpensive clay-based FCC catalysts that can be mixed with more expensive zeolite-containing FCC catalysts and used to process starting materials that are heavily contaminated with metals, sulfur and / or nitrogen compounds.

These and other objects of the present invention will readily become apparent to those skilled in the art upon reading the detailed description and specific examples below.

Broadly, the invention relates to improved catalytic materials (including catalysts and catalyst supports) containing an acid treated metakaolin obtained by heating (firing) kaolin 8301731 # 3 and reacting the resulting metakaolin with sufficient acid to not more than about 25 mol% of the aluminum oxide present in the coal (Alte.

More specifically, Applicant 5 has found that dense, hard, wear-resistant catalytic materials can be prepared from acid-treated metakaolin obtained by heating (firing) kaolin to a temperature of about 700 to 910 ° C and reacting it. resulting metakaolin with enough acid to react with less than about 25 mole percent and preferably about 5 to 15 mole percent of the structural aluminum oxide present in the metakaolin. The materials are formed into particles which can then be subjected to heat treatment (firing) at a temperature of about 300 to 800 ° C to obtain hard wear resistant catalysts or catalyst supports.

The acid-treated metakaolin catalysts described in the present application have significantly higher activity than the acid-leached clays described in the literature. This inexpensive, highly active acid-treated metakaolin provides a significant portion of the total cracking activity of the catalyst. Catalysts with substantial matrix cracking activity are highly desirable for cracking high-boiling starting materials and for the production of high octane gasoline.

Although the process is particularly useful for the preparation of FCC catalysts which can be used for catalytic cracking of a wide variety of hydrocarbon feedstocks, the invention also includes the preparation of catalyst supports used in the preparation of catalysts for hydrogenation processes , such as hydrocracking, hydrodesulfurizing and hydrodesaturation catalysts.

The reaction metakaolin is obtained by heat-treating kaolin at a temperature of about 700 to 910 ° C, preferably 800 to 900 ° C, for

___A

8301731 4 • * * a period of more than about a quarter of an hour, preferably a quarter to 8 hours, preferably a | up to 2 hours. The thermal treatment, or firing step, which can be performed in the presence of air, converts the raw kaolin into a reactive form which is characterized as metakaolin.

The reactive metakaolin is then reacted with an acid, such as hydrochloric or nitric acid, or an acidic salt solution thereof, such as aluminum chloride, aluminum nitrate, zirconyl chloride, etc.

The amount of acid reacted with the metakaolin is sufficient to react with about 2 to 25, preferably 5 to 15, mole% of the aluminum oxide (A 2 O 3) present in the metakaolin. The reaction in the case of hydrochloric acid typically proceeds according to the global reaction below, in which metakaolin has the formula 2 SiC 2.

2 Si02.Al2O3 + 1 HCl / 2 SiO2 (Al ^ g 9Hq 6_7 + 0.2 AlCl3 + 0.4 HCl

To achieve the desired degree of acid treatment, the amount of acid used is equal to or less than about 1.5 moles of acid per mole of aluminum oxide present in the clay. Applicant has found that an amount of no more than 0.25 mole of acid per mole of alumina is sufficient to provide the desired acid-reacted meta-kaolin product in less than about 24 hours.

The most preferred amount of acid is about 0.50 to 1.0 mole of acid per mole of alumina in the metakaolin. The desired amount of acid is combined with enough water to provide about 2.0 to 20 parts by weight of the acid solution per part by weight of metakaolin. The acid reaction is carried out at a temperature of about 60 to 100 ° C for a period of about 1 to 24 hours. The resulting acid / metakaolin reaction product contains about 5 to 50% by weight of clay solids, mixed with a liquid phase comprising an aqueous solution of a complex acid / aluminum reaction product, with a pH of about 2.0 to 4.0. This acidic aluminum reaction product solution, together with the acid leached metakaolin solids, includes the binder or the intermediate 8301731

> * X

Material used in the preparation of the catalysts and catalyst supports of the invention. The ratio of the acid leached clay solid to complex acidic aluminum compound in solution is from about 8: 1 to 9.8: 1, preferably 9: 1 to 9.5: 1 by weight.

To obtain a cracking catalyst comprising the above-described reaction product of acid and metakaolin, the reaction mixture of acid and metakaolin is spray dried or otherwise shaped into particles of the desired shape and size. It is also possible to react the acid-reacted metakaolin reaction product with enough base to raise the pH of the reaction mixture to a level of about 5.0 to 9.0 to precipitate the soluble aluminum component prior to the molding operation. .

Furthermore, the aluminum components can be autoprecipitated by keeping the reaction mixture at a temperature of 60 to 100 ° G for at least about 3 hours using high clay solid levels.

To prepare fluid cracking catalysts (FCC), the acid-reacted metakaolin is mixed with water to obtain a slurry-fed slurry containing about 20 to 60 weight percent solids. The slurry is then spray dried using conventional techniques to obtain FCC catalyst particles in the form of microspheres, which are then fired, either before or during use, at a temperature of about 300 to 800 ° C. These fired particles can then be subjected to ion exchange and / or washing to remove unwanted soluble salts. The FCC catalysts of the invention have a surface area of about 200 to 2,600 m / g, a density of about 0.50 to 0.80 g / cm, and a microactivity of about 40 to 80 vol% conversion after

treatment with 100% steam at 732 ° C for 8 hours (ASTM

35 method D3907). Furthermore, the catalysts have a high abrasion resistance as determined by the methods described in U.S. Pat. No. 4,217,420.

The FCC catalysts of the invention are particularly cost effective for catalytic cracking of hydrocarbon residue starting materials containing large amounts of contaminating metals (nickel and vanadium), sulfur and / or nitrogen. The catalysts can be mixed with standard zeolite activated cracking catalyst of the type described in U.S. Pat. Nos. 3,867,308 and 3,957,689. Physical mixtures containing about 20 to 80% by weight J0 zeolite FCC mixed with the FCC catalysts of the invention will be effective for processing residue starting materials that cause rapid deactivation of conventional catalysts by metal contamination.

In the case where the acid-treated metakaolin according to the invention is used to make supports, such as used in preparing catalysts for hydrogenation processes, the above-described acid-metakaolin reaction mixture is mixed with small amounts of water and formed into extrudates, pills or granules using conventional molding techniques.

It is also possible to react the acid-reacted metakaolin with a base to precipitate alumina prior to formation of the catalyst supports.

The resulting shaped particles are then fired, either before or during use, at a temperature of about 300 to 800 ° C, to obtain hard wear resistant particles. The resulting fired particles can then be combined with catalytically active metals, such as selected from Group VI and Group VIII of the Periodic Table of Elements, to obtain catalysts useful for hydrocracking and hydrodesulfurization, demetallization, etc. In particular about J to 2 wt% non-noble metals, such as cobalt, molybdenum, chromium and nickel, can be impregnated or applied to the catalyst supports of the present invention using conventional techniques. Furthermore, it is possible to combine about 0.1 to 2% by weight of precious metals, such as platinum, palladium and rhodium, with the carriers to provide useful catalytically active products.

The invention is illustrated by the following examples. The catalytic activity, expressed as the volume percent conversion, of the crane catalysts described in the examples was determined using the procedure of ASTM D3907).

Example I

This example describes the preparation of an acid-reacted metakaolin cracking catalyst of the invention. 67.5 ml of 37.0% HCl was diluted to a total volume of about 600 ml and 200 g of metakaolin prepared by firing kaolin at 840 ° C in a rotary oven for about 50 minutes was added. The resulting suspension was heated at reflux for 8 hours. The product was filtered off, washed until free of Cl, dried in a forced-ventilation oven and ground. This sample 2 had a specific surface area of 284 m / g, an alumina content of 38.8% and a catalytic microactivity of 40.7 after deactivation with 100% steam at 732 ° C for 8 hours.

Example II

This example uses the same HCl level and concentration as well as the same metakaolin as indicated in Example I, and shows that a high surface area catalyst is obtained when the duration of the reaction with acid is extended to 60 hours. 13.5 ml 37.0

% HCl was diluted to 120 ml, 40 g of the one in Example I.

The described metakaolin was added and the resulting suspension was aged at 107 ° C in a sealed Teflon bottle for 60 hours. The suspension was then filtered, freed from Cl by washing and dried in an oven at 12 ° C.

The resulting product had a surface area of 436-235 m / g, an alumina content of 36.6%, and a microactivity of 39.9 upon steam deactivation.

_____ 8301731 8

Example III

This example indicates that higher acid levels than those used in Examples I and II also give a high surface area catalyst. 59.0 ml of 37.0% HCl was diluted to 300 ml and 100 g of the same metakaolin as in Example 1 was added thereto. The resulting suspension was heated to reflux for 8 hours, filtered, dewaxed by washing and dried in an oven. This sample had a surface area of 277 m / g, an alumina content of 43.8%, and a catalytic activity of 34.8% after steam deactivation.

Example IV

This example and Examples V to VII show that undesirably high HCl levels reduce the alumina content of the catalyst product and reduce its activity. 202.5 ml of 37.0% HCl was diluted to 750 ml and 200 g of the same metakaolin as in Example 1 was added. A portion of the resulting suspension was removed after refluxing for one hour, filtered, dewaxed by Cl and washed in an oven.

2

This sample had a specific surface area of 157 m / g, an alumina content of 33.3% and an activity of 10.7 after steam deactivation.

Example V

This example was prepared by the same procedure as in Example IV except that 270 ml of 37% HCl was used. The resulting catalyst product had a specific surface area of 232 m / g, an alumina content of 23.6% and an activity of 13.4 after the steam deactivation.

Example VI

This sample was prepared according to the same procedure as in Example IV, except that 337.5 ml of 37.0% HCl was used. This product had a specific surface area of 337 m / g, an alumina content of 14.1% and an activity of 7.5% after steam deactivation.

8301731 »9

Example VII

This sample was prepared according to the same procedure as in Example IV, except that 405 ml of 37.0% HCl was used. This product had a specific surface area of 2 488 m / g, an alumina content of 6.18% and an activity of 7.0% after steam deactivation.

Table A below lists the results of Examples I to VII.

10 th ------_ ^ | 8301731 10

/ -N

Vw /

4J

• H

CU

AJ

• H

> ρ ^ σΝ00Γ ^ <ί · ΐΛθ • rH Λ Λ Λ Λ Λ Λ Λ 4J Ο CT \ ST Ο CO Ι '· »Η · 0 I ο sf co cn - - ο Ρ rt o 11.0 ^ • HM«

HO

0 -H frS

p S _ m ° 13 o

JJ

® 1 ai yy p -T3 2 <U · -H ¢ 0 8 Ό P O „„

(3 P ΓΟΟ 00 P

<Ü <U OH 00 vO CO Λ Ό "^ ® _Q J> (N <U ΛΛΛΛΛΛΛ V * 4 _Q · Η H & 0 * H0OvöoOCOC1si- \ O ® <up <| yy <dooco <-cics—>>

, C Η Η rH * H

P P Jxt + * at 2

MN W

(IJ W

(U JJ ® Ö0 ® Ai Αί T3 cd «C cu cd

<U * r4 r — I ÖO M

M P M-l> sO Γ ^ · CS 1 co P

cu p • HHcsoocor '»mcncoco P

öo> ü <uscs <rcs * - 'cscn- <r fl} p <' w 'oo M <u o, ft ρ · η w o 2

p μ P

N O

a ü u p ® rH CD IW M ®

flj g <U YY

_o co Ό öo ®

Pp Ρ H pp -y O

H P P O * H 2P -

> · Η ® P

mm® + J * rj

YY O P O

• H YY P Η HN ^ YY

<3) p T3> J300000CSCSCSCS · Η®

YY CO CO 00 ^ vO \ \ \ YY N

• H> i <P p - - - '- Ü S

> Η * n Ö ® O

• Η Ρ · Η ® O

JJ JJ Es JJ M S-S

ON O

P M '“J

O Hi SO

MP> on jp r- w

• HM® O

S ji co o

• Η Π O

M O CS

JJ I co ® S Γ> s 5 _ OH WO.

• HO r ^ t ^ cTiOr ^ cno <J o 3 S - - <cs m S3 oo o O - ® - o ^

JJ

co

P

H

CL)

Ο Η H

, Q Η Η> Η H

Μ Η Η Η H i>>>

O

O

> 8301731

Example VIII

1 «11

This example shows that the temperature used in firing the clay to obtain metakaolin affects the rate at which specific surface is formed. 100 g of a fired kaolin, prepared by heating kaolin clay at 732 ° C for about 50 minutes, was added to individual solutions of 37.1 ml of 37.0% HCl diluted to 330 ml. The resulting mixtures were aged for 16, 44 or 51 hours. The results listed in Table 10 show that although this metakaolin reacts more slowly than the metakaolin (840 ° Cl used in Examples I to VII), products with a high surface area are obtained using long acid reaction times.

15 Table B

Specific surface of metakaolin reacted with 17% stoichiometric HCl (50 min, at 732 ° C)

Duration at 100 ° C Specific surface area (m / g) 16 128 20 44 296 51 303

Example IX

This example shows the effect of acid solution volume / concentration on the development of the specific surface. Using the metakaolin of Example I, 33.5 ml portions of 37% HCl (corresponding to 17 mol% of the acid required to react with the aluminum oxide contained in the metakaolin) were diluted with water to give solutions with a volume of 125 to 300 ml. Table C shows results for six samples. Although all products have a high surface area, indicating good catalytic activity, the third or fourth sample appears to correspond to optimal concentration levels.

35 ________ Λ 8301 731 12 y a a

a

o / ->.

ns wi μ "~ ·· * A CD CM 'O Ui X 4 Ό 00 τΗ a) · Η g CO - p * O <- Ά C_> do iwwmcoco <ffniN fö A * 1-1

Is a 2 y 111 U A3

A Ar-C U

Ö0 CO> W

A y

A / -s 4J

> M g

S

, M. g cD J3 · Η Γ-ί> Λ> ο y ¢ 5: = = =: <u α · π ο A «AW w

-R-C A.

Α <u <u

A V- / Ό M

u co

13 A AA

• h a A r- <ly · Η> cw

• H rH

a O 6M f3

4) A = = = = = O

A ^ Γ "i — 1

co A - iH

4J CU

4J <U U 4-1 CU g <u

J3 g A

λ ÖO · Η ft ÖO w

O ¢ 50 = = = = = -PO

• HO cö O

(U iH 1- ce O

• H rH rHO

• U A + + + + + + A * A y

OH 03 r4rHiHrHrHrH AA

y cissesee <uo

r-1 A <U 'A

cu cu g o o o m o m ööo ja u a o m o f '· m cm op!

CdPi w cn cm cm - -> · Η

Eh o ^ y o y A <u y A O 0) Ά

Α · η y öo A

3 co A O

N / ~ \ A Ά · Η y

- cu A Ά A

<U v-r ft 3 · Η>

Ά co Ό <U

y 3 y Irf ij A ^ w A J3 i

AA <U> = = = = = AA

> Ά · Η O

o y ih y o y y a o vo

aft A IA A

A Η A 1H y

cy A Pi N H J

<y> H <3 0 W rid η / -η rH ^

S

m Λ "W Ξ *» <n and 0

a

y

a

y - cm cn ά · m vo cn

a

8301731 _ - * 13

Example X.

This example shows that nitric acid can be used in the preparation of the products of the invention. 19.3 ml of concentrated HNO4 was diluted to 225 ml, and 75 g of metakaolin (fired at 871 ° C for 50 minutes) was added. Three samples of the mixture were reacted in separate Teflon bottles for 4, 6 and 8 hours at 100 ° C. The results, shown in Table D, show that the high surface area product is formed after about 6 hours (samples 2 and 3).

Table D

Reaction of dilute HNQg with metakaolin

Sample no. Hot aging time (h) Specific surface area _ _ (m2 / g) _ 15 1 4 118 2 6 236 3 8 314

Example XI

This example shows that certain firing conditions reduce the reaction time required to obtain products with a high specific surface area. Individual samples of kaolin were placed in a hot oven at temperatures from 650 to 927 ° C for 1 hour. Samples of 50 g of each of the above fired clays were suspended in 150 ml of water containing 16.9 ml of concentrated HCl. The 50 g samples were divided into three separate samples and reacted in Teflon bottles for 4, 8 or 16 hours. The results, given in Table E, 3Q, indicate that the most effective firing temperature is 850 to 875 ° C. Clays fired at 927 ° C showed much lower reactivity.

_____ Λ 830 1 73 1 14 r · m oo vo CM cm cm co σ \ σ »| οο ον ο ι αν -a · - cm · AJ 00 - CM CM Μ ° 3 Ο 3 μ μ CO Cd

YOU

<ΰ 0) Ό. & ι— VO 00 Γ · »β fi Γ'.ι cm co in 0) cd co> - co <· μ> fi

Cl) 0) • H>

μ (U

U 60 ö «<r o ό cu fi 00 MT C3V öp cw 00 - CO CM fi cd co cd

rM

cd cu Ό μ

Ai ft 3 co oo m vo o

Ό 00 CM CM CO

o μ μ Ai

ft Ό O

• Ό O

μ »rt μ yes <u μ co

rfi CU <U

cH · μ öo 3 fi μ cm ~ oo i ".

^ acdo co co - «a · μ cd> cd 3 H <U fi

3M

r-t CU

> Ό fi

μ <U

CU fi * H

ft CU <-l ft o in «a- o O μ Ό 00 CM CM Cd, 3 VO Ai

Ai fi 0) μ cu

• H Cd rM

CH μ rM

• H CU <O ft <u S 'ft CU * - W μ <- ^ v— / Λ

O

O rC

^ A3 A.

VO

μ «a · oo - 3

Yy r * λ λ μ Ό Ό Ό

Cd «r-η · ρπ · τ“ 1 μ * μ · Η · Η 0) μ μ μ

ft 3 <U CU

S · η · α * μ CU μ μ μ μ υ ο ο Α! cd cd cd

Ο 3 CU CU

o fi fi fi μ w 8301731

Example XII

15

This example shows that low acid levels can be used to obtain the product of the invention. 225 g of fired kaolin (either 5 hours at 899 ° C, 1 hour at 871 ° C or 1 hour at 843 ° C) was suspended in 675 ml of solution containing 19.2 ml of concentrated HCl. The resulting suspensions were refluxed for 16 hours. All suspension samples were filtered, washed to remove 10 Cl, and oven dried. The results, given in Table F, indicate significant surface area development even at this relatively low acid level.

15 ...... ..... * 8301731 16 / - \

ÖO

Ö ^

G CM

C 6 G v- '• ri

r-i M

0 G

G r — t M> G g

G (U

0) ftvOr ^ OOOOQ - - - vO <NOOO

1 ftOooocoo'coinmo \ tnr, ^ r> *

OCMCMfOfO - <N (N <N - CMCSCN

0) M Ai μ 0) <U · Η> M-l • Η · γ4

Ό) O

0) ft ft O w T — 1 s co

YOU

G / -s «. -ö a ^ o • H "Ö

Pk -ö ·> “)

G * G

τ-Ι G G

GO GCOC''JstvOCOCM - <) * OOOOiM «d- ^ U · Η« -tl— »1- ^ T- * 1- * 1—« t-β ^ i— *

3 CO G

HO

• G- G

CN G

^ Pi

S

G

>

• H

3

M

8 o ö

G

* 3

G

rö 00

• H

* ϋ 3

GO CO CJ

• GO O O

ra n - SON = = = -it = =: r ^ = = = O CO 00 co

Ai O Λ ft ft

O O O O

G

¢, 0 ::: 3 :::, 0 ::: • rl

0) <N

I— {^ »- · T- * 8301731 4» 17

Example XIII

This example shows that a salt that can generate H + via hydrolysis can be used instead of mineral acids. 75 g portions of metakaolin (fired at 900 ° C for one hour) were added to 900 ml solutions containing varying amounts of AlCl 2. The suspensions were heated to reflux, the pH adjusted to 7.0 with 14% NH 2 OH, filtered, dewaxed by Cl and dried in an oven. The results, given in Table G, clearly show the development of materials with a very high specific surface area, even at low AlCl 2. levels.

----- j 8301731 r 18 a λ> u ootncofnomoO'DO <u ^ -vP ^ cn> - - σιοίΝΐη— · eu & ocsco-vf oimco-cfiN-d · α. · ^ »ΟιΜ

-Ü Α! S

• Η 0) β · Η rC m I — I · Η a) α β α) CQ o * co co

Ö0 β • H

CU

£ ~ t * 6 0 <u

β Ό M

O β β O * r-4 <U Ή

U3 Onion β CM

βO

CU 3H - O Ό> wbflmoovooovDoovooovo O ^ β - * - · * - * CM * i-i 5-i a · η <u v £> H 4-1

O

cn i-4 i-4

<0 CJ

Μ r-4 Ai β rt <J te 0 E-4 τ — 4 · τ-4 tJ>! r-4

• H 5-i O

β β β a cu axis r-4 (3.1 β <U O 4-1

β (U

> 0) g β Ai O β öfl a m u-ι m β · Η P * τ) ο \ Γπι> * ι> »« ™ σ \ σ \ νο \ ο QJ Q ΛΛΛΛΛΛΛΛΛ

β Cu cm Lor- ^ r> LOirooooCNCM

d n a r ^ cnoocMcM— · j> 4-5 · 4-4 β 00 ü a i-l

β U

> 4-1 β 1-4 m β <j Μ> Ö0 0301731

Example XIV

* J9

This example shows that ammoniation of the acid-reacted clay slurry benefits activity just prior to filtration. A reacted clay slurry was prepared and reacted as in Example 1 except that after the reaction, the pE of the slurry was adjusted to 6.0 with 14% ΝΗ, ΟΗ prior to filtration. . The specific surface area was 326 m / g and the activity was 49.2, which is considerably higher than the 40.7 observed for the product obtained in Example 1.

Example XV

This example shows that greater activity can be obtained by precipitating alumina in the presence of acid-reacted metakaolin. 5400 ml of concentrated HCl were diluted to about 48 liters with water and 16 kg of metakaolin (fired at 732 ° C for 3 hours) was added. The resulting mixture was allowed to react under reflux for 48 hours, after which it was filtered, and washed twice with 37.85 liters of hot water. This product had a specific surface area of 283 m / g. 50 g (on a dry basis, 304.2 g in the as-present state) of this filter cake was dispersed in 1 liter of water containing 26.3 g of AlCl 3. The pH was adjusted to 6.0 with 34% NiO4OH to precipitate alumina and the product was filtered, washed twice with 1 liter of hot water and dried at 320 ° C. The alumina treated sample had an activity of 48.6, against 36.1 for the untreated sample.

Example XVI

This example shows the preparation of a gelled acid-treated metakaolin according to the invention. 150 g of kaolin clay, fired at 900 ° C for one hour, was added to 1.0 liter of solution containing 50.7 ml of 37% HCl. Half of the slurry was refluxed for 4 hours and the other half was boiled for about 8 hours. Both samples were briefly drained, cooled, pH adjusted to 6.0 with 14% NH 2 OH to gel the aluminum oxide components, filtered the suspension and washed twice with 1 liter of hot deionized water and oven dried. The specific area of the 4 and 8 refluxed samples for hours was 2 respectively

295 and 402 m / g. The catalytic activity of the 4 and 8 hours refluxed samples was 46.4 and 50.5, respectively, according to the procedure of ASTM-D3907. Example XVII

This example shows that a significantly improved activity is observed upon addition of boehmite to the gelled acid-treated metakaolin of the invention. 200 g of kaolin clay, fired at 900 ° C for one hour, was added to 2.0 liters of solution containing 67.9 ml of J5 37% EC1 and refluxed for 24 hours. Varying amounts of boehmite were added to four separate cooled mixtures of the above suspension, the pE was adjusted to 7.0 with 14% NE 2 OE, the suspension was filtered and the filter cake washed twice with a 1 liter of hot deionized water. The samples were dried and the cracking catalyst activity of each of the samples was determined. The activity data, listed in Table E, show that the addition of boehmite to the gelled acid-treated metakaolin results in a significant improvement in activity.

8301731 Λ 21 ·· 3 3 • 3 • Η <υ, 3

rH

3 c Ό 00 U "φ -y <u g% U

U MU

<U ~ Ö ΛΙ 60% os s t ^ a § ω a N £. S 00 ° T3 w <U “§ u & 2

3 00 CJ Ο O

«“ CM S m, —I «Η -r-4 3} ® <UW ft ** m 60 W>» <U <UW · Γ> _ 60 N w · ”2 S» ° ° 4J OO CTi Ο O CO "<UA Λ Λ Λ Λ Η S 6-¾ ο σ \ ο σ> en. M in vc m κι wg cu 3 ^ g 6 ° 2 jg I μ

Wed M S

a) w „^ τ-Ι 3 5® S mg« J3 ^ · Η Ό Ü «- <gw S 5 S ί -1« So Ο T3 fM § * “, 3 00 C ° B Ο · Η« 2 δ o 9 * 60 M g «5 <U 3 O« ^ 2 ww os (U> S ss «

W C CO O

U <U W 9 (U, α <u I, u ÏÏ * S s i§ «H, 2 5 0® Ό qj« S; “·

O

rQ

• d w Μ o to o m

Q) A A A A

ο Ο Ά t- «O <N

> ~ 1-. CM CM

<You

W> d)

O

W.

H

..1¾ 8301731 t 22

Example xyill

Samples of hydrothermally acid-treated metakaolin were prepared by adding 25 g of kaolin (fired at 900 ° C for one hour) to 125 ml of water containing 8.5 ml of 37% HCl and heating over time and at the temperature, as indicated in Table I, in Teflon lined high pressure reactors. The suspensions were cooled, diluted with water to obtain a stirable suspension, adjusted to pH 7.0 with 14% filtration, washed twice with 10 µl hot water and dried in an oven at 120 ° C. The activity of the hydrothermal. acid-treated metakaolin is significantly higher than that of the refluxed sample at 100 ° C.

15 8301731 23 λ s λ O o N λ B tl s- '· · Η · 03 y n ο. u • H S >> O * «<u o + y n 4J · - 'CT>! N o σ \ o • r-i Bs? «« * Ifl o> · O N 0 \ CO «" · • Η η κι> fl ifl irt ft u O O w 0> s

<jv 60 S

ö.

• H 3 «j H 6

3 <U <—I

3 Ό <ü

S g 'S

«Λ 2 5 54 ψ-m fö 5 nj>» ✓ QJ J3 ft ^ * 2 g rt. ° <U Γ-Ι 2 4J> ιΰ Yy £ 0 3 OJ <U ca 3 öo ft / - »'Ö„

o ft 60 S CO

r * O -v. H

cm 2 2

1 g o η ό n .3 S

• H O ^ O - N Οι W _, £ 3 -Η · ί> J UI ffl ö üj μ o 60 · Η 2 * {c O 3 e rl <U §

OM "S

H Ή § g »r-t rt r * 5

O ij C3 * H

jü o 0) 4J

yy YY T3 Ί- * + J

H 3 '7 I | 3 4J <B g

N <U / -v -d "60 O

3 «5 7 & -S

3 O <ƒ vO 00 vO W

> s 00> s 3 * S 5 S g · s CH ft ^

KHO

M

Λ O · <u σ> o • ft <n o

OM Q CM

• η I cn O 2

μ <u H

3 ft M ft 3 M Co U / - »3 Λ ^ C1 μ o - cm o co ft · μ S ft o f— \

+ J U 4J

CU o ^ -r-4 · - / • u o o o m

o o <f <f MO

0 01 8301731 24

The above examples clearly demonstrate that by using the compositions of the present invention, valuable catalyst materials can be obtained.

8301731

Claims (18)

1 - 1. Catalytic material comprising an acid-reacted metafcaolin, characterized in that it is obtained by heating kaolin at a temperature of 700 to 910 ° C for at least about 15 minutes to obtain metakaolin and then reacting this metakaolin with sufficient acid selected from hydrochloric acid, nitric acid, and salts and mixtures thereof to react with at most about 25 mol% of the alumina present in the metakaolin. The material according to claim 1, characterized in that about 5 to 15 mole% of the aluminum oxide has reacted in the metakaolinic acid. Material according to claim 1, characterized in that the reacted aluminum oxide is precipitated. 4. Material according to condusion 1 or 2, characterized in that it is washed and spray dried to obtain a flowing catalytic cracking catalyst (FCC catalyst). Material according to claim 4, characterized in that it is mixed with a zeolite-containing fluid cracking catalyst. The material according to claim 5, characterized in that the zeolite-containing catalyst comprises a zeolite selected from the group consisting of X, Y and ZSM zeolite dispersed in an inorganic oxide matrix. Material according to claim 5, characterized in that the zeolite catalyst constitutes about 10 to 90% by weight of the material. Material according to claim 1, characterized in that it contains particulate aluminum oxide. 9. A material according to claim 3, characterized in that the aluminum oxide is precipitated by addition of a base. The material according to claim 9, not characterized in that the base is ammonium hydroxide. 11. Process for the preparation of a catalytic material, characterized in that (a) kaolin is fired at a temperature of 700 to 910 ° C for at least about 15 minutes to obtain metakaolin; (5) this metakaolin reacts with sufficient acid to react with up to 25 moles Z of the aluminum oxide present; and (cl the mixture forms into catalyst particles. 12. Process according to claim 11, characterized in that the product obtained in step (b) is reacted with a base to precipitate soluble alumina components before step (cl. Process according to claim 11, characterized in that the acid is selected from hydrochloric acid, nitric acid and salts thereof. 2. A method according to claim 11, characterized in that the mixture is formed by spray drying, extruding, pelleting or granulating. 15. Process according to claim 11, characterized in that the catalyst particles are heated to 300 to 800 ° C. A method according to claim 11, characterized in that the kaolin is fired in step (a) for a period of from about 15 minutes to 8 hours. 17. Process for hydrocarbon cracking, characterized in that a hydrocarbon feedstock is reacted in the presence of the catalyst according to any one of claims 4, 5, 6 or 7, under catalytic cracking conditions. 18. Methods and products in the main matter as described in description and / or the examples. ^ 8301731