CN-122006796-A - Catalytic cracking catalyst for improving gasoline octane number and preparation method thereof

CN122006796ACN 122006796 ACN122006796 ACN 122006796ACN-122006796-A

Abstract

The invention belongs to the technical field of catalysts, and discloses a catalytic cracking catalyst for improving gasoline octane number and a preparation method thereof. The catalyst constructs a composite system of a Y-type molecular sieve, an Mg-ZSM-5 shape selective molecular sieve and rare earth elements (lanthanum and yttrium) through a systematic solution of molecular sieve type optimization, acid precise regulation, metal cooperative modification, pore channel structure optimization and matrix composite reinforcement, and realizes functional complementation, wherein the Y-type molecular sieve ensures basic cracking activity, the Mg-ZSM-5 inhibits excessive cracking and liquefied gas generation through magnesium modification, the rare earth elements strengthen catalyst activity and hydrogen transfer reaction capacity, and the three cooperate to realize the core objective of overall process optimization of heavy oil cracking, product selective regulation and octane number improvement.

Inventors

Qiu Henge
SHI ZONGBO
WANG YE
ZHAO YULONG
ZHANG QING
ZHUO RUNSHENG

Assignees

润和催化剂股份有限公司

Dates

Publication Date: 20260512
Application Date: 20251224

Claims (10)

1. The catalytic cracking catalyst for improving the octane number of gasoline is characterized by comprising a matrix component, a molecular sieve component and a modified component; The matrix component comprises kaolin, alumina sol and pseudo-boehmite; The molecular sieve component comprises a Y-type molecular sieve auxiliary agent and a shape selective molecular sieve auxiliary agent; the modifying component comprises a rare earth compound.
2. The catalytic cracking catalyst for increasing the octane number of gasoline according to claim 1, wherein the Y-type molecular sieve additive is USY molecular sieve; The shape selective molecular sieve auxiliary agent is Mg-ZSM-5 molecular sieve.
3. The catalytic cracking catalyst for increasing the octane number of gasoline according to claim 1, wherein the matrix composition comprises, in dry weight, 2.0-2.5 kg of kaolin, 0.5-1.5 kg of alumina sol (calculated as Al 2 O 3 ) and 1.4-1.8 kg of pseudo-boehmite (calculated as Al 2 O 3 ).
4. The catalytic cracking catalyst for improving the octane number of gasoline according to claim 1, wherein 3.4-4.0 kg of Y-type molecular sieve auxiliary agent and 0.7-1.0 kg of shape selective molecular sieve auxiliary agent are calculated by dry weight in the molecular sieve component; and 0.4-1.6 kg of modified component (calculated by oxide).
5. A catalytic cracking catalyst for increasing the octane number of gasoline according to claim 1, wherein the rare earth compound is lanthanum chloride and/or yttrium carbonate.
6. The catalytic cracking catalyst for increasing gasoline octane number of claim 5, wherein the rare earth compound has a mass ratio of lanthanum chloride to yttrium carbonate of 2:1.
7. A method for preparing the catalytic cracking catalyst for improving the octane number of gasoline according to any one of claims 1 to 6, which is characterized by comprising the following steps: S1, adding kaolin, alumina sol and pseudo-boehmite into water, stirring at a high speed to fully and uniformly disperse solid powder, slowly adding a dilute hydrochloric acid solution under continuous stirring, and stirring at 70-80 ℃ for 1-1.2 h for acidizing to obtain slurry 1; S2, adding a Y-type molecular sieve auxiliary agent, a shape-selective molecular sieve auxiliary agent and a rare earth compound into the slurry 1, supplementing deionized water, and continuously pulping for 20-30 min to obtain mixed slurry; and S3, homogenizing the mixed slurry, spray-forming, roasting, washing and drying to obtain the catalytic cracking catalyst.
8. The method for preparing the catalytic cracking catalyst for improving the octane number of gasoline according to claim 7, wherein in the step S1, the high-speed stirring speed is 600-1200 rpm, and the duration is 15-30 min; The mass concentration of the dilute hydrochloric acid solution is 1-5%, the adding amount of the dilute hydrochloric acid solution is reduced to 3.0-4.5 according to the pH value of the whole slurry system, and the adding time is controlled to be optimal in 20-40 min; the matrix components were added to water, the mass of which was 6.0 kg.
9. The method for preparing a catalytic cracking catalyst for increasing gasoline octane number as recited in claim 7, wherein the amount of additional deionized water in S2 is 3 kg.
10. The method for preparing a catalytic cracking catalyst for increasing the octane number of gasoline according to claim 7, wherein in the step S3, the roasting temperature is 450-550 ℃ and the duration is 1-2 hours.

Description

Catalytic cracking catalyst for improving gasoline octane number and preparation method thereof Technical Field The invention belongs to the technical field of catalysts, and particularly relates to a catalytic cracking catalyst for improving the octane number of gasoline and a preparation method thereof. Background With the increasing weight and inferior quality of global crude oil resources, the processing proportion of crude oil with high sulfur, high nitrogen and high metal (especially high vanadium and high nickel) content is continuously increased. These impurities pose serious challenges to conventional FCC catalysts in that heavy metals (e.g., vanadium, nickel) poison catalyst active centers, destroy molecular sieve structures, resulting in dramatic decreases in cracking activity, selectivity (especially octane number selectivity), and stability. The method has the advantages that when the inferior oil is processed, the yield of gasoline is reduced, the yields of coke and dry gas are increased, the effects of improving the octane number of the gasoline and increasing the yield of olefins are greatly reduced, the coke selectivity and the yield of liquefied gas are difficult to control accurately, and the overall economic benefit is restricted. To address this challenge, the industry and academia have been innovated primarily along two technological paths, one to develop high performance FCC catalysts and one to develop functionalized FCC promoters. However, despite certain progress in the prior art, there are a plurality of limitations that make it difficult to achieve multiple objectives such as product yield distribution, catalyst life, anti-pollution capability, environmental protection and economy while increasing octane number. The prior art mainly focuses on two major categories, namely development of special auxiliary agents and improvement of the catalyst. Among them, the additive technology is the most active field of patent layout and industrial application at present because of its 'addition' flexibility (flexible addition according to requirement) and strong pertinence. The auxiliary agent technology aims at directionally regulating and controlling the reaction path by adding a small amount of materials with specific functions on the premise of not replacing the main catalyst so as to achieve the purposes of improving the octane number and the like. For example, patent CN111686791A adopts boron modification to create secondary mesopores to inhibit excessive cracking, patent CN113368888A adopts silicon modification Zn/P/ZSM-5 to improve isomerization capacity, patent CN114733557A adopts magnesium citrate treatment to passivate strong acid centers, reduce hydrogen transfer and excessive cracking, and improve vanadium resistance. Patent CN111686791A, CN107971031A, CN107970984a, et al, all focused on creating abundant mesopores by desilication, dealumination or special synthetic methods. In order to reduce the use of high-cost and toxic organic template agents, patent CN119425780A adopts a template-free method to synthesize ZSM-5, thereby simplifying the process and reducing the cost. In order to overcome the limitation of single octane number auxiliary agent, a composite auxiliary agent integrating multiple functions is developed. As in patent CN117258832a, the ZSM-5 with octane number increasing function is compounded with the porous magnesium-manganese-aluminum material with sulfur adsorbing/transferring function, so that the sulfur content of the gasoline is reduced while the octane number is increased, and the stricter environmental protection standard is satisfied. Patent CN119505952A, aiming at benzene-rich gasoline produced in the processes of catalytic reforming and the like, utilizes low-carbon olefin to react with benzene to generate high-octane alkylbenzene under the condition of hydrogen by a catalytic alkylation technology, and the benzene is reduced, the octyl is extracted and the liquefied gas is increased. Meanwhile, the method is not limited to the auxiliary agent, but the octane number is improved by optimizing the process flow. For example, in CN115895709a, a two-stage process of "catalytic cracking-catalytic folding" is used to fold the C4 and light gasoline fractions produced by FCC to produce a higher octane gasoline component, while reducing the olefin content. The FCC main catalyst is directly improved by representing the technology of China Petroleum and natural gas stock, so that the FCC main catalyst has high activity and high octane number selectivity. Such techniques are relatively few but more radical. The China petroleum and natural gas stock company modifies the USY molecular sieve by introducing rare earth elements, so that the hydrothermal stability and hydrogen transfer activity of the USY molecular sieve are enhanced. The hydrogen transfer reaction can reduce the olefin content of the gasoline, but the octane number is lost due to the excessive strength, s