Process for preparing bottoms cracking catalyst for fluid catalytic cracking unit

Abstract

To provide a process for preparing bottoms cracking catalyst for fluid catalytic cracking unit.SOLUTION: The present disclosure generally relates to the processing of petroleum-based materials. The present invention disclosure specifically relates to a process for preparing bottoms cracking catalyst for fluid catalytic cracking unit, wherein the process comprises treating Y zeolite with an organic acid, followed by treating with an alkali to obtain Meso Y zeolite; preparing an aqueous solution of pseudoboehmite alumina and phosphoric acid and mixing with the Meso Y zeolite to obtain a solution A; mixing a dispersion of colloidal silica and aqueous solution of boric acid to obtain a solution B; and mixing the solution A and the solution B to obtain the bottom cracking catalyst.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates generally to the processing of petroleum-based materials. Specifically, the present disclosure relates to a process for making a bottom cracking catalyst for a fluid catalytic cracking unit. [Background technology]

[0002] Fluid catalytic cracking (FCC) units play an important role in converting heavy hydrocarbons into light hydrocarbons. In the presence of an FCC catalyst, heavy hydrocarbons are cracked in the FCC unit.

[0003] The heavy fuel oil in the bottoms is composed of normal paraffins (C 14 ~C 34 ) and heavy aromatic molecules (C) with molecular sizes ranging from 12 to 25 Å 14 ~C 60 ), but the zeolites present in FCC additives have pore sizes less than 7.5 Å. Therefore, the hydrocarbons present in heavy fuel oils are too large to fit within the zeolite pores for cracking. As a result, the large hydrocarbon molecules are first cracked on the surface of the FCC catalyst matrix to produce smaller hydrocarbons, which are then cracked inside the zeolite pores. The overall process results in over-cracking of the hydrocarbons, which results in the formation of coke and dry gases.

[0004] To overcome the mass transport limitations of microporous zeolites, mesoporous zeolites have been prepared and utilized for bottom cracking.

[0005] In the present invention, the acidity of the alumina is also enhanced by peptization with phosphoric acid. Finally, the bottoms conversion is enhanced by the combination of mesozeolite and acidity-enhanced alumina with an alumina or silica binder. Summary of the Invention

[0006] The present disclosure relates to a process for making a bottom cracking catalyst for a fluid catalytic cracking unit, the process comprising treating Y zeolite with an organic acid and then with an alkali to obtain meso-Y zeolite, preparing an aqueous solution of pseudo-boehmite alumina and phosphoric acid and mixing it with the meso-Y zeolite to obtain solution A, mixing a dispersion of colloidal silica and an aqueous solution of boric acid to obtain solution B, and mixing solution A and solution B to obtain the bottom cracking catalyst. DETAILED DESCRIPTION OF THE INVENTION

[0007] For the purposes of promoting an understanding of the principles of the present disclosure, reference will now be made to the embodiments illustrated in the drawings, and specific language will be used to describe the same. However, it will be well understood that no limitation of the scope of the present disclosure is thereby intended, and that such changes and further modifications in the systems shown, and such further applications of the principles of the present disclosure as shown therein, are contemplated as would normally occur to one of ordinary skill in the art to which the present disclosure pertains. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present disclosure pertains. The systems, methods, and examples provided herein are illustrative only and are not intended to be limiting.

[0008] Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described. All publications mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in connection with which the publications are cited.

[0009] It must be noted that, as used herein and in the appended claims, the singular forms "a," "and," and "the" include plural referents unless the context dictates otherwise. Thus, for example, a reference to "a compound" includes a plurality of such compounds, and a reference to "the step" includes a reference to one or more steps and equivalents thereof known to those skilled in the art, etc.

[0010] The term "some," as used herein, is defined as "none, or one, or more than one, or all." Thus, the terms "none," "one," "more than one," "more than one but not all," or "all" all fall within the definition of "some." The term "some embodiments" may refer to no embodiments, or one embodiment, or some embodiments, or all embodiments. Thus, the term "some embodiments" is defined to mean "none, or one embodiment, or more than one embodiment, or all embodiments."

[0011] The terms and structures used herein are for the purpose of describing, teaching, and elucidating certain embodiments and their specific features and elements, and do not limit, restrict, or diminish the spirit and scope of the claims or their equivalents.

[0012] More specifically, any terms used herein, including, but not limited to, "includes," "comprises," "has," "consists," and grammatical variations thereof, are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. The specification will be understood to include embodiments having the transitional phrase "consisting of" or "consisting essentially of" in place of the transitional phrase "comprising." The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim, except for impurities related thereto. The transitional phrase "consisting essentially of" limits the scope of the claim to the specific materials or steps of the claimed disclosure "and which do not materially affect the basic and novel property(ies)."

[0013] Regardless of whether a particular feature or element is limited to being used only once, it may still be referred to as "one or more features" or "one or more elements" or "at least one feature" or "at least one element." Furthermore, the use of the term "one or more" or "at least one" feature or element does not exclude the absence of any of those features or elements, unless otherwise expressly stated by qualifying language such as "one or more are required" or "one or more elements are required."

[0014] As used herein, the term "about" is used to indicate the degree of variation or tolerance of a numerical or quantitative value, indicating that the disclosed values ​​are not intended to be strictly limiting and may vary by plus or minus 5% without departing from the scope of the present invention.

[0015] Unless otherwise defined, all terms used herein, particularly any technical and / or scientific terms, may have the same meaning as commonly understood by one of ordinary skill in the art.

[0016] Reference is made herein to several "embodiments." Embodiments are intended to be examples of possible implementations of any feature and / or element recited in the appended claims. It should be understood that some embodiments have been described for the purpose of highlighting one or more potential ways in which particular features and / or elements of the appended claims may satisfy requirements of uniqueness, utility, and non-obviousness.

[0017] Without limitation, terms such as "a first embodiment," "a further embodiment," "an alternative embodiment," "one embodiment," "an embodiment," "multiple embodiments," "some embodiments," "other embodiments," "further embodiment," "furthermore Use of phrases and / or terms such as "(an) embodiment," "an additional embodiment," or variations thereof does not necessarily refer to the same embodiment. Unless otherwise specified, one or more particular features and / or elements described in the context of one or more embodiments may be found in one embodiment, or in more than one embodiment, or in all or none of the embodiments. Although one or more features and / or elements may be described herein in the context of only a single embodiment, or alternatively, in the context of more than one embodiment, or further alternatively, in the context of all embodiments, said features and / or elements may instead be provided separately, in any suitable combination, or not provided at all. Conversely, any features and / or elements that are described in the context of separate embodiments may alternatively be realized as present together in the context of a single embodiment.

[0018] As referred to herein, the term "fluid catalytic cracking" refers to a conversion process used in petroleum refineries to convert the high-boiling, high-molecular-weight hydrocarbon fractions of petroleum (crude oil) into gasoline, alkene gas, and other petroleum products.

[0019] The terms "method" and "process" are used interchangeably herein.

[0020] The present disclosure discloses a process for making a bottom cracking catalyst for a fluid catalytic cracking unit.

[0021] In some embodiments, the process comprises the steps of: Treating Y zeolite with an organic acid and then treating it with an alkali to obtain meso-Y zeolite; preparing an aqueous solution of pseudoboehmite alumina and phosphoric acid, and mixing it with meso-Y zeolite to obtain solution A; mixing a dispersion of colloidal silica and an aqueous solution of boric acid to obtain a solution B; mixing the solution A and the solution B to obtain the bottom cracking catalyst; Includes.

[0022] The Y zeolite comprises a SiO2 / Al2O3 ratio ranging from 4.5 to 5.5, preferably said ratio is 5.1.

[0023] The organic acid is selected from the group consisting of citric acid, nitrilotriacetic acid, and combinations thereof.

[0024] The alkali is selected from the group consisting of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, potassium hydroxide, and combinations thereof.

[0025] In the solution A, the pseudoboehmite alumina has a concentration in the range of 25 to 65 (vol / vol) %, and the phosphoric acid has a concentration in the range of 5 to 15 (vol / vol) %.

[0026] In solution B, the colloidal silica has a concentration in the range of 5 to 50%, and the boric acid has a concentration in the range of 0.1 to 10 (wt / vol)%.

[0027] The mixture of solutions A and B is washed, dried, and calcined at a temperature in the range of 450°C to 550°C for 3 to 5 hours to obtain a bottom cracking catalyst.

[0028] The present disclosure is further illustrated by reference to the following examples, which are for illustrative purposes only and in no way limit the scope of the present disclosure. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein, but rather to illustrate representative features, methods, compositions, and results. These examples are not intended to exclude equivalents and variations of the present disclosure that would be apparent to one skilled in the art. [Example]

[0029] Example 1: Process for the synthesis of bottom cracking additive for fluid catalytic cracking units (a) Synthesis of meso-Y zeolite For the synthesis of meso-Y zeolite, 20 g of Y zeolite with SiO2 / Al2O3 of 5.2 was treated with citric acid at 60 °C for 2 h, followed by NaOH treatment at 40 °C. (b) Synthesis of Acidity-Enhanced Pseudoboehmite Alumina (AEA) To 75 mL of H2O, 18.0 g of pseudoboehmite alumina (LOI, 27.5% at 550 °C) was added, and to the meso-Y zeolite, 3.5 g of H3PO4 (85%) was added. The mixture was stirred at 30 °C for 2 h. (c) 5.0 g of Ludox HS-40 (d) was stirred for 30 minutes. 5.8 g of H3BO3 dissolved in 20 mL of hot water was added to (d) and stirred for 1 hour. Finally, the contents of (c) were added to the above mixture at 30 °C for 2 hours. The mixture was washed, dried, and finally calcined at 550 °C for 4 hours to obtain the final additive.

[0030] Example 2: Physicochemical properties of the prepared additives The physicochemical properties of the prepared additives are shown in Table 1.

[0031] [Table 1]

[0032] Example 3: Pretreatment of bottom cracking additives by hydrothermal deactivation method To maintain the desired level of conversion in an FCC unit (feed to useful products such as dry gas (DG), liquefied petroleum gas (LPG), gasoline, heavy naphtha, light cycle naphtha, clarified heavy oil, and coke), equilibrium catalyst is continuously removed from the regenerator and fresh catalyst is added. Accurate prediction of catalyst deactivation rates that will occur in a commercial unit under realistic laboratory operating conditions is essential not only for catalyst management strategies, but also for the catalyst evaluation process and selection. Catalyst deactivation of laboratory-developed and prepared additives was carried out in a metallocyclic deactivation unit at 815°C for 5 hours using an 80% steam treatment method prior to performance evaluation.

[0033] Example 4: Feedstock characterization The feed used in this test was vacuum gas oil (VGO), the properties of which are shown in Table 2 below.

[0034] [Table 2]

[0035] Example 5: Performance evaluation results Advanced Cracking Evaluation (ACE) - A Microactivity Test (MAT) unit (with online RGA) was used to measure the microactivity of the steam deactivation additive. The results show the importance of the combination of mesozeolite and B2O5. Detailed results are shown in Table 3.

[0036] [Table 3]

[0037] advantage: The advantages of the present invention include reduced bottoms yield and increased gasoline and light cycle oil yield.

Claims

1. 1. A process for making a bottom cracking catalyst for a fluid catalytic cracking unit, said process comprising: Treating Y zeolite with an organic acid and then treating with an alkali to obtain meso-Y zeolite; preparing an aqueous solution of pseudoboehmite alumina and phosphoric acid and mixing it with meso-Y zeolite to obtain solution A; mixing a dispersion of colloidal silica and an aqueous solution of boric acid to obtain a solution B; mixing the solution A and the solution B to obtain the bottom cracking catalyst; The process includes:

2. The Y zeolite has a SiO ratio in the range of 4.5 to 5.

5. ２ / Al ２ O ３ 2. The process of claim 1, comprising:

3. 2. The process of claim 1, wherein the organic acid is selected from the group consisting of citric acid, nitrilotriacetic acid, and combinations thereof.

4. 2. The process of claim 1, wherein the alkali is selected from the group consisting of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, potassium hydroxide, and combinations thereof.

5. 2. The process of claim 1, wherein in solution A, the pseudoboehmite alumina has a concentration in the range of 25 to 65 (vol / vol)% and the phosphoric acid has a concentration in the range of 5 to 15 (vol / vol)%.

6. 2. The process of claim 1, wherein in solution B, the colloidal silica is at a concentration ranging from 5 to 50% and the boric acid is at a concentration ranging from 0.1 to 10% (wt / vol).

7. 2. The process of claim 1, wherein the mixture of solution A and solution B is washed, dried, and calcined at a temperature ranging from 450° C. to 550° C. for 3 to 5 hours to obtain a bottom cracking catalyst.

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