Catalytic cracking catalyst and preparation method of binder thereof

Abstract

The invention provides a catalytic cracking catalyst and a preparation method of a binder thereof, and the preparation method of the binder comprises the following steps: mixing an aluminum source, a titanium source and water, then mixing with a dispersant and a modifier for reaction, adjusting the pH value to 0-8, and aging to obtain the binder for the catalytic cracking catalyst, wherein the aluminum source is calculated by aluminum, the titanium source is calculated by titanium, and the mass ratio of the titanium source to the aluminum source is (0.5-6): 10; the titanium source is titanium-containing waste liquid generated in polyolefin catalyst preparation; the dispersing agent is at least one of lysine, glutamic acid, gelatin, oxalic acid and citric acid; the modifier is at least one of a rare earth-containing compound and an alkaline earth metal-containing compound. The binder provided by the invention improves the bonding performance of aluminum sol, is beneficial to modulating the acidity of the catalyst, enhancing the stability of the catalyst, and improving the catalytic cracking reaction activity and carbon deposition resistance of the catalyst, so that the reaction modulation capability of the catalyst is enhanced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of catalytic cracking catalysts, and particularly relates to a catalytic cracking catalyst and a preparation method of a binder for the catalytic cracking catalyst. BACKGROUND

[0002] The commonly used binder in the matrix of the catalytic cracking catalyst is aluminum sol, silicon-aluminum sol, silica sol, peptized pseudo-boehmite, phosphorus-aluminum sol, etc., which all have their own unique properties and characteristics. When the most commonly used aluminum sol as a binder is used to prepare the catalyst, there are many deficiencies. Since the aluminum sol contains free chloride ions, when it is used as a binder for the catalytic cracking catalyst, the chloride ions will combine with hydrogen to produce hydrochloric acid in the spray drying process, which has adverse effects such as corrosion of the equipment. If the dechlorination treatment is not performed after the spray drying, the formed hydrochloric acid gas will destroy the crystal lattice structure of the molecular sieve, resulting in a decrease in catalytic activity, etc.

[0003] In the production process of the polyolefin catalyst, a large amount of titanium tetrachloride needs to be used, and the excessive proportion is very large. Therefore, after the catalyst solid is separated and precipitated in the production process of the polyolefin catalyst, a large amount of titanium-containing mother liquor is generated, in which titanium tetrachloride is the main component of the titanium-containing mother liquor, which is easy to react with water to generate corrosive hydrochloric acid gas, which constitutes a certain harm to the environment. In addition to unreacted titanium tetrachloride, the mother liquor may also contain hydrocarbon organic solvents, halogenated alkoxy titanium or alkoxy titanium, etc. If the waste liquid is directly discarded, it will inevitably cause environmental pollution and resource waste, so it needs to be effectively utilized and treated in a harmless manner.

[0004] Chinese patent CN107866211B discloses a TiO2sol and a catalytic cracking catalyst and their preparation methods, which relates to the field of TiO2sol and discloses a TiO2sol and its preparation method and application as well as a catalytic cracking catalyst and its preparation method. The TiO2sol has a titanium-chlorine molar ratio of (0.2-0.6):1, an erosion rate of ≤1g / m 2 h, a pH value of 5-8, and a viscosity of ≥1000mPa·s at 20℃. The TiO2sol provided by the present application has the characteristics of large viscosity, small erosion rate, and high pH value, which is beneficial to increase the specific surface area of the catalytic cracking catalyst, improve the sphericity of the catalytic cracking catalyst, enhance the activity of the catalytic cracking catalyst, improve the product distribution of the catalytic cracking reaction, and facilitate the generation of target product gasoline. However, the adhesion, wear resistance, strength, and carbon deposition resistance of the catalyst still need to be improved when the titanium sol is used for the catalytic cracking catalyst.

[0005] Chinese patent CN1552801 discloses a catalytic cracking catalyst containing silica sol binder and its preparation method, which is composed of 20-80 m% of clay, 5-30 m% of silica sol (calculated as SiO2), 0-30 m% of pseudo-boehmite (calculated as Al2O3), 5-40 m% of zeolite selected from the group consisting of zeolite with a cell constant of 2.432-2.472 nm, ZSM-5 zeolite, beta zeolite and their mixture, 0-5 m% (calculated as oxide) of compounds selected from the group consisting of antimony, mixed rare earth, titanium, magnesium, zinc, phosphorus, strontium or their mixture. It uses silica sol binder matrix or composite binder matrix combining silica sol and part of colloidal pseudo-boehmite, which not only enhances the macromolecular cracking capacity of the catalyst, but also ensures good wear resistance. However, the free chloride ion in the sol has a greater impact on the equipment.

[0006] Therefore, the binder for the catalytic cracking catalyst and the catalytic cracking catalyst still need to be further researched. SUMMARY

[0007] The main purpose of the present application is to provide a catalytic cracking catalyst and its preparation method of binder, so as to overcome the defects of the prior art, such as corrosion of equipment in the preparation process of the catalytic cracking catalyst, poor performance of the catalyst, etc.

[0008] In order to achieve the above purpose, the present application provides a preparation method of a binder for a catalytic cracking catalyst, comprising the following steps:

[0009] Mixing the aluminum source, titanium source and water, and then mixing and reacting with the dispersant and the modifier, adjusting the pH value to 0-8, aging to obtain the binder for the catalytic cracking catalyst;

[0010] Among them, the aluminum source is calculated as aluminum, the titanium source is calculated as titanium, and the mass ratio of the titanium source to the aluminum source is (0.5-6):10; the titanium source is titanium tetrachloride-containing waste liquid generated in the preparation of polyolefin catalyst; the dispersant is at least one of lysine, glutamic acid, gelatin, oxalic acid and citric acid; the modifier is at least one of rare earth compound and alkaline earth metal compound.

[0011] The preparation method of the binder for the catalytic cracking catalyst, wherein the titanium source is titanium tetrachloride-containing waste liquid generated in the preparation of polypropylene catalyst, and the mass content of titanium tetrachloride in the titanium tetrachloride-containing waste liquid is 80%-95%.

[0012] The preparation method of the binder for the catalytic cracking catalyst, wherein the aluminum source is selected from one or more of aluminum sheet, polyaluminum chloride, aluminum sol, one-water soft aluminum, three-water soft aluminum, bayerite, pseudo-boehmite and di-aluminum trioxide.

[0013] The preparation method of the catalyst binder for catalytic cracking catalyst, wherein the dispersant is added in an amount of 0.5% to 5% of the mass of the catalyst binder for catalytic cracking catalyst; and / or the modifier is added in an amount of 0.5% to 5% of the mass of the catalyst binder for catalytic cracking catalyst.

[0014] The preparation method of the catalyst binder for catalytic cracking catalyst, wherein the rare earth-containing compound is a chloride or nitrate of rare earth, and the rare earth is at least one of lanthanum, cerium, samarium, strontium and yttrium.

[0015] The preparation method of the catalyst binder for catalytic cracking catalyst, wherein the alkaline earth metal-containing compound is a chloride or nitrate of alkaline earth metal, and the alkaline earth metal is at least one of magnesium, calcium and barium.

[0016] The preparation method of the catalyst binder for catalytic cracking catalyst, wherein the aging temperature is 60 to 80℃, and the aging time is 1 to 5h.

[0017] The preparation method of the catalyst binder for catalytic cracking catalyst, wherein the pH value is adjusted by using an alkaline substance, and the alkaline substance is at least one of ammonia, magnesium oxide, calcium oxide, sodium hydroxide, sodium carbonate, sodium metaaluminate, potassium hydroxide, potassium carbonate and water glass.

[0018] To achieve the above-mentioned purpose, the application further provides a catalyst for catalytic cracking, wherein the binder is obtained by the above-mentioned preparation method.

[0019] The catalyst for catalytic cracking, wherein the catalyst further comprises a molecular sieve and a matrix material; the matrix material is at least one of kaolin, montmorillonite, diatomite, metahalloysite, halloysite, saponite, ledikite, hydrotalcite, sepiolite, bentonite and pseudo-boehmite; and the molecular sieve is at least one of REY, REHY, USY, Y and ZSM-5 molecular sieve.

[0020] The application has the following beneficial effects:

[0021] The binder of the application has titanium-containing substance, dispersant and modifier added in the aluminum sol, thereby improving the binding performance of the aluminum sol, facilitating the adjustment of the acidity of the catalyst, enhancing the stability of the catalyst, improving the catalytic cracking reaction activity and carbon deposition resistance of the catalyst, and enhancing the reaction adjustable capacity of the catalyst.

[0022] In addition, the titanium source of the application is obtained from the titanium tetrachloride-containing waste liquid generated in the preparation process of the industrial polypropylene catalyst, and the titanium tetrachloride-containing waste liquid generated in the preparation process of the industrial polypropylene catalyst is effectively utilized in a harmless manner. DETAILED DESCRIPTION

[0023] The technical solutions of the present application are described in detail below, and the following embodiments are implemented on the premise of the technical solutions of the present application, and detailed implementation processes are given, but the protection scope of the present application is not limited to the following embodiments, and the structures or experimental methods not marked with specific conditions in the following embodiments are usually according to conventional conditions.

[0024] The present application provides a preparation method of a binder for a catalytic cracking catalyst, comprising the following steps:

[0025] Mixing an aluminum source, a titanium source and water, and then mixing and reacting with a dispersant and a modifier, aging, adjusting the pH value to 0-8, to obtain a binder for a catalytic cracking catalyst;

[0026] Among them, the aluminum source is calculated by aluminum, the titanium source is calculated by titanium, and the mass ratio of the titanium source to the aluminum source is (0.5-6):10; the titanium source is a titanium-containing waste liquid generated in the preparation of a polyolefin catalyst; the dispersant is at least one of lysine, glutamic acid, gelatin, oxalic acid and citric acid; and the modifier is at least one of a rare earth compound and an alkaline earth metal compound.

[0027] The titanium-aluminum sol prepared by the present application as a binder for a catalytic cracking catalyst not only has good binding performance, but also can adjust the acidity of the catalyst, enhance the stability of the catalyst, and improve the catalytic cracking reaction activity and carbon deposition resistance of the catalyst. The catalytic cracking catalyst prepared by the present application can be used for catalytic cracking of heavy crude oil, and has high conversion rate and total liquid yield, and strong carbon deposition resistance.

[0028] The present application does not make special limitation to the aluminum source, and any conventional aluminum source in the art can be used, such as one or more of aluminum sheet, polyaluminum chloride, aluminum sol, one-water soft aluminum stone, three-water soft aluminum stone, bayer stone, pseudo-boehmite and di-aluminum oxide.

[0029] The titanium source of the present application is a titanium-containing waste liquid generated in the preparation of a polyolefin catalyst, so that the titanium-containing waste liquid can be effectively utilized, thereby reducing environmental pollution problems and reducing the amount of aluminum sol and the use cost of the catalytic cracking catalyst binder. More importantly, the problems of high cost and poor wear resistance of aluminum sol as a single catalyst binder are overcome, and the combination and modification of titanium and aluminum sol can make a large amount of free chloride ions and hydrogen ions in the aluminum sol combine to produce hydrogen chloride gas to volatilize, thereby avoiding corrosion of the industrial production device.

[0030] In an embodiment, the titanium source is a titanium tetrachloride-containing waste liquid generated in the preparation of a polypropylene catalyst, and the mass content of titanium tetrachloride in the titanium tetrachloride-containing waste liquid is 80%-95%.

[0031] The titanium-containing waste liquid refers to a mother liquor containing titanium after separation of catalyst solids in a polyolefin catalyst preparation process.

[0032] The dispersant is at least one of lysine, glutamic acid, gelatin, oxalic acid and citric acid, and the dispersant is added in an amount of 0.5% to 5% by mass of the binder for the catalytic cracking catalyst.

[0033] The modifier is at least one of a rare earth compound and an alkaline earth metal compound. In an embodiment, the rare earth compound is a chloride or nitrate of a rare earth, wherein the rare earth is at least one of lanthanum, cerium, samarium, strontium and yttrium. The alkaline earth metal compound is a chloride or nitrate of an alkaline earth metal, wherein the alkaline earth metal is at least one of magnesium, calcium and barium. The modifier is added in an amount of 0.5% to 5% by mass of the binder for the catalytic cracking catalyst.

[0034] The present application does not make special limitation to the conditions of the mixing reaction, for example, the reaction is carried out at normal temperature and pressure. After the reaction, the pH value is adjusted to 0 to 8. In an embodiment, the pH value is adjusted by using an alkaline substance as a reagent, for example, at least one of ammonia, magnesium oxide, calcium oxide, sodium hydroxide, sodium carbonate, sodium metaaluminate, potassium hydroxide, potassium carbonate and water glass, preferably ammonia. Then, aging is carried out, for example, at a temperature of 60 to 80°C for a time of 1 to 5h.

[0035] In an embodiment, the binder obtained by the method of the present application comprises an aluminum source, a titanium source, a pH value adjusting reagent, a dispersant and a modifier, and the rest is water. Among them, the aluminum source, the titanium source, the pH value adjusting reagent, the dispersant and the modifier account for 5% to 50% by mass of the binder on a dry basis.

[0036] The titanium-aluminum sol binder of the present application has simple preparation process, is green and environmentally friendly, has strong repeatability, and does not need to provide secondary heating. The binder prepared by the above-mentioned method of the present application can be used for a catalytic cracking catalyst, the abrasion resistance index of the catalyst can be controlled in the range of ≤2.0, the corrosion rate of the binder is ≤1g / (m 2 ·h), and the carbon deposition resistance, light oil yield and total liquid yield of the catalytic cracking catalyst are all improved.

[0037] In an embodiment, the catalytic cracking catalyst further comprises a molecular sieve and a matrix material; the matrix material is a matrix material with a large pore structure commonly used in the art, for example at least one of kaolin, montmorillonite, diatomite, metahalloysite, halloysite, saponite, ledikite, hydrotalcite, sepiolite, bentonite, preferably kaolin, diatomite, halloysite; the molecular sieve can be any commonly used molecular sieve, for example at least one of REY, REHY, USY, Y, ZSM-5 molecular sieve, wherein the Y molecular sieve can be a Y molecular sieve with different silicon-aluminum ratios prepared by a gas phase chemical method (SiCl4 removes Al and supplements Si), a liquid phase chemical method ((NH4)2SiF6 removes aluminum and supplements silicon), and other methods, or a modified Y molecular sieve.

[0038] The present application is not particularly limited to the preparation method of the catalytic cracking catalyst, for example, comprising: slushing the binder, the molecular sieve and the matrix material to obtain a catalyst slurry, spray drying and calcining the catalyst slurry to obtain the catalytic cracking catalyst.

[0039] The technical solutions of the present application will be further described in detail below through specific examples. In the examples of the present application, the element content in the sample is determined by X-ray fluorescence analysis method; the 20℃ viscosity of the titanium-aluminum sol is determined by a rotary viscometer (Shanghai Hengping Scientific Instrument Co., Ltd., NDJ-1 type rotary viscometer); the density of the titanium-aluminum sol is measured by specific gravity method using a glass density meter (Shenzhen Dingxinyi Experimental Equipment Co., Ltd.).

[0040] The raw materials used in the examples of the present application are as follows:

[0041] (1) Waste liquid containing titanium tetrachloride produced in the preparation process of polypropylene catalyst (hereinafter referred to as waste liquid containing titanium tetrachloride): titanium content 90wt% (calculated as TiCl4), provided by Lanzhou Chemical Research Center of Petrochemical Research Institute of China Petroleum;

[0042] (2) Pseudoboehmite (ignition loss 36wt%), aluminum sol (containing alumina 21.6wt%), water glass (SiO2 concentration 250g / L): taken from Lanzhou Petrochemical Company;

[0043] (3) Alumina, silica, magnesium aluminate spinel, ZSM-5 (ignition loss 8.3wt%), REY (ignition loss 15.4wt%), GUSY (ignition loss 4wt%), kaolin (ignition loss 29wt%), diatomite (ignition loss 2.6wt%), halloysite (ignition loss 28wt%), provided by Lanzhou Chemical Research Center of Petrochemical Research Institute of China Petroleum.

[0044] (4) Ammonia, hydrochloric acid, sodium hydroxide, magnesium nitrate (chemically pure reagent), polyaluminum chloride, purchased; lysine (Macklin, AR), glutamic acid (Macklin, AR), citric acid (Macklin, AR), yttrium chloride (Macklin, AR), ethylenediaminetetraacetic acid (Macklin, AR), lanthanum nitrate (Macklin, AR), ascorbic acid (Macklin, AR), strontium nitrate (Macklin, AR), ethylenediaminetetramethylene phosphonic acid (Macklin, AR), cerium nitrate (Macklin, AR), gelatin (Chengdu Kolon Chemical Co., Ltd., BR), D-malic acid (Macklin, 99%).

[0045] Example 1

[0046] Aluminum sol 231.5 g was poured into a glass beaker, then 3.52 g of titanium tetrachloride-containing waste liquid (containing 90% by weight of titanium tetrachloride) was added dropwise, followed by 329.8 g of deionized water, and stirred while adding dropwise in a fume hood at room temperature and normal pressure. After the system was mixed uniformly, 2.82 g of lysine (dispersant) and 2.82 g of yttrium chloride (modifier) were added. Then 18wt% ammonia water was added dropwise to adjust the pH value to 6.9, and the uniformly mixed slurry was aged at 60°C for 2 hours to obtain a titanium aluminum sol. Among them, the mass ratio of titanium aluminum in the feed Ti / Al was 0.5:10, and the measured pH after aging was 6.5. (denoted as TA-1)

[0047] Example 2

[0048] 94.41 g of pseudo-boehmite was poured into a glass beaker, then 7.05 g of titanium tetrachloride-containing waste liquid (containing 90% by weight of titanium tetrachloride) was added dropwise, followed by 384.5 g of deionized water, and stirred while adding dropwise in a fume hood at room temperature and normal pressure. After the system was mixed uniformly, 24.30 g of lysine (dispersant) and 1.88 g of lanthanum nitrate (modifier) were added. Then 18wt% ammonia water was added dropwise to adjust the pH value to 5.8, and the uniformly mixed slurry was aged at 80°C for 1 hour to obtain a titanium aluminum sol. Among them, the mass ratio of titanium aluminum in the feed Ti / Al was 1:10, and the measured pH after aging was 5.1. (denoted as TA-2)

[0049] Example 3

[0050] Aluminum sol 231.5 g was poured into a glass beaker, then titanium tetrachloride waste liquid (containing titanium tetrachloride 90% by weight) 14.10 g was added dropwise, followed by 493.4 g of deionized water, and stirred under normal temperature and pressure in the fume hood. After the system was mixed evenly, 29.56 g of citric acid (dispersant) and 10.10 g of cerium nitrate and 12.07 g of magnesium nitrate (modifier) were added. Then sodium hydroxide was added to adjust the pH value to 6.5, and the mixed slurry was aged at 80°C for 2 hours to obtain a titanium aluminum sol. Among them, the Ti / Al ratio in the raw material is 2:10, and the measured pH after aging is 5.7. (marked as TA-3)

[0051] Example 4

[0052] Pseudo-boehmite 94.41 g was poured into a glass beaker, then titanium tetrachloride waste liquid (containing titanium tetrachloride 90% by weight) 21.14 g was added dropwise, followed by 602.7 g of deionized water, and stirred under normal temperature and pressure in the fume hood. After the system was mixed evenly, 8.7 g of lanthanum nitrate (modifier) and 2.09 g of gelatin and 10.08 lysine (dispersant) were added. Then add water glass (SiO2 concentration is 250 g / L) to adjust the pH value to 3.7, and the mixed slurry is aged at 80°C for 2 hours to obtain a titanium aluminum sol. Among them, the Ti / Al ratio in the raw material is 3:10, and the measured pH after aging is 3.0. (marked as TA-4)

[0053] Example 5

[0054] Aluminum sol 231.5 g was poured into a glass beaker, then titanium tetrachloride waste liquid (containing titanium tetrachloride 90% by weight) 42.27 g was added dropwise, followed by 929.8 g of deionized water, and stirred under normal temperature and pressure in the fume hood. After the system was mixed evenly, 32.49 g of gelatin (dispersant) and 10.83 g of cerium nitrate and 8.89 g of strontium nitrate (modifier) were added. Then add magnesium oxide to adjust the pH value to 0.7, and the mixed slurry is aged at 80°C for 2 hours, then the aged slurry is cooled at room temperature to obtain a titanium aluminum sol. Above all, the Ti / Al ratio in the raw material is 6:10, and the measured pH after aging is 0.1. (marked as TA-5)

[0055] Comparative Example 1

[0056] According to the scheme provided in patent CN107866211A, a TiO2sol was prepared, and the preparation method is as follows:

[0057] (1) In beaker 1, 7g of TiCl4 was added, and 7g of ammonia water with a concentration of 18wt% was added dropwise into beaker 1 while stirring, so as to promote the mixing reaction of TiCl4 and NH3·H2O at a temperature of 50°C (water bath temperature control) for 30min, and then the mixed solution after the reaction was completed was left to stand at room temperature for 1h to obtain a sol-like first mixture. It was measured that the pH value of the first mixture obtained by the reaction was 9;

[0058] (2) In beaker 2, 19g of TiCl4 was added, and 2.94g of hydrochloric acid with a concentration of 31wt% was added dropwise into beaker 2 under stirring conditions, so as to promote the mixing reaction of TiCl4 and HCl at a temperature of 50°C (water bath temperature control) for 5min to obtain a second mixture;

[0059] (3) The sol first mixture obtained in step (1) was poured into the second mixture beaker in (2); the first mixture and the second mixture were promoted to carry out a third contact reaction at a temperature of 50°C (water bath temperature control) for 1.5h to obtain a third mixture, and deionized water was added to the third mixture until the pH value of the third mixture was in the interval of 5-8 to obtain a TiO2 sol (denoted as T-1).

[0060] Comparative Example 2

[0061] A titanium sol was prepared according to the method disclosed in patent CN00110406.3, and the preparation method was as follows:

[0062] TiCl4 was used as a raw material to react with NaOH solution to generate a precipitate, and the pH value was 6.5. After the precipitate was washed, water and a 31wt% hydrochloric acid solution were added, and the amount of added acid was H + / Ti molar ratio was 0.5, and the mixture was stirred at 60°C for 30h to obtain a TiO2 sol (denoted as T-2).

[0063] Comparative Example 3

[0064] A titanium sol was prepared according to the method disclosed in patent CN112744849A, and the preparation method was as follows:

[0065] (1) While stirring, 430g of ammonia water with a concentration of 18wt% was slowly added to 900g of aluminum chloride solution with a concentration of 20wt% at room temperature, and stirring was continued for 0.5h to obtain a first reaction liquid with a pH value of 3.4;

[0066] (2) The temperature of the first reaction liquid was increased to 50°C, and stirring was continued at this temperature for 0.5h;

[0067] (3) With stirring, 200 g of polyaluminum chloride (Al content 51.06 g) was introduced into the heated solution obtained in step (2), and 211 g of ammonia water with a concentration of 18 wt% was added, to obtain a second reaction solution with a pH of 3.9;

[0068] (4) The temperature of the second reaction solution was raised to 80°C, and the reaction was stirred at this temperature for 3 hours, and then cooled to ambient temperature, to obtain an aluminum sol S1 with a concentration of 5.4 wt% (calculated as Al2O3), and the aluminum-chlorine mass ratio of the aluminum sol S1 was 1.1. (denoted as A-1)

[0069] Comparative Example 4

[0070] The same as the scheme of Example 2, except that the addition of the modifier was cancelled, and the pH measured after aging was 4.9. (denoted as TA-6)

[0071] Comparative Example 5

[0072] The same as the scheme of Example 4, except that the addition of the dispersant was cancelled, and the pH measured after aging was 2.9. (denoted as TA-7)

[0073] The binder sols TA-1 to TA-5 and T-1, T-2, A-1, TA-6, TA-7 prepared in Examples 1-5 and Comparative Examples 1-5 were subjected to physical property testing, and the test results are shown in Table 1.

[0074] Table 1: Performance test evaluation data of the binder of Examples 1-5 and Comparative Examples 1-5

[0075]

[0076] As shown in Table 1, the titanium-aluminum sol prepared in the application has a lower attrition index and a higher viscosity.

[0077] Preparation of the catalyst:

[0078] According to the conventional preparation method of catalytic cracking catalyst, the binder-titanium-aluminum sols TA-1 to TA-4, titanium sols T-1, T-2, A-1, TA-6 prepared in Examples 1-4 and Comparative Examples 1-3, and molecular sieves and kaolin were mixed and homogenized, and then spray dried, calcined and solidified, washed with water and dried, to obtain a catalyst, and the attrition index of the catalyst was tested.

[0079] Catalyst Preparation Example 1

[0080] First, add 1145g of ZSM-5 molecular sieve to the reactor, then add 1618g of deionized water and mix thoroughly with the molecular sieve for 30–90 min. Next, add 1352g of kaolin, 833g of halloysite, and 1806g of TA-1 titanium-aluminum sol prepared according to the method in Example 1, and mix and slurry for 1–2 h. Then add 100ml of dilute hydrochloric acid (31wt%) and stir for 1–2 h. Spray dry the mixed slurry, and calcine the resulting catalyst microspheres at 500℃ for 2 h. The obtained catalyst sample is designated C-1.

[0081] Catalyst Preparation Example 2

[0082] First, add 532g of REY molecular sieve and 625g of GUSY molecular sieve to the reactor, then add 1606g of deionized water and mix thoroughly with the molecular sieves for 30-90 minutes. Next, add 1268g of kaolin, 938g of boehmite, and 1779g of TA-2 titanium-aluminum sol prepared according to the method in Example 2, and mix and slurry for 1-2 hours. Then add 100ml of dilute hydrochloric acid (31wt%) and stir for 1-2 hours. Spray dry the mixed slurry, and calcine the resulting catalyst microspheres at 500℃ for 2 hours. The obtained catalyst sample is designated C-2.

[0083] Catalyst Preparation Example 3

[0084] First, add 355g of REY molecular sieve, 313g of GUSY molecular sieve, and 491g of ZSM-5 molecular sieve to the reactor. Then, add 1605g of deionized water and mix thoroughly with the molecular sieves for 30–90 min. Next, add 1521g of kaolin, 667g of halloysite, and 1364g of TA-3 titanium-aluminum sol prepared in Example 3, and mix and slurry for 1–2 h. Then, add 100ml of dilute hydrochloric acid (31wt%) and stir for 1–2 h. Spray dry the mixed slurry and calcine the resulting catalyst microspheres at 500℃ for 2 h. The obtained catalyst sample is designated C-3.

[0085] Catalyst Preparation Example 4

[0086] First, add 469g of GUSY molecular sieve and 655g of ZSM-5 molecular sieve to the reactor, then add 1476g of deionized water and mix thoroughly with the molecular sieves for 30-90 minutes. Next, add 1225g of kaolin, 647g of diatomaceous earth, and 1247g of TA-4 titanium-aluminum sol prepared according to the method in Example 4, and mix and slurry for 1-2 hours. Then add 100ml of dilute hydrochloric acid (31wt%) and stir for 1-2 hours. Spray dry the mixed slurry, and calcine the resulting catalyst microspheres at 500℃ for 2 hours. The obtained catalyst sample is designated C-4.

[0087] Catalyst Preparation Comparative Example 1

[0088] A process for preparing a dual-aluminum binder FCC catalyst based on boehmite and aluminum sol. The preparation is carried out according to the method described in Chinese Patent CN1081218C.

[0089] 8295g of aluminum sol (prepared according to traditional aluminum sol prepared according to CN1081218C, i.e., prepared by adding hydrochloric acid to Al powder, with a solid content of 21.7wt% as Al2O3) was added to a reactor and stirred. 102.9kg of pseudoboehmite (Shandong Boehmite Plant, 68wt% loss on ignition) was added and stirred for 40min. 431g of kaolin was added, and the mixture was stirred and stirred for 60min. Then, 20g of 22% hydrochloric acid was added and stirred for 30min. 127.4g of REY-type molecular sieve slurry (produced by Qilu Branch of Sinopec Catalyst Co., Ltd., with a solid content of 31.4wt% and a rare earth oxide (La or Ce) content of 17-18wt%) was added and stirred for 30min, followed by spray drying. The resulting catalyst microspheres were calcined at 500℃ for 1h, then washed twice with 8 times the amount of dry-based decationized water, and dried at 120℃ for 2h to obtain sample C-5.

[0090] Catalyst Preparation Comparative Example 2

[0091] First, add 469g of GUSY molecular sieve and 655g of ZSM-5 molecular sieve to the reactor, then add 1476g of deionized water and mix thoroughly with the molecular sieves for 30–90 min. Next, add 1225g of kaolin, 647g of diatomaceous earth, and 1247g of TA-6 titanium-aluminum sol prepared according to method 4, and mix and slurry for 1–2 h. Then add 100ml of dilute hydrochloric acid (31wt%) and stir for 1–2 h. Spray dry the mixture, and calcine the resulting catalyst microspheres at 500℃ for 2 h. The obtained catalyst sample is designated C-6.

[0092] Catalyst preparation Comparative Example 3

[0093] 231.5g of aluminum sol was poured into a glass beaker, followed by 14.10g of titanium tetrachloride waste liquid (containing 90% by weight of titanium tetrachloride) added dropwise, and then 493.4g of deionized water. The mixture was added dropwise while stirring under ambient temperature and pressure in a fume hood. Sodium hydroxide was then added to adjust the pH to 6.5. The well-mixed slurry was then allowed to stand at 80℃ for 2 hours to age, yielding titanium-aluminum sol. The titanium-aluminum ratio (Ti / Al) in the initial feed was 2:10, and the pH after aging was measured to be 5.1 (denoted as TA-3').

[0094] First, add 355g of REY molecular sieve, 313g of GUSY molecular sieve, and 491g of ZSM-5 molecular sieve to the reactor. Then, add 1605g of deionized water and mix thoroughly with the molecular sieves for 30–90 min. Next, add 1521g of kaolin, 667g of halloysite, and 1364g of TA-3' titanium-aluminum sol, and mix and slurry for 1–2 h. Then, add 100ml of dilute hydrochloric acid (31wt%) and stir for 1–2 h. Spray dry the mixed slurry and calcine the resulting catalyst microspheres at 500℃ for 2 h. Then, add an aqueous solution containing 29.56g of citric acid (dispersant), 10.10g of cerium nitrate, and 12.07g of magnesium nitrate (modifier) ​​to the catalyst using an impregnation method. Stir thoroughly at 120℃ until homogeneous. After the sample is dried, it is recorded as catalyst sample C-7.

[0095] Catalyst evaluation

[0096] The catalytic cracking performance of the catalyst of this invention and the comparative catalyst were evaluated. The catalyst was aged at 800°C for 17 hours. The feedstock was from a 3 million tons / year catalytic cracking unit of a petrochemical company.

[0097] Table 2 shows the properties of the feedstock oil, and Table 3 shows the reaction evaluation results of the catalyst.

[0098] Table 2. Properties of Crude Oil

[0099]

[0100] Table 3. Catalyst reaction performance evaluation data for Catalyst Preparation Examples 1-4 and Comparative Examples 1 and 2.

[0101]

[0102] As shown in Table 3, when catalysts (C-1 to C-4) prepared using the titanium-aluminum sol (TA-1 to TA-4) of the present invention are used for heavy crude oil processing, the product conversion rate is higher, the liquid yield is higher, the amount of heavy oil is less, the C4 olefin selectivity is higher, and the catalyst anti-carbon deposition performance is better. These results exceed the levels of catalysts C5 and C6 prepared using aluminum sol in the prior art and are superior to the effect of catalyst C7.

[0103] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A process for the preparation of a binder for a catalytic cracking catalyst, characterized in that, The method comprises the following steps: Mixing an aluminum source, a titanium source and water, and then mixing and reacting with a dispersant and a modifier, adjusting the pH value to 0-8, aging to obtain a binder for catalytic cracking catalysts; The mass ratio of the titanium source to the aluminum source is (0.5-6):10; the titanium source is a titanium-containing waste liquid generated in the preparation of a polyolefin catalyst; the dispersant is at least one of lysine, glutamic acid, gelatin, oxalic acid and citric acid; the modifier is at least one of a rare earth compound and an alkaline earth metal compound.

2. The process for preparing a binder for a catalytic cracking catalyst according to claim 1, characterized by, The titanium source is a titanium tetrachloride-containing waste liquid generated in the preparation of a polypropylene catalyst, and the mass content of titanium tetrachloride in the titanium tetrachloride-containing waste liquid is 80%-95%.

3. The process for preparing a binder for a catalytic cracking catalyst according to claim 1, characterized by, The aluminum source is selected from one or more of aluminum metal, polyaluminum chloride, aluminum sol, one-water bauxite, three-water bauxite, bayerite, pseudo-boehmite and di-aluminum trioxide.

4. The process for preparing a binder for a catalytic cracking catalyst according to claim 1, characterized by, The dispersant is added in an amount of 0.5%-5% of the mass of the binder for catalytic cracking catalysts; and / or, the modifier is added in an amount of 0.5%-5% of the mass of the binder for catalytic cracking catalysts.

5. The process for preparing a binder for a catalytic cracking catalyst according to claim 1, characterized by, The rare earth compound is a chloride or nitrate of at least one of lanthanum, cerium, samarium, strontium and yttrium.

6. The process for preparing a binder for a catalytic cracking catalyst according to claim 1, characterized by, The alkaline earth metal compound is a chloride or nitrate of at least one of magnesium, calcium and barium.

7. The process for preparing a binder for a catalytic cracking catalyst according to claim 1, characterized by, The aging temperature is 60-80℃, and the aging time is 1-5h.

8. The process for preparing a binder for a catalytic cracking catalyst according to claim 1, characterized by, The pH value is adjusted by using an alkaline substance, which is at least one of ammonia, magnesium oxide, calcium oxide, sodium hydroxide, sodium carbonate, sodium meta-aluminate, potassium hydroxide, potassium carbonate and water glass.

9. A catalytic cracking catalyst characterized by, The binder is obtained by the preparation method of any one of claims 1-8.

10. The catalytic cracking catalyst according to claim 9, characterized in that, The binder further comprises a molecular sieve and a matrix material; the matrix material is at least one of kaolin, montmorillonite, diatomite, metahalloysite, halloysite, saponite, ledikite, hydrotalcite, sepiolite, bentonite and pseudo-boehmite; and the molecular sieve is at least one of REY, REHY, USY, Y and ZSM-5 molecular sieves.

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