Catalytic cracking catalyst, method for preparing the same, and use

Abstract

A catalytic cracking catalyst, a method for preparing the same, and its use are disclosed. The catalytic cracking catalyst contains a catalytic cracking active component, the catalytic cracking active component comprising a rare earth modified molecular sieve, a phosphorus oxide, and a magnesium oxide, wherein SO4 in the rare earth modified molecular sieve 2- The content of is 1 wt% or less, the crystallinity of the rare earth-modified molecular sieve is 50-80%, and the rare earth content in the rare earth-modified molecular sieve is 5-20 wt% in terms of RE2O3. The catalytic cracking catalyst of the present invention has excellent activity stability, a high heavy oil conversion rate, and a high diesel yield, as it uses a rare earth-modified molecular sieve with low sulfate ion content, high crystallinity, strong acidity, and excellent stability in combination with a phosphorus source and a magnesium source. It is particularly suitable for heavy oil catalytic cracking and exhibits high catalytic cracking activity and a high diesel yield in the heavy oil catalytic cracking process.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the benefits of Chinese Patent Application No. 202310812381.2, filed on 4 July 2023, the contents of which are incorporated herein by reference.

[0002] The present invention relates to the field of catalyst preparation, and more specifically to catalytic cracking catalysts and methods for preparing them, as well as the use of said catalytic cracking catalysts in heavy oil catalytic cracking. [Background technology]

[0003] Catalytic cracking units remain one of the most important pieces of equipment in China's petroleum refining process. Approximately 70% of gasoline, 40% of diesel, and 35% of propylene are produced in catalytic cracking units. The most important use of diesel is in diesel engines for automobiles and ships. Compared to gasoline engines, diesel engines are more thermally efficient, have higher output, lower fuel consumption, and are relatively economical, which is why diesel engines are used in some small cars and high-performance vehicles as well.

[0004] From 2010 to 2020, China's diesel production generally showed an upward trend followed by a decline. In 2017, diesel production increased by 16.417 million tons compared to 2011, reaching a peak of 183.18 million tons. However, China's diesel consumption has seasonal characteristics. The peak season for diesel is every spring and autumn, especially from September to November. This coincides with the busy agricultural season of autumn harvest, planting, and management; the end of coastal fishing bans, increasing demand for diesel fuel for fishing; the end of the rainy season in the south; the reduction of the rainy season in the north; and the entry of active production cycles for infrastructure, industrial and mining production, and logistics and transportation. During this period, logistics performance indices and China's water and land transport cargo handling volumes remain at relatively high levels throughout the year.

[0005] From another perspective, the price difference between diesel and crude oil is generally larger from September to November each year than in other months, which is an important indicator of the peak season for diesel consumption. In recent years, in particular, gasoline sales have clearly stagnated due to the impact of epidemics and the Russo-Ukrainian War, while diesel demand has continued to increase, and the diesel-to-gasoline consumption ratio has risen significantly. In addition, in countries with underdeveloped infrastructure, such as those in Africa, power generation facilities are very limited and they rely entirely on diesel power generation, so diesel demand is generally high.

[0006] As described above, while diesel supply generally exceeds demand, the diesel market still exhibits specific shortages, and diesel shortages can occur depending on the region and season. Therefore, improving the catalytic cracking yield of diesel, based on the efficient conversion of heavy fuel oil, remains an important research issue for petroleum refiners.

[0007] The basic design principle for catalytic cracking catalysts to produce more diesel is that the catalyst should have appropriate acid strength and acid density distribution, strong heavy oil cracking ability, and suppress further cracking of the diesel fraction by strong acids while converting heavy oil to diesel. US4843052, US4940531, US5248642, etc., mainly use modified kaolin to increase the yield of catalytic cracked diesel. CN1217231 discloses phosphorus-modified zeolite, a method that can improve diesel yield.

[0008] CN1307087 and CN1069513 disclose a technique for improving diesel yield by incorporating Y-type zeolite and type-selective zeolite as catalytic active ingredients. CN1861754A discloses a method for improving diesel yield by using alkali-treated kaolin microspheres. CN1683474A discloses a method for improving diesel yield by using in-situ crystallized kaolin microspheres modified with magnesium.

[0009] All existing patented technologies can improve diesel yield, and the mainstream technology still involves adjusting the acidity of the molecular sieve with elements such as P and Mg to improve diesel yield. However, Y-type molecular sieves modified with the active component RE have insufficient activity stability, resulting in insufficient fuel oil conversion capacity of the catalyst and an increase in slurry oil during the process of adjusting the acidity of the molecular sieve with elements such as P and Mg. Therefore, technological innovation is needed to improve the activity stability of the Y-type molecular sieve, thereby improving the activity, stability, fuel oil conversion capacity, and diesel yield of the catalytic cracking catalyst. [Overview of the Initiative] [Problems that the invention aims to solve]

[0010] The object of the present invention is to overcome the shortcomings of the prior art and provide a catalytic cracking catalyst. This catalyst contains a rare-earth modified molecular sieve with a low sulfate ion content, high crystallinity, and excellent stability. By adjusting the acidity of the molecular sieve with elements such as P and Mg, it is possible to improve the diesel yield while maintaining a high heavy oil conversion capacity. When used in the catalytic cracking reaction of heavy oil, this catalyst has excellent activity stability, a high heavy oil conversion rate, and a high diesel yield. [Means for solving the problem]

[0011] To achieve the above objective, a first aspect of the present invention provides a catalytic cracking catalyst, the catalytic cracking catalyst containing a catalytic cracking active component, the catalytic cracking active component comprising a rare earth modified molecular sieve, a phosphorus oxide, and a magnesium oxide, wherein SO4 in the rare earth modified molecular sieve 2- The content is 1 wt% or less, the crystallinity of the rare earth-modified molecular sieve is 50-80%, and the rare earth content in the rare earth-modified molecular sieve is 5-20 wt% in terms of RE2O3.

[0012] A second aspect of the present invention provides a method for preparing a catalytic cracking catalyst as described in the first aspect, wherein the preparation method is The step of mixing a catalytic cracking active component with a macroporous material source and a clay source in a solution state for contact to obtain a catalyst precursor, optionally shaping it, and then optionally drying and calcining is included. Preferably, the preparation method is as follows. Step (1) of mixing the rare earth modified molecular sieve, a phosphorus source, and water to form a slurry, then adding a macroporous material source, a binder source, and a clay source, mixing, homogenizing, drying, and calcining to obtain catalyst solid particles. Step (2) of mixing the catalyst solid particles obtained in step (1), water, a magnesium source, and an optional ammonium source, then filtering, washing with water, and drying to obtain a catalytic cracking catalyst.

[0013] The third aspect of the present invention provides the use of the catalytic cracking catalyst described in the first aspect in the heavy oil catalytic cracking.

Advantages of the Invention

[0014] Compared with the prior art, the present invention has the following beneficial effects.

[0015] (1) The catalytic cracking catalyst according to the present invention uses a rare earth modified molecular sieve with low sulfate ions, high crystallinity, strong acidity, and excellent stability in combination with phosphoric oxide and magnesium oxide, so it has the characteristics of excellent activity stability, high heavy oil conversion rate, and high diesel yield.

[0016] (2) The rare earth modified molecular sieve according to the present invention preferably has a precipitating agent (i.e., a first precipitating agent and a second precipitating agent) added to the Na-type molecular sieve after rare earth ion exchange and before ammonium sulfate exchange to generate a precipitate precursor of rare earth ions and rare earth oxides. This avoids the formation of precipitates between free rare earth ions and sulfate ions in the exchange system solution, on the molecular sieve surface, or in the supercage during the subsequent ammonium sulfate exchange and sodium reduction steps, thereby achieving the objective of reducing sulfate ions. As a result, the utilization rate of rare earths can be improved while improving the crystallinity and stability of the molecular sieve. Therefore, the molecular sieve has the characteristics of having few sulfate ions, high crystallinity, strong acidity, and excellent stability. In subsequent steps in which the acidity of the molecular sieve is adjusted with elements such as P and Mg, the diesel yield can be improved while maintaining a high heavy oil conversion capacity.

[0017] (3) The method for preparing a catalytic cracking catalyst according to the present invention is characterized by its ease of operation, simplified process flow, and ease of industrial production. By appropriately adjusting the acidity of the catalyst using P and Mg, the ratio of each reaction in the cracking process is controlled, improving the heavy oil conversion capacity and diesel yield of the catalyst.

[0018] (4) The catalytic cracking catalyst according to the present invention is particularly suitable for the catalytic cracking of heavy oil, and in the catalytic cracking process of heavy oil, it not only exhibits high catalytic cracking activity but also yields a high diesel yield. [Modes for carrying out the invention]

[0019] The endpoints and any values ​​of the ranges disclosed herein are not limited to such precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to them. In the case of numerical ranges, one or more new numerical ranges can be obtained by combining the endpoint values ​​of each range, the endpoint values ​​of each range and individual dot values, and individual dot values, and these numerical ranges are deemed to be specifically disclosed herein.

[0020] A first aspect of the present invention provides a catalytic cracking catalyst, the catalytic cracking catalyst containing a catalytic cracking active component, the catalytic cracking active component containing a rare earth modified molecular sieve, a phosphorus oxide, and a magnesium oxide, the rare earth modified molecular sieve containing SO4 2- The content of is 1 wt% or less, the crystallinity of the rare earth-modified molecular sieve is 50-80%, and the content of rare earths in the rare earth-modified molecular sieve is 5-20 wt% in terms of RE2O3.

[0021] In this invention, the catalytic cracking catalyst according to the present invention is characterized by excellent activity stability, high heavy oil conversion rate, and high diesel yield, achieved by using a rare earth-modified molecular sieve with low sulfate ion content, high crystallinity, strong acidity, and excellent stability in combination with phosphorus oxide and magnesium oxide.

[0022] In this invention, unless otherwise specified, the crystallinity parameter is measured by X-ray diffraction.

[0023] According to one preferred embodiment of the present invention, SO4 in the rare earth modified molecular sieve 2- The content is 0.5 wt% or less, preferably 0.01 to 0.45 wt%. By adopting the above embodiment, it is possible to improve the crystallinity and stability of the rare earth-modified molecular sieve while improving the utilization rate of rare earths. Therefore, in the process of adjusting the acidity of the molecular sieve with elements such as P and Mg, it is possible to improve the diesel yield while maintaining a high heavy oil conversion capacity. It has the characteristics of excellent activity stability, high heavy oil conversion rate, and high diesel yield. In the present invention, unless otherwise specified, SO4 2- The content parameters are measured by XRF fluorescence.

[0024] According to one preferred embodiment of the present invention, the sodium content in the rare earth-modified molecular sieve is 1.2 wt% or less, preferably 0.6 to 1.0 wt%, in terms of Na2O. By adopting the above embodiment, a catalytic cracking catalyst with excellent activity stability, high heavy oil conversion rate, and high diesel yield can be obtained.

[0025] According to one preferred embodiment of the present invention, the rare earth content in the rare earth-modified molecular sieve is 6 to 18 wt% in terms of RE2O3. By adopting the above embodiment, the activity stability of the rare earth-modified molecular sieve can be improved. By adjusting the acidity of the molecular sieve with elements such as P and Mg, a catalytic cracking catalyst with excellent activity stability, a high heavy oil conversion rate, and a high diesel yield can be obtained.

[0026] According to one preferred embodiment of the present invention, when the phosphorus oxide is converted to P2O5 and the magnesium oxide to MgO based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst contains 15-30% by weight of rare earth modified molecular sieve, 0.5-3% by weight of phosphorus oxide, and 0.2-1.5% by weight of magnesium oxide. By adopting the above embodiment, the content of each component is controlled within the above range, thereby obtaining a catalytic cracking catalyst with excellent activity stability, high heavy oil conversion rate, and high diesel yield.

[0027] In the present invention, the range of selectable types of molecular sieves in the rare earth-modified molecular sieve is wide, and any commonly used molecular sieve can be used in the present invention. According to one preferred embodiment of the present invention, the rare earth-modified molecular sieve is a rare earth-modified Y-type molecular sieve. By adopting the above embodiment, a catalytic cracking catalyst with excellent activity stability, high heavy oil conversion rate, and high diesel yield can be obtained.

[0028] According to one preferred embodiment of the present invention, the catalytic cracking catalyst comprises a macroporous material, clay, the catalytic cracking active component, and an optional binder.

[0029] According to one preferred embodiment of the present invention, the macroporous material is selected from macroporous alumina and / or macroporous silicon aluminum material, and is preferably macroporous silicon aluminum material. Preferably, the macroporous silicon aluminum material has a specific surface area of ​​400 to 500 m². 2The pore volume is 1-1.5 ml / g, and the average pore diameter is 40-50 nm.

[0030] By adopting the above-described embodiment, a catalytic cracking catalyst can be obtained that is advantageous for the diffusion and pre-cracking of heavy oil polymers, has superior activity stability, a higher heavy oil conversion rate, and a higher diesel yield. In this invention, the specific surface area, pore volume, and average pore diameter of the macroporous material are measured by the low-temperature nitrogen adsorption-desorption method, the instrument used being the TriStar3020 physicochemical adsorption instrument from Micromeritics, Inc., USA, and the test standard being the company standard NB / SH / T 0959.

[0031] According to one preferred embodiment of the present invention, the clay is at least one selected from kaolin, halloysite, porous stone, diatomaceous earth, and pumice, and is preferably kaolin. By employing the above embodiment, the roles of thermal protection and activity dilution of the rare earth-modified molecular sieve can be reliably achieved.

[0032] According to one preferred embodiment of the present invention, the binder is at least one selected from silicon dioxide, alumina, and phosphorus pentoxide, and is preferably alumina. In the present invention, the binder is obtained by roasting and converting the binder source. By employing the above embodiment, a catalytic cracking catalyst with excellent wear resistance can be prepared, and catalyst escape during the application process can be reduced.

[0033] According to one preferred embodiment of the present invention, the catalytic cracking catalyst contains a rare earth-modified molecular sieve, a macroporous material, a binder, clay, a phosphorus oxide, and a magnesium oxide. Based on the total weight of the catalytic cracking catalyst, the phosphorus oxide is converted to P2O5 and the magnesium oxide to MgO, and the catalytic cracking catalyst contains 15-30% by weight of the rare earth-modified molecular sieve, 2-15% by weight of the macroporous material, 5-30% by weight of the binder, 40-75% by weight of the clay, 0.5-3% by weight of the phosphorus oxide, and 0.2-1.5% by weight of the magnesium oxide. By adopting the above embodiment, the content of each component is controlled within the above range, thereby obtaining a catalytic cracking catalyst with excellent activity stability, a high heavy oil conversion rate, and a high diesel yield.

[0034] If the rare earth-modified molecular sieve has the aforementioned features of the present invention, the objective of the present invention can be achieved, and there are no special requirements for its preparation method. Therefore, the present invention provides a method for preparing a rare earth-modified molecular sieve.

[0035] According to one preferred embodiment of the present invention, the method for preparing the rare earth-modified molecular sieve is as follows: Step (1) involves subjecting a Na-type molecular sieve to rare earth ion exchange to obtain a rare earth ion exchange slurry, Step (2) involves adding a first precipitating agent to cause some of the rare earth ions in the rare earth ion exchange slurry to undergo first precipitation, thereby obtaining a first precipitate slurry. Step (3) involves sequentially performing filtration, first ammonium sulfate exchange, first water washing, and first roasting on the first precipitate slurry to obtain an exchange roasted molecular sieve-dried powder, The process includes (4) adding a second precipitating agent so that some of the rare earth ions in the exchanged roasted molecular sieve dried powder undergo a second precipitate, and then sequentially performing a second ammonium sulfate exchange, a second water wash, and an optional second roast to obtain a rare earth modified molecular sieve.

[0036] In this invention, the rare earth-modified molecular sieve is the main active component of the catalytic cracking catalyst, and its performance determines the performance of the catalytic cracking catalyst.

[0037] The rare earth-modified molecular sieve according to the present invention, by adding precipitants (i.e., a first precipitant and a second precipitant) to a Na-type molecular sieve after rare earth ion exchange and before ammonium sulfate exchange to generate a precipitate precursor of rare earth ions and rare earth oxides, avoids the formation of precipitates of free rare earth ions and sulfate ions in the exchange system solution, on the molecular sieve surface, or within the supercage during the subsequent ammonium sulfate exchange and sodium reduction steps, thereby achieving the objective of reducing sulfate ions in the molecular sieve. As a result, the utilization rate of rare earths can be improved while improving the crystallinity and stability of the molecular sieve. Therefore, the molecular sieve has the characteristics of having few sulfate ions, high crystallinity, strong acidity, and excellent stability, and when used as an active ingredient in a catalytic cracking catalyst, the cracking activity and hydrothermal stability of the catalytic cracking catalyst are improved accordingly.

[0038] In subsequent processes where the acidity of the molecular sieve is adjusted with elements such as P and Mg, the diesel yield can be improved while maintaining a high heavy oil conversion capacity.

[0039] In this invention, unless otherwise specified, "first" and "second" are not used to indicate priority or limitation of the respective materials or steps, but only to confirm that they are not the same steps or materials. For example, "first" and "second" in "first ammonium sulfate exchange" and "second ammonium sulfate exchange" are used only to indicate that they are not the same ammonium sulfate exchange.

[0040] According to one preferred embodiment of the present invention, in step (1), the rare earth ion exchange process includes mixing the Na-type molecular sieve with water, and then adding a soluble rare earth source to perform the rare earth ion exchange.

[0041] According to one preferred embodiment of the present invention, in step (1), the weight ratio of the Na-type molecular sieve to water is any value within the range of 1:(1.5~30), for example, 1:1.5, 1:2, 1:3, 1:4, 1:5, 1:10, 1:20, 1:30, and any two values, preferably 1:(2~5).

[0042] According to one preferred embodiment of the present invention, in step (1), the mass ratio of the soluble rare earth source on an RE2O3 basis to the amount of the Na-type molecular sieve used on a dry basis is any value within the range of 1 to 20:100, for example, 1:100, 4:100, 6:100, 10:100, 14:100, 16:100, 20:100, and any two values, preferably 6 to 16:100. By adopting the above embodiment, it is further advantageous to reduce the sulfate ion content in the rare earth modified molecular sieve, thereby eliminating the effect of sulfate ions on the performance of the rare earth modified molecular sieve, and further improving the crystallinity, stability and catalytic performance of the rare earth modified molecular sieve.

[0043] According to one preferred embodiment of the present invention, in step (1), the conditions for the rare earth ion exchange include a temperature of 25 to 180°C, preferably 50 to 80°C, and / or a pH of 2.8 to 6.5, preferably 3.5 to 4.5, and / or a time of 0.3 to 3.5 hours, preferably 0.5 to 1.5 hours. By adopting the above embodiment, the exchange between the Na-type molecular sieve and rare earth ions can be performed more effectively, which is advantageous in reducing the sulfate ion content in the rare earth modified molecular sieve, thereby eliminating the influence of sulfate ions on the performance of the rare earth modified molecular sieve, and further improving the crystallinity, stability, and catalytic performance of the rare earth modified molecular sieve.

[0044] In the present invention, the type of Na-type molecular sieve is not particularly limited, and the Na-type molecular sieves are known to those skilled in the art. According to one preferred embodiment of the present invention, in step (1), the silica / alumina ratio of the Na-type molecular sieve is 2 to 100:1, preferably 2 to 50:1, and more preferably the Na-type molecular sieve is at least one selected from NaY molecular sieve, NaHY molecular sieve, NaUSY molecular sieve, NaREHY molecular sieve, and NaREUSY molecular sieve, preferably NaY molecular sieve and / or NaHY molecular sieve.

[0045] In the present invention, in the rare earth ion exchange process, the rare earth ions in the soluble rare earth source adhere completely to the surface and internal channels of the Na-type molecular sieve. Therefore, the weight ratio of the Na-type molecular sieve on a dry basis to the soluble rare earth source on an RE2O3 basis is 100:(1~20), preferably 100:(6~16). In the present invention, solubility means readily dissolving in water or readily dissolving in water with the help of an additive, unless otherwise specified. According to one preferred embodiment of the present invention, in step (1), the soluble rare earth source is selected from chlorates and / or nitrates containing rare earths, where the rare earth is at least one selected from lanthanum, cerium, and yttrium, preferably lanthanum and / or yttrium.

[0046] According to one preferred embodiment of the present invention, in step (2), the amount of the first precipitant used satisfies the molar ratio of the first precipitate of rare earth ions present in the Na-type molecular sieve at a content of 1 to 4 wt%, and more preferably, the amount of the first precipitant used satisfies the molar ratio of the first precipitate of rare earth ions present in the Na-type molecular sieve at a content of 1.5 to 2.5 wt%. By adopting the above embodiment, it is even more advantageous to reduce the sulfate ion content in the rare earth modified molecular sieve, thereby eliminating the influence of sulfate ions on the performance of the rare earth modified molecular sieve, and further improving the crystallinity, stability and catalytic performance of the rare earth modified molecular sieve.

[0047] According to one preferred embodiment of the present invention, in step (2), the conditions for the first precipitation include a temperature of 25 to 180°C, preferably 50 to 80°C, and / or a time of 0.1 to 5 hours, preferably 0.1 to 2 hours. By employing the above embodiment, the first precipitant and rare earth ions can be more effectively promoted to form a precipitate precursor of rare earth oxides, thereby achieving the objective of avoiding precipitation of free rare earth ions and sulfate ions in the exchange system solution, on the molecular sieve surface, or in the supercage during the subsequent ammonium sulfate exchange and sodium reduction steps, thereby reducing the sulfate ion content in the molecular sieve, and thereby improving the crystallinity and stability of the molecular sieve, as well as the utilization rate of rare earths.

[0048] In the present invention, the type of the first precipitant is not particularly limited, as long as it can generate the rare earth ions and rare earth oxides. According to one preferred embodiment of the present invention, in step (2), the first precipitant is at least one selected from ammonium carbonate, ammonium bicarbonate, ammonium oxalate, ammonium acetate, aqueous ammonia, and urea, and preferably at least one selected from ammonium carbonate, ammonium bicarbonate, ammonium oxalate, and aqueous ammonia. By employing the above embodiment, a precipitate precursor of rare earth ions and rare earth oxides can be preferentially generated, thereby avoiding the formation of precipitates between free rare earth ions and sulfate ions in the exchange system solution, on the molecular sieve surface, or in the supercage during the subsequent ammonium sulfate exchange and sodium reduction steps, thereby achieving the objective of reducing the sulfate ion content in the molecular sieve, and thereby improving the crystallinity and stability of the molecular sieve, as well as the utilization rate of rare earths.

[0049] In the present invention, the purpose of the first ammonium sulfate exchange is to remove Na from the Na-type molecular sieve. + The further exchange is to replace the first ammonium sulfate. According to one preferred embodiment of the present invention, in step (3), the process of the first ammonium sulfate exchange comprises subjecting the filtration product and the first aqueous ammonium sulfate solution to the first ammonium sulfate exchange.

[0050] According to one preferred embodiment of the present invention, in step (3), the weight ratio of the first aqueous ammonium sulfate solution in terms of ammonium sulfate to the Na-type molecular sieve is 5 to 50:100, for example, 5:100, 10:100, 15:100, 20:100, 25:100, 30:100, 40:100, 50:100, and any value within the range consisting of any two values, preferably 10 to 25:100. By adopting the above-described embodiment, Na in the Na-type molecular sieve + can be exchanged better.

[0051] According to one preferred embodiment of the present invention, in step (3), the concentration of ammonium sulfate in the first aqueous ammonium sulfate solution is 20 to 400 g / L, for example, 20 g / L, 50 g / L, 80 g / L, 120 g / L, 160 g / L, 200 g / L, 250 g / L, 300 g / L, 400 g / L, and any value within the range consisting of any two values, preferably 120 to 250 g / L. By adopting the above-described embodiment, Na in the Na-type molecular sieve + can be exchanged better.

[0052] According to one preferred embodiment of the present invention, in step (3), the conditions for the first ammonium sulfate exchange include that the temperature is 15 to 150 °C, preferably 50 to 80 °C, and / or the time is 0.1 to 5 h, preferably 0.5 to 2 h. By adopting the above-described embodiment, the first ammonium sulfate exchange can be carried out better, and Na in the Na-type molecular sieve + can be further exchanged.

[0053] According to one preferred embodiment of the present invention, in step (3), the amount of water used in the first water washing is 1 to 8 times the weight of the Na-type molecular sieve, for example, 1 time, 2 times, 3 times, 5 times, 7 times, 8 times, and any value within the range consisting of any two values, preferably 2 to 5 times.

[0054] According to one preferred embodiment of the present invention, in step (3), the conditions for the first roasting include a 100% water vapor atmosphere and / or a temperature of 400 to 700°C, preferably 500 to 650°C, and / or a time of 0.1 to 5 hours, preferably 0.5 to 3 hours.

[0055] According to one preferred embodiment of the present invention, in step (4), the amount of the second precipitant used satisfies the molar ratio of the second precipitate of rare earth ions present in the exchanged roasted molecular sieve dry powder at a content of 0.5 to 3 wt%, and more preferably, the amount of the second precipitant used satisfies the molar ratio of the second precipitate of rare earth ions present in the exchanged roasted molecular sieve dry powder at a content of 1 to 2 wt%. By adopting the above embodiment, the sulfate ion content in the rare earth modified molecular sieve can be further reduced, thereby better eliminating the influence of sulfate ions on the performance of the rare earth modified molecular sieve, and further improving the crystallinity, stability, and catalytic performance of the rare earth modified molecular sieve.

[0056] According to one preferred embodiment of the present invention, in step (4), the conditions for the second precipitation include a temperature of 15 to 40°C, preferably 20 to 30°C, and / or a time of 0.1 to 5 hours, preferably 0.1 to 2 hours. By employing the above embodiment, the second precipitant and rare earth ions can be more effectively promoted to form a precipitate precursor of rare earth oxides, thereby achieving the objective of reducing the sulfate ion content in the molecular sieve by avoiding the formation of precipitates between free rare earth ions and sulfate ions in the exchange system solution, on the molecular sieve surface, or in the supercage during the subsequent ammonium sulfate exchange and sodium reduction steps, thereby improving the crystallinity and stability of the molecular sieve, as well as the utilization rate of rare earths.

[0057] According to one preferred embodiment of the present invention, in step (4), the second precipitant is at least one selected from ammonium carbonate, ammonium bicarbonate, ammonium oxalate, ammonium acetate, aqueous ammonia, and urea, preferably at least one selected from ammonium carbonate, ammonium bicarbonate, ammonium oxalate, and aqueous ammonia. By employing the above embodiment, a precipitate precursor of rare earth ions and rare earth oxides can be preferentially generated, thereby achieving the objective of avoiding the formation of precipitates between free rare earth ions and sulfate ions in the exchange system solution, on the molecular sieve surface, or in the supercage during the subsequent ammonium sulfate exchange and sodium reduction steps, thereby reducing the sulfate ion content in the molecular sieve, and thereby improving the crystallinity and stability of the molecular sieve, as well as the utilization rate of rare earths.

[0058] According to one preferred embodiment of the present invention, in step (4), the process of the second ammonium sulfate exchange comprises subjecting the second precipitate product and the aqueous solution of the second ammonium sulfate to the second ammonium sulfate exchange.

[0059] According to one preferred embodiment of the present invention, in step (4), the weight ratio of the second ammonium sulfate aqueous solution in terms of ammonium sulfate to the exchange roasted molecular sieve-dried powder is any value within the range of 5 to 50:100, for example, 5:100, 10:100, 15:100, 20:100, 25:100, 30:100, 40:100, 50:100, and any two values, preferably 10 to 25:100.

[0060] According to one preferred embodiment of the present invention, in step (4), the concentration of ammonium sulfate in the second aqueous ammonium sulfate solution is any value within the range of 20 to 400 g / L, for example, 20 g / L, 50 g / L, 80 g / L, 120 g / L, 150 g / L, 200 g / L, 250 g / L, 300 g / L, 400 g / L, and any two of these values, preferably 120 to 250 g / L.

[0061] According to one preferred embodiment of the present invention, in step (4), the conditions for the second ammonium sulfate exchange include a temperature of 20 to 85°C, preferably 50 to 80°C, and / or a time of 0.1 to 5 hours, preferably 0.1 to 2 hours. By employing the above embodiment, the second ammonium sulfate exchange can be performed more effectively, and Na in the Na-type molecular sieve + Exchange it further.

[0062] According to one preferred embodiment of the present invention, in step (4), the amount of water used in the second wash is 1 to 8 times the weight of the exchanged roasted molecular sieve-dried powder, for example, any value within the range of 1, 2, 3, 4, 5, 8 times and any two values, preferably 2 to 5 times.

[0063] According to one preferred embodiment of the present invention, in step (4), the conditions for the second roasting include a 20-100% water vapor atmosphere and / or a temperature of 400-700°C, preferably 450-650°C, and / or a time of 0.1-10 hours, preferably 0.5-5 hours.

[0064] According to one preferred embodiment of the present invention, in step (4), the exchange roasted molecular sieve-dried powder and water are mixed before the second precipitation.

[0065] According to one preferred embodiment of the present invention, in step (4), the weight ratio of the exchange roasted molecular sieve-dried powder to water is any value within the range of 1:(1.5~30), for example, 1:1.5, 1:2, 1:3, 1:4, 1:5, 1:10, 1:20, 1:30, and any two values, preferably 1:(2~5).

[0066] Any catalytic cracking catalyst having the aforementioned features of the present invention can achieve the objectives of the present invention, and there are no special requirements for its preparation method.

[0067] A second aspect of the present invention provides a method for preparing a catalytic cracking catalyst as described in the first aspect, the preparation method comprising the steps of mixing a catalytic cracking active component with a macroporous material source and a clay source in solution and bringing them into contact to obtain a catalyst precursor, optionally shaping it, and optionally drying and roasting it.

[0068] According to one preferred embodiment of the present invention, the preparation method is Step (1) involves mixing the rare earth-modified molecular sieve, phosphorus source, and water to form a slurry, then adding a macroporous material source, binder source, and clay source, mixing, homogenizing, drying, and roasting to obtain catalyst solid particles. The process includes (2) mixing the catalyst solid particles obtained in step (1), water, a magnesium source, and an optional ammonium source, then filtering, washing with water, and drying to obtain a catalytic cracking catalyst.

[0069] The present invention provides a method for preparing a catalytic cracking catalyst that is easy to operate, has a simplified process flow, and facilitates industrial production. By appropriately adjusting the acidity of the catalyst using P and Mg, the ratio of each reaction in the cracking process is controlled, improving the catalyst's heavy oil conversion capacity and diesel yield.

[0070] According to one preferred embodiment of the present invention, in step (1), with respect to 100 parts of the dry basis mass of the catalyst, the phosphorus source is calculated as follows: 15 to 30 parts of rare earth modified molecular sieve, 0.5 to 3 parts of phosphorus source, 2 to 15 parts of macroporous material source, 5 to 30 parts of binder source, 40 to 75 parts of clay source, and water are mixed to obtain a slurry with a solid content of 25 to 50 wt%. By adopting the above embodiment, the content of each component is controlled within the preferred range, thereby obtaining a catalytic cracking catalyst with excellent catalytic activity, a high heavy oil conversion rate, and a high diesel yield.

[0071] According to one particularly preferred embodiment of the present invention, in step (1), with respect to 100 parts of the dry basis mass of the catalyst, the phosphorus source is calculated as follows: 18 to 27 parts of rare earth modified molecular sieve, 0.9 to 2 parts of phosphorus source, 3 to 7 parts of macroporous material source, 5.5 to 25 parts of binder source, 45 to 65 parts of clay source, and water are mixed to obtain a slurry with a solid content of 35 to 45 wt%. By adopting the above embodiment, the content of each of the above components can be controlled within a more preferred range, thereby obtaining a catalytic cracking catalyst with superior catalytic activity, a higher heavy oil conversion rate, and a higher diesel yield.

[0072] In this invention, in step (1), there are no special requirements for the steps and methods of mixing the rare earth-modified molecular sieve, phosphorus source, water, macroporous material source, binder source, and clay source to form a slurry, and then drying and roasting it. Since these steps can be carried out using general techniques, they will not be described in detail here.

[0073] In this invention, there are no special requirements for the various raw materials used, and the objective of this invention can be achieved by preparing them according to the steps described above.

[0074] In the present invention, the type of phosphorus source is not particularly limited, and the phosphorus source is one that is generally selected in the art. According to one preferred embodiment of the present invention, in step (1), the phosphorus source is at least one selected from diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium phosphate, and is preferably diammonium hydrogen phosphate.

[0075] According to one preferred embodiment of the present invention, in step (1), the macroporous material source is selected from macroporous alumina and / or macroporous silicon aluminum material, and is preferably macroporous silicon aluminum material.

[0076] In the present invention, the binder source is not particularly limited and may be any of the existing binders available for use in catalytic cracking catalysts. According to one preferred embodiment of the present invention, in step (1), the binder source is at least one selected from alumina sol, acidic pseudoboehmite, acidic silica sol, and phosphoalumina sol, preferably alumina sol and / or acidic pseudoboehmite, more preferably alumina sol and acidic pseudoboehmite.

[0077] According to one preferred embodiment of the present invention, the clay source is at least one selected from kaolin, halloysite, porous stone, diatomaceous earth, and pumice, and is preferably kaolin.

[0078] In this invention, there are no special requirements for the drying and roasting steps and methods, and conventional techniques known to those skilled in the art can be employed, so they will not be described in detail here. Specifically, in this invention, illustratively, for example, the drying temperature is 100 to 150°C, the drying time is 8 to 15 hours, the roasting temperature is 400 to 500°C, and the roasting time is 20 to 50 minutes.

[0079] According to one preferred embodiment of the present invention, in step (2), the weight ratio of water to catalyst solid particles is 0.5 to 35:1 according to the drying criteria of the catalyst solid particles.

[0080] According to one preferred embodiment of the present invention, in step (2), the amount of magnesium source added is any value within the range of 0.2 to 1.5 wt%, for example, 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt%, 1.0 wt%, 1.2 wt%, 1.5 wt%, and any two values, preferably 0.6 to 1.2 wt%. By employing the above embodiment, the catalyst is modified with magnesium to be adjusted to have an appropriate acidity, thereby controlling the ratio of each reaction in the cracking process and improving the heavy oil conversion capacity and diesel yield of the catalytic cracking catalyst.

[0081] In the present invention, the type of magnesium source is not particularly limited, and the magnesium source is one that is generally selected in the art. According to one preferred embodiment of the present invention, in step (2), the magnesium source is selected from magnesium chloride and / or magnesium nitrate, and is preferably magnesium chloride. By employing the above embodiment, the catalyst can be better modified and adjusted to have appropriate acidity, thereby controlling the ratio of each reaction in the cracking process and improving the heavy oil conversion rate and diesel yield of the catalytic cracking catalyst.

[0082] In the present invention, the type of ammonium source is not particularly limited, and the ammonium source is one that is generally selected in the art. According to one preferred embodiment of the present invention, in step (2), the ammonium source is selected from ammonium chloride and / or ammonium nitrate, and is preferably ammonium chloride.

[0083] According to one preferred embodiment of the present invention, in step (2), the conditions for washing include a temperature of 20 to 100°C, preferably 25 to 50°C, and / or a time of 0.1 to 0.3 hours, preferably 0.15 to 0.25 hours.

[0084] A third aspect of the present invention provides the use of the catalytic cracking catalyst described in the first aspect in heavy oil catalytic cracking.

[0085] In this invention, the catalytic cracking catalyst according to the present invention is particularly suitable for heavy oil catalytic cracking, exhibiting high catalytic cracking activity during the heavy oil catalytic cracking process, and also enabling the acquisition of higher diesel yields.

[0086] In this invention, the catalyst composition is the composition calculated based on the input materials.

[0087] The present invention will be described in detail below with reference to examples.

[0088] The raw materials used in the following examples and comparative examples are as follows: NaY molecular sieve: silica / alumina ratio 5.1, crystallinity 95%, manufactured by Changtian Catalyst Co., Ltd. Soluble rare earth sources: lanthanum chloride, lanthanum nitrate, yttrium chloride (all industrial products, extracted from Lanzhou Petrochemical Company's catalyst plant). Ammonium sulfate, ammonium oxalate, ammonium carbonate, aqueous ammonia, ammonium chloride, ammonium dihydrogen phosphate, magnesium chloride (all at analytical purity). Pseudoboehmite (loss on ignition 36.7%), kaolin (loss on ignition 18.4%), macroporous silicon aluminum material (solids content 15.4%, pore volume 1.15 ml / g, specific surface area 458 m²) 2 ( / g, average pore size 43.5nm) Solid; Alumina sol: Alumina content 22.6% by weight; Silica sol: Silica content 30.5% by weight (both are industrial standard products).

[0089] In the following examples and comparative examples, Using XRF fluorescence spectroscopy, SO42 in rare-earth modified Y-type molecular sieves - The content of [substance], the content of Na2O, the content of RE2O3, and the content of Na2O, P2O5, and MgO in the catalytic cracking catalyst are measured. The degree of crystallinity (C / C0) and silica / alumina ratio of rare-earth modified Y-type molecular sieves are measured using X-ray diffraction.

[0090] Test method for micro-reaction activity: Samples are pre-treated at 800°C and 100% steam for different durations. The reaction material is light diesel from Daminato, the reaction temperature is 460°C, the reaction time is 70 s, the catalyst load is 5 g, the catalyst-to-oil weight ratio is 3.2, and the total conversion rate is defined as the micro-reaction activity.

[0091] Evaluation of Catalytic Cracking Selectivity: Evaluation of the selectivity of the catalytic cracking reaction in an ACE heavy oil microreactor: The catalyst was pre-treated for 10 hours at 800°C and 100% steam. The crude oil used for the reaction was the feedstock oil for a 3 million ton heavy oil catalyst plant from Lanzhou Petrochemical. Its specific composition was 63.2% saturated hydrocarbons, 33.2% aromatic hydrocarbons, and 3.6% gums. Its properties included a molecular weight of 437 g / mol, 4.2% residual carbon, and heavy metals of Ca 2.2 ppm, V 4.69 ppm, Ni 4.42 ppm, and Fe 4.28 ppm. The reaction temperature was 510°C, and the catalyst-to-oil ratio was 5.

[0092] Example 1 (1) Preparation of rare earth-modified molecular sieves (a) After slurring 1000g of NaY molecular sieve (dry weight) with 5L of deionized water, a LaCl3 solution with a concentration of 298g / L (La2O3 equivalent) is prepared (La 3+ 0.537 L of (0.98 mol) was added and rare earth ion exchange (at 80°C for 0.5 h) was performed to obtain a rare earth ion exchange slurry. The LaCl3 content, calculated as La2O3, in the NaY molecular sieve based on dryness was 16 wt%.

[0093] (b) Add ammonium oxalate monohydrate (32 g, 0.225 mol) to the above rare earth ion exchange slurry to obtain 2.4 wt% La 3+ The mixture was subjected to a first precipitate (at a temperature of 80°C for 0.5 hours) to obtain a first precipitate slurry.

[0094] (c) The above first precipitate slurry was filtered and dried by suction, 0.833 L of ammonium sulfate aqueous solution with a concentration of 180 g / L was added, the mixture was changed at 60°C for 1 hour, dried by suction, rinsed with 3 L of water, and then roasted at 500°C for 2 hours in a 100% steam atmosphere to obtain a changed roasted molecular sieve dried powder.

[0095] (d) After slurring 1000 g (dry weight) of the above exchange roasted molecular sieve dried powder with 5 L of deionized water, ammonium oxalate monohydrate (25.6 g, 0.18 mol) is added to the above exchange roasted molecular sieve dried powder to obtain 2 wt% La 3+The sample was subjected to a second precipitate (at 25°C for 0.5 hours), then 0.6 L of ammonium sulfate aqueous solution with a concentration of 250 g / L was added, the mixture was changed at 80°C for 1.5 hours, filtered, and dried by suction. 5 L of water was added for rinsing, and the sample was roasted at 450°C for 2 hours in a 100% water vapor atmosphere to obtain rare earth-modified Y-type molecular sieve Z1.

[0096] (2) Preparation of catalytic cracking catalyst To 100 parts of the dry mass of the catalyst, 23 parts by weight of the above-mentioned rare earth-modified Y-type molecular sieve Z1, 1.1 parts by weight of ammonium dihydrogen phosphate (P2O5 equivalent), and water were mixed and slurryed for 30 minutes. Then, 57.9 parts by weight of kaolin, 6 parts by weight of macroporous silicon aluminum material, 6 parts by weight of alumina sol, and 6 parts by weight of acidic pseudoboehmite were added and mixed for 1 hour at 25°C to obtain a slurry with a solid content of 48 wt%.

[0097] Subsequently, homogenization and spray molding were performed in sequence, and the resulting microspheres were roasted at 450°C for 25 minutes to obtain a catalytic decomposition catalyst precursor.

[0098] According to the drying standards for catalyst solid particles, 200 g of the above catalytic cracking catalyst precursor was mixed with water to form a slurry containing 20 wt% solids of the catalyst precursor. Magnesium chloride was then added and mixed, with a weight ratio of 1:100 between magnesium chloride (MgO equivalent) and the slurry containing the catalyst precursor. The slurry was then filtered, washed with 1 kg of water (the amount used for washing was 5 times the mass of the catalyst precursor) at 25°C for 0.2 hours, and dried at 100°C for 12 hours to obtain catalytic cracking catalyst C1.

[0099] Here, using the total weight of the catalytic cracking catalyst as a reference, the amount of Na in the catalytic cracking catalyst C1 is calculated as Na2O. + The content of [substance] was 0.14 wt%, the phosphorus content (calculated as P2O5) was 1.12 wt%, and the magnesium content (calculated as MgO) was 0.92 wt%.

[0100] Example 2 (1) Preparation of rare earth-modified molecular sieves (a) After slurring 1000g of NaY molecular sieve (dry weight) with 5L of deionized water, a La(NO3)3 solution with a concentration of 280g / L (La2O3 equivalent) (La 3+ 0.358 L of (0.615 mol) was added and rare earth ion exchange (at 50°C for 1.5 hours) was performed to obtain a rare earth ion exchange slurry. The La(NO3)3 content, calculated as La2O3, in the NaY molecular sieve based on dryness was 10 wt%.

[0101] (b) Add ammonium oxalate monohydrate (25.6 g, 0.18 mol) to the above metal ion exchange slurry to obtain 2 wt% La 3+ The mixture was subjected to a first precipitate (at a temperature of 50°C for 0.5 hours) to obtain a first precipitate slurry.

[0102] (c) The above first precipitate slurry was filtered and dried by suction, 1.111 L of ammonium sulfate aqueous solution with a concentration of 180 g / L was added, the mixture was changed at 80°C for 1 hour, dried by suction, rinsed with 3 L of water, and then roasted at 600°C for 2 hours in a 100% steam atmosphere to obtain a changed roasted molecular sieve dried powder.

[0103] (d) After slurring 1000g (dry weight) of the above exchange roasted molecular sieve dried powder with 5L of deionized water, ammonium carbonate (13g, 0.135mol) is added to obtain 1.5wt% of La from the above exchange roasted molecular sieve dried powder. 3+ The mixture was subjected to a second precipitate (at 25°C for 0.5 hours), 1.666 L of ammonium sulfate aqueous solution with a concentration of 120 g / L was added, the mixture was changed at 50°C for 1 hour, filtered, dried by suction, rinsed with 2 L of water, and roasted at 500°C for 2.5 hours in an 80% water vapor atmosphere to obtain rare earth-modified Y-type molecular sieve Z2.

[0104] (2) Preparation of catalytic cracking catalyst To 100 parts of the dry mass of the catalyst, 27 parts by weight of the above-mentioned rare earth-modified Y-type molecular sieve Z2, 1.8 parts by weight of ammonium dihydrogen phosphate (P2O5 equivalent), and water were mixed and slurryed for 30 minutes. Then, 48.7 parts by weight of kaolin, 3 parts by weight of macroporous silicon aluminum material, 4.5 parts by weight of alumina sol, and 15 parts by weight of acidic pseudoboehmite were added and mixed for 1 hour at 25°C to obtain a slurry with a solid content of 39 wt%. Subsequently, homogenization and spray molding were carried out in order, and the resulting microspheres were roasted at 460°C for 30 minutes to obtain a catalytic decomposition catalyst precursor.

[0105] According to the drying standards for catalyst solid particles, 200 g of the above catalytic cracking catalyst precursor was mixed with water to form a slurry containing 25 wt% solids of the catalyst precursor. Magnesium chloride was then added and mixed, with a weight ratio of 0.65:100 between magnesium chloride (MgO equivalent) and the slurry containing the catalyst precursor. The slurry was then filtered, 1.6 kg of water (the amount used for washing was 8 times the mass of the catalyst precursor) was added, and the slurry was washed at 30°C for 0.15 hours. Finally, it was dried at 120°C for 8 hours to obtain catalytic cracking catalyst C2.

[0106] Here, based on the total weight of the catalytic cracking catalyst, the amount of Na in the catalytic cracking catalyst C2 is calculated as Na2O. + The content was 0.17 wt%, the phosphorus content (calculated as P2O5) was 1.72 wt%, and the magnesium content (calculated as MgO) was 0.63 wt%.

[0107] Example 3 (1) Preparation of rare earth-modified molecular sieves (a) After slurring 1000g of NaY molecular sieve (dry weight) with 5L of deionized water, a YCl3 solution (Y) with a concentration of 246g / L (calculated as Y2O3) is prepared. 3+ 0.407 L of (0.513 mol) was added and rare earth ion exchange (at 60°C for 1 hour) was performed to obtain a rare earth ion exchange slurry. The YCl3 content, calculated as Y2O3, in the NaY molecular sieve based on dryness was 5.97 wt%.

[0108] (b) Add ammonium oxalate monohydrate (32 g, 0.225 mol) to the metal ion exchange slurry to obtain 1.7 wt% Y from the above metal ion exchange slurry. 3+ The mixture was subjected to a first precipitate (at a temperature of 60°C for 0.5 hours) to obtain a first precipitate slurry.

[0109] (c) The above first precipitate slurry was filtered and dried by suction, 1.389 L of ammonium sulfate aqueous solution with a concentration of 180 g / L was added, and the mixture was changed at 60°C for 1.5 hours, dried by suction, rinsed with 3 L of water, and then roasted at 650°C for 2 hours in a 100% steam atmosphere to obtain a changed roasted molecular sieve dried powder.

[0110] (d) After slurring 1000g (dry weight) of the above-mentioned exchange roasted molecular sieve dried powder with 5L of deionized water, ammonium oxalate monohydrate (22.6g, 0.16mol) is added to the above-mentioned exchange roasted molecular sieve dried powder to a concentration of 1.2wt% Y 3+ The sample was subjected to a second precipitate (at 25°C for 0.5 hours), then 1.389 L of ammonium sulfate aqueous solution with a concentration of 180 g / L was added, the mixture was changed at 50°C for 1 hour, filtered, and dried by suction. 3 L of water was added for rinsing, and the sample was roasted at 650°C for 2 hours in a 60% water vapor atmosphere to obtain rare earth-modified Y-type molecular sieve Z3.

[0111] (2) Preparation of catalytic cracking catalyst To 100 parts of the dry mass of the catalyst, 18 parts by weight of the above-mentioned rare earth-modified Y-type molecular sieve Z3, 0.9 parts by weight of ammonium dihydrogen phosphate (P2O5 equivalent), and water were mixed and slurryed for 30 minutes. Then, 53.1 parts by weight of kaolin, 7 parts by weight of macroporous silicon aluminum material, 3 parts by weight of alumina sol, and 18 parts by weight of acidic pseudoboehmite were added and mixed for 1 hour at 25°C to obtain a slurry with a solid content of 36 wt%. Subsequently, homogenization and spray molding were carried out in order, and the resulting microspheres were roasted at 470°C for 35 minutes to obtain a catalytic decomposition catalyst precursor.

[0112] According to the drying standards for catalyst solid particles, 200 g of the above catalytic cracking catalyst precursor was mixed with water to form a slurry containing 20 wt% solids of the catalyst precursor. Magnesium chloride was then added and mixed, with a weight ratio of 1.2:100 between magnesium chloride (MgO equivalent) and the slurry containing the catalyst precursor. The slurry was then filtered, 1 kg of water (the amount used for washing was 5 times the mass of the catalyst precursor) was added, and the slurry was washed at 35°C for 0.25 hours. Finally, it was dried at 110°C for 10 hours to obtain catalytic cracking catalyst C3.

[0113] Here, using the total weight of the catalytic cracking catalyst as a reference, the amount of Na in the catalytic cracking catalyst C3 is calculated as Na2O. + The content was 0.10 wt%, the phosphorus content (calculated as P2O5) was 0.89 wt%, and the magnesium content (calculated as MgO) was 1.13 wt%.

[0114] Example 4 (1) Preparation of rare earth-modified molecular sieves (a) 1000 g of NaY molecular sieve (dry weight) was slurryed with 5 L of deionized water, and then a mixed RECl3 solution with a concentration of 326 g / L (RE2O3 equivalent) was prepared (the weight ratio of Ce2O3 to La2O3 is 6:4, RE 3+ 0.43 L of (0.9287 mol) was added and rare earth ion exchange (at 60°C for 1 hour) was performed to obtain a rare earth ion exchange slurry. The RECl3 content, calculated as RE2O3, in NaY molecular sieve based on dryness was 14 wt%.

[0115] (b) Add ammonium oxalate monohydrate (25.6 g, 0.18 mol), then add 5 mL of 28% industrial ammonia water to obtain 2.4 wt% of the above rare earth ion exchange slurry. 3+ The mixture was subjected to a first precipitate (at a temperature of 60°C for 0.5 hours) to obtain a first precipitate slurry.

[0116] (c) The above first precipitate slurry was filtered and dried by suction, 1.222 L of ammonium sulfate aqueous solution with a concentration of 180 g / L was added, and the mixture was changed at 100°C for 0.5 hours, dried by suction, rinsed with 5 L of water, and then roasted at 600°C for 2 hours in a 100% steam atmosphere to obtain a changed roasted molecular sieve dried powder.

[0117] (d) After slurring 1000g (dry weight) of the above exchange roasted molecular sieve dried powder with 5L of deionized water, ammonium carbonate (18g, 0.187mol) is added to obtain 1.8wt% RE from the above exchange roasted molecular sieve dried powder. 3+ The mixture was subjected to a second precipitate (at 25°C for 0.5 hours), 1 L of ammonium sulfate aqueous solution with a concentration of 120 g / L was added, the mixture was changed at 25°C for 1 hour, filtered, dried by suction, rinsed with 4 L of water, and roasted at 550°C for 2 hours in a 20% water vapor atmosphere to obtain rare earth-modified Y-type molecular sieve Z4.

[0118] (2) Preparation of catalytic cracking catalyst To 100 parts of the dry mass of the catalyst, 25 parts by weight of the above-mentioned rare earth-modified Y-type molecular sieve Z4, 1.5 parts by weight of ammonium dihydrogen phosphate (P2O5 equivalent), and water were mixed and slurryed for 30 minutes. Then, 50.5 parts by weight of kaolin, 5 parts by weight of macroporous silicon aluminum material, 6 parts by weight of alumina sol, and 12 parts by weight of acidic pseudoboehmite were added and mixed for 1 hour at 25°C to obtain a slurry with a solid content of 42 wt%. Subsequently, homogenization and spray molding were carried out in order, and the resulting microspheres were roasted at 450°C for 40 minutes to obtain a catalytic decomposition catalyst precursor.

[0119] According to the drying standards for catalyst solid particles, 200 g of the above catalytic cracking catalyst precursor was mixed with water to form a slurry containing 20 wt% solids of the catalyst precursor. Magnesium chloride was then added and mixed, with a weight ratio of 1.2:100 between magnesium chloride (MgO equivalent) and the slurry containing the catalyst precursor. The slurry was then filtered, washed with 1.2 kg of water (the amount used for washing was 6 times the mass of the catalyst precursor) at 25°C for 0.2 hours, and dried at 110°C for 10 hours to obtain catalytic cracking catalyst C4.

[0120] Here, using the total weight of the catalytic cracking catalyst as a reference, the amount of Na in the catalytic cracking catalyst C4 is calculated as Na2O. + The content was 0.18 wt%, the phosphorus content (calculated as P2O5) was 1.43 wt%, and the magnesium content (calculated as MgO) was 0.85 wt%.

[0121] Example 5 The preparation was carried out according to the method of Example 1, except for the following: In the process of preparing the rare earth modified molecular sieve, in step (a), the 0.537 L of LaCl3 solution with a concentration of 298 g / L (La2O3 equivalent) was changed to 0.67 L of LaCl3 solution with a concentration of 298 g / L (La2O3 equivalent) to make the LaCl3 content in the NaY molecular sieve on a dry basis 20 wt% (La2O3 equivalent), but the remaining conditions were kept the same to obtain the rare earth modified Y-type molecular sieve Z5.

[0122] In the process of preparing the catalytic cracking catalyst, catalytic cracking catalyst C5 was obtained by keeping the remaining conditions the same, except that rare earth-modified Y-type molecular sieve Z1 was replaced with rare earth-modified Y-type molecular sieve Z5.

[0123] Here, using the total weight of the catalytic cracking catalyst as a reference, the amount of Na in the catalytic cracking catalyst C5 is calculated as Na2O. + The content was 0.13 wt%, the phosphorus content (calculated as P2O5) was 1.18 wt%, and the magnesium content (calculated as MgO) was 0.94 wt%.

[0124] Example 6 The preparation was carried out according to the method of Example 1, except for the following: In the process of preparing the rare earth modified molecular sieve, in step (b), ammonium oxalate monohydrate (32 g, 0.225 mol) is changed to ammonium oxalate monohydrate (12.8 g, 0.09 mol), and 1 wt% of La in the above rare earth ion exchange slurry is added. 3+ Rare-earth modified Y-type molecular sieve Z6 was obtained by subjecting the sample to a first precipitate (at a temperature of 80°C for 0.5 hours), with the remaining conditions being the same.

[0125] In the process of preparing the catalytic cracking catalyst, catalytic cracking catalyst C6 was obtained by keeping the remaining conditions the same, except that rare earth-modified Y-type molecular sieve Z1 was replaced with rare earth-modified Y-type molecular sieve Z6.

[0126] Here, using the total weight of the catalytic cracking catalyst as a reference, the amount of Na in the catalytic cracking catalyst C6 is calculated as Na2O. + The content was 0.18 wt%, the phosphorus content (calculated as P2O5) was 1.10 wt%, and the magnesium content (calculated as MgO) was 0.92 wt%.

[0127] Example 7 The preparation was carried out according to the method of Example 1, except for the following: In the process of preparing the rare earth-modified molecular sieve, in step (d), ammonium oxalate monohydrate (25.6 g, 0.18 mol) is replaced with ammonium oxalate monohydrate (6.4 g, 0.045 mol), and 0.5 wt% of La in the above-mentioned exchanged roasted molecular sieve dried powder is added. 3+ Rare-earth modified Y-type molecular sieve Z7 was obtained by subjecting the sample to a second precipitate (at a temperature of 25°C for 0.5 hours), with the remaining conditions being the same.

[0128] In the process of preparing the catalytic cracking catalyst, catalytic cracking catalyst C7 was obtained by keeping the remaining conditions the same, except that rare earth-modified Y-type molecular sieve Z1 was replaced with rare earth-modified Y-type molecular sieve Z7.

[0129] Here, using the total weight of the catalytic cracking catalyst as a reference, the amount of Na in the catalytic cracking catalyst C7 is calculated as Na2O. + The content of [substance] was 0.19 wt%, the phosphorus content (calculated as P2O5) was 1.17 wt%, and the magnesium content (calculated as MgO) was 0.97 wt%.

[0130] Comparative Example 1 (1) Preparation of rare earth-modified molecular sieves Prepared according to the method disclosed in CN200610087535.2, specifically including the following:

[0131] 1000g (dry weight) of NaY molecular sieve was taken and slurryed with 8L of deionized water. Then, 0.385L of RECl3 solution with a concentration of 312g / L (La2O3 equivalent) was added, followed by 240g of aluminum sulfate. The mixture was changed at 90°C for 1 hour, then 75g of ammonium bicarbonate was added and stirred at constant temperature for 0.25 hours. After filtration, 5L of water was added for rinsing, and the filtered cake was roasted at 600°C in a 100% steam atmosphere for 2 hours to obtain exchange-roasted molecular sieve dry powder.

[0132] 1000g (dry weight) of this exchange-roasted molecular sieve dried powder was taken, slurryed with 6L of deionized water, then 300g of ammonium sulfate was added, the mixture was changed at 75°C for 1 hour, filtered, rinsed with 6L of water, and the filtered cake was dried to obtain rare earth-modified Y-type molecular sieve DZ1.

[0133] (2) Preparation of catalytic cracking catalyst To 100 parts of the dry mass of the catalyst, 30 parts by weight of the rare earth-modified Y-type molecular sieve DZ1, 0.9 parts by weight of ammonium dihydrogen phosphate (P2O5 equivalent), and water were mixed and slurryed for 30 minutes. Then, 52.1 parts by weight of kaolin, 7 parts by weight of alumina sol, and 10 parts by weight of acidic pseudoboehmite were added and mixed for 1 hour at 25°C to obtain a slurry with a solid content of 37 wt%. Subsequently, homogenization and spray molding were carried out in order, and the resulting microspheres were roasted at 440°C for 30 minutes to obtain a catalytic decomposition catalyst precursor.

[0134] According to the drying standards for catalyst solid particles, 200 g of the above catalytic cracking catalyst precursor was mixed with water to form a slurry containing 20 wt% solids of the catalyst precursor. Next, ammonium chloride was added and mixed, with a weight ratio of ammonium chloride to the slurry containing the catalyst precursor of 4:100. After filtration, 0.8 kg of water (the amount used for washing was 4 times the mass of the catalyst precursor) was added and washed at 25°C for 0.2 hours, and dried at 105°C for 10 hours to obtain catalytic cracking catalyst DC1.

[0135] Here, using the total weight of the catalytic cracking catalyst as a reference, the amount of Na in the catalytic cracking catalyst DC1 is calculated as Na2O. +The content was 0.25 wt%, and the phosphorus content, calculated on a P2O5 basis, was 0.78 wt%.

[0136] Comparative Example 2 (1) Preparation of rare earth-modified molecular sieves A rare-earth modified Y-type molecular sieve was prepared according to the method of Example 1, except that the following was omitted. Rare-earth modified Y-type molecular sieve DZ2 was obtained under the same conditions as before, except that ammonium oxalate monohydrate (32 g, 0.225 mol) was not added in step (b).

[0137] (2) Preparation of catalytic cracking catalyst To 100 parts of the dry mass of the catalyst, 28 parts by weight of the rare earth-modified Y-type molecular sieve DZ2, 1.5 parts by weight of ammonium dihydrogen phosphate (P2O5 equivalent), and water were mixed and slurryed for 30 minutes. Then, 50.5 parts by weight of kaolin, 5 parts by weight of alumina sol, and 15 parts by weight of acidic pseudoboehmite were added and mixed for 1 hour at 25°C to obtain a slurry with a solid content of 35 wt%. Subsequently, homogenization and spray molding were carried out in order, and the resulting microspheres were roasted at 470°C for 35 minutes to obtain a catalytic decomposition catalyst precursor.

[0138] According to the drying standards for catalyst solid particles, 200 g of the above catalytic cracking catalyst precursor was mixed with water to form a slurry containing 20 wt% solids of the catalyst precursor. Next, ammonium chloride was added and mixed, with a weight ratio of 3:100 between ammonium chloride and the slurry containing the catalyst precursor. After filtration, 0.8 kg of water (the amount used for washing was four times the mass of the catalyst precursor) was added and the mixture was washed at 25°C for 0.2 hours, and then dried at 120°C for 10 hours to obtain catalytic cracking catalyst DC2.

[0139] Here, using the total weight of the catalytic cracking catalyst as a reference, the amount of Na in the catalytic cracking catalyst DC2 is calculated as Na2O. + The content was 0.22 wt%, and the phosphorus content, calculated on a P2O5 basis, was 1.42 wt%.

[0140] Comparative Example 3 (1) Preparation of rare earth-modified molecular sieves A rare-earth modified Y-type molecular sieve was prepared according to the method of Example 2, except that the following was omitted: In step (d), ammonium oxalate monohydrate (25.6 g, 0.18 mol) was not added, and the remaining conditions were the same to obtain the rare-earth modified Y-type molecular sieve DZ3.

[0141] (2) Preparation of catalytic cracking catalyst To 100 parts of the dry mass of the catalyst, 32 parts by weight of the rare earth-modified Y-type molecular sieve DZ3, 1.5 parts by weight of ammonium dihydrogen phosphate (P2O5 equivalent), and water were mixed and slurryed for 30 minutes. Then, 45.5 parts by weight of kaolin, 8 parts by weight of alumina sol, and 13 parts by weight of acidic pseudoboehmite were added and mixed for 1 hour at 25°C to obtain a slurry with a solid content of 35 wt%. Subsequently, homogenization and spray molding were carried out in order, and the resulting microspheres were roasted at 430°C for 35 minutes to obtain a catalytic decomposition catalyst precursor.

[0142] According to the drying standards for catalyst solid particles, 200 g of the above catalytic cracking catalyst precursor was mixed with water to form a slurry containing 20 wt% solids of the catalyst precursor. Next, ammonium chloride was added and mixed, with a weight ratio of ammonium chloride to the slurry containing the catalyst precursor of 5:100. After filtration, 1.2 kg of water (the amount used for washing was 6 times the mass of the catalyst precursor) was added and washed at 25°C for 0.2 hours, and dried at 100°C for 10 hours to obtain catalytic cracking catalyst DC2.

[0143] Here, using the total weight of the catalytic cracking catalyst as a reference, the amount of Na in the catalytic cracking catalyst DC3 is calculated as Na2O. + The content was 0.20 wt%, and the phosphorus content, calculated on a P2O5 basis, was 1.32 wt%.

[0144] Comparative Example 4 (1) Preparation of rare earth-modified molecular sieves The preparation was carried out according to the method of Example 4, with the following exceptions: In step (b), ammonium oxalate monohydrate (25.6 g, 0.18 mol) and 5 mL of 28% industrial aqueous ammonia were not added, and in step (d), ammonium carbonate (18 g, 0.187 mol) was not added. The remaining conditions were the same to obtain rare earth-modified Y-type molecular sieve DZ4.

[0145] (2) Preparation of catalytic cracking catalyst The catalyst was prepared according to the method of Example 1, except that rare earth-modified Y-type molecular sieve Z1 was replaced with rare earth-modified Y-type molecular sieve DZ4. Catalytic cracking catalyst DC4 was obtained under the same conditions as before.

[0146] Here, using the total weight of the catalytic cracking catalyst as a reference, the amount of Na in the catalytic cracking catalyst DC4 is calculated as Na2O. + The content of [substance] was 0.21 wt%, the phosphorus content (calculated as P2O5) was 1.09 wt%, and the magnesium content (calculated as MgO) was 0.91 wt%.

[0147] Table 1 shows all the physical properties of the rare earth-modified molecular sieves (Z1-Z7 and DZ1-DZ4) prepared in Examples 1-7 and Comparative Examples 1-4 of the present invention.

[0148] [Table 1]

[0149] Test Example 1 Hydrothermal stability tests were conducted on the rare earth-modified molecular sieves (Z1-Z7 and DZ1-DZ4) prepared in Examples 1-7 and Comparative Examples 1-4. The test conditions were as follows: 100g (dry basis) of each rare earth-modified molecular sieve (Z1-Z7 and DZ1-DZ4) was formed into tablets and then pulverized to 20-40 mesh particles. After aging at 800°C for 10 hours under 100% steam in a fixed-bed hydrothermal treatment apparatus, the microactivity index (MA) was measured using an automated catalytic cracking microreaction activity evaluation device. The test results are shown in Table 2.

[0150] [Table 2]

[0151] Test Example 2 The reaction performance of the catalytic cracking catalysts (C1-C7 and DC1-DC4) prepared in Examples 1-7 and Comparative Examples 1-4 was tested. The test conditions were as follows: The catalytic cracking catalysts (C1-C7 and DC1-DC4) and the feedstock oil from a 3 million ton heavy oil catalyst system manufactured by Lanzhou Petrochemical Co., Ltd. were added to an ACE heavy oil microreactor, and catalytic cracking was carried out (temperature 510°C, weight ratio of catalytic cracking catalyst to feedstock oil from the 3 million ton heavy oil catalyst system manufactured by Lanzhou Petrochemical Co., Ltd. was 5:1) to obtain catalytic cracking products. The catalytic cracking products included dry gas, liquefied gas, gasoline, diesel, heavy oil, and coke. The test results are shown in Table 3.

[0152] [Table 3]

[0153] Note: 1 - Refers to the crude oil conversion rate of a 3 million ton heavy oil catalyst unit manufactured by Lanzhou Petrochemical Co., Ltd., and 2 - Refers to the total yield of liquefied gas, gasoline, and diesel.

[0154] The catalytic cracking catalyst according to the present invention, by using a rare-earth modified molecular sieve with low sulfate ion content, high crystallinity, strong acidity, and excellent stability in combination with a phosphorus source and a magnesium source, exhibits excellent activity stability, a high heavy oil conversion rate, and a high diesel yield. This catalyst is particularly suitable for heavy oil catalytic cracking, and in the heavy oil catalytic cracking process, it not only shows high catalytic cracking activity but also yields a high diesel yield.

[0155] Although preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, several simple modifications can be made to the technical solutions of the present invention, and these can be combined in any other suitable way that includes each technical feature, and these simple modifications and combinations should also be considered as part of the disclosure of the present invention and all fall within the scope of protection of the present invention.

Claims

1. A catalytic cracking catalyst, The catalytic cracking catalyst contains a catalytic cracking active component, the catalytic cracking active component contains a rare earth modified molecular sieve, a phosphorus oxide, and a magnesium oxide, and the SO in the rare earth modified molecular sieve 4 2- The content is 1 wt% or less, the degree of crystallinity of the rare earth modified molecular sieve is 50-80%, and the content of rare earths in the rare earth modified molecular sieve is RE 2 O 3 A catalytic cracking catalyst characterized by being in an amount of 5 to 20 wt% in terms of conversion.

2. SO in the rare earth-modified molecular sieve 4 2- The content is 0.5 wt% or less, and / or The sodium content in the aforementioned rare earth modified molecular sieve is Na 2 It is 1.2 wt% or less in terms of oxygen, and / or The content of rare earth in the rare earth-modified molecular sieve is RE 2 O 3 in terms of conversion is 6 to 18 wt%, and / or Based on the total weight of the catalytic cracking catalyst, the phosphorus oxide is P 2 O 5 The catalyst according to claim 1, wherein, when converted to MgO, the catalytic cracking catalyst contains 15 to 30% by weight of rare earth modified molecular sieve, 0.5 to 3% by weight of phosphorus oxide, and 0.2 to 1.5% by weight of magnesium oxide.

3. SO in the rare earth-modified molecular sieve 4 2- The content is 0.01 to 0.45 wt%, and / or The sodium content in the aforementioned rare earth modified molecular sieve is Na 2 The catalyst according to claim 2, wherein the amount is 0.6 to 1.0 wt% in terms of oxygen.

4. The aforementioned rare-earth modified molecular sieve is a rare-earth modified Y-type molecular sieve. The catalyst according to claim 1, wherein the catalytic cracking catalyst comprises a macroporous material, clay, the catalytic cracking active component, and an optional binder.

5. The macroporous material is selected from macroporous alumina and / or macroporous silicon aluminum material, and / or The clay is at least one selected from kaolin, halloysite, porous stone, diatomaceous earth, and pumice, and / or The catalyst according to claim 4, wherein the binder is at least one selected from silicon dioxide, alumina, and phosphorus pentoxide.

6. The macroporous material is selected from macroporous silicon aluminum materials and / or, The clay is selected from kaolin and / or, The catalyst according to claim 5, wherein the binder is selected from alumina.

7. The catalytic cracking catalyst contains a rare earth-modified molecular sieve, a macroporous material, a binder, clay, phosphorus oxide, and magnesium oxide, and the phosphorus oxide is P based on the total weight of the catalytic cracking catalyst. 2 O 5 When converted to MgO, the catalytic cracking catalyst comprises 15 to 30% by weight of rare earth modified molecular sieve, 2 to 15% by weight of macroporous material, 5 to 30% by weight of binder, 40 to 75% by weight of clay, 0.5 to 3% by weight of phosphorus oxide, and 0.2 to 1.5% by weight of magnesium oxide, as described in claim 1.

8. The method for preparing the rare earth-modified molecular sieve is as follows: Step (1) involves subjecting a Na-type molecular sieve to rare earth ion exchange to obtain a rare earth ion exchange slurry, Step (2) involves adding a first precipitating agent to cause a portion of the rare earth ions in the rare earth ion exchange slurry to undergo first precipitation, thereby obtaining a first precipitate slurry. Step (3) involves sequentially performing filtration, first ammonium sulfate exchange, first water washing, and first roasting on the first precipitate slurry to obtain an exchange roasted molecular sieve-dried powder, The catalyst according to claim 1, comprising the step (4) of adding a second precipitating agent so that a portion of the rare earth ions in the exchanged roasted molecular sieve dried powder undergo a second precipitate, and then sequentially performing a second ammonium sulfate exchange, a second water wash, and an optional second roast to obtain a rare earth modified molecular sieve.

9. In step (1), The catalyst according to claim 8, wherein the rare earth ion exchange process includes mixing the Na-type molecular sieve with water, and then adding a soluble rare earth source to perform the rare earth ion exchange.

10. The weight ratio of the Na-type molecular sieve to water is 1:(1.5 to 30), and / or RE 2 O 3 The mass ratio of the soluble rare earth source used and the amount of the Na-type molecular sieve used on a dry basis is 1 to 20:100, and / or The conditions for the rare earth ion exchange are as follows: The temperature must be between 25 and 180°C, and / or The pH is between 2.8 and 6.5, and / or This includes the fact that the time is between 0.3 and 3.5 hours. and / or, The silica / alumina ratio of the Na-type molecular sieve is 2 to 100:1, and / or The catalyst according to claim 9, wherein the soluble rare earth source is selected from chlorates and / or nitrates containing rare earths, and the rare earth is at least one selected from lanthanum, cerium, and yttrium.

11. The weight ratio of the Na-type molecular sieve to water is 1:(2-5), and / or RE 2 O 3 The mass ratio of the soluble rare earth source used and the amount of the Na-type molecular sieve used on a dry basis is 6 to 16:100, and / or The conditions for the rare earth ion exchange are as follows: The temperature must be between 50 and 80°C, and / or The pH is 3.5 to 4.5, and / or This includes the fact that the time is between 0.5 and 1.5 hours. and / or, The silica / alumina ratio of the Na-type molecular sieve is 2 to 50:1, and / or The Na-type molecular sieve is at least one selected from NaY molecular sieve, NaHY molecular sieve, NaUSY molecular sieve, NaREHY molecular sieve, and / or, The catalyst according to claim 10, wherein the rare earth element is selected from lanthanum and / or yttrium.

12. The catalyst according to claim 11, wherein the Na-type molecular sieve is selected from a NaY molecular sieve and / or a NaHY molecular sieve.

13. In step (2), The amount of the first precipitant used is such that it satisfies the molar ratio of the first precipitation of rare earth ions whose content in the Na-type molecular sieve is 1 to 4 wt%, and / or The catalyst according to claim 8, wherein the first precipitating agent is at least one selected from ammonium carbonate, ammonium bicarbonate, ammonium oxalate, ammonium acetate, aqueous ammonia, and urea.

14. The amount of the first precipitant used satisfies the molar ratio of the rare earth ions present in the Na-type molecular sieve at a content of 1.5 to 2.5 wt% due to the first precipitation. and / or, The conditions for the first precipitation are: The temperature must be between 25 and 180°C, and / or The catalyst according to claim 13, wherein the time is 0.1 to 5 hours.

15. The conditions for the first precipitation are: The temperature must be between 50 and 80°C, and / or Including the time being between 0.1 and 2 hours, and / or, The catalyst according to claim 14, wherein the first precipitant is at least one selected from ammonium carbonate, ammonium bicarbonate, ammonium oxalate, and aqueous ammonia.

16. In step (3), The process of the first ammonium sulfate exchange comprises subjecting the filtration product and the first aqueous ammonium sulfate solution to the first ammonium sulfate exchange, and / or The amount of water used in the first rinse is 1 to 8 times the weight of the Na-type molecular sieve, and / or The conditions for the first roasting process are: 100% water vapor atmosphere, and / or, The temperature is between 400 and 700°C, and / or, The catalyst according to claim 8, wherein the time is 0.1 to 5 hours.

17. The weight ratio of the first ammonium sulfate aqueous solution to the Na-type molecular sieve, calculated on an ammonium sulfate basis, is 5 to 50:100, and / or The concentration of ammonium sulfate in the aforementioned first aqueous ammonium sulfate solution is 20 to 400 g / L. and / or, The conditions for the first ammonium sulfate exchange are: The temperature must be between 15 and 150°C, and / or Including the time being between 0.1 and 5 hours, and / or, The amount of water used in the first rinse is 2 to 5 times the weight of the Na-type molecular sieve. and / or, The conditions for the first roasting process are: 100% water vapor atmosphere, and / or, The temperature must be between 500 and 650°C, and / or The catalyst according to claim 16, wherein the time is 0.5 to 3 hours.

18. The weight ratio of the first ammonium sulfate aqueous solution to the Na-type molecular sieve, calculated on an ammonium sulfate basis, is 10 to 25:100, and / or The concentration of ammonium sulfate in the first aqueous solution of ammonium sulfate is 120 to 250 g / L, and / or The conditions for the first ammonium sulfate exchange are: The temperature must be between 50 and 80°C, and / or The catalyst according to claim 17, wherein the time is 0.5 to 2 hours.

19. In step (4), The amount of the second precipitant used is such that it satisfies the molar ratio of the second precipitant of rare earth ions present in the exchanged roasted molecular sieve-dried powder at a content of 0.5 to 3 wt%, and / or The process of the second ammonium sulfate exchange comprises subjecting the second precipitate product and the second ammonium sulfate aqueous solution to the second ammonium sulfate exchange, and / or The amount of water used in the second washing is 1 to 8 times the weight of the exchanged roasted molecular sieve dried powder, and / or The conditions for the second roasting described above are: 20-100% water vapor atmosphere, and / or, The temperature is between 400 and 700°C, and / or, Including the time being between 0.1 and 10 hours, and / or, The catalyst according to claim 8, wherein the exchange roasted molecular sieve-dried powder and water are mixed before the second precipitation.

20. The amount of the second precipitant used is such that it satisfies the molar ratio of the second precipitant of rare earth ions present in the exchanged roasted molecular sieve-dried powder at a content of 1 to 2 wt%, and / or The second precipitating agent is at least one selected from ammonium carbonate, ammonium bicarbonate, ammonium oxalate, ammonium acetate, aqueous ammonia, and urea. and / or, The conditions for the second precipitation are: The temperature must be between 15 and 40°C, and / or Including the time being between 0.1 and 5 hours, and / or, The weight ratio of the above-mentioned ammonium sulfate aqueous solution (in terms of ammonium sulfate) to the exchange roasted molecular sieve-dried powder is 5 to 50:100, and / or The concentration of ammonium sulfate in the aforementioned second ammonium sulfate aqueous solution is 20 to 400 g / L. and / or, The conditions for the second ammonium sulfate exchange are: The temperature must be between 20 and 85°C, and / or Including the time being between 0.1 and 5 hours, and / or, The amount of water used in the second washing is 2 to 5 times the weight of the exchanged roasted molecular sieve dried powder. and / or, The conditions for the second roasting described above are: 20-100% water vapor atmosphere, and / or, The temperature is between 450 and 650°C, and / or This includes the fact that the time is between 0.5 and 5 hours. and / or, The catalyst according to claim 19, wherein the weight ratio of the exchange-roasted molecular sieve-dried powder to water is 1:(1.5 to 30).

21. The second precipitating agent is at least one selected from ammonium carbonate, ammonium bicarbonate, ammonium oxalate, and aqueous ammonia. and / or, The conditions for the second precipitation are: The temperature must be between 20 and 30°C, and / or Including the time being between 0.1 and 2 hours, and / or, The weight ratio of the above-mentioned ammonium sulfate aqueous solution (in terms of ammonium sulfate) to the exchange roasted molecular sieve-dried powder is 10 to 25:100, and / or The concentration of ammonium sulfate in the aforementioned second aqueous solution of ammonium sulfate is 120 to 250 g / L. and / or, The conditions for the second ammonium sulfate exchange are: The temperature must be between 50 and 80°C, and / or Including the time being between 0.1 and 2 hours, and / or, The catalyst according to claim 20, wherein the weight ratio of the exchange-roasted molecular sieve-dried powder to water is 1:(2-5).

22. A method for preparing a catalytic cracking catalyst according to any one of claims 1 to 21, wherein the preparation method is: A preparation method characterized by comprising the steps of mixing a catalytic decomposition active ingredient with a macroporous material source and a clay source in solution and bringing them into contact to obtain a catalyst precursor, optionally shaping it, and optionally drying and roasting it.

23. The aforementioned preparation method is Step (1) involves mixing the rare earth-modified molecular sieve, phosphorus source, and water to form a slurry, then adding a macroporous material source, binder source, and clay source, mixing, homogenizing, drying, and roasting to obtain catalyst solid particles. The preparation method according to claim 22, comprising step (2) mixing catalyst solid particles obtained in step (1), water, a magnesium source, and an optional ammonium source, then filtering, washing with water, and drying to obtain a catalytic cracking catalyst.

24. In step (1), For every 100 parts of the dry mass of the catalyst, add the phosphorus source P 2 O 5 The preparation method according to claim 23, wherein, in terms of conversion, 15 to 30 parts of rare earth modified molecular sieve, 0.5 to 3 parts of phosphorus source, 2 to 15 parts of macroporous material source, 5 to 30 parts of binder source, 40 to 75 parts of clay source, and water are mixed to obtain a slurry with a solid content of 25 to 50 wt%.

25. For every 100 parts of the dry mass of the catalyst, add the phosphorus source P 2 O 5 Converted to this, 18-27 parts of rare earth modified molecular sieve, 0.9-2 parts of phosphorus source, 3-7 parts of macroporous material source, 5.5-25 parts of binder source, 45-65 parts of clay source, and water are mixed to obtain a slurry with a solid content of 35-45 wt%, and / or The roasting conditions are as follows: The temperature is 400-500°C, and / or, The preparation method according to claim 24, wherein the time is 20 to 50 minutes.

26. The phosphorus source is at least one selected from diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium phosphate, and / or The macroporous material source is selected from macroporous alumina and / or macroporous silicon aluminum material, and / or The binder source is at least one selected from alumina sol, acidic pseudoboehmite, acidic silica sol, and phosphate alumina sol, and / or The clay source is at least one selected from kaolin, halloysite, porous stone, diatomaceous earth, and pumice. and / or, The roasting conditions are as follows: The temperature is 450-480°C, and / or, The preparation method according to claim 25, wherein the time is 25 to 40 minutes.

27. The phosphorus source is diammonium hydrogen phosphate, and / or The macroporous material source is selected from macroporous silicon aluminum material and / or, The binder source is selected from alumina sol and / or acidic pseudoboehmite, and / or The preparation method according to claim 26, wherein the clay source is selected from kaolin.

28. In step (2), When the catalyst solid particles are converted on a dry basis and the magnesium source is converted to MgO, The weight ratio of the water to the catalyst solid particles is 0.5 to 35:1, and / or The amount of magnesium source added is 0.6 to 1.2 wt%, and / or, The aforementioned conditions for flushing are: The temperature must be between 20 and 100°C, and / or, A preparation method according to any one of claims 23 to 27, comprising the condition that the time is 0.1 to 0.3 hours.

29. The amount of the magnesium source added is 0.6 to 1.2 wt%, and / or The magnesium source is selected from magnesium chloride and / or magnesium nitrate, and / or The ammonium source is selected from ammonium chloride and / or ammonium nitrate. and / or, The aforementioned conditions for flushing are: The temperature must be between 25 and 50°C, and / or The preparation method according to claim 28, further comprising the condition that the time is 0.15 to 0.25 hours.

30. Use of the catalytic cracking catalyst according to any one of claims 1 to 21 in heavy oil catalytic cracking.

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