A heavy oil cracking catalyst and a method for preparing the same

Abstract

The present application provides a heavy oil cracking catalyst and a preparation method thereof, the composition of the heavy oil cracking catalyst comprises: 0-10% ZSM-5 molecular sieve on a dry basis, 15-50% Y-type molecular sieve on a dry basis, 10-55% clay on a dry basis, 0-30% pseudo-boehmite on a dry basis, 4-70% titanium-containing composite binder on a dry basis, 0-15% binder on an oxide basis, 0-30% inorganic oxide carrier material on an oxide basis, and 0.2-5% modified metal compound on an oxide basis; wherein the titanium-containing composite binder is prepared by mixing calcined clay, water and titanium tetrachloride solution. The heavy oil cracking catalyst can promote efficient conversion of heavy oil, reduce the tendency of coke formation, has excellent reaction selectivity and use performance, improves the economic benefit of the catalytic cracking device, and reduces the carbon emission of the catalytic cracking device.

Description

Technical Field

[0001] This invention belongs to the field of refining catalysts, and relates to a heavy oil cracking catalyst, particularly a heavy oil cracking catalyst for reducing heavy oil yield and coke selectivity, and its preparation method. Background Technology

[0002] In the industrial production of polyolefins, the most widely used catalyst is the Ziegler-Natta catalyst, a titanium-based catalyst. Regarding the preparation of titanium-based polyolefin catalysts, for example, patent CN102336851B discloses a propylene polymerization catalyst comprising magnesium, titanium, halogens, and a mixture of one of the internal electron donor compounds, diisobutyl phthalate, diethyl phthalate, or di-n-butyl phthalate, and a succinate ester; patent CN107434832B discloses a propylene polymerization catalyst mainly composed of magnesium alkoxides, titanium compounds, and phosphate ester electron donor compounds. Currently, a common method for preparing titanium-based catalysts is as follows: first, magnesium halide alcohols are prepared, for example, by heating and dissolving magnesium halide with an alcohol, followed by high-pressure spraying or high-speed stirring, and then solidifying into microspheres in a cooling medium; specific steps are described in CN1110281A. Then, the magnesium halide alcohol particles are reacted with a halogen-containing compound such as titanium tetrachloride to prepare a magnesium-supported catalyst, during which various promoters can be added for modification. In the catalyst preparation process described above, a large amount of titanium tetrachloride is required, with a significant excess. Simultaneously, the obtained solid catalyst component needs to be washed with a hydrocarbon solvent (such as hexane) to remove unloaded titanium tetrachloride. Therefore, in the production of polyolefin catalysts, after separating and precipitating the solid catalyst, a large amount of catalyst mother liquor containing at least one of the following substances is generated: titanium tetrachloride, unreacted hydrocarbons, unreacted haloalkoxytitanium, alkoxymagnesium, and unreacted esters. The preparation of titanium-based polypropylene catalysts generates a large amount of waste liquid containing titanium tetrachloride, which, in addition to containing titanium tetrachloride (at least 80%), also contains small amounts of alkoxytitanium complexes (e.g., approximately 2-5%), small amounts of lipids, and n-hexane. Directly discarding this waste liquid would inevitably cause environmental pollution and resource waste; therefore, its effective utilization is necessary.

[0003] Regarding the preparation of titanium sol, titanium-containing molecular sieves, titanium-containing catalytic materials, titanium-containing catalysts, and additives from titanium tetrachloride, patent CN107866211B discloses a TiO2 sol and a catalytic cracking catalyst, as well as their preparation methods. The titanium-chloride molar ratio of the TiO2 sol is (0.2-0.6):1; and the corrosion rate of the TiO2 sol is ≤1 g / m³. 2The provided TiO2 sol, with a pH of 5-8 and a viscosity ≥1000 mPa·s at 20℃, possesses high viscosity, low corrosion rate, and high pH value. When used as a binder in the preparation of catalytic cracking catalysts, it helps increase the specific surface area of ​​the catalyst, improves its sphericity, enhances its activity, and improves the product distribution of the catalytic cracking reaction, primarily benefiting the formation of the target product, gasoline.

[0004] Patent CN102114429B discloses a method for increasing the Brønsted acid content of ZSM-5 molecular sieve and achieving increased production of low-carbon olefins. This method involves simultaneously modifying the ZSM-5 molecular sieve with iron and titanium. After modification, the mass ratio of iron to titanium in the molecular sieve is 0.3-3:1, which improves the catalytic reactivity of the molecular sieve and promotes the conversion of long-chain alkanes and aromatics with long-chain alkyl side chains, such as cumene, thereby significantly increasing the yield of low-carbon olefins.

[0005] Patent CN109694721B discloses a macroporous kaolinite and its preparation and application. The macroporous kaolinite contains a modified metal, has an average pore diameter of 2-50 nm, and pores with a diameter of 10-50 nm account for more than 80% of the total pore volume. The modified metal is one or more of alkaline earth metals, titanium, and zirconium. The preparation method of the macroporous kaolinite includes: first calcining kaolin; mixing the first calcined kaolin with a first acid, water, and optionally a modified metal compound, performing a first treatment, then performing a second calcination, followed by a second treatment with a second acid, water, a pore-expanding agent, and optionally a modified metal compound, filtering, and drying to obtain the macroporous kaolinite. At least one step in the first and second treatments involves adding a modified metal compound. The macroporous kaolinite can be used to prepare cracking catalysts, resulting in catalysts with high heavy oil conversion activity, high gasoline and liquefied petroleum gas yields, low dry gas selectivity, and low coke selectivity.

[0006] Patent CN105618107B discloses a catalytic cracking catalyst and its preparation method. Based on the total weight of the catalyst, the catalyst contains 10-60 wt% titanium and / or zirconium-modified Y molecular sieve, 10-60 wt% clay, and 5-50 wt% binder; the titanium and / or zirconium-modified Y molecular sieve contains 1.0 wt%-15.0 wt% titanium and / or zirconium metal oxide. The catalyst preparation method includes the steps of preparing the titanium and / or zirconium-modified Y molecular sieve, preparing a catalyst slurry, and spray drying. The titanium and / or zirconium-modified Y molecular sieve includes the following steps: (1) dispersing a titanium and / or zirconium-containing compound in water and adjusting the pH of the mixture to 3-10; (2) mixing the molecular sieve with the mixture obtained in step (1) and stirring; optionally filtering and / or drying; (3) calcining at 300-700℃. This catalyst exhibits high heavy oil conversion capacity and gasoline yield.

[0007] In existing technologies, none of them address the treatment of waste liquid containing titanium tetrachloride generated during the preparation of polypropylene catalysts. Moreover, the preparation process of titanium-containing kaolinite is complex, requiring multiple additions of acid and filtration treatments during the preparation process.

[0008] Therefore, in order to solve the problem of treating the large amount of titanium tetrachloride-containing waste liquid generated during the preparation of polypropylene catalysts, and to address the unfavorable factors of high heavy oil yield and high coke production during heavy oil cracking, despite recent catalyst technologies, there is still a need for new heavy oil cracking catalyst preparation technologies that are simple and feasible to prepare while possessing excellent performance. Summary of the Invention

[0009] To address the aforementioned problems, the present invention aims to provide a heavy oil cracking catalyst and its preparation method. This heavy oil cracking catalyst can promote efficient conversion of heavy oil, reduce coking tendency, exhibit excellent reaction selectivity and performance, improve the economic efficiency of catalytic cracking units, and reduce carbon emissions from catalytic cracking units.

[0010] To achieve the above objectives, the present invention provides a heavy oil cracking catalyst, which, calculated by weight (100%), comprises: 0-10% (dry basis) ZSM-5 molecular sieve, 15-50% (dry basis) Y-type molecular sieve, 10-55% (dry basis) clay, 0-30% (dry basis) boehmite, 4-70% (dry basis) titanium-containing composite binder, 0-15% (dry basis) binder, 0-30% (dry basis) inorganic oxide support material, and 0.2-5% (dry basis)... Modified metal compounds; wherein, the preparation method of the titanium-containing composite adhesive includes the following steps: (1) mixing calcined clay, water, and titanium tetrachloride solution to obtain a mixture; (2) reacting the above mixture at 40-120℃ for 0.5-6h to obtain the titanium-containing composite adhesive; based on the dry basis of the titanium-containing composite adhesive being 100%, the composition of the titanium-containing composite adhesive includes 7-45wt% titanium as oxide, 0.6-40wt% aluminum as oxide, and 30-92wt% silicon as oxide.

[0011] According to a specific embodiment of the present invention, preferably, the heavy oil cracking catalyst, calculated by weight of 100%, comprises: 1-8% ZSM-5 molecular sieve on a dry basis, 20-45% Y-type molecular sieve on a dry basis, 10-45% clay on a dry basis, 5-25% boehmite on a dry basis, 6-55% titanium-containing composite binder on a dry basis, 3-15% binder on an oxide basis, 2-15% inorganic oxide support material on an oxide basis, and 0.5-3% modified metal compound on an oxide basis.

[0012] According to a specific embodiment of the present invention, preferably, the solid content of the titanium-containing composite adhesive is 10-45 wt%.

[0013] According to a specific embodiment of the present invention, preferably, the titanium-containing composite adhesive comprises 7-30 wt% titanium as oxide, 8-40 wt% aluminum as oxide, and 35-70 wt% silicon as oxide, based on a dry basis of 100%.

[0014] According to a specific embodiment of the present invention, preferably, in the preparation method of the titanium-containing composite binder, the mixed raw materials also include a dispersant.

[0015] According to a specific embodiment of the present invention, preferably, the content of the dispersant is less than 10%, calculated based on a dry basis of 100% for the titanium-containing composite binder.

[0016] According to a specific embodiment of the present invention, preferably, the content of the dispersant is 0.3-5%.

[0017] According to a specific embodiment of the present invention, preferably, the dispersant comprises one or more of 1,3,5-trimethylbenzene, 1,3,5-triisopropylbenzene, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, and polyethylene glycol.

[0018] According to a specific embodiment of the present invention, preferably, in the preparation method of the titanium-containing composite binder, the titanium tetrachloride solution is titanium tetrachloride waste liquid; more preferably, the titanium tetrachloride waste liquid is titanium tetrachloride-containing waste liquid generated during the preparation of polypropylene catalyst, and the titanium in the titanium-containing composite binder comes from the titanium tetrachloride-containing waste liquid generated during the preparation of polypropylene catalyst.

[0019] According to a specific embodiment of the present invention, preferably, in the preparation method of the titanium-containing composite adhesive, the titanium tetrachloride solution is pure titanium tetrachloride.

[0020] According to a specific embodiment of the present invention, preferably, in the preparation method of the titanium-containing composite binder, the clay includes one or more of kaolin, hydrous kaolin, montmorillonite, diatomite, halloysite, sepiolite, and bentonite; more preferably, the clay is one or more of kaolin, hydrous kaolin, diatomite, halloysite, and sepiolite.

[0021] According to a specific embodiment of the present invention, preferably, in the preparation method of the titanium-containing composite binder, the calcination is carried out at 400-900°C for 0.5-6 hours.

[0022] According to a specific embodiment of the present invention, preferably, the preparation method of the titanium-containing composite adhesive includes the following steps: mixing clay calcined at 550-850℃ for 1-3 hours, water, and waste liquid containing titanium tetrachloride to form a mixture, and heating to 60-120℃ to react for 0.5-3 hours to obtain the titanium-containing composite adhesive.

[0023] According to a specific embodiment of the present invention, preferably, in the preparation method of the titanium-containing composite adhesive, after the reaction in step (2) is completed, the pH value of the reaction system is 0.5-8, more preferably, the pH value of the reaction system is adjusted to 0.5-8 using an alkaline substance.

[0024] According to a specific embodiment of the present invention, preferably, in step (1), the clay is pulverized before or after calcination until the average particle size D(v, 0.5) < 4 μm, and then mixed with water and titanium tetrachloride solution.

[0025] According to a specific embodiment of the present invention, preferably, the alkaline substance is selected from one or more combinations of ammonia, ammonium carbonate, ammonium bicarbonate, water glass, sodium aluminate, magnesium oxide, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide, and calcium carbonate.

[0026] According to a specific embodiment of the present invention, the ZSM-5 molecular sieve contains 0.2-6% phosphorus and 0-5% a second element, based on oxides, wherein the second element includes one or more of the elements selected from iron, zinc, magnesium, calcium, titanium, zirconium, lanthanum, cerium, and yttrium.

[0027] According to a specific embodiment of the present invention, preferably, the Y-type molecular sieve includes one or a combination of two or more of HY, NH4Y, hydrothermally ultrastable Y molecular sieve, silicon tetrachloride gas-phase ultrastable Y molecular sieve, rare earth-containing Y-type molecular sieve, and phosphorus-modified ultrastable Y molecular sieve.

[0028] According to a specific embodiment of the present invention, preferably, the rare earth-containing Y-type molecular sieve includes one or a combination of two of the following: rare earth-modified ultrastable Y-type molecular sieve and phosphorus and rare earth co-modified ultrastable Y-type molecular sieve.

[0029] According to a specific embodiment of the present invention, preferably, the clay includes one or more combinations of kaolin, hydrous kaolin, montmorillonite, diatomite, halloysite, sepiolite, and bentonite; more preferably, the clay includes one or more combinations of kaolin, hydrous kaolin, diatomite, halloysite, and sepiolite.

[0030] According to a specific embodiment of the present invention, preferably, the adhesive comprises one or a combination of two or more of aluminum sol, silica sol, aluminosilicate, and aluminum phosphate adhesive.

[0031] According to a specific embodiment of the present invention, preferably, the inorganic oxide carrier material includes one or more of the following: silica, alumina material containing Brønsted acid centers, and aluminosilicate material containing Brønsted acid centers; the alumina material containing Brønsted acid centers and the aluminosilicate material containing Brønsted acid centers have high pore volume, large specific surface area, dual pore distribution, high thermal stability and high acidity, and contain Brønsted acid centers.

[0032] According to a specific embodiment of the present invention, preferably, the modified metal compound includes one or more of the following: oxides, chlorides, nitrates, carbonates, sulfates, oxalates, and acetates of zinc, magnesium, calcium, titanium, zirconium, lanthanum, cerium, and yttrium.

[0033] According to a specific embodiment of the present invention, preferably, the composition of the heavy oil cracking catalyst further includes a pore structure improver.

[0034] According to a specific embodiment of the present invention, preferably, the weight of the pore structure improver is 0.1-10% of the total weight of the heavy oil cracking catalyst, more preferably 0.3-5%; the pore structure improver (addition amount, for example, 0.3-6%) is added during the catalyst preparation process to improve the pore structure, specific surface area and other properties of the catalyst.

[0035] According to a specific embodiment of the present invention, preferably, the pore structure improver includes one or more of 1,3,5-trimethylbenzene, 1,3,5-triisopropylbenzene, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, and polyethylene glycol.

[0036] In the preparation process of the titanium-containing composite binder in the heavy oil cracking catalyst feedstock of the present invention, the crystal structure of the clay is changed after high-temperature calcination. For example, the silicon and aluminum contained in kaolinite are mainly in the kaolinite structure. After high-temperature calcination, the kaolinite undergoes a phase transformation to form active silicon and active aluminum. These active silicon and active aluminum can react with acids or bases. Titanium tetrachloride hydrolyzes to produce titanium oxide and hydrogen chloride. Utilizing the aforementioned properties of clay and titanium tetrachloride, calcined clay is treated using waste liquid containing titanium tetrachloride. The calcined clay is mixed with water and the waste liquid containing titanium tetrachloride, allowing the hydrochloric acid produced from the hydrolysis of titanium tetrachloride to react with the active aluminum in the calcined clay, thus preparing a titanium-clay composite binder. Because the active aluminum in the clay reacts with the hydrochloric acid produced from the hydrolysis of titanium tetrachloride, the active aluminum detaches from the clay, forming mesoporous and macroporous pores within the clay. Simultaneously, the active aluminum reacting with the hydrochloric acid and the fine titanium oxide particles produced from hydrolysis together form a titanium-aluminum mixture, which, together with the aforementioned mesoporous clay, forms the titanium-clay composite binder. This titanium-containing composite binder not only functions as a binder but also contains mesoporous and macroporous clay components, which is beneficial for improving the pore structure of the catalyst, increasing the proportion of mesoporous and macroporous particles in the catalyst, and improving diffusion performance.

[0037] The present invention also provides a method for preparing the above-mentioned heavy oil cracking catalyst, which includes the following steps: (1) mixing and slurrying the ZSM-5 molecular sieve, Y-type molecular sieve, clay, pseudoboehmite, inorganic oxide support material, titanium-containing composite binder, binder, and modified metal compound (preferably with added pore structure improver) to obtain a slurry; (2) spray drying the slurry to form a shape, then calcining and curing, washing to reduce sodium, and drying to obtain the heavy oil cracking catalyst.

[0038] According to a specific embodiment of the present invention, preferably, the molecular sieve in step (1) is subjected to sand milling before mixing and pulping and / or the slurry in step (2) is subjected to sand milling before spray drying, so that the average particle size D(v, 0.5) of the molecular sieve in step (1) and / or the slurry in step (2) is less than 4 μm.

[0039] According to a specific embodiment of the present invention, preferably, the average particle size D(v, 0.5) of the slurry is < 4 μm.

[0040] According to a specific embodiment of the present invention, preferably, the pseudoboehmite is acidified and then aged at 40-90°C for 0.5-3 hours before use.

[0041] According to a specific embodiment of the present invention, preferably, in the process of acid sol-gelling of boehmite, the acid is an inorganic acid, more preferably one or a combination of two or more of hydrochloric acid, sulfuric acid, and nitric acid.

[0042] According to a specific embodiment of the present invention, preferably, the pseudo-boehmite is first mixed with a titanium-containing composite binder and aged at 40-90°C for 0.5-3 hours to achieve gelation before use.

[0043] According to a specific embodiment of the present invention, preferably, the ZSM-5 molecular sieve is a mesoporous ZSM-5 molecular sieve.

[0044] This invention is not limited to a spray drying method; techniques known to those skilled in the art can be employed, with process conditions such as controlling the spray tower furnace temperature at 450-550℃ and the spray exhaust gas temperature at 200-300℃. This invention can control the sieving distribution of spray-formed catalyst microspheres by controlling spray forming conditions such as spray pressure and nozzle size.

[0045] The titanium tetrachloride-containing wastewater generated during the preparation of polypropylene catalysts, with a titanium tetrachloride content of approximately 80%-95% (by weight), will inevitably cause environmental pollution and resource waste if discharged into the environment. This invention utilizes the titanium tetrachloride-containing wastewater generated during the polypropylene catalyst preparation process to prepare a titanium- and clay-containing composite binder, which is then used to prepare a catalytic cracking catalyst. This solves the utilization problem of the titanium tetrachloride-containing wastewater, avoids its environmental pollution, reduces the high treatment costs of this wastewater, and overcomes the shortcomings of existing technologies. The preparation process of the titanium-containing composite binder is simple and feasible, the pH value is adjustable, and the titanium content can be varied within a wide range.

[0046] The heavy oil cracking catalyst of the present invention has a simple and feasible preparation process, and the titanium content can be adjusted within a wide range. The prepared heavy oil cracking catalyst can be used in catalytic cracking units, has excellent anti-wear properties and large pore volume. When used in the heavy oil cracking process, it promotes efficient conversion of heavy oil, reduces heavy oil yield, reduces coking tendency, has excellent reaction selectivity and performance, improves the economic benefits of catalytic cracking units, and reduces carbon emissions from catalytic cracking units. Detailed Implementation

[0047] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0048] The elemental content of the following samples and catalysts was determined by X-ray fluorescence analysis. The attrition index of the catalyst was analyzed using an MS-C / 6 attrition index analyzer manufactured by Shenyang Kehui Instrument Manufacturing Co., Ltd. The pore volume of the catalyst was determined using the water droplet method.

[0049] The origin and specifications of the raw materials used are as follows:

[0050] (1) Waste liquid containing titanium tetrachloride generated during the preparation of polypropylene catalyst (hereinafter referred to as: waste liquid containing titanium tetrachloride): titanium content 90% (calculated as TiCl4), provided by Lanzhou Chemical Research Center of Petroleum and Chemical Research Institute of China National Petroleum Corporation; kaolin (loss on ignition 29wt%), halloysite (loss on ignition 16.6wt%), pseudoboehmite (loss on ignition 36wt%), alumina sol (containing alumina 21.6wt%), ordinary ZSM-5 molecular sieve (silicon-alumina ratio 31, mesopore volume 0.04mL / g), REHY molecular sieve (Na2O content 1.2wt%, RE2O3 content 8.3wt%, reduced by 4wt%), GUSY-1 molecular sieve (silicon tetrachloride gas-phase ultrastable molecular sieve, Na2O content 1.2wt%, RE2O3 content 2.5wt%, relative crystallinity 57%, cell constant (15wt% reduction), REUSY molecular sieve (Na2O content 1.4wt%, RE2O3 content 2.3wt%, 5wt% reduction), rare earth chloride solution (content of RE2O3 289.3g / L): all are industrial products, sourced from Lanzhou Petrochemical Company Catalyst Plant.

[0051] (2) Mesoporous ZSM-5 molecular sieve: silica-alumina ratio 30, mesopore volume 0.29 mL / g;

[0052] (3) Diatomaceous earth (loss on ignition 2.6 wt%): Industrial grade;

[0053] (4) Titanium tetrachloride, oxalic acid, magnesium chloride, magnesium oxide, cerium oxide, yttrium nitrate, yttrium oxide, zirconium oxide, polyethylene glycol, and carboxymethyl cellulose: are all chemical reagents;

[0054] (5) Hydrochloric acid: 36% concentration, chemical reagent; Nitric acid: 65-68% concentration, chemical reagent; Ammonia: 18% concentration, chemical reagent.

[0055] The spray drying methods for the heavy oil cracking catalysts in Examples 1-7 and Comparative Examples 1-9 used the following process conditions: the temperature of the spray tower furnace was controlled at 450°C, the temperature of the spray tail gas was controlled at 200°C, and the particle size range of the obtained catalyst was 65-78 μm.

[0056] Example 1

[0057] This embodiment provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0058] (1) Preparation of titanium- and clay-containing composite binders:

[0059] Kaolin was calcined at 750℃ for 2 hours to obtain calcined material. 1674g (dry basis) of the calcined material was crushed to an average particle size D(v, 0.5) < 4μm. 5.16L of decationized water was added and stirred. 332g of waste liquid containing titanium tetrachloride and 18g of polyethylene glycol were added. The temperature was raised to 70℃ and stirred for 1 hour. The pH value was 3.5, and a composite binder M-1 containing titanium and clay was obtained.

[0060] The composition of the titanium-clay composite binder M-1 is as follows: 93 wt% (dry basis) of kaolin roasting material, 7 wt% (calculated as titanium oxide) of titanium from waste liquid containing titanium tetrachloride, and the solid content of composite binder M-1 is 25 wt%.

[0061] (2) Preparation of heavy oil cracking catalyst:

[0062] Add 1.524 kg halloysite (dry basis), 1.68 kg composite binder M-1, 0.15 kg aluminum sol (alumina basis), 72.6 mL rare earth chloride solution and 0.54 kg deionized water to a pulping tank and pulp.

[0063] 0.84 kg of REUSY molecular sieve (dry basis), 152.5 g of yttrium nitrate and 1.29 kg of deionized water were mixed and pulped for 1.5 h, then added to the first pulping tank, followed by 30 g of carboxymethyl cellulose, and pulped for 2 h. The resulting slurry was then sand-milled to make the average particle size D(v, 0.5) less than 4 μm, and spray-dried to obtain catalyst microspheres.

[0064] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst CAT-1.

[0065] The heavy oil cracking catalyst CAT-1 has the following composition: halloysite 50.8 wt% (dry basis), solids from composite binder M-1 14 wt% (dry basis), alumina from alumina sol 5 wt%, REUSY molecular sieve 28 wt% (dry basis), yttrium oxide from yttrium nitrate 1.5 wt%, rare earth oxide from rare earth chloride solution 0.7 wt%, and the catalyst has a gel solids content of 42%.

[0066] Example 2

[0067] This embodiment provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0068] (1) Preparation of titanium- and clay-containing composite binders:

[0069] Halloysite was pulverized to an average particle size D(v, 0.5) < 4 μm and calcined at 600 °C for 5 hours to obtain calcined material. 1499 g (dry basis) of the calcined material was added to 7.3 L of decationized water and stirred. 793 g of waste liquid containing titanium tetrachloride was added, the temperature was raised to 90 °C, and the mixture was stirred for 2 hours. The pH value was adjusted to 2.5 with ammonia water to obtain composite binder M-2 containing titanium and clay.

[0070] The composition of the titanium-clay composite binder M-2 is as follows: 83.3 wt% halloysite calcined material (dry basis), 16.7 wt% titanium from waste liquid containing titanium tetrachloride (calculated as titanium oxide), and the solid content of composite binder M-2 is 18 wt%.

[0071] (2) Preparation of heavy oil cracking catalyst:

[0072] Add 0.675 kg of kaolin (dry basis) and 5 kg of composite binder M-2 to a pulping tank and pulp. Then add 0.36 kg of pseudoboehmite (dry basis) and 155.5 mL of rare earth chloride solution, stir for 1.5 h, then add 42 mL of hydrochloric acid, stir for 0.5 h, and then age at 50 °C for 1 h.

[0073] 0.9 kg of GUSY-1 molecular sieve (dry basis), 60 g of ordinary ZSM-5 molecular sieve (dry basis), 60 g of yttrium oxide and 1.5 kg of deionized water were mixed and pulped for 0.5 h. The mixture was then added to the first pulping tank, followed by the addition of 15 g of polyethylene glycol. The mixture was pulped for 1 h. The resulting slurry was then milled to make the average particle size D(v, 0.5) less than 4 μm. Finally, it was spray-dried to obtain catalyst microspheres.

[0074] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst CAT-2.

[0075] The heavy oil cracking catalyst CAT-2 has the following composition: 22.5 wt% kaolin (dry basis), 12 wt% alumina from boehmite, 30 wt% solids from composite binder M-2 (dry basis), 30 wt% GUSY-1 molecular sieve (dry basis), 2 wt% (dry basis) ordinary ZSM-5 molecular sieve, 2 wt% yttrium oxide, 1.5 wt% rare earth oxide from rare earth chloride solution, and a catalyst gel solids content of 32%.

[0076] Example 3

[0077] This embodiment provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0078] (1) Preparation of titanium- and clay-containing composite binders:

[0079] Kaolin and diatomaceous earth were pulverized to an average particle size D(v, 0.5) < 4 μm and calcined at 850℃ for 2.5 hours to obtain calcined materials. 900 g (dry basis) of calcined kaolin, 100.8 g (dry basis) of calcined diatomaceous earth, and 72 g of carboxymethyl cellulose were added to 2.0 L of decationized water and stirred. 2109 g of waste liquid containing titanium tetrachloride was added, the temperature was raised to 60℃, and the mixture was stirred for 3 hours. The pH value was adjusted to 3.0 with ammonia water to obtain composite binder M-3 containing titanium and clay.

[0080] The composite binder M-3 containing titanium and clay is composed of: 50 wt% (dry basis) of kaolin roasting material, 5.6 wt% (dry basis) of diatomaceous earth roasting material, and 44.4 wt% (calculated as titanium oxide) of titanium from waste liquid containing titanium tetrachloride. The solid content of composite binder M-3 is 30 wt%.

[0081] (2) Preparation of heavy oil cracking catalyst:

[0082] 0.645 kg of kaolin (dry basis), 0.18 kg of diatomaceous earth (dry basis), 0.24 kg of composite binder M-3 (solid content), 0.18 kg of alumina sol, 15 g of cerium oxide, 45 g of zirconium oxide and 1.53 kg of deionized water were added to a pulping tank and pulped. Then 0.54 kg of pseudoboehmite (dry basis) was added and stirred for 1 h. Then 30 mL of nitric acid was added and stirred for 1 h. After that, it was aged at 50 °C for 1.2 h.

[0083] 0.72 kg of GUSY-1 molecular sieve (dry basis), 0.18 kg of REHY molecular sieve (dry basis), 0.24 kg of mesoporous ZSM-5 molecular sieve (dry basis), 76.2 g of magnesium chloride, and 1.74 kg of deionized water were mixed and pulped for 0.5 h. The mixture was then added to the first-step pulping tank, followed by the addition of 150 g of carboxymethyl cellulose. The mixture was pulped for 1.8 h. The resulting slurry was then milled to ensure that the average particle size D(v, 0.5) was less than 4 μm. Finally, the mixture was spray-dried to obtain catalyst microspheres.

[0084] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst CAT-3.

[0085] The heavy oil cracking catalyst CAT-3 consists of: 21.5 wt% kaolin (dry basis), 6 wt% diatomaceous earth (dry basis), 18 wt% alumina from boehmite, 8 wt% solids from composite binder M-3 (dry basis), 6 wt% alumina from alumina sol, 24 wt% GUSY-1 molecular sieve (dry basis), 6 wt% REHY molecular sieve (dry basis), 8 wt% mesoporous ZSM-5 molecular sieve (dry basis), 1.5 wt% zirconium oxide, 0.5 wt% cerium oxide, and 0.5 wt% magnesium oxide from magnesium chloride. The catalyst has a gel solids content of 36%.

[0086] Example 4

[0087] This embodiment provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0088] (1) Preparation of titanium- and clay-containing composite binders:

[0089] Kaolin was pulverized to an average particle size D(v, 0.5) < 4 μm and calcined at 850 °C for 2 hours to obtain calcined material. 1674 g (dry basis) of the calcined material was added to 5.19 L of decationized water and stirred. 299 g of titanium tetrachloride and 9 g of polyethylene glycol were added, the temperature was raised to 85 °C, and the mixture was stirred for 4 hours. The pH value was 3.6, thus obtaining the titanium-clay composite binder M-4.

[0090] The composite binder M-4 containing titanium and clay has the following composition: 93 wt% kaolin roasting material (dry basis), 7 wt% titanium from titanium tetrachloride (calculated as titanium oxide), and the solid content of composite binder M-4 is 25 wt%.

[0091] (2) Preparation of heavy oil cracking catalyst:

[0092] Add 0.9 kg halloysite (dry basis), 0.75 kg kaolin (dry basis), 0.48 kg composite binder M-4, 0.414 kg aluminum sol (alumina basis), 20.7 mL rare earth chloride solution and 0.82 kg deionized water to a pulping tank and pulp.

[0093] 0.45 kg of REUSY molecular sieve (dry basis), 0.3 kg of mesoporous ZSM-5 molecular sieve (dry basis), 203.4 g of yttrium nitrate and 1.13 kg of deionized water were mixed and pulped for 1 hour, and then added to the first-step pulping tank. 15 g of carboxymethyl cellulose was added and pulped for 0.5 hours. The resulting slurry was sand-milled to make the average particle size D(v, 0.5) of the slurry less than 4 μm. After spray drying, catalyst microspheres were obtained.

[0094] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst CAT-4.

[0095] The heavy oil cracking catalyst CAT-4 has the following composition: halloysite 30 wt% (dry basis), kaolin 25 wt% (dry basis), solids from composite binder M-4 4 wt% (dry basis), alumina from alumina sol 13.8 wt%, REUSY molecular sieve 15 wt% (dry basis), mesoporous ZSM-5 molecular sieve 10 wt% (dry basis), yttrium oxide from yttrium nitrate 2 wt%, rare earth oxide from rare earth chloride solution 0.2 wt%, and the catalyst has a gel solids content of 40%.

[0096] Example 5

[0097] This embodiment provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0098] Add 11.67 kg of composite binder M-2 and 51.8 mL of rare earth chloride solution to the pulping tank for pulping;

[0099] 0.84 kg of GUSY-1 molecular sieve (dry basis) and 45 g of yttrium oxide were added to the first step slurry tank, followed by 3 g of polyethylene glycol. The slurry was slurried for 1 hour. The resulting slurry was then milled to make the average particle size D(v, 0.5) less than 4 μm. The slurry was then spray-dried to obtain catalyst microspheres.

[0100] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst CAT-5.

[0101] The composition of the heavy oil cracking catalyst CAT-5 is as follows: 70 wt% (dry basis) of solids from composite binder M-2, 28 wt% (dry basis) of GUSY-1 molecular sieve, 1.5 wt% of yttrium oxide, 0.5 wt% of rare earth oxides from rare earth chloride solution, and 21.3% of catalyst gel solids.

[0102] Example 6

[0103] This embodiment provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0104] Add 0.84 kg of kaolin (dry basis), 0.72 kg of composite binder M-1, 0.9 kg of pseudoboehmite (dry basis), 39 g of cerium oxide and 3.40 kg of deionized water to a pulping tank and pulp. Then add 45 mL of hydrochloric acid, stir for 0.5 h, and age at 60 °C for 0.5 h.

[0105] 0.9 kg of REUSY molecular sieve (dry basis), 30 g (dry basis) of mesoporous ZSM-5 molecular sieve, 90 g of yttrium oxide, 21 g of magnesium oxide and 1.47 kg of deionized water were mixed and pulped for 0.5 h. The mixture was then added to the first pulping tank, followed by the addition of 15 g of carboxymethyl cellulose. The mixture was pulped for another 0.5 h. The resulting slurry was then milled to make the average particle size D(v, 0.5) less than 4 μm. Finally, it was spray-dried to obtain catalyst microspheres.

[0106] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst CAT-6.

[0107] The composition of the heavy oil cracking catalyst CAT-6 is as follows: 28 wt% kaolin (dry basis), 6 wt% solids from composite binder M-1 (dry basis), 30 wt% alumina from boehmite, 30 wt% REUSY molecular sieve (dry basis), 1 wt% mesoporous ZSM-5 molecular sieve (dry basis), 3 wt% yttrium oxide, 1.3 wt% cerium oxide, 0.7 wt% magnesium oxide, and the catalyst gel content is 32%.

[0108] Example 7

[0109] This embodiment provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0110] Add 0.57 kg of kaolin (dry basis), 1.667 kg of composite binder M-2, 0.45 kg of alumina sol, 0.12 kg of boehmite (dry basis), and 30 g of cerium oxide to a pulping tank and pulp. Then add 6 mL of hydrochloric acid, stir for 0.5 h, and age at 60 °C for 0.5 h.

[0111] 1.5 kg of GUSY-1 molecular sieve (dry basis), 101.7 g of yttrium nitrate and 2.35 kg of deionized water were mixed and pulped for 1 hour, then added to the first pulping tank, followed by 15 g of carboxymethyl cellulose, and pulped for 0.5 hours. The resulting slurry was then sand-milled to make the average particle size D(v, 0.5) less than 4 μm, and spray-dried to obtain catalyst microspheres.

[0112] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain CAT-7, a heavy oil cracking catalyst.

[0113] The heavy oil cracking catalyst CAT-7 has the following composition: 19 wt% kaolin (dry basis), 4 wt% alumina from boehmite, 10 wt% solids from composite binder M-2 (dry basis), 15 wt% alumina from alumina sol, 50 wt% GUSY-1 molecular sieve (dry basis), 1 wt% yttrium oxide from yttrium nitrate, 1 wt% cerium oxide, and a catalyst gel solids content of 34%.

[0114] Comparative Example 1

[0115] This comparative example provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0116] (1) A macroporous kaolinite, prepared according to the method disclosed in Example 8 of CN109694721B for preparing macroporous kaolinite. The specific preparation method is as follows:

[0117] Kaolin was calcined at 750℃ for 2 hours to obtain calcined material (referred to as the first calcined material). 1680g (dry basis) of the calcined material was added to decationized water (pH=3.1, the same below) and stirred to prepare a slurry with a solid content of 25wt%. 5000g of 1mol / L hydrochloric acid, 1000g of oxalic acid, and 120g of TiCl4 (analytical grade) were added. The mixture was heated to 70℃ and stirred for 1 hour. The mother liquor was then removed by filtration, and the filter cake was dried to obtain the first step product. 1200g of the product was calcined at 750℃ for 2 hours to obtain calcined material (referred to as second calcined material). 1000g (dry basis) of the second calcined material was added to decationized water and stirred to obtain a slurry with a solid content of 25wt%. 2000g of 1mol / L hydrochloric acid, 500g of oxalic acid, 500g of polyethylene glycol, and 70g of TiCl4 (analytical grade) were added. The temperature was raised to 70℃ and stirred for 1 hour. Then the mother liquor was removed by filtration, and the filter cake was dried to obtain macroporous kaolinite DM-1.

[0118] (2) Preparation of heavy oil cracking catalyst:

[0119] Add 1.434 kg halloysite (dry basis), 0.42 kg macroporous kaolinite DM-1 (dry basis), 0.24 kg aluminum sol (alumina basis), 72.6 mL rare earth chloride solution and 0.44 kg deionized water to a pulping tank and pulp.

[0120] 0.84 kg of REUSY molecular sieve (dry basis), 152.5 g of yttrium nitrate and 1.29 kg of deionized water were mixed and pulped for 1.5 h, then added to the first pulping tank and pulped for 2 h. The resulting slurry was homogenized and spray-dried to obtain catalyst microspheres.

[0121] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst DCAT-1.

[0122] The composition of the heavy oil cracking catalyst DCAT-1 is as follows: halloysite 47.8 wt% (dry basis), macroporous kaolinite DM-1 14 wt% (dry basis), alumina from alumina sol 8 wt%, REUSY molecular sieve 28 wt% (dry basis), yttrium oxide from yttrium nitrate 1.5 wt%, rare earth oxide from rare earth chloride solution 0.7 wt%, and the catalyst solids content is 42%.

[0123] Comparative Example 2

[0124] This comparative example provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0125] (1) A modified halloysite, the preparation method of which is as follows:

[0126] Halloysite was pulverized to an average particle size D(v, 0.5) < 4 μm and calcined at 600 °C for 5 hours to obtain calcined material. 1499 g (dry basis) of the calcined material was added to 5.3 L of decationized water and stirred. 1526 g of hydrochloric acid was added, and the mixture was heated to 90 °C and stirred for 2 hours to obtain modified halloysite DM-2. The solid content of modified halloysite DM-2 was 18 wt%.

[0127] (2) Preparation of heavy oil cracking catalyst:

[0128] Add 0.675 kg of kaolin (dry basis) and 5 kg of modified halloysite DM-2 to a pulping tank and pulp. Then add 0.36 kg of pseudoboehmite (dry basis) and 155.5 mL of rare earth chloride solution, stir for 1.5 h, then add 42 mL of hydrochloric acid, stir for 0.5 h, and then age at 50 °C for 1 h.

[0129] 0.9 kg of GUSY-1 molecular sieve (dry basis), 60 g of ordinary ZSM-5 molecular sieve (dry basis), 60 g of yttrium oxide and 1.5 kg of deionized water were mixed and pulped for 0.5 h, then added to the first pulping tank and pulped for 1 h. The resulting slurry was homogenized and spray-dried to obtain catalyst microspheres.

[0130] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst DCAT-2.

[0131] The composition of the heavy oil cracking catalyst DCAT-2 is as follows: 22.5 wt% kaolin (dry basis), 12 wt% alumina from boehmite, 30 wt% modified halloysite DM-2 (dry basis), 30 wt% GUSY-1 molecular sieve (dry basis), 2 wt% ordinary ZSM-5 molecular sieve (dry basis), 2 wt% yttrium oxide, 1.5 wt% rare earth oxide from rare earth chloride solution, and the catalyst has a cementitious solids content of 32%.

[0132] Comparative Example 3

[0133] This comparative example provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0134] 1.395 kg of kaolin (dry basis) and 0.18 kg of aluminum sol (alumina basis) were added to a pulping tank and pulped. Then, 0.36 kg of boehmite (dry basis) and 155.5 mL of rare earth chloride solution were added and stirred for 1.5 h. Then, 42 mL of hydrochloric acid was added and stirred for 0.5 h. Finally, the mixture was aged at 50 °C for 1 h.

[0135] 0.9 kg of GUSY-1 molecular sieve (dry basis), 60 g of ordinary ZSM-5 molecular sieve (dry basis), 60 g of yttrium oxide and 1.5 kg of deionized water were mixed and pulped for 0.5 h, then added to the first pulping tank and pulped for 1 h. The resulting slurry was homogenized and spray-dried to obtain catalyst microspheres.

[0136] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst DCAT-3.

[0137] The composition of the heavy oil cracking catalyst DCAT-3 is as follows: 46.5 wt% kaolin (dry basis), 12 wt% alumina from boehmite, 6 wt% alumina from alumina sol (dry basis), 30 wt% GUSY-1 molecular sieve (dry basis), 2 wt% ordinary ZSM-5 molecular sieve (dry basis), 2 wt% yttrium oxide, 1.5 wt% rare earth oxide from rare earth chloride solution, and the catalyst solids content is 32%.

[0138] Comparative Example 4

[0139] This comparative example provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0140] (1) A titanium-containing, clay-based, non-calcined comparative binder, the preparation method of which is as follows:

[0141] 1674g (dry basis) of kaolin was pulverized to an average particle size D(v, 0.5) < 4μm. Without calcination, 4.2L of decationized water was added and stirred. 332g of waste liquid containing titanium tetrachloride and 18g of polyethylene glycol were added. The mixture was heated to 70℃ and stirred for 1 hour. The pH value was adjusted to 3.5 with ammonia water to obtain the titanium- and clay-containing comparative binder DM-3.

[0142] The composition of the titanium- and clay-containing comparative binder DM-3 is as follows: 93 wt% kaolin (dry basis), 7 wt% titanium (calculated as titanium oxide) from waste liquid containing titanium tetrachloride, and the solid content of the comparative binder DM-3 is 25 wt%.

[0143] (2) Preparation of heavy oil cracking catalyst:

[0144] Add 1.524 kg halloysite (dry basis), 1.68 kg of comparative binder DM-3, 0.15 kg of aluminum sol (alumina basis), 72.6 mL of rare earth chloride solution and 0.54 kg of deionized water to a pulping tank and pulp.

[0145] 0.84 kg of REUSY molecular sieve (dry basis), 152.5 g of yttrium nitrate and 1.29 kg of deionized water were mixed and pulped for 1.5 h, then added to the first pulping tank, followed by 30 g of carboxymethyl cellulose, and pulped for 2 h. The resulting slurry was then sand-milled to make the average particle size D(v, 0.5) less than 4 μm, and spray-dried to obtain catalyst microspheres.

[0146] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst DCAT-4.

[0147] The composition of the heavy oil cracking catalyst DCAT-4 is as follows: halloysite 50.8 wt% (dry basis), solids from the comparative binder DM-3 14 wt% (dry basis), alumina from alumina sol 5 wt%, REUSY molecular sieve 28 wt% (dry basis), yttrium oxide from yttrium nitrate 1.5 wt%, rare earth oxide from rare earth chloride solution 0.7 wt%, and the catalyst gel solids content is 42%.

[0148] Comparative Example 5

[0149] This comparative example provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0150] (1) A titanium- and clay-containing comparative binder:

[0151] Comparative binder DM-4 was prepared using the same method as the titanium- and clay-containing composite binder M-3 in Example 3, except that ammonia was not used to adjust the pH value. The preparation method is as follows:

[0152] Kaolin and diatomaceous earth were pulverized to an average particle size D(v, 0.5) < 4 μm and calcined at 850℃ for 2.5 hours to obtain calcined materials. 900 g (dry basis) of calcined kaolin, 100.8 g (dry basis) of calcined diatomaceous earth, and 72 g of carboxymethyl cellulose were added to 2.0 L of decationized water and stirred. 2109 g of waste liquid containing titanium tetrachloride was added, the temperature was raised to 60℃, and the mixture was stirred for 3 hours to obtain titanium- and clay-containing comparative binder DM-4.

[0153] The composition of the titanium- and clay-containing comparative binder DM-4 is as follows: 50 wt% (dry basis) of kaolin roasted material, 5.6 wt% (dry basis) of diatomaceous earth roasted material, and 44.4 wt% (calculated as titanium oxide) of titanium from waste liquid containing titanium tetrachloride.

[0154] (2) Preparation of heavy oil cracking catalyst:

[0155] 0.645 kg of kaolin (dry basis), 0.18 kg of diatomaceous earth (dry basis), 0.24 kg of DM-4 binder (solid content), 0.18 kg of alumina sol, 15 g of cerium oxide, 45 g of zirconium oxide, and 1.53 kg of deionized water were added to a pulping tank and pulped. Then, 0.54 kg of pseudoboehmite (dry basis) was added and stirred for 1 hour. Then, 30 mL of nitric acid was added and stirred for 1 hour. After that, the mixture was aged at 50°C for 1.2 hours.

[0156] 0.72 kg of GUSY-1 molecular sieve (dry basis), 0.18 kg of REHY molecular sieve (dry basis), 0.24 kg of mesoporous ZSM-5 molecular sieve (dry basis), 76.2 g of magnesium chloride, and 1.74 kg of deionized water were mixed and pulped for 0.5 h. The mixture was then added to the first-step pulping tank, followed by the addition of 150 g of carboxymethyl cellulose. The mixture was pulped for 1.8 h. The resulting slurry was then milled to ensure that the average particle size D(v, 0.5) was less than 4 μm. Finally, the mixture was spray-dried to obtain catalyst microspheres.

[0157] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst DCAT-5.

[0158] The composition of the heavy oil cracking catalyst DCAT-5 is as follows: 21.5 wt% kaolin (dry basis), 6 wt% diatomaceous earth (dry basis), 18 wt% alumina from boehmite, 8 wt% solids from the comparative binder DM-4 (dry basis), 6 wt% alumina from alumina sol, 24 wt% GUSY-1 molecular sieve (dry basis), 6 wt% REHY molecular sieve (dry basis), 8 wt% mesoporous ZSM-5 molecular sieve (dry basis), 1.5 wt% zirconium oxide, 0.5 wt% cerium oxide, and 0.5 wt% magnesium oxide from magnesium chloride. The catalyst gel solids content is 36%.

[0159] Comparative Example 6 (compared to Example 4)

[0160] This comparative example provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0161] Add 0.9 kg halloysite (dry basis), 0.84 kg kaolin (dry basis), 0.444 kg aluminum sol (alumina basis), 20.7 mL rare earth chloride solution and 1.03 kg deionized water to a pulping tank and pulp.

[0162] 0.45 kg of REUSY molecular sieve (dry basis), 0.3 kg of mesoporous ZSM-5 molecular sieve (dry basis), 203.4 g of yttrium nitrate and 1.13 kg of deionized water were mixed and pulped for 1 hour, and then added to the first-step pulping tank. 15 g of carboxymethyl cellulose was added and pulped for 0.5 hours. The resulting slurry was sand-milled to make the average particle size D(v, 0.5) of the slurry less than 4 μm. After spray drying, catalyst microspheres were obtained.

[0163] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst DCAT-6.

[0164] The composition of the heavy oil cracking catalyst DCAT-6 is as follows: halloysite 30 wt% (dry basis), kaolin 28 wt% (dry basis), alumina from alumina sol 14.8 wt%, REUSY molecular sieve 15 wt% (dry basis), mesoporous ZSM-5 molecular sieve 10 wt% (dry basis), yttrium oxide from yttrium nitrate 2 wt%, rare earth oxide from rare earth chloride solution 0.2 wt%, and the catalyst has a gel solids content of 40%.

[0165] Comparative Example 7 (compared to Example 5)

[0166] This comparative example provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0167] Add 2.1 kg of kaolin (dry basis), 51.8 mL of rare earth chloride solution and 8.71 kg of deionized water to a pulping tank and pulp.

[0168] 0.84 kg of GUSY-1 molecular sieve (dry basis) and 45 g of yttrium oxide were added to the first step slurry tank, followed by 3 g of polyethylene glycol. The slurry was slurried for 1 hour. The resulting slurry was then milled to make the average particle size D(v, 0.5) less than 4 μm. The slurry was then spray-dried to obtain catalyst microspheres.

[0169] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst DCAT-7.

[0170] The composition of the heavy oil cracking catalyst DCAT-7 is as follows: 70 wt% kaolin (dry basis), 28 wt% GUSY-1 molecular sieve (dry basis), 1.5 wt% yttrium oxide, 0.5 wt% rare earth oxide from rare earth chloride solution, and 21.3% catalyst gel content.

[0171] Comparative Example 8 (compared to Example 6)

[0172] This comparative example provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0173] 1.02 kg of kaolin (dry basis), 0.9 kg of boehmite (dry basis), 39 g of cerium oxide and 3.87 kg of deionized water were added to a pulping tank and pulped. Then 45 mL of hydrochloric acid was added, and the mixture was stirred for 0.5 h and aged at 60 °C for 0.5 h.

[0174] 0.9 kg of REUSY molecular sieve (dry basis), 30 g (dry basis) of mesoporous ZSM-5 molecular sieve, 90 g of yttrium oxide, 21 g of magnesium oxide and 1.47 kg of deionized water were mixed and pulped for 0.5 h. The mixture was then added to the first pulping tank, followed by the addition of 15 g of carboxymethyl cellulose. The mixture was pulped for another 0.5 h. The resulting slurry was then milled to make the average particle size D(v, 0.5) less than 4 μm. Finally, it was spray-dried to obtain catalyst microspheres.

[0175] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst DCAT-8.

[0176] The composition of the heavy oil cracking catalyst DCAT-8 is as follows: 34 wt% kaolin (dry basis), 30 wt% alumina from boehmite, 30 wt% REUSY molecular sieve (dry basis), 1 wt% mesoporous ZSM-5 molecular sieve (dry basis), 3 wt% yttrium oxide, 1.3 wt% cerium oxide, 0.7 wt% magnesium oxide, and the catalyst gel content is 32%.

[0177] Comparative Example 9 (compared to Example 7)

[0178] This comparative example provides a heavy oil cracking catalyst, the preparation method of which is as follows:

[0179] Add 0.87 kg of kaolin (dry basis), 0.45 kg of aluminum sol (alumina basis), 0.12 kg of boehmite (dry basis), and 30 g of cerium oxide to a pulping tank and pulp. Then add 6 mL of hydrochloric acid, stir for 0.5 h, and age at 60 °C for 0.5 h.

[0180] 1.5 kg of GUSY-1 molecular sieve (dry basis), 101.7 g of yttrium nitrate and 2.35 kg of deionized water were mixed and pulped for 1 hour, then added to the first pulping tank, followed by 15 g of carboxymethyl cellulose, and pulped for 0.5 hours. The resulting slurry was then sand-milled to make the average particle size D(v, 0.5) less than 4 μm, and spray-dried to obtain catalyst microspheres.

[0181] The catalyst microspheres obtained by spray drying were calcined, washed to remove sodium, and dried to obtain the heavy oil cracking catalyst DCAT-9.

[0182] The composition of the heavy oil cracking catalyst DCAT-9 is as follows: 29 wt% kaolin (dry basis), 4 wt% alumina from boehmite, 15 wt% alumina from alumina sol, 50 wt% GUSY-1 molecular sieve (dry basis), 1 wt% yttrium oxide from yttrium nitrate, 1 wt% cerium oxide, and the catalyst gel content is 34%.

[0183] Test Example 1

[0184] The anti-wear properties and pore volume of the heavy oil cracking catalysts CAT-1, CAT-2, and CAT-3 prepared in Examples 1-7, and the comparative catalysts DCAT-1, DCAT-2, and DCAT-3 prepared in Comparative Examples 1-9 were analyzed and tested. The test results are shown in Table 1.

[0185] Table 1. Performance test results of catalysts CAT-1, CAT-2, CAT-3, and comparative catalysts DCAT-1, DCAT-2, DCAT-3, etc.

[0186]

[0187]

[0188] The results in Table 1 show that, compared with the comparative catalysts DCAT-1, DCAT-2, DCAT-3, DCAT-6, and DCAT-8 prepared in Comparative Examples 1, 2, 3, 6, and 8, the heavy oil cracking catalysts CAT-1 to CAT-7 prepared in Examples 1-7 of this invention have a smaller wear index, better anti-wear performance, and larger pore volume. Compared with the comparative catalyst DCAT-5 prepared in Comparative Example 5, although the anti-wear performance of both DCAT-5 and the heavy oil cracking catalyst CAT-3 prepared in Example 3 of this invention can meet the requirements for catalyst use (generally, the wear index should be less than 3.5%), the catalyst CAT-3 of this invention has a larger pore volume. In Table 1, the wear indices of DCAT-4, DCAT-7, and DCAT-9 are too high and cannot meet the requirements for catalyst use (generally, the wear index should be below 3.5%). Compared with DCAT-4, catalyst CAT-1 has a lower wear index and good anti-wear performance. Compared with DCAT-7, catalyst CAT-5 has a lower wear index and good anti-wear performance. Compared with DCAT-9, catalyst CAT-7 has a lower wear index and good anti-wear performance.

[0189] Test Example 2

[0190] This test case is used to evaluate the performance of the heavy oil cracking catalysts in Examples 1-3.

[0191] The heavy oil cracking catalysts CAT-1, CAT-2, and CAT-3 prepared in Examples 1, 2, and 3, and the comparative heavy oil cracking catalysts DCAT-1, DCAT-2, DCAT-3, and DCAT-5 prepared in Comparative Examples 1, 2, 3, and 5, were subjected to aging treatment at 800°C and 100% water vapor for 17 hours. Then, using feedstock oil processed by the 3 million tons / year catalytic cracking unit of Lanzhou Petrochemical Company as feedstock oil, the catalytic cracking reaction performance was evaluated on a heavy oil micro-reaction evaluation unit (ACE).

[0192] The evaluation results are shown in Table 2.

[0193] In Table 2, total liquid yield = LPG yield + gasoline yield + diesel yield; coke factor = (100 - conversion rate) × coke yield / conversion rate.

[0194] Table 2. Results of reaction selectivity evaluation of heavy oil cracking catalysts in Examples 1-3, Comparative Examples 1-3, and Comparative Example 5.

[0195]

[0196]

[0197] Table 2 shows that, compared with the comparative catalytic cracking catalyst DCAT-2, the catalyst CAT-2 prepared in Example 2 exhibits a 0.62 percentage point increase in reaction conversion rate, a 1.37 percentage point increase in total liquid yield (LPG + gasoline + diesel), a 0.67 percentage point decrease in heavy oil yield, a 0.65 percentage point decrease in coke yield, and a lower coke factor, demonstrating excellent heavy oil conversion and reduced coking characteristics. Compared with the comparative catalyst DCAT-3, the catalyst CAT-2 prepared in Example 2 exhibits a 2.19 percentage point increase in reaction conversion rate, a 3.02 percentage point increase in total liquid yield (LPG + gasoline + diesel), a 1.10 percentage point decrease in coke yield, and a lower coke factor. Compared with the comparative catalyst DCAT-5, the catalyst CAT-3 prepared in Example 3 exhibits a 1.93 percentage point increase in reaction conversion rate, a 2.11 percentage point increase in total liquid yield (LPG + gasoline + diesel), a 0.89 percentage point decrease in coke yield, and a lower coke factor.

[0198] Compared with the comparative heavy oil cracking catalysts DCAT-1, DCAT-2, DCAT-3, and DCAT-5 prepared in Comparative Examples 1, 2, 3, and 5, the heavy oil cracking catalysts CAT-1, CAT-2, and CAT-3 of the present invention exhibit improved reaction conversion rates, reduced heavy oil yields, and decreased coke factors. This indicates that using the heavy oil cracking catalysts of the present invention can promote efficient conversion of heavy oil, reduce coking tendency, and improve the selectivity of catalytic cracking reactions.

Claims

1. A heavy oil cracking catalyst, comprising, based on 100% by weight of the heavy oil cracking catalyst: 0-10% ZSM-5 molecular sieve on a dry basis, 15-50% Y-type molecular sieve on a dry basis, 10-55% clay on a dry basis, 0-30% boehmite on a dry basis, 4-70% titanium-containing composite binder on a dry basis, 0-15% binder on an oxide basis, 0-30% inorganic oxide carrier material on an oxide basis, and 0.2-5% modified metal compound on an oxide basis; in, The preparation method of the titanium-containing composite adhesive includes the following steps: (1) Mix the calcined clay, water, and titanium tetrachloride solution to obtain a mixture, and calcinate it at 400-900℃ for 0.5-6h; (2) The above mixture is reacted at 40-120℃ for 0.5-6h to obtain the titanium-containing composite adhesive; the titanium-containing composite adhesive comprises 7-45 wt% titanium as oxide, 0.6-40 wt% aluminum as oxide, and 30-92 wt% silicon as oxide, based on a dry basis of 100%. Wherein, the titanium tetrachloride solution is titanium tetrachloride waste liquid; the titanium tetrachloride waste liquid is titanium tetrachloride-containing waste liquid generated during the preparation of polypropylene catalyst; after the reaction in step (2) is completed, the pH value of the reaction system is 0.5-8.

2. The heavy oil cracking catalyst according to claim 1, wherein, Based on the weight of the heavy oil cracking catalyst as 100%, its composition includes: 1-8% ZSM-5 molecular sieve on a dry basis, 20-45% Y-type molecular sieve on a dry basis, 10-45% clay on a dry basis, 5-25% boehmite on a dry basis, 6-55% titanium-containing composite binder on a dry basis, 3-15% binder on an oxide basis, 2-15% inorganic oxide carrier material on an oxide basis, and 0.5-3% modified metal compound on an oxide basis.

3. The heavy oil cracking catalyst according to claim 1 or 2, wherein, The titanium-containing composite adhesive has a solid content of 10-45 wt%.

4. The heavy oil cracking catalyst according to claim 3, wherein, Based on a dry basis of 100%, the titanium-containing composite adhesive comprises 7-30 wt% titanium as oxide, 8-40 wt% aluminum as oxide, and 35-70 wt% silicon as oxide.

5. The heavy oil cracking catalyst according to claim 1 or 2, wherein, In the preparation method of the titanium-containing composite adhesive, the raw materials mixed in step (1) also include a dispersant; the content of the dispersant is less than 10% based on the dry basis of the titanium-containing composite adhesive being 100%.

6. The heavy oil cracking catalyst according to claim 1 or 2, wherein, In the preparation method of the titanium-containing composite binder, the clay includes one or more of kaolin, montmorillonite, diatomite, and sepiolite.

7. The heavy oil cracking catalyst according to claim 1 or 2, wherein, In the preparation method of the titanium-containing composite binder, the clay includes halloysite.

8. The heavy oil cracking catalyst according to claim 1 or 2, wherein, In the preparation method of the titanium-containing composite binder, the clay includes bentonite and / or hydrous kaolin.

9. The heavy oil cracking catalyst according to claim 1 or 2, wherein, The preparation method of the titanium-containing composite adhesive includes the following steps: mixing clay calcined at 550-850℃ for 1-3 hours, water, and waste liquid containing titanium tetrachloride to form a mixture, and heating to 60-120℃ to react for 0.5-3 hours to obtain the titanium-containing composite adhesive.

10. The heavy oil cracking catalyst according to claim 1 or 2, wherein, In the preparation method of the titanium-containing composite adhesive, after the reaction in step (2) is completed, the pH value of the reaction system is adjusted to 0.5-8 using an alkaline substance.

11. The heavy oil cracking catalyst according to claim 1 or 2, wherein, In step (1), the clay is crushed before or after calcination until the average particle size D(v, 0.5) < 4 μm, and then mixed with water and titanium tetrachloride solution.

12. The heavy oil cracking catalyst according to claim 1 or 2, wherein, Based on oxides, the ZSM-5 molecular sieve contains 0.2-6% phosphorus and 0-5% a second element, which includes one or more of the elements iron, zinc, magnesium, calcium, titanium, zirconium, lanthanum, cerium, and yttrium.

13. The heavy oil cracking catalyst according to claim 1 or 2, wherein, The Y-type molecular sieve includes one or more of HY, NH4Y, hydrothermally ultrastable Y molecular sieve, silicon tetrachloride gas-phase ultrastable Y molecular sieve, rare earth-containing Y-type molecular sieve, and phosphorus-modified ultrastable Y molecular sieve; the rare earth-containing Y-type molecular sieve includes one or more of rare earth-modified ultrastable Y molecular sieve and phosphorus and rare earth-modified ultrastable Y molecular sieve.

14. The heavy oil cracking catalyst according to claim 1 or 2, wherein, In 10-55% clay on a dry basis, the clay includes one or more of kaolin, montmorillonite, diatomite, and sepiolite.

15. The heavy oil cracking catalyst according to claim 1 or 2, wherein, In clay comprising 10-55% on a dry basis, the clay includes halloysite.

16. The heavy oil cracking catalyst according to claim 1 or 2, wherein, In 10-55% clay on a dry basis, the clay includes bentonite and / or hydrous kaolin.

17. The heavy oil cracking catalyst according to claim 1 or 2, wherein, The inorganic oxide carrier material includes one or more of the following: silica, alumina containing Brønsted acid centers, and aluminosilicate containing Brønsted acid centers.

18. The heavy oil cracking catalyst according to claim 1 or 2, wherein, The modified metal compound includes one or more of the following: oxides, chlorides, nitrates, carbonates, sulfates, oxalates, and acetates of zinc, magnesium, calcium, titanium, zirconium, lanthanum, cerium, and yttrium.

19. The heavy oil cracking catalyst according to claim 1 or 2, wherein, The heavy oil cracking catalyst also includes a pore structure improver; the weight of the pore structure improver is 0.1-10% of the total weight of the heavy oil cracking catalyst.

20. The heavy oil cracking catalyst according to claim 19, wherein, The pore structure improver includes one or more of 1,3,5-trimethylbenzene, 1,3,5-triisopropylbenzene, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, and polyethylene glycol.

21. A method for preparing the heavy oil cracking catalyst according to any one of claims 1-20, comprising the following steps: (1) The ZSM-5 molecular sieve, Y-type molecular sieve, clay, pseudoboehmite, inorganic oxide carrier material, titanium-containing composite binder, binder, and modified metal compound are mixed and pulped to obtain a slurry; (2) The slurry is spray-dried and shaped, then calcined and cured, washed to reduce sodium content, and dried to obtain the heavy oil cracking catalyst.

22. The preparation method according to claim 21, wherein, The average particle size D(v, 0.5) of the slurry in step (2) is <4 μm.

23. The preparation method according to claim 21, wherein, The ZSM-5 molecular sieve is a mesoporous ZSM-5 molecular sieve.

24. The preparation method according to claim 21, wherein, The pseudoboehmite is added with acid and then aged at 40-90℃ for 0.5-3 hours before being gelled; during the gelling process of the pseudoboehmite with acid, the acid is an inorganic acid.

25. The preparation method according to claim 21, wherein, The pseudo-boehmite is first mixed with a titanium-containing composite binder and aged at 40-90℃ for 0.5-3 hours before being used.

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