Assistant for increasing gasoline octane number and reducing oil slurry without increasing liquefied gas, preparation method and application

Abstract

The invention discloses an additive for increasing gasoline octane number and reducing oil slurry without increasing liquefied gas as well as a preparation method and application of the additive. The preparation method comprises the following steps: step 1, stirring kaolin, pseudo-boehmite, alumina sol and a first solvent to obtain first slurry; step 2, adding an H-ZSM-5 molecular sieve, two Zn-containing compounds, a phosphorus-containing compound and a second solvent into the first slurry in the step 1 to obtain second slurry; and step 3, adjusting the pH value of the second slurry, adding macroporous bauxite, and continuing pulping, homogenizing, forming and roasting to obtain the additive for increasing the gasoline octane number and reducing the oil slurry without increasing liquefied gas. According to the catalytic cracking aid developed by the invention, the octane number of gasoline can be increased by 1-2 points under the conditions that the liquefied gas yield is not greatly increased and the gasoline yield is not reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of catalytic cracking of petroleum hydrocarbons, and in particular to an additive for increasing gasoline octane number and reducing oil slurry without increasing liquefied gas, a preparation method and application thereof. Background Art

[0002] In today's petroleum refining industry, with the continued rise in global vehicle ownership and increasingly stringent environmental regulations, the demand for gasoline quality has reached unprecedented heights. As a core technology for gasoline production, catalytic cracking (FCC) has a processing capacity exceeding 200 million tons per year in my country. The gasoline produced by FCC dominates the domestic gasoline supply, accounting for approximately 70% of the total gasoline composition. However, in actual operation, the traditional FCC process has gradually exposed a series of problems that seriously affect product quality and production efficiency.

[0003] Gasoline octane rating is a key indicator of gasoline's anti-knock performance and is closely related to engine efficiency and stability. As automotive engines evolve toward high-performance features such as high compression ratios and turbocharging, demand for high-octane gasoline is rapidly increasing. Low-octane gasoline is prone to causing knock in engines, which not only reduces engine power and increases fuel consumption, but can also cause irreversible damage to the engine over time. Therefore, increasing gasoline octane rating has become a necessity for refineries to meet market demand and enhance product competitiveness.

[0004] Among the existing technical means of improving the octane number of gasoline, the use of additives containing specific molecular sieves is a relatively common and effective method. Among them, ZSM-5 molecular sieve has a significant effect on improving the octane number of gasoline due to its unique pore structure and acidity, and is widely used in various octane additives. However, ZSM-5 molecular sieve has a drawback that is difficult to overcome. It is highly acidic and has a complex straight and branched pore structure, which makes the diffusion resistance of reactants and products in the pores extremely large. During the catalytic cracking process, this diffusion resistance causes gasoline molecules to easily undergo excessive cracking reactions under the action of ZSM-5 molecular sieve, and a large amount of them are converted into liquefied gas, resulting in a significant reduction in gasoline yield. Although many researchers and companies have invested a lot of energy in technological improvements, and related patents such as CN201610921658.5, CN200910237005.5, and CN201110180702.9 have optimized additives from different angles, they have not yet found an effective method to significantly improve the octane number of gasoline while effectively controlling the amount of liquefied gas produced, thereby stabilizing or even improving the gasoline yield. CN114733557A and CN114904564B respectively disclose an octane additive, using ZSM-5 with a silicon-aluminum ratio of 60 to 100 and 100 to 450, respectively. Since high-silicon-aluminum ratio molecular sieves are difficult to prepare without a template, the cost of high-silicon-aluminum ratio ZSM-5 molecular sieves is much higher than that of low-silicon-aluminum ratio ZSM-5 molecular sieves, which led to the development of applications for these octane additives. CN113368888A uses silicon-modified Zn / P / ZSM5 molecular sieves, and uses small-pore pseudo-boehmite, rare earth-modified large-pore pseudo-boehmite and other colloid-forming materials to make additives for increasing the octane number of gasoline. This invention uses a ZSM-5 molecular sieve with a silicon-aluminum ratio of ≥50, and the Zn / P / ZSM5 needs to be modified with Zn and P first, resulting in higher preparation costs.

[0005] On the other hand, the handling of slurry oil produced during catalytic cracking has long plagued the refining industry. Slurry oil is rich in impurities such as incompletely cracked heavy hydrocarbons and catalyst fines. Directly discharging the slurry oil would not only result in a significant waste of precious petroleum resources but also cause serious environmental pollution. Furthermore, the ash content in the slurry oil (primarily derived from catalyst fines) can severely impact the quality of subsequent products. For example, in the production of high-value-added products such as carbon black and needle coke, the presence of ash can reduce product purity and performance, increasing the difficulty and cost of quality control during production. Therefore, reducing slurry oil yield and efficiently removing ash from slurry oil to achieve resource utilization have become urgent technical challenges for the refining industry. Currently, most slurry oil additives on the market enhance cracking activity for heavy hydrocarbons by increasing the content of mesopores and macropores, improving matrix acidity, or increasing the molecular sieve content in the additive, thereby reducing slurry oil yield. However, in actual industrial applications, these methods are less than ideal, with limited reductions in slurry oil yield, failing to meet the industry's demand for efficient resource utilization. Regarding slurry oil ash removal technology, additive sedimentation has been widely used in refineries both domestically and internationally due to its advantages such as simple equipment, convenient operation, and low cost. For example, patents CN201310220492.0, CN201711139849.7, and CN201610838587.2 utilize additives such as polyethers to remove catalyst powder from slurry oil. However, these methods generally suffer from low removal efficiency and long sedimentation times. Although the introduction of positively charged substances can accelerate the flocculation process and improve the deashing effect to a certain extent, it often requires compounding of multiple components, and common cationic polymers have poor solubility in oil slurry, which greatly limits the further improvement of the deashing rate and cannot fundamentally solve the problems of oil slurry ash pollution and resource waste.

[0006] Therefore, there is an urgent need to develop a novel additive that can significantly increase gasoline octane without increasing liquefied gas production, effectively reduce slurry oil yield, and efficiently remove slurry oil ash. This is crucial for oil refining companies to improve economic efficiency, fulfill their environmental responsibilities, and enhance their market competitiveness. This invention was developed precisely in response to this industry background and technological demand, aiming to overcome the bottlenecks of existing technologies, provide an innovative and practical solution for the oil refining industry, and promote the industry's development towards a green, efficient, and sustainable direction. Summary of the Invention

[0007] The present invention aims to solve the problems of low gasoline octane number and high oil slurry yield in current petroleum refining, and provides an additive for increasing gasoline octane number and reducing oil slurry without increasing liquefied gas, as well as a preparation method and application.

[0008] In order to achieve the above technical objectives, the technical solution provided by the present invention is: A method for preparing an additive for increasing gasoline octane number and reducing oil slurry without increasing liquefied gas comprises the following steps: Step 1: stirring kaolin, pseudo-boehmite, aluminum sol, and a first solvent to obtain a first slurry; Step 2: adding low-silicon H-ZSM-5 molecular sieve, a soluble Zn-containing salt, an alkaline Zn compound, a phosphorus-containing compound, and a second solvent to the first slurry prepared in step 1 to obtain a second slurry; Step 3: Adjust the pH of the second slurry and add macroporous aluminum stone, continue beating, homogenizing, shaping, and roasting to obtain an additive for increasing gasoline octane number and reducing oil slurry without increasing liquefied gas.

[0009] Furthermore, based on the total dry weight of the additive, the amount of aluminum sol added in step 1 is greater than 11%.

[0010] Furthermore, based on the total dry weight of the additive, the amount of aluminum sol added is preferably 13-16%.

[0011] Furthermore, the SiO2 / Al2O3 molar ratio in the low-silicon H-ZSM-5 molecular sieve is 25-30.

[0012] Furthermore, in step 2, the alkaline Zn compound includes either zinc oxide or zinc carbonate, and the addition amount of zinc oxide or zinc carbonate is 0.5-2%.

[0013] Furthermore, the soluble Zn-containing salt includes any one of zinc chloride, zinc nitrate, and zinc acetate.

[0014] Furthermore, based on the total dry weight of the additive, the total added amount of the soluble Zn salt and the alkaline Zn compound is 1-6%.

[0015] Furthermore, based on the total dry weight of the additive, the total added amount of the soluble Zn salt and the alkaline Zn compound is preferably 2.5-5%.

[0016] Furthermore, the phosphorus-containing compound includes any one of phosphoric acid and ammonium dihydrogen phosphate.

[0017] Furthermore, based on the total dry weight of the additive, the phosphorus-containing compound is added in an amount of 1.5-2.5%.

[0018] Furthermore, in step 3, the method for adjusting the pH of the second slurry is to use HCl to adjust the pH to 3.1-3.4.

[0019] Furthermore, in step 3, the amount of macroporous aluminum stone added is 3-6% based on the total dry weight of the additive.

[0020] Another aspect of the present invention provides an additive for increasing gasoline octane number and reducing oil slurry without increasing liquefied gas.

[0021] Another aspect of the present invention provides an application of an additive for increasing gasoline octane number and reducing oil slurry without increasing liquefied gas in petroleum catalytic cracking.

[0022] The present invention has the following beneficial effects: 1. The present invention uses the inexpensive low silicon-aluminum ratio ZSM-5 molecular sieve and the developed octane value additive. When 5% of the octane value additive is added, the octane value of gasoline can be increased by 1-3 percentage points without significantly increasing the liquefied gas, and the gasoline yield can be reduced by less than 1 percentage point.

[0023] 2. The present invention uses 1-6% of two Zn-containing compounds (preferably 2.5-5%) to modify the low silicon-aluminum ratio ZSM-5 molecular sieve. The two Zn-containing compounds selected are zinc chloride or zinc oxide, or zinc carbonate. The content of the selected zinc oxide or zinc carbonate is 0.5-2%. This step is an important step to suppress the increase of liquefied gas.

[0024] 3. In the present invention, 1.5-2.5% phosphoric acid or ammonium dihydrogen phosphate is added to the aluminum sol to form an AlPO4 structure in the binder, thereby providing appropriate protection for the molecular sieve.

[0025] 4. After adding the molecular sieve, the pH of the entire reaction slurry is adjusted to 3.1-3.4, and then 3-6% macroporous aluminum stone is added to prevent the macroporous structure from being destroyed by acid.

[0026] 5. The amount of aluminum sol added in the present invention is greater than 11%, preferably 13-16%, so as to ensure that the additive has a good wear index. On the one hand, it can be stored in the reaction system for a long time. On the other hand, during the long reaction process, ZSM-5 undergoes moderate dealumination, so as to ensure that the liquefied gas does not increase significantly. DETAILED DESCRIPTION

[0027] The following is a clear and complete description of the technical solution of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0028] In addition, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0029] In each embodiment, the specific surface area of ​​the sample is measured by BET low-temperature nitrogen adsorption method, the elemental composition of the sample is measured by X-ray fluorescence spectrometer, and the wear index of the sample is measured by wear index analyzer.

[0030] The catalytic cracking reactions in the Examples and Comparative Examples were evaluated in a microfluidized bed reactor (ACE) and a gas chromatograph. The research octane number (RON) was analyzed using an Agilent 7980A gas chromatograph. The catalytic cracking performance of the catalysts in the Examples and Comparative Examples is shown in Tables 1 and 2.

[0031] For other tests, please refer to (National Standard for Testing Methods for Petroleum and Petroleum Products, published by China Standards Press in 1989).

[0032] Example 1: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.1 kg (dry weight) of zinc oxide, 0.2 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added, and the pH of the slurry was adjusted to 3.2 by HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 / g). The slurry was beaten for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours to obtain the gasoline octane enhancer MGR-1.

[0033] The wear index of MGR-1 is 1.3 wt% / h and the BET surface area is 215 m 2 / g, and the pore volume is 0.28 cm 3 After aging at 800℃ with 100% steam for 17 hours, the cracking performance of the catalyst in the catalytic cracking process and the PONA and octane number of the cracked gasoline are shown in Tables 1 and 2.

[0034] Example 2: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.15 kg (dry weight) of zinc carbonate, 0.25 kg (dry weight) of ammonium dihydrogen phosphate and 5.5 kg of deionized water was added, and the pH of the slurry was adjusted to 3.2 by HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 The slurry was then beaten for 30 minutes. After homogenization, the slurry was spray-formed and calcined at 550°C for 2 hours to obtain the gasoline octane enhancer MGR-2.

[0035] The wear index of MGR-2 is 1.6 wt% / h and the BET surface area is 216 m 2 / g, and the pore volume is 0.29 cm3 After aging at 800℃ with 100% steam for 17 hours, the cracking performance of the additive in the catalytic cracking process and the PONA and octane number of the cracked gasoline are shown in Tables 1 and 2.

[0036] Example 3: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.4 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.05 kg (dry weight) of zinc oxide, 0.25 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added, and the pH of the slurry was adjusted to 3.3 by HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 / g). The slurry was further beaten for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours to obtain MGR-3, a gasoline octane enhancer and gasoline octane number increase additive.

[0037] The wear index of MGR-3 is 2.1 wt% / h and the BET surface area is 218 m 2 / g, and the pore volume is 0.28 cm 3 After aging at 800℃ with 100% steam for 17 hours, the cracking performance of the additive in the catalytic cracking process and the PONA and octane number of the cracked gasoline are shown in Tables 1 and 2.

[0038] Example 4: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.35 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.05 kg (dry weight) of zinc oxide, 0.2 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added, and the pH of the slurry was adjusted to 3.2 by HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 / g). The slurry was further beaten for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours to obtain MGR-4, a gasoline octane enhancer and gasoline octane number increase additive.

[0039] The wear index of MGR-4 is 2.5 wt% / h and the BET surface area is 216 m 2 / g, and the pore volume is 0.28 cm 3 After aging at 800℃ with 100% steam for 17 hours, the cracking performance of the additive in the catalytic cracking process and the PONA and octane number of the cracked gasoline are shown in Tables 1 and 2.

[0040] Example 5: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 1 kg (dry weight) of pseudo-boehmite, and 1.4 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.4 kg (dry weight) of zinc chloride, 0.1 kg (dry weight) of zinc oxide, 0.25 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added. The pH of the slurry was then adjusted to 3.3 by HCl, and 0.3 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 The slurry was then beaten for 30 minutes. After homogenization, the slurry was spray-formed and calcined at 550°C for 2 hours to obtain MGR-5, a gasoline octane enhancer.

[0041] The wear index of MGR-5 is 1.4 wt% / h and the BET surface area is 219 m 2 / g, and the pore volume is 0.27 cm 3 After aging at 800℃ with 100% steam for 17 hours, the cracking performance of the additive in the catalytic cracking process and the PONA and octane number of the cracked gasoline are shown in Tables 1 and 2.

[0042] Example 6: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.2 kg (dry weight) of zinc oxide, 0.2 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added. The pH of the slurry was then adjusted to 3.2 by HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 / g). The slurry was further beaten for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours to obtain MGR-6, a gasoline octane enhancer and gasoline octane number increase additive.

[0043] The wear index of MGR-6 is 1.1 wt% / h and the BET surface area is 211 m 2 / g, and the pore volume is 0.28 cm 3 / g.

[0044] Example 7: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.2 kg (dry weight) of zinc oxide, 0.15 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added, and the pH of the slurry was adjusted to 3.2 by HCl, and 0.5 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 / g). The slurry was beaten for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours to obtain MGR-7, a gasoline octane enhancer and gasoline octane number increase additive.

[0045] The wear index of MGR-7 is 1.2 wt% / h and the BET surface area is 216 m 2 / g, and the pore volume is 0.29 cm 3 / g.

[0046] Example 8: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.2 kg (dry weight) of zinc oxide, 0.15 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added, and the pH of the slurry was adjusted to 3.2 by HCl, and 0.6 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 The slurry was then beaten for 30 minutes. After homogenization, the slurry was spray-formed and calcined at 550°C for 2 hours to obtain MGR-8, a gasoline octane enhancer.

[0047] The wear index of MGR-8 is 1.8 wt% / h and the BET surface area is 214 m 2 / g, pore volume is 0.30 cm 3 / g.

[0048] Example 9: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5.5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 30), 0.3 kg (dry weight) of zinc chloride, 0.1 kg (dry weight) of zinc oxide, 0.2 kg (dry weight) of phosphoric acid and 6 kg of deionized water was added, and the pH of the slurry was adjusted to 3.2 by HCl, and 0.3 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 / g). Beating was continued for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours to obtain MGR-9, a gasoline octane enhancer and gasoline octane number increase additive.

[0049] The wear index of MGR-9 is 1.9 wt% / h and the BET surface area is 221 m 2 / g, and the pore volume is 0.27 cm 3 / g.

[0050] Example 10: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 4 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 25), 0.3 kg (dry weight) of zinc chloride, 0.1 kg (dry weight) of zinc oxide, 0.2 kg (dry weight) of phosphoric acid and 6 kg of deionized water was added, and the pH of the slurry was adjusted to 3.2 by HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 / g). The slurry was further beaten for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours to obtain MGR-10, a gasoline octane enhancer and gasoline octane number increase additive.

[0051] The wear index of MGR-10 is 0.8 wt% / h and the BET surface area is 209 m 2 / g, and the pore volume is 0.28 cm 3 / g.

[0052] Comparative Example 1: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.2 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added. The pH of the slurry was then adjusted to 3.2 with HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 / g). Beating was continued for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours to obtain the gasoline octane enhancer REF-1.

[0053] The wear index of REF-1 is 0.9 wt% / h and the BET surface area is 216 m 2 / g, and the pore volume is 0.28 cm 3 After aging at 800℃ with 100% steam for 17 hours, the cracking performance of the additive in the catalytic cracking process and the PONA and octane number of the cracked gasoline are shown in Tables 1 and 2.

[0054] Comparative Example 2: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.2 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added. The pH of the slurry was then adjusted to 3.2 with HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97cm 3 / g). Beating was continued for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours to obtain the gasoline octane enhancer REF-2.

[0055] The wear index of REF-2 is 1.3 wt% / h and the BET surface area is 217 m 2 / g, and the pore volume is 0.29 cm 3 After aging at 800℃ with 100% steam for 17 hours, the cracking performance of the additive in the catalytic cracking process and the PONA and octane number of the cracked gasoline are shown in Tables 1 and 2.

[0056] Comparative Example 3: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 200), 0.3 kg (dry weight) of zinc chloride, 0.1 kg (dry weight) of zinc oxide, 0.2 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added, and the pH of the slurry was adjusted to 3.2 by HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 The slurry was then beaten for 30 minutes. After homogenization, the slurry was spray-formed and calcined at 550°C for 2 hours to obtain the gasoline octane enhancer REF-3.

[0057] The wear index of REF-3 is 1.6 wt% / h and the BET surface area is 219 m 2 / g, and the pore volume is 0.28 cm 3 After aging at 800℃ with 100% steam for 17 hours, the cracking performance of the additive in the catalytic cracking process and the PONA and octane number of the cracked gasoline are shown in Tables 1 and 2.

[0058] Comparative Example 4: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.1 kg (dry weight) of zinc oxide and 5.5 kg of deionized water was added, and the pH of the slurry was adjusted to 3.2 by HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 The slurry was then beaten for 30 minutes. After homogenization, the slurry was spray-formed and calcined at 550°C for 2 hours to obtain the gasoline octane enhancer REF-4.

[0059] The wear index of REF-4 is 1.3 wt% / h and the BET surface area is 216 m 2 / g, and the pore volume is 0.28 cm 3 After aging at 800℃ with 100% steam for 17 hours, the cracking performance of the additive in the catalytic cracking process and the PONA and octane number of the cracked gasoline are shown in Tables 1 and 2.

[0060] Comparative Example 5: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (al2o3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of P-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a P2O5 content of 4.2 wt%, and a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.1 kg (dry weight) of zinc oxide, 0.2 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added. The pH of the slurry was then adjusted to 3.2 by HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3The slurry was then beaten for 30 minutes. After homogenization, the slurry was spray-formed and calcined at 550°C for 2 hours to obtain the gasoline octane enhancer REF-5.

[0061] The wear index of REF-5 is 1.2 wt% / h and the BET surface area is 211 m 2 / g, and the pore volume is 0.27 cm 3 After aging at 800℃ with 100% steam for 17 hours, the cracking performance of the additive in the catalytic cracking process and the PONA and octane number of the cracked gasoline are shown in Tables 1 and 2.

[0062] Comparative Example 6: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.0 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.1 kg (dry weight) of zinc oxide, 0.2 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added, and the pH of the slurry was adjusted to 3.2 by HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 The slurry was then beaten for 30 minutes. After homogenization, the slurry was spray-formed and calcined at 550°C for 2 hours to obtain REF-6, a gasoline octane enhancer.

[0063] The wear index of REF-6 is 4.2 wt% / h and the BET surface area is 221 m 2 / g, pore volume is 0.30 cm 3 Comparing MGR-1 and REF-6, the wear index of REF-6 is too large, which indicates that the added aluminum sol content is greater than 13%, which is an important reason to ensure that the wear index is lower than 2.5.

[0064] After aging treatment at 800℃ with 100% steam for 17 hours, the cracking performance of the additive in the catalytic cracking process and the PONA and octane number of the cracked gasoline are shown in Tables 1 and 2.

[0065] Comparative Example 7: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.6 kg (Al2O3 dry weight) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.1 kg (dry weight) of zinc oxide, 0.2 kg (dry weight) of phosphoric acid and 5.5 kg of deionized water was added, and the pH of the slurry was adjusted to 2.9 by HCl, and 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m2) was added. 2 / g, pore volume 0.97 cm 3 / g). Beating was continued for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours to obtain REF-7, a gasoline octane enhancer and gasoline octane number increase additive.

[0066] The wear index of REF-7 is 1.5 wt% / h and the BET surface area is 217 m 2 / g, and the pore volume is 0.22 cm 3 After aging at 800℃ with 100% steam for 17 hours, the cracking performance of the additive in the catalytic cracking process and the PONA and octane number of the cracked gasoline are shown in Tables 1 and 2.

[0067] Comparative Example 8: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, 0.4 kg (dry weight) of macroporous diaspore (specific surface area 237 m 2 / g, pore volume 0.97 cm 3 / g), 1.6 kg (based on Al2O3 dry weight) of aluminum sol was added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.1 kg (dry weight) of zinc oxide, 0.2 kg (dry weight) of phosphoric acid, and 5.5 kg of deionized water was added. The pH of the slurry was then adjusted to 3.2 with HCl. Beating was continued for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours. This resulted in REF-8, a gasoline octane enhancer and gasoline octane number increase additive.

[0068] The wear index of REF-8 is 1.8 wt% / h and the BET surface area is 213 m 2 / g, and the pore volume is 0.23 cm3 / g.

[0069] Comparative Example 9: Under stirring conditions, 2.4 kg (dry weight) of kaolin, 0.8 kg (dry weight) of pseudo-boehmite, and 1.3 kg (based on dry weight of Al2O3) of aluminum sol were added to 3 kg of deionized water and stirred at high speed for 2 hours until the kaolin was completely dispersed in the slurry. After stirring for 30 minutes, a mixed slurry consisting of 5 kg (dry weight) of H-ZSM-5 molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 27), 0.3 kg (dry weight) of zinc chloride, 0.1 kg (dry weight) of zinc oxide, 0.2 kg (dry weight) of phosphoric acid, and 5.5 kg of deionized water was added. The pH of the slurry was then adjusted to 3.2 with HCl. The slurry was further beaten for 30 minutes. After homogenization, the slurry was spray-formed and calcined at 550°C for 2 hours. This resulted in REF-9, a gasoline octane enhancer and gasoline octane number increaser.

[0070] The wear index of REF-9 is 1.3 wt% / h and the BET surface area is 216 m 2 / g, and the pore volume is 0.22 cm 3 / g.

[0071] The catalysts in the comparative examples and examples were aged at 800°C in 100% steam for 17 hours before being evaluated for catalytic cracking performance on an ACE unit. The reaction feed was hydrotreated residual oil, the reaction temperature was 530°C, the catalyst-to-oil ratio was 5, the oil feed rate was 1.2 g / min, and the oil feed time was 1 minute. The catalyst was either a balancer (blank) or a balancer mixed with 5% of a promoter. The catalytic cracking product distributions of the examples and comparative examples are shown in Table 1. The PONA analysis and gasoline octane number (RON) of the catalytic gasoline of the examples and comparative examples are shown in Table 2.

[0072] Table 1 Distribution of catalytic cracking products of examples and comparative examples Compared with MGR-1, MGR-2 and REF-1, the addition of zinc oxide or zinc carbonate helps to inhibit the formation of liquefied gas and improve the gasoline yield.

[0073] Compared with MGR-1 and REF-5, the use of H-ZSM-5 instead of P-element modified ZSM-5 molecular sieve helps to inhibit the formation of liquefied gas and improve the gasoline yield.

[0074] Comparing MGR-1 and REF-7, the pore volume of REF-7 is significantly smaller. Adding 5% REF-7 reduces the cracking conversion rate and increases the diesel and slurry oil yields.

[0075] Table 2 PONA analysis of catalytic gasoline and gasoline octane number RON of the samples of the examples and comparative examples Compared with MGR-1 and REF-2, the addition of zinc compounds helps to improve the octane number of gasoline.

[0076] Compared with MGR-1 and REF-3, the use of low silicon-aluminum ratio molecular sieve helps to improve the octane number of gasoline.

[0077] Compared to MGR-1, MGR-2, and REF-4, the addition of phosphoric acid or ammonium dihydrogen phosphate helps improve gasoline octane rating. Phosphoric acid or ammonium dihydrogen phosphate, combined with aluminum sources such as alumina sol, creates a small amount of phosphorus-aluminum structure, which improves the stability of HZSM-5 and inhibits dealumination.

[0078] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

[0079] The above specific implementation methods are detailed descriptions of the present invention. It cannot be considered that the specific implementation methods of the present invention are limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, they can make several simple deductions and substitutions without departing from the concept of the present invention, which should be regarded as falling within the scope of protection of the present invention.

Claims

1. A method for preparing an additive for increasing gasoline octane number and reducing oil slurry without increasing liquefied gas, characterized in that: The steps include: Step 1: stirring kaolin, pseudo-boehmite, aluminum sol, and a first solvent to obtain a first slurry; Step 2: adding low-silicon H-ZSM-5 molecular sieve, a soluble Zn-containing salt, an alkaline Zn compound, a phosphorus-containing compound, and a second solvent to the first slurry prepared in step 1 to obtain a second slurry; Step 3: Adjust the pH of the second slurry and add macroporous aluminum stone, continue beating, homogenizing, shaping, and roasting to obtain an additive for increasing gasoline octane number and reducing oil slurry without increasing liquefied gas.

2. The method for preparing a gasoline octane increase and oil slurry reduction additive without increasing liquefied gas according to claim 1, characterized in that: Based on the total dry weight of the additive, the amount of aluminum sol added in step 1 is greater than 11%.

3. The method for preparing a gasoline octane increase and oil slurry reduction additive without increasing liquefied gas according to claim 2, characterized in that: Based on the total dry weight of the additive, the amount of aluminum sol added is preferably 13-16%.

4. The method for preparing a gasoline octane increase and oil slurry reduction additive without increasing liquefied gas according to claim 1, characterized in that: The SiO2 / Al2O3 molar ratio in the low-silicon H-ZSM-5 molecular sieve is 25-30.

5. The method for preparing a gasoline octane increase and oil slurry reduction additive without increasing liquefied gas according to claim 1, characterized in that: In step 2, the alkaline Zn compound includes any one of zinc oxide and zinc carbonate, and the addition amount of zinc oxide or zinc carbonate is 0.5-2%.

6. The method for preparing a gasoline octane increase and oil slurry reduction additive without increasing liquefied gas according to claim 1, characterized in that: The soluble Zn-containing salt includes any one of zinc chloride, zinc nitrate and zinc acetate.

7. The method for preparing a gasoline octane increase and oil slurry reduction additive without increasing liquefied gas according to claim 1, characterized in that: Based on the total dry weight of the additive, the total added amount of the soluble Zn salt and the alkaline Zn compound is 1-6%.

8. The method for preparing a gasoline octane increase and oil slurry reduction additive without increasing liquefied gas according to claim 7, characterized in that: Based on the total dry weight of the additive, the total added amount of the soluble Zn salt and the alkaline Zn compound is preferably 2.5-5%.

9. The method for preparing a gasoline octane increase and oil slurry reduction additive without increasing liquefied gas according to claim 1, characterized in that: The phosphorus-containing compound includes any one of phosphoric acid and ammonium dihydrogen phosphate.

10. The method for preparing a gasoline octane increase and oil slurry reduction additive without increasing liquefied gas according to claim 9, characterized in that: Based on the total dry weight of the additive, the phosphorus-containing compound is added in an amount of 1.5-2.5%.

11. The method for preparing a gasoline octane increase and oil slurry reduction additive without increasing liquefied gas according to claim 1, characterized in that: In step 3, the method for adjusting the pH of the second slurry is to use HCl to adjust the pH to 3.1-3.

4.

12. The method for preparing a gasoline octane increase and oil slurry reduction additive without increasing liquefied gas according to claim 1, characterized in that: In step 3, the amount of macroporous aluminum stone added is 3-6% based on the total dry weight of the additive.

13. An additive for increasing gasoline octane number and reducing oil slurry without increasing liquefied gas, obtained by a preparation method according to any one of claims 1 to 12.

14. Use of the auxiliary agent according to claim 13 in petroleum catalytic cracking.

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