Layer-column clay catalyst for heavy-oil catalytic thermal cracking and its preparation

Heavy oil catalytic thermal cracking layered clay catalyst and its preparation

The invention relates to a heavy oil catalytic thermal cracking catalyst and a preparation method thereof. Specifically, the present invention relates to a pillared clay cracking catalyst used for cracking heavy hydrocarbons in a catalytic thermal cracking process to produce ethylene, propylene and butene and its preparation method.

Low-carbon olefins, mainly ethylene, are important chemical raw materials, and their demand is increasing day by day. In the prior art, ethylene mostly comes from the thermal cracking process of light oil; propylene and butene mostly come from the catalytic cracking process using acidic catalysts.

Catalytic thermal cracking of heavy oil refers to the introduction of catalysts into the thermal cracking process to crack heavy petroleum hydrocarbon feedstocks to obtain the highest possible yields of ethylene, propylene and butene. However, the catalyst used in this process must first have the basic properties of conventional cracking catalysts, such as good attrition strength and qualified heap ratio, it must also have the following characteristics different from conventional cracking catalysts: 1. High hydrothermal stability Generally, the conventional catalytic cracking reaction temperature is 460~520°C, and the thermal cracking reaction temperature is 550~800°C. In the catalytic thermal cracking reaction, although the reaction temperature can be appropriately lowered due to the use of a catalyst, it is still hot Within the cracking reaction temperature range, the catalyst used for this reaction must have high hydrothermal stability.

2. High heavy oil conversion activity. Because the catalytic thermal cracking process is a method of producing ethylene, propylene and butene from heavy petroleum hydrocarbons, the catalyst used in this process must be able to effectively crack heavy oil, that is, the catalyst must have a high The conversion activity of heavy oil.

3. Excellent selectivity as a catalytic thermal cracking catalyst, it must not only have a high yield of ethylene, propylene and butene, but also must have a low dry gas yield and a slightly higher coke yield than conventional cracking catalysts in order to maintain Heat balance of high temperature reaction and regeneration process.

In the prior art, the catalysts containing layered pillared clay are all solid acid catalysts used in catalytic cracking processes. For example: CN 1107080A reported a layered pillared clay catalyst, which is used in ordinary catalytic cracking processes to produce more isobutylene and isoamylene. Although the pillared clay component can increase the activity, but at the same time it will have an adverse effect on the strength of the catalyst, so the content of pillared clay in the catalyst in this patent is only below 50% by weight. Moreover, the patent does not provide qualified strength data about the catalyst. Another example: the applicant proposed a modified pillared clay catalyst for producing more olefins in the application of CN1160743A, which is also a pillared clay catalyst that produces more isobutylene and isopentene in the conventional catalytic cracking process. The pillared clay used therein is modified with polyvinyl alcohol. The application also failed to provide data on intensity. The two above-mentioned pillared clay catalysts are not catalytic thermal cracking catalysts, and they are not suitable for direct use in industrial catalytic thermal cracking processes to produce ethylene, propylene and butene.

The applicant disclosed a method for catalytic thermal cracking of petroleum hydrocarbons in ZL CN 92109775.1. In this method, the pillared clay catalyst used in the conventional catalytic cracking process, the catalyst with the brand name of CRP and the mixture of the two catalysts are used. The pillared clay catalyst used is a pillared rectorite catalyst containing 5% by weight of USY prepared according to the method disclosed in ZL CN87104718. The CRP catalyst used is a high-silica zeolite (CN 1058382A) prepared with a five-membered ring containing rare earth for the production of low-carbon olefins. Although the columnar clay catalyst in this patent has an ethylene yield of more than 20% by weight at an average reaction temperature of 700°C, and a sum of triene (C2=~4) yields of up to 50% by weight, it is not 790°C. Or the result after 17 hours of deactivation treatment with 100% steam at 800°C is actually only the result of deactivation treatment with 100% steam at 760°C for 6 hours, which cannot meet the requirements of catalytic thermal cracking process for catalyst stability.

The purpose of the present invention is to provide a pillared clay cracking catalyst for catalytic thermal cracking of heavy oil to produce more ethylene, propylene and butene on the basis of the above-mentioned prior art. The catalyst has qualified abrasion resistance and heap ratio, high hydrothermal stability, high heavy oil conversion activity and olefin selectivity, and suitable dry gas and coke yields.

Another object of the present invention is to provide an industrially implementable preparation method of the above-mentioned catalyst.

A further object of the present invention is to provide the use of the above-mentioned catalyst.

The composition of the catalyst provided by the present invention is: 30 to 75% by weight of pillared clay, 10 to 40% by weight of inorganic oxide binder, 0 to 30% by weight of five-membered ring structure high silica zeolite, 0 to 10% by weight The modified components and 0-50% by weight of kaolin clay.

The layered pillared clay is an important active component of the catalyst for the conversion of heavy oil. It has high hydrothermal stability. It is layered with polyaluminum hydroxychloride or aluminum sol with a high degree of alkalinity (OH/Al about 2.5). Aluminum cross-linked layered clay of the precursor of the intermediate support. The layered clay refers to various natural or artificially swelling regular interlayer mineral clays or single-layer mineral clays including rectorite and smectite, preferably rectorite or smectite, It is best to be rectorite. The structural features of rectorite have been described in detail in ZL CN 87104718, and will not be repeated here.

The said inorganic oxide binder is one or more materials selected from sol or gel containing aluminum, silicon, zirconium or modified by polyethylene glycol, preferably selected Inorganic oxide formed from aluminum sol or pseudo-thin aluminum hydroxide sol or gel or their mixture or the above sol or gel modified by polyethylene glycol after drying and calcining.

The five-membered ring structure high silica zeolite is an auxiliary active component used to increase the production of olefins. It can be a ZSM-5 zeolite, or it can be a pentasil structure with ZSM-5 and a trade name of ZRP series. Among hydrothermally stable zeolites, ZRP-I zeolite or zeolite modified with phosphorus and magnesium or calcium or aluminum is preferred.

The precursor of the modified component is selected from one or more substances selected from the group consisting of magnesium, aluminum, phosphorus or tin-containing compounds or polyethylene glycol. Among them, the use of magnesium, aluminum, phosphorus compounds and polyethylene glycol can improve the selectivity of the catalyst or increase the strength of the catalyst, and the tin-containing compounds can improve the hydrothermal stability of the catalyst.

Among them, the kaolin group clay support component is preferably hallucinite.

The above-mentioned catalyst product provided by the present invention is made by mixing layered clay, binder, ZSM-5 or ZRP series zeolite or their modified products, and kaolin clay according to a predetermined amount of product composition, mixing, beating, and spraying to form microspheres. Then it is made by cross-linking aging reaction and adding modified components. The specific operation method is as follows: 1. Preparation of microspheres (1) Change the natural calcium-type layered clay to sodium or rare earth type according to the conventional ion exchange method; (2) Change the modified layered clay and binder precursor, zeolite, and kaolin The components of the family clay are mixed according to a predetermined ratio and beaten with an appropriate amount of water to prepare a slurry with a solid content of 20-40% by weight, which is spray-dried into microspheres according to conventional methods.

2. Cross-linking aging reaction (1) Dilute commercially available aluminum sol or polyaluminum hydroxychloride formulated according to the prior art (such as USP 4,176,090 or USP 4,248,739) to 10-100mmol Al/liter, and use NH4OH Or adjust and maintain the pH of 5-6 with NaOH, maintain at 65-75°C for 2-12 hours, and place at room temperature for 2-12 hours to obtain an aluminum crosslinking agent with an alkalinity of OH/Al of about 2.5; (2) per gram Add the above-mentioned shaped microspheres to the cross-linking agent with a mixing ratio of 2.0-10.0mmol Al cross-linking agent for clay, adjust and maintain its pH 5-6 with NH4OH, and carry out the cross-linking reaction at 65-75°C for 2 to 3 hours , Then filter, wash, dry, and calcinate at 650°C for 1 to 3 hours.

3. Adding the modified component (1) The modified component polyethylene glycol can be added during the beating process before spray molding, or during the crosslinking aging reaction after spray molding.

(2) The modified component containing magnesium, aluminum, phosphorus or tin compounds can be impregnated onto the ZRP or ZSM-5 zeolite, or directly impregnated onto the crosslinked and calcined pillared clay catalyst. The concentration of the immersion liquid is preferably 0.1-5 g/liter.

The raw material layered clay used in the above preparation method refers to various natural or artificially swellable regular interlayer mineral clays or single-layer mineral clays including rectorite and smectite. Rectorite or smectite, preferably rectorite. The structural characteristics of rectorite can be found in ZLCN87104718.

The precursor of the binder used is selected from one or more of sols or gels containing aluminum, silicon, and zirconium or modified by polyethylene glycol, preferably selected from aluminum sol Or pseudo-thin aluminum hydroxide sol or gel or their mixture or the above-mentioned sol or gel modified by polyethylene glycol.

The used modifying component containing magnesium, aluminum, and phosphorus compounds is preferably selected from MgCl2, Mg(AC)2, Mg(OH)2, aluminum sol, and phosphoric acid. The tin-containing compound used is preferably an aqueous solution of SnCl2 in hydrochloric acid.

Compared with the prior art, the present invention has the following advantages: 1. The catalyst product provided by the invention has the best composition and performance. Among them, the pillared clay component with high alkalinity (OH/Al about 2.5) has high hydrothermal stability and can effectively crack heavy oil, and its hydrogen transfer activity is low, and it is easy to retain olefins in the product. Therefore, the catalyst Compared with the currently widely used catalyst with Y-type zeolite as the active component, it can better meet the requirements of the catalytic thermal cracking process. The use of ZSM-5 or ZRP series zeolite in the catalyst of the present invention can make it have better olefin selectivity, especially when combined with modified components, it can further improve olefin selectivity and hydrothermal stability. Therefore, the catalyst of the present invention can still maintain a high olefin yield under severe aging and deactivation conditions. The binder modified by polyethylene glycol or the catalyst modified by phosphorous compound used in the catalyst of the present invention can easily obtain good abrasion resistance. Therefore, when the content of pillared clay and zeolite is high, the catalyst of the present invention There is still acceptable strength. The reasonable formulation of the catalyst of the present invention brings the excellent performance of the product itself. After the catalyst is aged and deactivated at 790°C and 100% steam for 14 hours, the average reaction temperature is 700°C, the catalyst-oil ratio is 10, and the weight hourly space velocity is 10 hours. -1. Under the evaluation conditions of 0.8 water injection, the ethylene yield reaches more than 21% by weight, and the sum of C2=~C4=triene yield reaches more than 53% by weight. Although the ethylene yield in the prior art can reach more than 21% by weight, the sum of the triene yields is only 50% by weight, and more importantly, the catalyst in the prior art has only undergone 760 and 100% steam aging 6 After hours of deactivation treatment, it is obvious that the activity stability and olefin selectivity of the catalyst provided by the present invention are better than similar products in the prior art.

2. The catalyst product provided by the invention has a wide range of uses. The catalyst can be used as a conventional hydrocarbon catalytic cracking catalyst, and it can also be impregnated with various other elements to meet the needs of different products. It can also be mixed with other catalysts for specific purposes. Of course, it can also be used as an adsorbent or carrier. However, it is particularly suitable for cracking heavy feedstock oil in the catalytic thermal cracking process to produce more ethylene, propylene and butene.

3. The preparation method provided by the invention is easy to implement. In the post-crosslinking process of the prior art (such as ZL CN87105686), the strength of the catalyst product is easily affected by the reversible dissolution of binders such as aluminum sol, and the strength of the sample after crosslinking is often lower than the strength of the sample before crosslinking. The post-crosslinking preparation process adopted in the method of the present invention uses special technical means of adding polyethylene glycol or impregnating zeolite or catalyst with phosphorus-containing compounds to change the properties of binders such as aluminum sol, so that the strength of the catalyst product is guaranteed and It is improved, easy to operate, and easy to implement in industry.

4. The method for improving the strength by adding polyethylene glycol or phosphorus-containing compounds provided by the present invention is suitable for preparing other aluminum-containing sol or aluminum gel-containing microsphere catalysts.

The following examples will further illustrate the present invention.

Example 1 This example shows that the catalyst of the present invention prepared according to the method of the present invention has better performance than the prior art catalyst in the catalytic thermal cracking process.

According to the weight ratio of calcium-type rectorite: RECl3: decationized water=1:0.05:10, ion exchange is performed on natural calcium-type rectorite at room temperature for 1 hour to convert the calcium-type rectorite into rare earth type.

ZRP-I zeolite (produced by Shandong Zhoucun Catalyst Factory) was impregnated with an aqueous solution containing 0.04% of magnesium and 0.21% of phosphorus for 15 minutes, filtered and dried to obtain phosphorus- and magnesium-modified ZRP-I zeolite.

Take 7.75Kg of rare earth rectorite with a solid content of 64.5% by weight, 7.4Kg of pseudo-thin aluminum hydroxide with a solid content of 33.7% by weight, and 4.1Kg of the above-mentioned modified ZRP-I zeolite slurry with a solid content of 36% by weight , 0.62 Kg of halloysite with a solid content of 81% by weight, 0.69Kg of commercially available hydrochloric acid, and 18Kg of water are mixed, and beating and spray-dried according to the conventional method of preparing microsphere catalysts to prepare columnar rectorite containing 50% by weight. Microspheres of weight% ZRP-I zeolite, 30 weight% pseudo-thin water alumina binder and 5 weight% kaolin.

Dilute the aluminum sol (produced by Shandong Zhoucun Catalyst Factory) with an Al2O3 content of 21.8% by weight with water to 98.6mmol Al/L, adjust the pH to 5-6 with 3% NH4OH, maintain at 70°C for 2.5 hours, and cool to room temperature. The aluminum cross-linking agent with high alkalinity can be obtained overnight.

Add 1.1Kg of the above microspheres to 19 liters of the above aluminum crosslinking agent, adjust and maintain the pH of the slurry with NH4OH from 5 to 6, conduct crosslinking aging reaction at 70°C for 2.5 hours, and then filter, wash, and Dry and calcine at 650°C for 2 hours. Thus, a columnar rectorite catalyst containing 50% by weight of pillared rectorite, 15% by weight of ZRP-I zeolite, 30% by weight of Al2O3 binder from pseudo-thin aluminum hydroxide sol and 5% by weight of kaolin was prepared. .

The chemical composition of the catalyst analyzed by standard chemical methods is listed in Table 1. The BET specific surface and pore volume measured by low-temperature nitrogen adsorption, and the strength (wear index) measured by the fluidized abrasion method are listed in Table 2. The results of catalytic thermal cracking performance evaluated with a small fixed fluidized bed are shown in Table 3. The samples were deactivated at 790°C and 100% water vapor for 14 hours before evaluation. The evaluation conditions are as follows: Daqing wax oil in the distillation range of 350 to 500°C is used as the raw material, the average reaction temperature is 700°C, the catalyst-to-oil ratio is 10, the weight hourly space velocity is 10 o'clock -1, and the water injection volume is 80% by weight of the raw oil. For comparison, the data obtained by evaluating the catalyst A used in the prior art ZL CN9210775.1 under the same conditions are also listed in Table 3.

It can be seen from Table 2 and Table 3 that the catalyst of the present invention has qualified strength and heap ratio; after aging at 790°C and 100% steam for 14 hours, the ethylene yield can reach more than 21% by weight. The sum of the triene yields can reach 54% by weight. However, the sum of triene yields of the prior art catalyst after aging at 760°C and 100% steam for 6 hours is significantly lower than that of the catalyst of the present invention. Obviously, the catalyst provided by the present invention has better activity, stability and low-carbon olefin selectivity than the prior art.

Table 1

Table 2

Table 3 Average reaction temperature: 700°C

Example 2 This example shows that the catalyst containing phosphorus and magnesium modified components prepared according to the method of the present invention has high strength, hydrothermal stability and olefin selectivity.

According to the method of Example 1, microspheres containing 50% by weight layered rectorite, 15% by weight ZRP-I zeolite, 30% by weight Al2O3 binder and 5% by weight kaolin were prepared.

Add 192 ml of commercially available phosphoric acid (H3PO485% by weight) and 40 g of magnesium hydroxide into 40 liters of water, and stir until the magnesium hydroxide is completely dissolved.

1.1 Kg of the above-mentioned microspheres were added to the above-mentioned phosphorus and magnesium-containing solution, stirred and immersed for 15 minutes at room temperature, filtered, and dried at 120°C to obtain the phosphorus and magnesium modified catalyst sample provided by the present invention.

The strength and bulk ratio data of this sample are listed in Table 4. The results of catalytic performance evaluated with a small fixed fluidized bed are shown in Table 5. Before evaluation, the sample was deactivated with 100% water vapor at 800°C for 17 hours. Except that the average reaction temperature is 680°C, the rest of the evaluation conditions are the same as in Example 1. For comparison, the data obtained by evaluating the catalyst A used in the prior art ZLCN92109775.1 under the same conditions are also listed in Table 5.

It can be seen from Table 4 and Table 5 that the strength of the catalyst of the present invention is significantly improved; after aging at 800°C and 100% steam for 17 hours, when the average reaction temperature drops to 680°C, the ethylene yield can reach 19.5 wt. %, the sum of the triene yields can reach 52.45% by weight, while the prior art catalyst has only been aged at 760°C and 100% steam for 6 hours, and the sum of the ethylene yield and the triene yield is significantly lower than that of the catalyst of the present invention .

Table 4

Table 5 Average reaction temperature: 680 °C

Example 3 This example shows that the catalyst containing tin modified components prepared according to the method of the present invention has high hydrothermal stability and low-carbon olefin selectivity.

According to the method of Example 1, a microsphere catalyst A containing 50% by weight of layered rectorite, 15% by weight of ZRP-I zeolite, 30% by weight of pseudo-thin water Al2O3 binder and 5% by weight of kaolin was prepared.

Dilute 550 ml of SnCl2 hydrochloric acid aqueous solution with a tin content of 2.9 g/L to 5 liters with water.

Add 550 grams of microspheres A to the above tin solution after calcination at 650°C for 2 hours, stir at room temperature for 15 minutes, filter and wash to remove free SnCl2·HCl, and then slurry the filter cake with 18 liters of water and use 3% Adjust the pH to 5-6 with NH4OH, maintain at 70°C for 2.5 hours, filter, and dry to obtain the tin-modified catalyst provided by the present invention, which is recorded as sample B.

The catalytic performance results of the unmodified and tin-modified samples evaluated with a small fixed fluidized bed are listed in Table 6. The processing conditions of the sample before evaluation and the conditions used in the evaluation reaction are the same as in Example 2.

It can be seen from Table 6 that the columnar rectorite catalyst containing tin modified components provided by the present invention has a conversion rate of 88.36% by weight and a cracked gas yield at 800°C and 100% steam deactivation for 17 hours. It is 65.14% by weight, while the corresponding values of the samples without tin modification are only 85.59% by weight and 63.76% by weight, respectively. It can be seen that tin modification can indeed achieve the effect of improving hydrothermal stability.

Table 6 Average reaction temperature: 680°C

Example 4 This example illustrates the improved strength, activity and olefin selectivity of the catalyst containing phosphorus and aluminum modified components prepared according to the method of the present invention.

According to the method of Example 1, a microsphere A containing 50% by weight layered rectorite, 15% by weight ZRP-I zeolite, 30% by weight pseudo-thin water Al2O3 binder and 5% by weight kaolin was prepared.

Mix 8 liters of decationized water, 2 liters of aluminum sol with an Al2O3 content of 21.8% by weight, and 100 ml of commercially available phosphoric acid.

The microspheres A calcined at 650°C for 2 hours were added to the aluminum phosphate sol solution and stirred for 15 minutes, filtered, and dried to obtain the phosphorus and aluminum modified catalyst provided by the present invention, which was recorded as sample C.

Table 7 lists the abrasion resistance of the unmodified and modified samples, and the light oil micro-reactivity and heavy oil micro-reactivity of the samples after being treated with 800°C and 100% steam for 4 hours. The evaluation conditions of light oil micro-reactivity are: 221~349°C Dagang light diesel as raw material, reaction temperature 500°C, fuel-to-oil ratio 3.2, weight hourly space velocity 16:00-1. The evaluation conditions for the micro-reactivity of heavy oil are: Shengli vacuum wax oil at 239~537°C is the raw material oil, the reaction temperature is 520°C, the catalyst-oil ratio is 3, and the weight hourly space velocity is 16:00-1.

The catalytic properties of the modified and unmodified samples evaluated with a small fixed fluidized bed are listed in Table 8. The processing conditions of the sample before evaluation and the conditions used in the evaluation reaction are the same as in Example 2.

It can be seen from Table 7 and Table 8 that the layered rectorite catalyst containing phosphorus and aluminum modified components provided by the present invention has much better abrasion resistance, catalytic cracking activity and low-carbon olefins than the unmodified one. Selective.

Table 7

Table 8 Average reaction temperature: 680°C

Example 5 This example shows that adding polyethylene glycol according to the method of the present invention can effectively improve the strength of the catalyst while ensuring that the activity and stability are not affected.

According to the method of Example 1, microspheres containing 50% by weight rectorite, 15% by weight ZRP-I zeolite, 20% by weight pseudo-thin water Al2O3, 10% by weight aluminum sol Al2O3, and 5% by weight kaolin were prepared.

The cross-linking agent was prepared according to the method of Example 1, except that the commercially available polyethylene glycol was added to the aluminum cross-linking agent at an amount of 0.005 g of polyethylene glycol per gram of rectorite, and then the method of Example 1 was used. Cross-linking reaction, filtration, washing, drying, and calcination at 650° C. for 2 hours are performed to prepare the polyethylene glycol-modified catalyst D provided by the present invention.

Polyethylene glycol was not added to the aluminum crosslinking agent, and the crosslinking reaction, filtration, washing, drying, and calcination were carried out in the same manner as described above to prepare a catalyst E that was not modified by polyethylene glycol for comparison.

Table 9 lists the abrasion resistance of the modified and unmodified samples and the activity data obtained by the heavy oil micro-reverse evaluation according to Example 4. The aging treatment of the samples before the evaluation is the same as that of Example 4.

It can be seen from Table 9 that the strength of the sample modified with polyethylene glycol is significantly improved under the premise that the catalytic activity is basically not affected.

Table 9

Example 6 This example shows that using ZSM-5 zeolite as one of the components of the catalyst of the present invention can also obtain higher triene yields.

According to the method of Example 1, but changing the ZRP-I zeolite to HZSM-5 zeolite (produced by Shandong Zhoucun Catalyst Factory) without adding kaolin component, the preparation contains 50% by weight rectorite and 20% by weight HZSM- 5 zeolite, 30 wt% pseudo-thin water Al2O3 binder microspheres.

The cross-linking reaction was carried out according to the method and operating conditions of Example 1, followed by filtration and drying to obtain the catalyst provided by the present invention.

The catalytic performance results evaluated by the small fixed fluidized bed are listed in Table 10. Before evaluation, the samples were treated with 790°C, 100% steam for 14 hours. The evaluation conditions were: Daqing wax oil as raw material, average reaction temperature of 680°C, solvent oil The ratio is 6, the weight hourly space velocity is 10 o'clock -1, and the water injection is 80% by weight of the raw oil.

For comparison, the industrially used ZSM-5-containing pro-olefin balancer (trade name: CHP-1) was evaluated under the same conditions and the results obtained are listed in Table 10.

It can be seen from Table 10 that even if the catalyst provided by the present invention is aged under more severe conditions than the balancer, it still has a higher triene yield than the prior art.

Table 10 Average reaction temperature: 700°C

Example 7 This example shows that the catalyst provided by the present invention can still obtain high ethylene yield even when all auxiliary components are zero.

According to the method of Example 1, 75 parts of layered clay, 20 parts of Al2O3 from commercially available aluminum sol and 5 parts of Al2O3 from pseudo-thin aluminum hydroxide were mixed and beaten, sprayed into microspheres, and dried at 300°C for 0.5 hours.

According to the method of Example 1, the cross-linking aging reaction was carried out, filtered, washed, dried, and calcined at 650°C for 2 hours to obtain the multi-product olefin catalyst provided by the present invention containing 75% by weight of pillared clay and 25% by weight of Al2O3 binder.

The catalytic thermal cracking performance of the sample was evaluated according to the conditions of Example 4. The results are shown in Table 11. The samples were treated with 100% steam at 790°C for 14 hours before evaluation.

It can be seen from Table 11 that although the catalyst provided by the present invention has been aged at 790°C and 100% steam for 14 hours, which is more severe than the equilibrium condition of the CHP-1 balance agent in Example 6, its ethylene yield is still higher than that of CHP. -1, the former is 18.48% by weight, while the latter is 17.25% by weight.

Table 11

Example 8 This example shows that the catalyst provided by the present invention can not only be used as a catalytic thermal cracking catalyst, but also can be used for catalytic cracking to produce more isoolefins.

The columnar clay catalyst prepared in Example 1 containing 50% by weight of pillared clay, 15% by weight of ZRP-I zeolite, 30% by weight of Al2O3 binder and 5% by weight of kaolin was aged for 4 hours at 800°C and 100% steam. Then the conventional catalytic cracking performance was evaluated on the heavy oil micro-reactor. The evaluation conditions are as follows: Shengli vacuum wax oil at 239~537°C as raw material, reaction temperature at 520°C, catalyst-oil ratio 3.2, weight hourly space velocity 16:00-1. The evaluation results are shown in Table 12. For comparison, Table 12 also lists the evaluation results of the industrial catalyst for producing more olefins (trade name: CRP-1) under the same conditions.

The results in Table 12 show that the catalytic thermal cracking catalyst of Example 1 also has better catalytic performance in the catalytic cracking process, that is to say, the catalyst provided by the present invention can be used not only as a catalytic thermal cracking catalyst, but also as a catalytic cracking catalyst.

Table 12