JPH01266853A - Production of catalyst - Google Patents

Abstract

PURPOSE: To improve hardness and wear resistance by calcining particles consisting of a mixture composed of zeolite contg. <0.6 wt.% alkaline metal and zeolite and aluminum chlorohydrol, thereby forming a catalyst. CONSTITUTION: The raw materials consisting of an aluminum chlorohydrol soln., a zeolite slurry and a clay slurry are mixed with a mixer to obtain a uniform aq. slurry. This aq. slurry is spray dried and is converted to a granular solid composite and thereafter, this composite is calcined to form the hard and wear resistant particles. This catalyst composite is then subjected to an ion exchange by using an ammonium salt soln., such as ammonium sulfate and/or rare earth chloride, by which the catalyst composite is obtd. The resulted catalyst composite adequately contains <=0.5 wt.% alkali metal oxide and the moisture content thereof is 5 to 25 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to the production of catalysts, and more particularly to the production of hard, wear-resistant, zeolite-containing catalysts with high activity for the catalytic conversion of hydrocarbons.

Hydrocarbon conversion catalysts, such as inorganic oxide matrices (
Fluid cracking catalysts (FCCs) consisting of crystalline zeolite dispersed in a matrix are typically spray-dried from an aqueous slurry of the zeolite, clay and a suitable binder, such as silica-alumina and a drogel, silica sol or alumina sol. Manufactured by The spray-dried catalyst particles can be calcined and ion-exchanged to remove undesirable alkali metal impurities.

Canadian Patent No. 967136 discloses a hydrocarbon conversion catalyst consisting of zeolite, clay, and an alumina sol binder. This catalyst is made of low sodium ion exchanged zeolite (low 5oda ionexchange zeolite).
ed zeolite), clay, and alumina sol (chlorohydrol), and calcining the spray-dried particles to produce a hard, wear-resistant catalyst.

U.S. Pat. No. 3,425,956 describes a method for preparing a zeolite-containing tarraking catalyst, in which a spray-dried composite of partially ion-exchanged zeolite and silica-alumina hydrogel is calcined; Next, perform ion exchange.

This calcination step stabilizes the zeolite and increases the removal rate of alkali metal oxides.

The modern cranking catalyst industry is particularly interested in producing catalysts that are highly attrition resistant, active and selective for the production of gasoline fractions.

It is therefore an object of the present invention to provide a process by which highly active, attrition-resistant catalysts can be produced economically.

It is another object of the present invention to provide a method for producing a hydrocarbon conversion catalyst using zeolite that can omit a multi-step high temperature calcination step.

It is also another objective to produce a thermally stable catalytic cracking catalyst capable of producing gasoline fractions at high rates.

Furthermore, it is an object to provide a zeolite containing a fluidized cracking catalyst that is selective for the production of high octane gasoline fractions.

These and other objects of the present invention will be readily apparent to those skilled in the art from the following detailed description and illustrations consisting of block flow diagrams outlining the steps embodying the method of the present invention. It will become clear.

Briefly, the present invention involves calcining a dry granular composite comprising an alkali metal-containing zeolite and an aluminum chlorohydrol binder, followed by ion exchange to reduce the alkali metal content by less than about 1 ffiffi%. It consists of causing A catalytic process containing alumina-bonded zeolites is directed.

More specifically, by calcining a granular catalyst complex bound with aluminum chlorohydrol containing an alkali metal-containing zeolite, the alumina chlorohydrol is converted to an alumina binder and the catalyst complex is simultaneously It has been found that it can be cured and activated for subsequent sodium removal by ion exchange.

The present invention can be more clearly understood by reference to the figures illustrating catalyst manufacturing methods that can be used in carrying out the invention.

As shown in this figure, the raw materials of aluminum chlorohydrol solution, zeolite slurry and clay slurry are mixed in a mixer to obtain a homogeneous aqueous slurry. As shown in this figure, this mixed chlorohydrol/zeolite/
The clay slurry is subjected to a spray drying process during which it is converted into a particulate solid composite of zeolite and clay particles bound by aluminum chlorohydrol. These composites are calcined to produce hard, wear-resistant particles. During the calcination step, the alumina chlorohydrol is converted to a strong alumina binder and by-product acid chloride, which is removed from the composite. Moreover, by this calcination step, the alkali metal oxides present in the zeolite component can be more easily removed by the subsequent ion exchange.

As shown in this figure, the calcined catalyst composite is ion exchanged and/or washed to remove excess alkali metal oxide and any other soluble impurities that may be present. This ion exchange step can be carried out using ammonium salt solutions such as ammonium sulfate and/or rare earth chloride solutions. This ion-exchanged complex is washed to remove soluble impurities. Following ion exchange and washing, the catalyst composite, which now contains less than about 111j1% alkali metal oxide, preferably less than 0.5% by weight, is dried to a moisture content of about 5-25% by weight.

Aluminum chlorohydrol solutions used in the practice of this invention are readily available commercially and typically have the formula A122. ff1(OH)3□CQ6, where m has a value of about 4 to 12.

Aluminum chlorohydrol solution also corresponds in the art to aluminum chlorohydroxide, which is a polymer derived from a polycationic hydroxyaluminum complex or a monomeric precursor having the general formula AJ(OH)scQ-2JO. . For application to the present invention this binder component would correspond to aluminum chlorohydrol. The preparation of this aluminum chlorohydrol solution is typically described in US Pat. No. 2,196,016, Canadian Patent No. 967,136, and US Pat.
It is shown in No. 0. Typically, the production of aluminum chlorohydrol involves reacting metallic aluminum and hydrochloric acid in amounts to yield a composition having the above formula. Furthermore, this aluminum chlorohydrol can be used with various aluminum raw materials, such as alumina (A7220
3) can be obtained using clay and/or alumina and/or a mixture of clay and metallic aluminum. Preferably, the aqueous aluminum chlorohydrol solution used in the practice of this invention will have an AC203 solids content of about 15-30% by weight.

The zeolite component used in the present invention is typically a synthetic faujasite zeolite, such as sodium Y zeolite (N a Y), which contains about 10-15% by weight Na2O. The zeolite can also be partially ion-exchanged to reduce its sodium content before incorporation into the catalyst. Typically, the zeolite component is a partially ammonium-exchanged Y containing about 3-4% by weight Na2O.
type zeolite (NH*N a Y ). Furthermore, the zeolite can be partially exchanged with polyvalent metal ions, such as rare earth metal ions, calcium and magnesium. The zeolite component can also be replaced with a mixture of metal and ammonium and/or acid ions. This zeolite component is also composed of mordenite and ZSM.
It can consist of a mixture of zeolites such as synthetic faujasite blended with type zeolites. Preferably, the zeolite is combined with the aluminum chlorohydrol and clay component as an aqueous slurry containing about 20-60% solids by weight.

Catalysts of the invention may contain substantial amounts of clay, such as kaolin. However, this clay component is optional and comprises from about 0 to about 80% by weight (dry basis) of the total catalyst plastic. While kaolin is the preferred clay component, thermally modified kaolins such as metakaolin can also be included in the catalyst composition.

As shown in the figure, during the mixing process, about 20-60゜1% by weight of solids, 5-25% by weight of the solids as AQ,
A slurry is obtained to feed the spray dryer consisting of ~60% by weight zeolite and a viscosity of 0-90% by weight. Although this figure describes the method of spray-drying a slurry for catalyst production to obtain a fluidized tartaring catalyst, larger particle sizes, i.e., granular catalysts of the order of ca. It is obtained by molding, which is then subjected to hydroprocessing.
ng) Catalysts, such as hydrocracking, hydrodesulphurization and hydrodenitrification, and demetallization (demetallizat 1
on) are particularly useful in the preparation of catalysts.

The spray drying process is carried out using an inlet temperature in the range of about 300-400°C and an outlet gas temperature of about 100-200°C. During the spray drying process, the moisture content of the particles is reduced to approximately 10-3
Reduce to 0% by weight. Catalyst composite is 20-150μm
It has a particle size of about.

After spray drying, the catalyst composite is calcined at a temperature on the order of about 300-700°C for about 3 hours, preferably about 2 hours. During this calcination step, aluminum chlorohydrol is converted to solid aluminum binder and volatile acid chloride, which is removed from the calcination zone as part of the exhaust gas stream. By removing the acid chloride at high temperature, the aluminum chlorohydrol is converted to an aluminum oxide binder, which produces strong, wear-resistant catalyst particles. Furthermore, the calcination step activates the catalyst, ie the residual alkali metal oxides present in the zeolite component are liberated and easily removed in a subsequent ion exchange and/or washing step.

The ion exchange step to reduce the alkali metal oxide content of the catalyst complex to less than about 1% by weight is carried out using water and/or a solution of a polyvalent metal such as an aqueous ammonium salt solution such as an ammonium sulfate solution and/or a rare earth chloride solution. . Typically these ion exchange solutions contain 1-10% by weight of dissolved salts. A multistage exchange is often advantageous in order to remove the alkali metal oxides to the desired degree. Typically, this exchange is 50~
It is carried out at a temperature of about 100°C. Following ion exchange, the catalyst components are typically washed with water to reduce the amount of soluble impurities to the desired amount.

Following ion exchange and washing, the catalyst composite is dried, typically at a temperature in the range of about 100 DEG to 200 DEG C., to reduce its moisture content, preferably to an amount of about 15% by weight or less.

The cranking catalyst obtained by this method shows high activity in the catalytic cracking of hydrocarbons. Typically, the activity of these catalysts is increased by deactivation and heating followed by baking at 60°C.
It can be seen that the conversion is in the range of ~90% by volume. Furthermore,
This catalyst is found to be highly selective in the production of gasoline, particularly in the production of cracked gasoline fractions with high octane numbers. Furthermore, this catalyst is extremely strong and wear-resistant.

The main components of this catalyst are zeolite, aluminum, chlorohydrol and optionally clay, but other components such as granular alumina and rare earth impregnated alumina are added to enhance the SOx suppression performance of this catalyst. It is also understood that additions can be made. Furthermore, it is understood that the catalyst may be formulated with small amounts (1-1 OOppm) of platinum and palladium, which are added to enhance the CO oxidation properties of the catalyst. The wear characteristics of this catalyst are described in U.S. Patent No. 4,247,420.
Davison 1ndex measured earlier by No.
(DI) and Jersey Index (JI)
It shall be expressed by

Having described the basic features of the present invention, the following examples are presented to illustrate specific examples thereof.

Example 1 The following ingredients were combined in an 810 gallon stainless steel mixing kettle: Aluminum chlorohydride having the formula A(lzc(1(OH)2) and containing 23.5% by weight A420. Roll solution 3404j?; Kaolin 75
00,? (Dry basis); Calcined rare earth exchanged Y-type zeolite (CREY) 1500N (Dry basis)
; and sufficient water to obtain a slurry containing 25% solids by weight. (NaY was ion-exchanged with a mixed rare earth chloride aqueous solution at pH=5, followed by 538°C! (10
A calcined rare earth exchanged Y-type zeolite is obtained by calcination for 3 hours at 00"F), which has 15
゜02% by weight RE20. and 3.8% by weight of Na, O
It contained. ) The slurry was thoroughly stirred and spray dried using a gas inlet temperature of 320°C and a gas outlet temperature of 150°C. Calcining The spray-dried catalyst particles containing 25% by weight of water and 0.5% by weight of Na2O were calcined (ie, heated) in a Matsufuru furnace at a temperature of 538°C (looo'F) for 1 hour. Following calcination, this catalyst was
Dry at a temperature of °C. Table 1 shows the results of chemical analysis of this catalyst and its cracking properties.

Example 2 The manufacturing method of Example 1 was repeated. However, ion exchange was carried out by contacting 300 CI of calcined catalyst particles with 9000 m4 of ammonium sulfate solution containing 3% by weight ammonium sulfate. The analysis results and characteristics of this catalyst are shown in Table 1.

Example 3 The manufacturing method of Example 1 was repeated. However, the zeolite contained 12.5% by weight RE20. and sail 5f
It consisted of ammonium-exchanged, calcined Y-type zeolite containing fii% Na2O.

This catalyst was not ion exchanged following calcination.

The characteristics of this catalyst material are shown in Table 1.

Example 4 The manufacturing method of Example 1 was repeated. However, 13.4 wt% RE2O3 and 3.2 wt% Na
A red-calcined rare earth-exchanged Y-type zeolite containing 2O was used. This catalyst sample was not ion exchanged following calcination. The properties of this catalyst are shown in Table 1.

Example 5 The catalyst manufacturing method of Example 4 was repeated.

However, following calcination, the calcined catalyst 30009
was ion-exchanged with 9000 mff of ammonium sulfate solution containing 3% by weight of ammonium sulfate.

The properties of this catalyst are shown in Table 1.

Example 6 The catalyst manufacturing method of Example 1 was repeated.

However, this processed catalyst contained 25% by weight of sodium ammonium zeolite Y containing 3.8% by weight Na2O obtained by replacing the sodium zeolite Y with ammonium sulfate. Following calcination, this catalyst 3001 was washed with 9000 ml of water. The properties of this catalyst are shown in Table 1.

Example 7 The catalyst manufacturing method of Example 6 was repeated.

However, following calcination, 3% by weight of catalyst 30007
Ammonium sulfate solution containing ammonium sulfate 900
Ion exchange was carried out at 0 m12. The characteristics of these catalysts are as follows.
Shown in the table.

Example 8 The catalyst manufacturing method of Example 1 was repeated.

However, zeolites are
It consisted of 25% by weight ammonium-exchanged, calcined, stabilized Y-type zeolite (Z14us zeolite) prepared according to the method of No. 49070.

This Z14US zeolite is about 3.
It contained 8% by weight Na2O. Calcination followed by catalyst 3
000. ? was ion-exchanged with 9000 mQ of ammonium sulfate solution.

The properties of this catalyst are shown in Table 2.

Example 9 The catalyst manufacturing method of Example 1 was repeated.

However, a catalyst containing 40% by weight of ammonium exchanged Y-type zeolite containing 3.8% by weight of Na2O was prepared. Furthermore, the amount of chlorohydrol was adjusted to give an alumina binder content of 15% by weight, and the kaolin content was adjusted to 45% by weight. This catalyst baking was not followed by cleaning. The characteristics of this catalyst are shown in Table 2.

Example 10 The catalyst manufacturing method of Example 9 was repeated.

However, following calcination the catalyst 30007
Washed with 0mQ. The characteristics of this catalyst are shown in Table 2.

Example 11 The catalyst manufacturing method of Example 9 was repeated.

However, following calcination, 3% by weight of catalyst 30007 was added.
Ammonium sulfate solution containing ammonium sulfate 900
The characteristics of this catalyst are shown in Tables ① and ②.
Shown in the table.

Example 12 A commercial comparative catalyst containing 40% by weight Z14US zeolite, 23% by weight Nricazol binder, and 37% by weight kaolin clay was prepared by the method described in US Pat. No. 3,957,689. The catalyst was washed with ammonium sulfate and its properties are shown in Table 1.

Example 13 A catalyst was prepared by the method shown in Example 9. however,
The zeolite component consisted of 40% by weight Z14US type zeolite ion-exchanged with ammonium sulfate in an amount of about 0.2% Nano. This catalyst baking was not followed by ion exchange or washing. The characteristics of this catalyst are shown in Table 2.

Example 14 In this example, the properties of the catalysts prepared in Examples 1 to 5 were determined and are shown in Table 1 below: Table 1 Catalyst of Example No. 1 2 345 Analysis Results Na20i Amount % 0 .51 0,14
0.18 0.44 0.18RE203% by weight
2.2f3 2.33 2.43 2
．． 77 2.74SO, weight% 0.1
8 1.31 0.15 0.13 0.67
Surface area m2/9 133 133 14
8 148 146 Density 9/cm20.84 0
,84 0.84 0.87 0.87 (capacity%
Conversion rate) (1) 5-13°5: 538°C (l
OOO) for 3 hours, followed by 8 hours at 732°C (1350'F) in 100% steam at 15 psig.

(2) 1500: 5 hours at 1500'F in 100% steam on Opsig.

From the data shown in Table 1, the activity of the catalysts containing rice-calcined Y-type zeolite I (Examples 4 and 5) and those containing pre-calcined zeolite I- (Examples 1.2 and 3) The thing that makes me more worried is γ1.

Example 15 In this example the properties of the catalysts prepared in Examples 6.7 and 8 are determined and compared in Table 1 below.

Table ■ Catalyst of Example No. 6 7 8Na20
Weight% 0.58 0.13 0.
27 unit cell (person) 24.62 24.6
2 24.50 Research Octane Number 89.5 90
．． 3 90.6 motor octane number 78.2 7
9,0 79.3(3) 5-20: 827°C
(1520 below), 20% water vapor, 80% air, Qpsi
g for 18 hours.

From the data presented in Table 1, the octane selectivity for the catalysts prepared by the method of the present invention (Examples 6 and 7) is approximately comparable to the catalyst containing precalcined Z14US Y-type zeolite (Example 8). It is noteworthy that this is the case.

In Example 1, the catalysts obtained in Examples 9, 10 and 11 were compared, and are shown in Table 1 below.

Table ■Catalyst Examples No, 9 10 11N
a20wt% 2.11 0.91 0.5
After 4s-13,5 deactivation 16 50 67
Ammonium sulfate solution (Example +1)
It can be seen that sodium can be substantially removed by carrying out the present invention even when only water (Example 10) is used in place of water.

Example 17 The properties of the catalysts shown in Examples 11, 12 and I3 are compared and summarized in Table 1 below.

Table 3 Catalyst Examples No. 11 12 1
3Na20% by weight 0.22 0.54
0.04s-13,5 after deactivation 69 6
7 69 Micro Activity Research Octane Number 92.8 92.7 93.
0 motor octane number 81.3 80.2 81
．． USY (4
) 1400: 538°C in air (below 1000)
16 hours at 760'0 (1400''F) in 100% steam at Opsig.

From the above data, by using the method shown in the present invention (Examples +1 and 13), the conventional catalyst (Example 12)
It can be seen that a catalyst with high activity and good octane selectivity can be obtained compared to the above.

[Brief explanation of the drawing]

The accompanying drawings are schematic illustrations of the steps of the method of the invention.

Claims (1)

Claims: (a) mixing a zeolite with an aluminum chlorohydrol binder; (b) forming the mixture into particles; and (c) calcining the particles to obtain a hard, wear-resistant catalyst. A method for preparing a catalyst composition comprising: a zeolite containing about 3 to 6% by weight of an alkali metal oxide in an amount to entrain an active catalyst containing less than about 0.6% by weight of an alkali metal oxide; , an improved method of making a catalyst composition consisting essentially of mixing.