JPS6241782B2 - - Google Patents

Description

[Detailed description of the invention]

The present 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 fluid cracking catalysts (FCC), which consist of crystalline zeolites dispersed in an inorganic oxide matrix, typically include the zeolite, a clay, and a suitable binder;
For example, it is produced by spray drying an aqueous slurry of silica-alumina hydrogel, silica sol or alumina sol. 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 by spray drying a mixture of low sodium ion exchanged zeolite, clay and alumina sol (chlorohydrol).
The spray-dried particles are then calcined to produce a hard, wear-resistant catalyst. U.S. Pat. No. 3,425,956 describes a method for preparing a zeolite-containing cracking catalyst, in which a spray-dried composite of partially ion-exchanged zeolite and silica-alumina hydrogel is calcined; Next, ion exchange is performed. This calcination step stabilizes the zeolite and increases the removal rate of alkali metal oxides. The modern cracking 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 another object 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 invention are brought to light in the following detailed description and block flow diagram outlining steps embodying the method of the invention.
It will be readily apparent to those skilled in the art from the diagram consisting of: 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 to less than about 1% by weight. The object of the present invention is to provide a method for producing a catalyst containing an alumina-bonded zeolite, which comprises reducing the amount of alumina-bonded zeolite. 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 subsequently activated by removing sodium 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/clay slurry is subjected to a spray drying process during which the slurry is transformed into a granular solid composite consisting of zeolite and clay particles bound by aluminum chlorohydrol. Transform into the body. These composites are calcined to produce hard, wear-resistant particles. During the calcination process, 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, at this point less than about 1% by weight,
Preferably, the catalyst composite containing less than 0.5% by weight alkali metal oxide is dried to a moisture content of about 5 to 25% by weight. Aluminum chlorohydrol solutions used in the practice of this invention are readily available commercially and typically have the formula Al _2+n (OH) _3n Cl ₆ where m is about 4 It has a value of ~12. Aluminum chlorohydrol solution is also referred to in this field as aluminum chlorohydrol, which is a polymer derived from a polymeric cationic hydroxyaluminum complex or a monomeric precursor having the general formula Al ₂ (OH) ₅ Cl−2H ₂ O. Corresponds to For application to the present invention this binder component would correspond to aluminum chlorohydrol.
The preparation of this aluminum chlorohydrol solution is typically shown in US Pat. No. 2,196,016, Canadian Patent No. 967,136, and US Pat. No. 4,176,090. Typically, the production of aluminum chlorohydrol involves reacting metallic aluminum and hydrochloric acid in amounts to yield a composition having the above formula. Furthermore, the aluminum chlorohydrol can be obtained using various aluminum raw materials, such as alumina (Al ₂ O ₃ ), clay and/or mixtures of alumina and/or clay with aluminum metal. Preferably, the aqueous aluminum chlorohydrol solution used in the practice of this invention will have an _Al2O3 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 (NaY), 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 may consist of partially ammonium-exchanged type Y zeolite ( _NH4NaY ) containing about 3-4% by weight _Na2O . Furthermore, the zeolite can be partially exchanged with polyvalent metal ions, such as rare earth metal ions, calcium and magnesium. It is also possible to replace this zeolite component with a mixture of metal and ammonium and/or acid ions. This zeolite component also contains mordenite and mordenite.
It can consist of a mixture of zeolites, such as synthetic phojasite blended with ZSM type zeolites. Preferably, the zeolite is combined with the aluminum chlorohydrol and clay components 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 viscosity component is optional and may comprise from about 0 to about 80% by weight (dry basis) of the total catalyst composition. While kaolin is the preferred clay component, thermally modified kaolins such as metakaolin can also be included in the catalyst composition. During the mixing process, about 20-60% by weight as shown in the figure
of solids, with 5-25% by weight of the solids being Al ₂ O ₃
A slurry is obtained to feed the spray dryer consisting of aluminum chlorohydrol (dry basis), 0 to 60% by weight of zeolite, and a viscosity of 0 to 90% by weight. This figure describes how a slurry for catalyst production is spray-dried to obtain a fluidized cracking catalyst, but with larger particle sizes, i.e. about 1/2
Granular catalysts of the order of 2-2 mm can also be obtained from the compositions of the invention by shaping into beads or spheres, which can be used as hydroprocessing catalysts, such as hydrocracking, hydrodesulfurization and hydrodenitrification, and It is particularly useful in the preparation of demetallization 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 this particle is reduced to approximately 10~
Reduce to 30% by weight. Catalyst complex is 20~150μ
It has a particle size of about m. After spray drying, the catalyst composite is heated at a temperature of about 300 to 700°C for about 1/4 to 3 hours, preferably about 1/2 to 2
Calcinate for an hour. 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. Additionally, the calcination step activates the catalyst,
That is, residual alkali metal oxides present in the zeolite component are liberated and easily removed in the subsequent ion exchange and/or washing step. The ion exchange step that reduces the alkali metal oxide content of the catalyst composite to less than about 1% by weight uses water and/or
Alternatively, an aqueous ammonium salt solution such as an ammonium sulfate solution and/or a polyvalent metal solution such as a rare earth chloride solution is used. Typically these ion exchange solutions contain 1-10% by weight of dissolved salt. 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℃. 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 100-200°C, to reduce its moisture content, preferably to an amount of about 15% by weight or less. The cracking catalyst obtained by this method shows high activity in the catalytic cracking of hydrocarbons. Typically, the activity of these catalysts is found to be in the range of about 60-90% conversion by volume following deactivation and temperature elevation. 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. Although the main components of this catalyst are zeolite, aluminum chlorohydrol and possibly clay, the catalyst may also contain other components such as granular alumina and rare earth impregnated alumina to enhance SOx suppression performance. It is also understood that it is possible to add Furthermore, a small amount (1~
It is understood that platinum and palladium (100 ppm) can be included in the catalyst;
It is added to enhance CO oxidation properties. The wear characteristics of this catalyst were determined by the Davison Index (DI) and
It shall be expressed by Jersey Index (JI). 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 a 10 gallon stainless steel mixing kettle: an aluminum chlorohydrol solution having the formula _Al2Cl (OH) ₂ and containing 23.5% _by weight _Al2O3 . 3404g; Kaolin 7500g
(dry basis); calcined rare earth exchanged Y
Type zeolite (CREY) 1500g (dry base);
and enough water to obtain a slurry containing 25% solids by weight. NaY was ion-exchanged using mixed rare earth chloride aqueous solution at PH=5 followed by 538℃
(1000〓) for 3 hours to obtain a calcined rare earth-exchanged Y-type zeolite.
This one contains 15.02 wt% RE ₂ O ₃ and 3.8 wt%
Contains _Na2O . This slurry was thoroughly stirred, and the gas inlet temperature was 320℃ and the gas outlet temperature was 320℃.
Spray drying was performed using 150°C. The spray-dried catalyst particles containing about 25% by weight water and 0.5% by weight Na ₂ O were calcined (ie, heated) in a Matsufuru furnace at a temperature of 538° C. (1000°) for 1 hour. Following calcination, the catalyst was dried at a temperature of 150°C. The chemical analysis results of this catalyst and its cracking properties are shown in Table 1. Example 2 The manufacturing method of Example 1 was repeated. However, 3000 g of calcined catalyst particles at 3% by weight
ammonium sulfate solution containing ammonium sulfate
Ion exchange was performed by contacting with 9000ml. The analysis results and characteristics of this catalyst are shown in Table 1. Example 3 (Control) The manufacturing method of Example 1 was repeated. However, zeolite contains 12.5% by weight RE ₂ O ₃ and
ammonium exchanged with 0.5 wt% _Na2O ,
It consisted of calcined Y-type zeolite. This catalyst was not ion exchanged following calcination. The properties of this catalyst sample are shown in Table 1. Example 4 The manufacturing method of Example 1 was repeated. However, 13.4 wt% RE ₂ O ₃ and 3.2 wt%
An uncalcined rare earth exchanged Y-type zeolite containing Na ₂ O 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, calcination followed by calcined catalyst 3000
g was ion-exchanged with 9000 ml of ammonium sulfate solution containing 3% by weight ammonium sulfate. The properties of this catalyst are shown in Table 1. Example 6 The catalyst manufacturing method of Example 1 was repeated.
However, the processed catalyst contained 25% by weight of sodium ammonium zeolite Y containing 3.8% by weight Na ₂ O obtained by replacing the sodium Y zeolite with ammonium sulfate. 3000g of this catalyst was calcined followed by 9000g of water.
Washed to ml. The properties of this catalyst are shown in Table 1. Example 7 The catalyst manufacturing method of Example 6 was repeated.
However, following calcination, 3000 g of catalyst were ion-exchanged with 9000 ml of ammonium sulfate solution containing 3% by weight ammonium sulfate. The properties of these catalysts are shown in Table 1. Example 8 The catalyst manufacturing method of Example 1 was repeated.
However, the zeolite consisted of 25% by weight ammonium-exchanged, calcined, stabilized Y-type zeolite (Z14US zeolite) prepared according to the method of US Pat. No. 3,449,070, previously indicated. This Z14US zeolite contained approximately 3.8% by weight Na ₂ O when incorporated into the catalyst. Following calcination, 3000 g of catalyst was added to 9000 ml of ammonium sulfate solution.
Ion exchange was performed. The properties of this catalyst are shown in Table 1. Example 9 (Control) 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 Na ₂ O was prepared. Additionally, 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. The catalyst was not washed following calcination.
The properties of this catalyst are shown in Table 1. Example 10 The catalyst manufacturing method of Example 9 was repeated.
However, following calcination, 3000 g of catalyst was mixed with 9000 g of water.
Washed with ml. The properties of this catalyst are shown in Table 1. Example 11 The catalyst manufacturing method of Example 9 was repeated.
However, following calcination, 3000 g of catalyst were washed with 9000 ml of ammonium sulfate solution containing 3% by weight ammonium sulfate. The properties of this catalyst are shown in Tables 1 and 2. Example 12 (Control) A commercially available comparative catalyst containing 40% by weight Z14US zeolite, 23% by weight silica sol 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 the table. Example 13 (Control) A catalyst was prepared by the method shown in Example 9. However, this zeolite component contains about 0.2% by weight.
It consisted of 40% by weight of Z14US type zeolite ion-exchanged with ammonium sulfate to the extent of Na ₂ O. The catalyst was not ion exchanged or washed following calcination. The properties of this catalyst are shown in Table 1. Example 14 In this example, the properties of the catalysts prepared in Examples 1-5 were determined and are shown in the table below:

【table】

[Table] From the data shown in the table, the activity of catalysts containing uncalcined Y-type zeolite (Examples 4 and 5) and those containing precalcined zeolite (Examples 1 and 2)
and 3) is noteworthy. Example 15 In this example the properties of the catalysts prepared in Examples 6, 7 and 8 are determined and compared in the table below.

[Table] From the data shown in the table, the octane selectivity for the catalysts prepared by the method of the present invention (Examples 6 and 7) is compared to that of the catalyst containing precalcined Z14US Y-type zeolite (Example 8). It is noteworthy that they are almost comparable. Example 16 In this example the catalysts obtained in Examples 9, 10 and 11 are compared and are shown in the table below.

[Table] Chloroactivity From the above data, it was found that sodium could be substantially removed by carrying out the present invention even if only water (Example 10) was used instead of the ammonium sulfate solution (Example 11). Ru. Example 17 The properties of the catalysts shown in Examples 11, 12 and 13 are compared and summarized in the table below.

[Table] According to the above data, by using the method shown in the present invention (Examples 11 and 13), a catalyst with higher activity and better octane selectivity than the conventional catalyst (Example 12) was produced. I know what I can get.

[Brief explanation of the drawing]

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

Claims (1)

[Claims] 1. (a) preparing an aqueous mixture of an alkali metal-containing zeolite and aluminum chlorohydrol; (b) forming the mixture into a granular zeolite containing more than about 1% by weight of an alkali metal oxide; /aluminum chlorohydrol composite; (c) calcining the composite at a temperature greater than about 300°C. 2. The method of claim 1, wherein the calcined composite is ion-exchanged and washed to produce catalyst particles having an alkali metal oxide content of less than about 1.0% by weight. 3. The method of claim 2, wherein the ion exchange step includes contacting the calcined particles with a solution containing ammonium ions and/or rare earth ions. 4 The aluminum chlorohydrol has the formula Al _2+n
4. A process according to any of claims 1 to ₃ , having (OH) _3nCl6 , with m having a value of about 4 to 12. 5. The method according to any one of claims 1 to 4, wherein the zeolite is a Y-type zeolite. 6. A method according to any of claims 1 to 5, wherein the aqueous mixture prepared in step (a) comprises clay. 7. The method according to any one of claims 1 to 6, wherein the mixture is shaped by spray drying in step (b). 8. The method of claim 1, wherein the zeolite provides a catalyst comprising from about 3 to 6 weight percent alkali metal oxides and less than about 0.6 weight percent alkali metal oxides.