JP5052340B2 - FCC process using mesoporous catalyst - Google Patents

Abstract

This invention relates to a mesoporous catalytic cracking catalyst, a process for the production of such catalysts, and a process utilizing such catalysts in cracking operations. The mesoporous fluidized catalytic cracking catalyst is selective for minimizing the production of coke and light gas. The catalyst comprises an amorphous, porous matrix having pores ranging in diameter from 1 Å to 10 Å and ranging in diameter from 40 Å to 500 Å , but substantially free of pores ranging in diameter from 10 Å to 40 Å.

Description

  The present invention relates to a catalyst composition or catalyst, a method for producing a catalytic catalyst precursor, a method for producing a catalyst composition or a catalyst, and a catalytic cracking method.

  In particular, but not exclusively, the present invention relates to mesoporous catalytic cracking catalysts, methods for producing these catalysts, and methods for using these catalysts in cracking operations. More particularly, the present invention relates to a mesoporous fluid catalytic cracking catalyst selective to minimize the production of coke and light gases, a process for producing these catalysts, and the use of these catalysts in fluid catalytic cracking operations. Regarding the method.

  Catalytic cracking, particularly fluid catalytic cracking (“FCC”), is a conventional (for converting higher-boiling hydrocarbons of higher average molecular weight to lower-value hydrocarbons of higher value and lower average molecular weight ( That is, a well-known process. The product is useful as a fuel for transportation, heating and the like. In the process, the conversion step is usually performed by contacting a hydrocarbon feedstock (eg, heavy gas oil) with a moving bed of particulate catalyst at an elevated temperature in the substantial absence of hydrogen.

  The FCC process is cyclic and includes, for example, separation zones for catalytic feed conversion, steam stripping, and catalyst regeneration zones. In the cycle, the feedstock is mixed with the FCC catalyst in a catalytic reactor (typically a riser reactor) for catalytic conversion to product. The lower boiling product is separated from the catalyst in a separator (eg, a cyclone separator), and the deactivated catalyst is directed to a stripper and contacted with steam to remove contaminating hydrocarbons. The latter can be combined with steam from the cyclone separator and both can be routed out of the process. The stripped deactivation catalyst contains carbonaceous residues (referred to as “coke”). Stripped catalyst removed from the stripper is directed to a regenerator (ie, fluidized bed regenerator) where it is contacted with combustion gas (eg, air) at high temperature to burn off coke and regenerate the catalyst. The regenerated catalyst is then mixed with the feedstock that enters the riser to complete the cycle.

  In continuous circulation operation, exothermic coke combustion in the regenerator provides at least a portion of the amount of heat necessary to meet the endothermic feedstock decomposition in the reactor. However, the presence of coke in excess of the required amount for heat balance is undesirable because conversion of the feedstock hydrocarbon to catalyst coke reduces the amount of hydrocarbon product obtained from the feedstock. Accordingly, there is a need for a catalyst that selectively produces higher amounts of hydrocarbon products, but less catalytic coke.

  Mesoporous FCC catalysts (such as those described in Patent Document 1) are effective in converting raw materials into high-value hydrocarbon products (such as light olefins). These catalysts have the desirable property that undesirably high catalyst coke levels are avoided in FCC operation. However, these catalysts include a mesoporous silica-alumina matrix formed from a silica sol that undesirably increases catalyst manufacturing costs. In addition, conventional sols are acidic and thus may have an undesirable effect on catalyst components (such as zeolites) during catalyst synthesis. Therefore, there is a need to improve mesoporous catalysts.

US Pat. No. 5,221,648 US Pat. No. 3,702,886 US Pat. No. 3,770,614 US Pat. No. 3,709,979 U.S. Pat. No. 3,832,449 US Pat. No. 3,948,758 U.S. Pat. No. 4,076,842 US Pat. No. 4,016,245 U.S. Pat. No. 4,440,871 U.S. Pat. No. 4,310,440 EP-A229,295 specification US Pat. No. 4,254,297 US Pat. No. 4,500,651 U.S. Pat. No. 4,229,424 "Zeolite Molecular Sieves" by Breck (1974) Anderson et al. (J. Catalysis, 58, 114, 1979) "The Atlas of Zeolite Structure Types" (WH Meier), edited by DH Olson, Butterworth-Heineman, 3rd edition, 92 Year) "The Atlas of Zeolite Structure Types" (WH Meier, DH Olson, and Ch. Baerlocher, Elsevier, 1996) “Advances in Fluid Catalytic Cracking” (Catalytica, Mountain View, Calif., Part 355, 1987) J. et al. R. Anderson, "Structure of Metallic Catalysts" (Chapter 6, 384-385, 1975) Ralph K. "The chemistry of silica; solubility, polymerizability, colloidal and surface properties, and biochemistry (The Chemistry of Silica: Solubility, Polymerization, Colloid and Surface Properties, and Biochem.)" By Ralph K. Iler. Science Publication (A Wiley Interscience Publication, 1979)

  According to an embodiment of the present invention, a catalyst composition or catalyst, a method for producing a cracking medium precursor, a method for producing a catalyst composition or a catalyst, and a catalytic cracking method are provided. This is defined in any of the appended claims.

  In one embodiment, the present invention relates to a composition, a catalyst composition or a catalyst. This includes at least one amorphous porous matrix, each matrix having pores with a diameter in the range of 1 to 10 mm and pores with a diameter in the range of 40 to at least 500 mm, For the range 50 に to 250 Å, there is a single maximum in the differential pore volume distribution in the range 50 Å to 250 Å. The base material may be a single amorphous body or a mixture of two or more separate amorphous base materials. However, each base material individually satisfies the requirements for the differential pore volume distribution.

  The catalyst composition of the present invention is highly selective for the production of liquids (especially olefins) in fluid catalytic cracking operations and has low coke make, while the wear resistance of these catalysts is that of conventional mesoporous FCC catalysts. Considerably higher than

  In one embodiment, the matrix of the composition has a differential pore volume as a function of the maximum pore diameter. This function has a maximum value of 50 to 250 cm, preferably 50 to 150 cm. The integrated differential pore volume of the matrix pores having a diameter of 1 to 10 cm cannot be distinguished from the zeolite pore volume typically used in this application. Therefore, it is not possible to predict the pore volume for pores less than 10 mm. This is because no distinction can be made between the pore volume of the matrix and that of the zeolite. The integrated maximum pore volume with respect to the volume of the matrix pores having a diameter of 10-40 mm is less than 0.03 cc / g, preferably less than 0.01 cc / g, more preferably less than 0.006 cc / g.

（式中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は、独立してＨまたはＣ_１〜Ｃ_４アルキルであり、Ｘは硫黄または酸素である）
を有する少なくとも一種の尿素化合物、および少なくとも一種のリン酸塩を組み合わせて、第一の混合物を形成する工程；
（ｂ）前記第一の混合物を十分量のアルカリ性シリケート水溶液と組み合わせて、アルカリ性シリケート水溶液のゲル化を防止するのに十分なｐＨを有するスラリーを形成する工程；
（ｃ）前記スラリーを、水分を除去して第一の固形分を形成するための乾燥温度で乾燥する工程であって、前記固形分は、好ましくは、ケイ酸アンモニウム、アルカリ性シリケートおよびアルカリ性カルボネート、尿素化合物、クレー、少なくとも一種の水酸化アルミニウムまたはオキシ水酸化アルミニウム、並びにモレキュラーシーブを含む工程；および
（ｄ）前記第一の固形分を、水およびイオン交換組成物と組み合わせて、触媒前駆体を形成する工程であって、
前記イオン交換組成物は、一種以上の鉱酸（好ましくは硫酸）、鉱酸のアルミニウム塩（硫酸アルミニウムなど）および／または鉱酸のアンモニウム塩（硫酸アンモニウムなど）を含み、
前記触媒前駆体は、前記第一の固形分に比べてより低い濃度のアルカリ金属を有する工程
を含む。 In another embodiment, the present invention relates to a method for producing a cracking catalyst precursor. The method
(A) water, at least one molecular sieve, at least one aluminum hydroxide or aluminum oxyhydroxide, at least one clay,

Where R ₁ , R ₂ , R ₃ and R ₄ are independently H or C ₁ -C ₄ alkyl, and X is sulfur or oxygen.
Combining at least one urea compound having: and at least one phosphate to form a first mixture;
(B) combining the first mixture with a sufficient amount of an aqueous alkaline silicate solution to form a slurry having a pH sufficient to prevent gelation of the aqueous alkaline silicate solution;
(C) drying the slurry at a drying temperature for removing moisture to form a first solid content, wherein the solid content is preferably ammonium silicate, alkaline silicate and alkaline carbonate, Including a urea compound, clay, at least one aluminum hydroxide or aluminum oxyhydroxide, and molecular sieve; and (d) combining the first solid with water and an ion exchange composition to produce a catalyst precursor. A process of forming,
The ion exchange composition comprises one or more mineral acids (preferably sulfuric acid), aluminum salts of mineral acids (such as aluminum sulfate) and / or ammonium salts of mineral acids (such as ammonium sulfate),
The catalyst precursor includes a step having a lower concentration of alkali metal compared to the first solid content.

In another embodiment, the present invention relates to a method for producing a catalyst from a catalyst precursor. The method includes the following further steps. That is,
(E) the catalyst precursor is combined with water and an independently selected second ion exchange composition to be ion exchanged with a lower concentration of alkali metal compared to the first and second solids; Forming a catalyst precursor comprising:
The independently selected second ion exchange composition comprises one or more mineral acids (such as sulfuric acid), aluminum salts of mineral acids (such as aluminum sulfate) and / or ammonium salts of mineral acids (such as ammonium sulfate). Process;
(F) calcination of the ion-exchanged catalyst precursor at a temperature in the range of 250 ° C. to 850 ° C. for a calcination time to produce an ion-exchanged catalyst precursor; and (g) In this step, the calcined and ion-exchanged catalyst precursor is brought into contact with steam at a temperature in the range of 650 ° C. to 850 ° C. for a steaming time. The preferred steaming time is 4 to 48 hours. The cracking catalyst is deactivated by steaming. This simulates deactivation in a commercial FCC unit operating at a much lower time at substantially lower moisture pressures.

  In yet another embodiment, the present invention relates to a catalytic cracking method. The method comprises contacting a hydrocarbon feedstock with a catalytically effective amount of cracking catalyst under catalytic conversion conditions, wherein the cracking catalyst has a zeolite and pores and diameters ranging from 1 to 10 mm in diameter. Having a single maximum value in the differential pore volume distribution in the range of 50 有 し to 250 有 し having a pore in the range of 40 Å to at least 500 、, for a pore range of 50 Å to 250 Å.

  In other embodiments, the catalyst conversion conditions include a temperature of 450 ° C. to 700 ° C., a hydrocarbon partial pressure of 10 to 40 psia (69 to 276 kPa), a cracking catalyst / raw material (weight / weight) ratio of 3 to 100, and atmospheric pressure. Includes pressures in the range of ~ 45 psig (411 kPa), and raw material residence times of 0.1 to 20 seconds. Here, the weight of the catalyst is the total weight of the cracking catalyst.

（式中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は、独立してＨまたはＣ_１〜Ｃ_４アルキルであり、Ｘは硫黄または酸素である）
を有する工程；
（ｂ）前記第一の混合物を十分量のアルカリ性シリケート水溶液と組み合わせて、アルカリ性シリケート水溶液のゲル化を防止するのに十分なｐＨを有するスラリーを形成する工程；
（ｃ）前記スラリーを、水分を除去して第一の固形分を形成するための乾燥温度で乾燥する工程；
（ｄ）前記第一の固形分を、水およびイオン交換組成物と組み合わせて、触媒前駆体を形成する工程であって、
前記イオン交換組成物は、硫酸、硫酸アルミニウムおよび／または硫酸アンモニウムの一種以上を含み、
前記触媒前駆体は、前記第一の固形分に比べてより低い濃度のアルカリ金属を有する工程；
（ｅ）触媒前駆体を、水および独立して選択された第二のイオン交換組成物と組み合わせて、前記第一の固形分および触媒前駆体に比べてより低い濃度のアルカリ金属を有するイオン交換された触媒前駆体を形成する工程であって、
前記独立して選択された第二のイオン交換組成物は、硫酸、硫酸アルミニウムおよび／または硫酸アンモニウムの一種以上を含む工程；
（ｆ）前記イオン交換された触媒前駆体を、２５０℃〜８５０℃の範囲の温度で、焼成されイオン交換された触媒前駆体を製造するための焼成時間で焼成する工程；および
（ｇ）前記焼成されイオン交換された触媒前駆体を、スチームと、６５０℃〜８５０℃の範囲の温度で、分解触媒を製造するためのスチーミング時間で接触させる工程であって、好ましいスチーミング時間は４〜８時間である工程
である。 In a further embodiment, the cracking catalyst is produced by the following steps. That is,
(A) combining water, at least one molecular sieve, at least one aluminum hydroxide, at least one clay, a urea compound, and at least one phosphate to form a first mixture, the urea compound comprising: The following formula:

Where R ₁ , R ₂ , R ₃ and R ₄ are independently H or C ₁ -C ₄ alkyl, and X is sulfur or oxygen.
A process comprising:
(B) combining the first mixture with a sufficient amount of an aqueous alkaline silicate solution to form a slurry having a pH sufficient to prevent gelation of the aqueous alkaline silicate solution;
(C) drying the slurry at a drying temperature for removing moisture to form a first solid content;
(D) combining the first solid with water and an ion exchange composition to form a catalyst precursor,
The ion exchange composition comprises one or more of sulfuric acid, aluminum sulfate and / or ammonium sulfate,
The catalyst precursor has a lower concentration of alkali metal compared to the first solid content;
(E) an ion exchange having a lower concentration of alkali metal in combination with the first solids and the catalyst precursor in combination with water and an independently selected second ion exchange composition. Forming a formed catalyst precursor comprising the steps of:
The independently selected second ion exchange composition comprises one or more of sulfuric acid, aluminum sulfate and / or ammonium sulfate;
(F) calcination of the ion-exchanged catalyst precursor at a temperature in the range of 250 ° C. to 850 ° C. for a calcination time to produce an ion-exchanged catalyst precursor; and (g) The step of bringing the calcined and ion-exchanged catalyst precursor into contact with steam at a temperature in the range of 650 ° C. to 850 ° C. for a steaming time for producing a cracking catalyst, wherein a preferable steaming time is 4 to This is a process that takes 8 hours.

(I) Catalytic cracking catalyst In embodiments, the present invention relates to a catalytic cracking catalyst composition comprising a cracking catalyst (generally in particulate form) and optionally other reactive and non-reactive components. One or more types of catalysts may be present in the composition. Typically, the catalyst comprises a matrix and at least one crystalline molecular sieve, the matrix comprising at least one clay, at least one hydroxide or aluminum oxyhydroxide, and a binder colloid. The molecular sieve may be an aluminosilicate (such as zeolite) having an average pore diameter of 3 to 15 angstroms. The pore diameter is also often referred to as the effective pore diameter. This may be measured using standard adsorption techniques and known minimum kinetic diameter hydrocarbons. See Non-Patent Document 1, Non-Patent Document 2, and Non-Patent Document 3. More than one type of catalyst may be present in the composition. For example, the individual catalyst particles may include large pore zeolites, shape selective zeolites, and mixtures thereof. In addition to the catalyst particles, the composition may also include fine particles, inert particles, particles containing a metal species such as platinum, and compounds thereof.

  In addition to the matrix and molecular sieves, the catalyst can further (in addition to the cracking function) further catalytic functions such as metals such as platinum, cocatalyst species such as phosphorus-containing species, and bottom cracking and metal passivation. It can contain seeds to confer. These additional catalytic functions may be provided by, for example, aluminum-containing species.

  The inorganic matrix combines the components together so that (i) the catalyst is sufficiently wear resistant (ie, wear resistant) to withstand particle-to-particle and reactor wall collisions, and (ii) molecular A porous inorganic oxide matrix component to provide some size selectivity with respect to molecules that can be degraded on or in the sieve. The inorganic oxide matrix may be made, for example, from an inorganic oxide sol, which is then dried. Conventional sols may be used. Examples of conventional sols include silica sols derived from the reaction of sodium silicate and sulfuric acid / aluminum sulfate solutions, ions represented by materials having trade names such as “Ludox” and “Nyacol”. Silica sol prepared by the exchange method, 5/6 basic aluminum chlorohydroxide represented by materials such as “Chlorhydrol”, and peptized alumina slurry (acid and aluminum pseudoboehmite “Versal”). Versal) "series, etc., which can be made from reaction with substances such as). The base material itself may generally have acidic catalytic properties. However, the catalytic activity of the matrix is not required. In an embodiment, the base material includes silicon and aluminum oxides. The base material can include one or more oxide phases. For example, aluminum oxyhydroxide-γ-alumina, boehmite, diaspore, and transition alumina (such as α-alumina, β-alumina, γ-alumina, δ-alumina, ε-alumina, κ-alumina, and ρ-alumina) is there. In related embodiments, the alumina species is aluminum hydroxide such as gibbsite, bayerite, nordstrandite, or doyelite. The matrix material may contain phosphorus or aluminum phosphate and, although generally undesirable, a small amount of sodium. The matrix may also include clays such as kaolin, bentonite, attapulgite, montmorillonite, hectorite, and pyrophyllite.

  The catalyst in the composition will now be described in more detail. The catalyst comprises a matrix, the matrix comprising at least one clay, at least one hydroxide or aluminum oxyhydroxide, and a binder colloid, 5 wt% to 100 wt%, based on the total weight of the catalyst, Preferably it is included in an amount ranging from 8% to 95% by weight. Inside, a crystalline molecular sieve is dispersed. In an embodiment, the molecular sieve is a crystalline aluminosilicate, i.e. natural or synthetic zeolite. This typically has uniform pores with a silica / alumina molar ratio (Si / Al) of 2 or more and a diameter in the range of 3-15. The zeolite content of the catalyst ranges from 0% to 95% by weight, based on the total weight of the catalyst. Preferably they are 5%-92%, More preferably, they are 10%-60%.

  Based on IUPAC, micropores refer to pores in the range of 2 to 20 inches, and mesoporous refers to those in the range of 20 to 500 inches. As defined in the present invention, the respective ranges are from 1 Å to 10 に 対 し て for micropores, from 40 Å to at least 500 Å, preferably from 40 Å to 250 に 対 し て for intermediate pores. As used herein, the functional definition of “medium pore” is a porosity that extends beyond the range normally associated with adsorption of middle distillate in FCC, particularly standard commercial FCC zeolites (shown in Non-Patent Document 4). Porosity of pores having a larger diameter than that associated with structure type FAU).

  As shown in FIG. 1, the differential pore volume of the base material pores has a maximum value of 40 to 250 mm in diameter. This figure shows that in the pore range of 50 to 250 cm, the single maximum value of the differential mercury pore volume is in the range of 50 to 250 cm.

  For matrix pores less than 250 angstroms in diameter, the pore volume measured using mercury is 60-80% of the pore volume measured using mercury, as shown in FIG. Included in less than.

  Mercury cannot measure pore volumes below 35 angstroms. Although gas phase adsorption performed under very specific conditions may be able to capture this range of pore volumes, the inhibition by the pores associated with the zeolites contained in the system can result in two in this range. Accurate measurement of different types of pores is hindered.

  The base material substantially does not include pores having a diameter in the range of 10 to 40 mm. That is, these pore diameters are not substantially present in the matrix pore distribution. “Substantially free” means that the integrated maximum pore volume is less than 0.03 cc / g, preferably less than 0.01 cc / g, more preferably 0 with respect to the volume of the matrix pores having a diameter of 10 to 40 mm. It means less than 0.006 cc / g. It has been discovered that a proper indication of pore volume less than 35 angstroms is obtained by a differential mercury porosimetry gradient, as shown in FIG. The line in contact with the differential mercury intrusion curve at a point less than 50 angstroms is a positive slope with a positive slope at a value of 0 angstroms or more (most preferably 10 angstroms or more when the dV / dD value is 0.0000) When intersecting the diameter axis, the catalyst of the present invention results in a lower coke yield. For the two different materials of the present invention, the following plots in FIG. 3 show tangents that intersect the pore diameter with values of 10 and 25 Angstroms, respectively.

  For FIG. 3, which is a plot of [dV / dD: pore diameter], the maximum pore volume of pores 10-40 mm is 0.0004 cc Hg / (g-angstrom) × 30 angstrom ÷ 2 = 0.006 cc. / G.

  In an embodiment, the matrix has an amorphous porous material having pores having a size in the range of 1 to 10 and 40 to 500, but substantially free of pores having a size in the range of 10 to 40 It is a silica-alumina base material. However, in the pore range of 50 to 250 cm, the single maximum value of the differential pore volume distribution is in the range of 50 to 250 cm.

  In related embodiments, the matrix of the composition has a differential pore volume as a function of the matrix pore diameter. This function has a maximum value between 50 and 150 inches. The integrated differential pore volume for matrix pores having a diameter of 1 to 10 cm cannot be distinguished from the zeolite pore volume typically used in catalysts. The integrated maximum pore volume with respect to the volume of the matrix pores having a diameter of 40 to 500 mm is in the range of 0.06 cc / g to 0.12 cc / g, and the integrated pore for the matrix pores having a diameter of 10 to 40 mm The volume is less than 0.03 cc / g, preferably less than 0.01 cc / g.

  These types of catalysts are remarkably selective for the production of liquids (especially olefins) in a fluid catalytic cracking operation and have a low coke make. The wear resistance of these catalysts is very high. This is indicated by a low Davison index in the range 1-8, most frequently and preferably 1-5, measured by the Davison index. See Non-Patent Document 5.

  Preferred catalyst particles are: (a) amorphous porous solid acid matrix (alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, silica-alumina-rare earth And) (b) zeolite (such as faujasite). The matrix can include a ternary composition. Silica-alumina-tria, silica-alumina-zirconia, magnesia, silica-magnesia-zirconia and the like. The base material may also be in the form of a cogel. Silica-alumina is particularly preferable for the base material, and can contain 10 to 40% by weight of alumina. As described, a cocatalyst may be added.

  In an embodiment, the catalyst zeolite includes zeolite Y and a zeolite that is closely related. These include rare earth hydrogen and ion exchange types such as the ultrastable (USY) type. The zeolite may have a crystallite size in the range of 0.1 to 10 microns, preferably 0.3 to 3 microns. The relative concentrations of the anhydrous base zeolite component and the matrix can vary widely, and the zeolite content is 1 to 100%, preferably 10 to 99%, more usually 10 to 80% by weight of the dry composition. % Range.

The amount of zeolite component in the catalyst particles will generally range from 1 to 60 wt%, preferably from 5 to 60 wt%, more preferably from 10 to 50 wt%, based on the total weight of the catalyst. As described, the catalyst is typically included in the composition in the form of catalyst particles. When in the form of particles, the catalyst particle size will range from 10 to 300 microns in diameter and the average particle size will be 60 microns. After artificial deactivation in steam at higher pressures in commercial operation [ie pressures of 1 atm (101.3 kPa)], the surface area of the matrix material is ≦ 350 m ² / g, preferably 50 200 m ² / g, more preferably it will be 50 to 100 m ² / g. Surface area of the catalyst, although it will depend like the type and amount of zeolite and matrix components used, it is usually, 500 meters less than ² / g, preferably 50 to 300 m ² / g, more preferably 50 to 250 m ² / g, most preferably 100-250 m ² / g.

  Another preferred catalyst comprises a mixture of zeolite Y and a second zeolite (such as zeolite beta). The first and second zeolites may be on the same catalyst particles, different particles, or some combination thereof. The amount of zeolite and the type and properties of the matrix are as indicated in the description of the Y zeolite catalyst. In a related embodiment, the second zeolite is a shape selective zeolite species (such as ZSM-5). Alternatively, the shape selective zeolite may be used in a catalyst that does not contain the first zeolite. The Y zeolite, the shape selective zeolite, or both may be on the same catalyst particles, different particles, or some combination thereof.

  Shape selective zeolite species useful in the present invention include medium pore size zeolites that generally have a pore size of 0.5 nm to 0.7 nm. These zeolites include, for example, zeolites of the MFI, MFS, MEL, MTW, EUO, MTT, HEU, FER, and TON structure types (IUPAC zeolite nomenclature committee). Non-limiting examples of these intermediate pore size zeolites include ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, Silicalite and silicalite 2 are included. Most preferred is ZSM-5, which is described in US Pat. ZSM-11 is described in Patent Document 4, ZSM-12 is described in Patent Document 5, ZSM-21 and ZSM-38 are described in Patent Document 6, ZSM-23 is described in Patent Document 7, and ZSM-35 is described in Patent Document 8. The

  Although shape selective species are described by zeolites, it may be shape selective (ie, medium pore size) molecular sieves. In embodiments, suitable intermediate pore size molecular sieves include silicoaluminophosphate (SAPO) (such as SAPO-4 and SAPO-11 described in US Pat. Iron silicate; aluminum phosphate (ALPO) (such as ALPO-11 described in Patent Document 10); titanium aluminosilicate (TASO) (such as TASO-45 described in Patent Document 11); boron silicate (patent document) 12); titanium aluminophosphate (TAPO) (such as TAPO-11 described in Patent Document 13); and iron aluminosilicate.

  Large pores (eg, zeolite Y) and shape selective zeolites in the catalyst species may include “crystalline mixtures”. This is believed to be the result of defects that occur in the crystals or crystalline regions during the synthesis of the zeolite. Examples of crystalline mixtures of ZSM-5 and ZSM-11 are disclosed, for example, in US Pat. The crystalline mixture is itself an intermediate pore size (ie, shape selective) zeolite, and different crystals of different zeolite crystallites are present in the physically same catalyst composition or hydrothermal reaction mixture. It should not be confused with an artificial mixture.

(II) Preparation Method of Catalytic Cracking Catalyst The catalyst of the present invention contains a catalytically active molecular sieve dispersed in a mesoporous inorganic matrix. In embodiments, the crystalline aluminosilicate zeolite, or zeolite (suitably USY or high silica USY zeolite) is preferably water, urea compound, phosphate, clay (eg kaolin), and aluminum hydroxide (eg gibbsite). These solids are slurried. An aqueous silica solution, such as silica sol (binder colloid), is added to the aqueous slurry. The sol should not be gelable. The mixed component slurry is dried, ion exchanged to remove sodium, calcined, and then steamed to form a catalyst.

The catalyst precursor may be produced by the following steps. That is,
(A) a molecular sieve, (i) an aqueous solution containing an alkaline silicate (eg, sodium silicate), (ii) urea, (iii) a phosphate (such as an alkali metal phosphate, ammonium phosphate, or both), and (Iv) a step of forming a slurry in combination with a clay component (such as bentonite, kaolin, or both),
(B) a step of spray drying the slurry, and (c) a step of removing sodium by an ion exchange operation.

  Gibbsite may be added to the catalyst precursor as a component of part (a) above. The order of addition of component (a) may vary. The catalyst may be made by further ion exchange followed by calcination and steaming if it is necessary to further remove sodium from the precursor. Firing and steaming may be conventional. Firing may be performed at a temperature in the range of 250 ° C to 850 ° C. The firing time depends on the temperature selected, but is typically over 1 hour. Steaming is preferably performed at 650 ° C. to 850 ° C. for 4 to 48 hours.

The matrix can be characterized by pore size distribution after steaming. This is measured by mercury porosimetry (Non-Patent Document 6; θ = 140 °, Hg surface tension = 474 erg / cm ² ). Based on IUPAC, micropores refer to pores in the range of 2-20 inches.

式中、Ｒ_１、Ｒ_２、Ｒ_３、およびＲ_４は、独立して、ＨまたはＣ_１〜Ｃ_４アルキル、好ましくはＨであり、Ｘは、硫黄または酸素、好ましくは酸素である。好ましい尿素化合物は、尿素（即ちＨ_２ＮＣＯＮＨ_２）である。 The urea compound has the following general formula:

In which R ₁ , R ₂ , R ₃ and R ₄ are independently H or C ₁ -C ₄ alkyl, preferably H, and X is sulfur or oxygen, preferably oxygen. A preferred urea compound is urea (ie H ₂ NCONH ₂ ).

  Urea may be added to the slurry in stoichiometric amounts based on the reaction of urea with sodium in sodium silicate to form sodium carbonate and ammonia. The amount of urea may vary from 0.8 to 1.2 times the stoichiometric amount based on the amount of sodium silicate. The addition of urea to the slurry generally results in an increase in the pore volume of the catalyst of the present invention.

The phosphate is a water-soluble phosphate, typically sodium or ammonium phosphate, preferably sodium phosphate. The salt may be a primary, secondary, or tertiary salt. NaH ₂ PO ₄ , (NH ₄ ) ₂ HPO ₄ , (NH ₄ ) ₃ PO ₄ , Na ₂ HPO ₄ , Na ₃ PO ₄ , as well as polyphosphates such as (NaPO ₃ ) _n and Na ₄ P ₂ O ₇ Etc. The amount of phosphate is preferably less than that required to react with the total aluminum present.

  The clay used in the slurry may be kaolin, bentonite, attapulgite, montmorillonite, hectorite, and pyrophyllite. Preferred clays are kaolin or bentonite, especially kaolin. In embodiments, zeolite, clay, phosphate, sodium silicate, at least one aluminum hydroxide or aluminum oxyhydroxide, and urea are added simultaneously or sequentially in any order and at ambient temperature, Slurried in a limited and controlled amount of water. In general, it has been found that the weight ratio of water to solids in the slurry may range from 1: 1 to 4: 1, preferably 1.5: 1 to 3: 1. A water: solids weight ratio close to 2: 1 has been found to be remarkably successful in forming high quality catalysts. If the water: solids weight ratio is less than 1: 1, the viscosity of the slurry is too high for spray drying, while the water: solids weight ratio above 4: 1 is a certain environment. Below, it may lead to a loss of wear resistance of the catalyst. The pH of the slurry at this point is in the range of 10-12 to avoid gelation of the silica sol. In embodiments, the silica in the sol has an average diameter ranging from 1.0 nm (nanometers) to 22.0 nm, preferably from 1.5 nm to 15.0 nm. Silica sol is described in Non-Patent Document 7. Water may be added to the sodium silicate sol to maintain a water: solid weight ratio of 1: 1 to 3: 1. A preferred solids content is 28 to 45% by weight, based on the catalyst precursor. The density of the slurry is preferably in the range of 1.2 to 1.4 upon completion of the starting material addition. More preferably, it is 1.20-1.35. Also preferably, the viscosity of the slurry at this point is in the range of 60-300 cP (60000-300000 Pa · s), more preferably 80-200 cP (80000-200000 Pa · s) (22 ° C.).

  After mixing the zeolite, clay, at least one aluminum hydroxide or aluminum oxyhydroxide, urea, sodium silicate, and phosphate, adjusting the water content, density, preferably also pH and viscosity, the slurry is It can be dried in conventional processing equipment (eg spray drying equipment) to form the catalyst precursor.

  In an embodiment, the slurry removes moisture, preferably at / below ambient temperature, to form microspheres with average particle diameters ranging from 10 microns to 200 microns, preferably 60 microns to 100 microns. To a drying device (preferably a spray-drying device) at a sufficient temperature. The temperature is high enough to dry the slurry and form a hard structure, but the alkali metal component (eg, sodium from sodium silicate) is occluded in the zeolite and it is washed and ion exchanged. It is not high enough to prevent removal from the zeolite. Typically, the slurry is fed to a dryer, preferably a spray dryer, with an average inlet temperature in the range of 250 ° C to 500 ° C and an outlet temperature in the range of 125 ° C to 225 ° C.

Following drying, the catalyst precursor is washed, preferably in powder form of microsphere particles, with deionized water, for example at ambient temperature to 100 ° C. The washed precursor is then ion exchanged for a time sufficient to remove alkali metal (eg, sodium) from the zeolite. In the embodiment, one or more of sulfuric acid, aluminum sulfate, and ammonium sulfate are used. Preferably, aluminum sulfate hydrate and ammonium sulfate are used. Preferably, a stoichiometric amount of aluminum sulfate hydrate / ammonium sulfate is used based on the amount of sodium present. Preferably, a 2/3 atomic ratio of Al ³⁺ / NH ₄ ⁺ in sulfate is used. The following data in Tables 2.3 and 2.5 show that the optimal Al ³⁺ / NH ₄ ⁺ molar ratio is at this atomic ratio for sodium removal from the catalyst precursor.

  If necessary, a second ion exchange step may be used to further reduce the amount of sodium. The ion exchange particles are generally washed again, for example at ambient temperatures to 100 ° C. The zeolite portion of the catalyst, after ion exchange and washing, typically contains less than 0.4% alkali metal, based on the weight of the catalyst. A small amount of aluminum from the aluminum sulfate hydrate is believed to be incorporated into the catalyst during ion exchange.

  While not wishing to be bound by any theory or model, the presence of phosphate in the slurry is believed to affect the matrix microporosity. It is believed that the phosphate interacts with the aluminum species in the slurry to produce aluminum phosphate. Since aluminum phosphate has a similar isoelectric point to silica, it is clear that the particles in the slurry have a similar charge and agglomeration is avoided. Aggregation is believed to result in a decrease in the microporosity characteristics of the catalyst. Another factor believed to result in the unique pore distribution of the catalyst of the present invention relates to the use of sodium silicate in combination with urea as the directing compound in the binder system.

(III) Catalytic cracking method In yet another embodiment, the present invention relates to a catalytic cracking method. The catalytic cracking process may be carried out in a fixed bed, moving bed, ebullated bed, slurry, transfer line (dispersed phase), or fluidized bed operation. Suitable hydrocarbon feedstocks (ie, main feedstocks) for the catalytic cracking process described herein include natural and boiling boiling in the range of 430 ° F to 1050 ° F (221.11 ° C to 565.56 ° C). Synthetic hydrocarbonaceous oil is included. Gas oils; heavy hydrocarbonaceous oils containing substances boiling above 1050 ° F. (565.56 ° C.); heavy and truncated petroleum crude oils; petroleum atmospheric distillation bottoms; petroleum vacuum distillation bottoms; pitch, asphalt, bitumen, Other heavy hydrocarbon residues; tar sand oil; shale oil; liquid products derived from coal liquefaction processes; naphtha, and mixtures thereof.

  In embodiments, the catalytic cracking method is performed in one or more FCC process equipment. Each apparatus includes a reaction zone (usually a riser reaction zone), a stripping zone, a catalyst regeneration zone, and at least one separation zone. In the FCC process, the feedstock is sent to the reaction zone where it is injected, where the main feed comes into contact with the flow source of the hot regenerated catalyst. The high-temperature catalyst vaporizes and decomposes the raw material at a temperature of 450 ° C. to 650 ° C., preferably 500 ° C. to 600 ° C. The cracking reaction causes carbonaceous hydrocarbons or coke to deposit on the catalyst, thereby deactivating the catalyst. The cracked product may be separated from the coking catalyst and a portion of the cracked product may be sent to a separation zone such as a fractionator. A fraction such as a naphtha fraction can be separated from the cracked product in the separation zone and derived from the process.

  FCC process conditions in the reaction zone of the riser reactor include a temperature of 450 ° C. to 700 ° C., a hydrocarbon partial pressure of 10 to 40 psia (69 to 276 kPa), preferably 20 to 35 psia (138 to 241 kPa), and catalyst / main feed ( Weight / weight) ratio of 3 to 100 (catalyst weight is the total weight of the catalyst composition). Total pressure is from atmospheric pressure to 45 psig (411 kPa). Although not required, steam is still introduced into the reaction zone with the raw materials at the same time. Here, the steam preferably constitutes 50% by weight or less, preferably 2 to 10% by weight of the main raw material. The residence time of the raw material in the reaction zone is preferably less than 20 seconds, preferably 0.1 to 20 seconds, more preferably 1 to 5 seconds.

  The present methods and catalysts provide both economic and technical advantages over the state of artistic commercial FCC catalysts. Three main binders are currently used to make FCC catalysts. These are acidified silica sol binders, aluminum chlorohydrol, and peptized alumina. These three coupled systems are acidic and this acidity can adversely affect the physical properties of the acid sensitive active substance. Previous mesoporous catalysts based on silica used Ludox® as the silica source. This is a more expensive component than basic sodium silicate.

In this process, sodium silicate (base system) can successfully bind the FCC catalyst. Furthermore, incorporation of urea with sodium silicate into the raw material of the spray dryer produces a catalyst that is more mesoporous and more selective than a catalyst that has not been so treated. Neutralization of sodium contained in sodium silicate is performed using an ammonium salt of an acid stronger than silicic acid. The cheapest acid source is sulfuric acid. Neutralization with sulfuric acid requires careful control, or gelation will result in reduced catalyst strength and integrity. Carbonic acid is a somewhat stronger acid than silicic acid and as such may also be used to neutralize sodium silicate. However, neutralization with carbonic acid results in gelation because carbonic acid forms a silica sol at a pH at which gelation readily occurs. Urea is an anhydrous diammonium carbonate that slowly hydrolyzes to form the basic solution ammonia and sodium carbonate. Incorporating urea into the binder system allows the reaction to occur after drying, so that silica gel does not form before drying, resulting in a weaker product. Incorporation of urea may also promote the formation of this mesoporous structure. This improves the selectivity of the product. The alkali metal salt of phosphate appears to be particularly effective in forming a pore structure. This improves the selectivity for products other than coke. The following Comparative Examples 1, 2, and 3 show that materials made with ammonium phosphate cannot provide advantageous product selectivity. Figure 4 and 5, 221 ° C. ^- indicates that during conversion to selectivity for products other than coke, is insufficient for producing substances using ammonium phosphate. That is, the substances labeled “1.11”, “2.11”, “3.11”, “1.12”, “2.12”, and “3.12” are alkali metal phosphates. It is shown that it is inadequate compared to materials made using, ie those labeled “4.11” and “5.11”. FIG. 8 shows that the porosity in the region below 50 Angstroms is greater for materials made with ammonium phosphate.

  The following comparative examples and examples are given to illustrate the present invention. This should not be considered limiting in any way.

Comparative Example 1: No Urea / Diammonium Hydrogen Phosphate This is a comparative (base case) example where sodium silicate is used as the silica source in the binder but no urea is added during catalyst preparation.

To 3000 g of water in a 2 gallon (7570 m ³ ) plastic bucket, zeolite Z-14G NaUSY 1319.3 g, 12.5 g of diammonium hydrogen phosphate, 728 g of Hydrite UF kaolin clay, and Spacelite ) 560 g of S-11 gibbsite was added. The resulting mixture was stirred for 30 minutes with a Cowles mixer.

  1742.2 g of “N” marked sodium silicate was diluted with 1700 g of deionized water, added to the water / zeolite / diammonium hydrogen phosphate / clay slurry and then subjected to a colloid mill. The slurry subjected to the colloid mill had a pH of 10.8 (22 ° C.). The viscosity of the slurry was 188 cP (188000 Pa · s) (100 rpm), and the density of the slurry was 1.322 g / cc.

The slurry was spray dried in a Bowen # 1 tower spray dryer at an outlet temperature of 121 ° C. [air flow 250 cfm (7.08 m ³ / min) (80 ° C.) at a rate of 7/35 kg / hour. ] 787g of 50% solids greater than 74.4 microns was collected from the main tower pot. The slurry and product properties are summarized in Table 1.

The following solution of ammonium sulfate and aluminum sulfate was used to ion exchange this material. That is,
360 g of Al ₂ (SO ₄ ) ₃ · 16H ₂ O was dissolved in 2040 g of DI water.
106.2 g of (NH ₄ ) ₂ SO ₄ was dissolved in 2294 g of DI water.

200 g Al ₂ (SO ₄ ) ₃ · 16H ₂ O solution and 200 g (NH ₄ ) ₂ SO ₄ solution were added to 120 g product of the spray dryer. The mixture was shaken in a shaking bath at 80 ° C. and 260 rpm for 1 hour, cooled, then washed three times at 80 ° C. with 500 g of DI (deionized) water on the filter and air dried. The product from this first ion exchange (Comparative Example 1.1) was analyzed. The remaining sample was added to 200 g of dilute aluminum sulfate solution, and then 200 g of dilute ammonium sulfate solution was added. This was shaken at 80 ° C. and 260 rpm for 1 hour, washed three times with 500 g of deionized water, dried at 120 ° C. for 2 hours, and baked to obtain Comparative Example 1.2. Table 2 contains the analysis results of these samples.

Comparative Example 2: Urea / diammonium hydrogen phosphate This is a further comparative example. Unlike standard commercial FCC catalysts, the preparation is performed in a basic atmosphere. One mole of urea is believed to neutralize 2 moles of sodium. This is due to decomposition to form ammonium silicate and sodium carbonate.

To 2500 g of water in a 2 gallon (7570 m ³ ) plastic bucket, zeolite Z-14G NaUSY 1319.3 g, 12.5 g diammonium hydrogen phosphate, 728 g Hydrite UF kaolin clay, and Spacelite ) 560 g of S-11 gibbsite was added. The resulting mixture was stirred for 30 minutes with a Cowles mixer.

1742.2 g of “N” marked sodium silicate was diluted with 2275 g of deionized water, added to the water / zeolite / diammonium hydrogen phosphate / clay slurry and then subjected to a colloid mill. The slurry subjected to the colloid mill had a pH of 11.0 (21 ° C.). The viscosity of the slurry was 247 cP (247000 Pa · s) (100 rpm). The slurry was spray dried in a Bowen # 1 tower spray dryer at an outlet temperature of 145 ° C. [air flow 250 cfm (7.08 m ³ / min) (80 ° C.) at a rate of 7/35 kg / hour. ]

  1436 g of solids was collected from the main tower pot. The composition of the slurry and product is summarized in Table 3.

A dilute sulfuric acid solution was prepared by dissolving 52.4 g of H ₂ SO _{4 in} 1548 g of DI water.

270 g of Al ₂ (SO ₄ ) ₃ · 16H ₂ O was dissolved in 1530 g of DI water to prepare a diluted aluminum sulfate solution of 4.5 × 10 ⁻⁴ mol Al ³⁺ / g solution.

70.8 g of (NH ₄ ) ₂ SO ₄ was dissolved in 1529.2 g of DI water to prepare a dilute ammonium sulfate solution of 6.7 × 10 ⁻⁴ mol NH ₄ ⁺ / g solution.

  The solution of Table 4 was added to 100 g of the product of the spray dryer.

  They were shaken in a shaking bath at 80 ° C. for 1 hour, filtered and washed three times with 400 g DI water at 80 ° C. for 0.5 hour. This was heated to 120 ° C. at 1 ° C./min and dried at 120 ° C. for 6 hours.

  The elemental analysis results for these samples are included in Table 5.

The Al ₂ O ₃ / SiO ₂ weight ratio is 0.60 for Comparative Example 2.4 (NH ₄ ⁺ / Al ³⁺ preparation) and simply 0.55 for Comparative Example 2.5 (NH ₄ ⁺ Preparation). Please note that. This is because the system incorporates approximately 0.60 / 0.55-1 = 9.1% alumina or 0.091 × 35 = 3.2% alumina (1.6 g alumina). , Which is added to the original weight of the catalyst. This alumina comes from 100/1800 × 270 × 102/666 = 2.3 g in the exchange solution.

  To further illustrate the nature of this interaction, the product of the spray dryer of Comparative Example 2 was replaced with a second series in which only dilute aluminum sulfate solution and dilute ammonium sulfate solution were used. This is outlined in Table 6. The solution of Table 6 was added to 50 g of the product of the spray dryer.

  These were shaken in a shaking bath at 80 ° C. for 1 hour, filtered and washed three times with 400 g DI water at 80 ° C. for 0.5 hours. This was heated to 120 ° C. at 1 ° C./min and dried at 120 ° C. for 6 hours. Table 7 clearly shows that for these sodium silicate-bound catalysts, sodium removal is most effective with specific combinations of aluminum and ammonium salts (ie 2 moles of Al / 3 moles of ammonia). Is shown.

  To show that sodium removal from the catalyst is completed by sequential ion exchange, 120 g of the product of the spray dryer of Comparative Example 2 was added to 200 g of dilute aluminum sulfate solution, followed by 200 g of dilute ammonium sulfate solution. . This was shaken at 80 ° C. and 260 rpm for 1 hour, washed three times with 500 g of deionized water, and dried at 120 ° C. for 4 hours to obtain Comparative Example 2.9. The remaining sample was added to 200 g of dilute aluminum sulfate solution, and then 200 g of dilute ammonium sulfate solution was added. This was shaken at 80 ° C. and 260 rpm for 1 hour, washed three times with 500 g of deionized water, dried at 120 ° C. for 2 hours, and baked to obtain Comparative Example 2.10. The analysis results for Comparative Examples 1.9 and 1.10 that do not contain volatile substances are included in Table 8.

Comparative Example 3: 2x urea / diammonium hydrogen phosphate This comparative example shows the removal of sodium by ion exchange from the product from the spray dryer. This is prepared as follows. To 3000 g of water in a 2 gallon (7570 m ³ ) plastic bucket, zeolite NaUSY 1319.3 g, diammonium hydrogen phosphate 12.5 g, Hydrite UF® kaolin clay 728 g, urea 403.5 g , And 560 g of Spacerite® S-11 gibbsite. The resulting mixture was stirred for 30 minutes with a Cowles mixer.

  1742.2 g of "N" (R) marked sodium silicate was diluted with 1700 g of deionized water, added to the water / zeolite / diammonium hydrogen phosphate / clay slurry and then subjected to a colloid mill. The slurry subjected to the colloid mill had a pH of 10.79 (17 ° C.). The viscosity of the slurry was 199 cP (199,000 Pa · s) (100 rpm), and the density of the slurry was 1.293 g / cc.

The slurry was spray dried in a Bowen # 1 tower spray dryer at an outlet temperature of 160 ° C. [air flow 250 cfm (7.08 m ³ / min) (80 ° C.) at a rate of 7/35 kg / hour. ] After drying, the solids were collected from the bottom of the main tower and weighed. The solid content from the bottom of the cyclone was a yield of 1129 g of 50% solid content exceeding 66.0 microns. Nominal slurry and product compositions are shown in Table 9.

  120 g of the product of the spray drying apparatus of Comparative Example 3 was added to 200 g of dilute aluminum sulfate solution, and then 200 g of dilute ammonium sulfate solution was added. This was shaken at 80 ° C. and 260 rpm for 1 hour, washed three times with 500 g of deionized water, and dried at 120 ° C. for 4 hours to obtain Comparative Example 3.1. The remaining sample was added to 200 g of dilute aluminum sulfate solution, and then 200 g of dilute ammonium sulfate solution was added. This was shaken at 80 ° C. and 260 rpm for 1 hour, washed three times with 500 g of deionized water, dried at 120 ° C. for 2 hours, and baked to obtain Comparative Example 3.2. The analysis results for Comparative Examples 3.1 and 3.2 that do not contain volatile substances are included in Table 10.

Example 4: Urea / disodium hydrogen phosphate This example is the catalyst of the present invention. In its preparation, alkaline phosphate, urea, and sodium silicate are used to make a spray-dried product. This is ion exchanged with an optimal mixture of aluminum and ammonium salts to make the final catalyst. When this catalyst was then deactivated with steam, it had a pore structure according to the catalyst and method of the present invention. To 3000 g of water in a 2 gallon (7570 m ³ ) plastic bucket, 13.4 g of disodium hydrogen phosphate, 200 g of urea, 373 g of Alcoa C-33 gibbsite, 137 g of zeolite NaUSY 1319.3 g, and Hydrite ) 874 g of UF Kaolin clay was added. The resulting mixture was stirred with a Cowles mixer until it flowed smoothly.

1742.2 g of “N” marked sodium silicate was diluted with 2400 g of deionized water and to this was added a slurry of water / disodium hydrogenphosphate / urea / gibbsite / zeolite / clay. This slurry was then subjected to a colloid mill twice. The slurry subjected to the colloid mill had a pH of 10.8 (22 ° C.). The viscosity of the slurry was 188 cP (188000 Pa · s) (100 rpm), and the density of the slurry was 1.288 g / cc. The slurry was spray dried in a Bowen # 1 tower spray dryer at an outlet temperature of 150 ° C. [Air flow 250 cfm (7.08 m ³ / min) (80 ° C.) at a rate of 7/35 kg / hour. ] 939 g solids were collected from the main tower pot.

  120 g of the product of the spray drying apparatus of Example 4 was added to 200 g of dilute aluminum sulfate solution, and then 200 g of dilute ammonium sulfate solution was added. This was shaken at 80 ° C. and 260 rpm for 1 hour and washed three times with 200 g of deionized water. The wet cake was added to 200 g of dilute aluminum sulfate solution, followed by 200 g of dilute ammonium sulfate solution. This was shaken at 80 ° C. and 260 rpm for 1 hour, washed three times with 200 g of deionized water, dried at 150 ° C. for 1 hour, and calcined at 760 ° C. for 1 hour to obtain Example 4.1. Table 11 includes the analysis results.

Example 5: Urea / tetrasodium pyrophosphate This example is a catalyst according to the catalyst and method of the present invention. To 3000 g of water in a 2 gallon (7570 m ³ ) plastic bucket, 21.0 g of tetrasodium pyrophosphate, 200 g of urea, 373 g of Alcoa C-33 gibbsite, 1319.3 g of zeolite NaUSY, and Hydrite ) 874 g of UF Kaolin clay was added. The resulting mixture was stirred with a Cowles mixer until it flowed smoothly.

1742.2 g of “N” marked sodium silicate was diluted with 2400 g of deionized water and to this was added a slurry of water / tetrasodium pyrophosphate / urea / gibbsite / zeolite / clay. This slurry was then subjected to a colloid mill twice. The pH of the slurry subjected to the colloid mill was 11.0 (22 ° C.). The viscosity of the slurry was 189 cP (189,000 Pa · s) (100 rpm), and the density of the slurry was 1.26 g / cc. The slurry was spray dried in a Bowen # 1 tower spray dryer at an outlet temperature of 150 ° C. [Air flow 250 cfm (7.08 m ³ / min) (80 ° C.) at a rate of 7/35 kg / hour. ] 980 g solids were collected from the main tower pot.

  120 g of the product of the spray drying apparatus of Example 5 was added to 200 g of dilute aluminum sulfate solution, and then 200 g of dilute ammonium sulfate solution was added. This was shaken at 80 ° C. and 260 rpm for 1 hour and washed three times with 200 g of deionized water. The wet cake was added to 200 g of dilute aluminum sulfate solution, followed by 200 g of dilute ammonium sulfate solution. This was shaken at 80 ° C. and 260 rpm for 1 hour, washed three times with 200 g of deionized water, dried at 150 ° C. for 1 hour, and calcined at 760 ° C. for 1 hour to obtain Example 5.1. Table 12 includes the analysis results.

Example 6
Comparative Examples 1, 2, and 3 and Examples 4 and 5 were fired at 760 ° C. Comparative Examples 1, 2, and 3 were then steamed at a temperature of 760 ° C. for 16 hours to give Comparative Examples 1.11, 2.11, and 3.11 in Table 6, then steamed at 788 ° C. for 16 hours. Teaming was performed to obtain Comparative Examples 1.12, 2.12, and 3.12. Examples 4 and 5 were steamed at 788 ° C. for 16 hours to produce catalysts 4.11 and 5.11 for evaluation in ACE FCC. The ACE device is a commercially available device made for FCC laboratory evaluation and manufactured by Xytel Co. (Elk Grove Village, Ill.). The properties of the steamed catalyst are shown in Table 13.

  Comparative Examples 1.11, 2.11, 3.11, 1.12, 2.12 and 3.12 as comparative catalysts and 4.11 and 5.11 of the present invention were then subjected to the following physical properties: The reduced pressure gas oil having was evaluated by injecting it over the catalyst of a fixed fluidized bed reactor. Its operation is described in the published literature. The conditions under which the device operated are as follows.

  The raw material used was a Gulf Coast reduced pressure gas oil having the following characteristics.

Consistent with the observed differences in the pore size distribution of the steamed and artificially deactivated catalyst, the base case, and the two embodiments of the present invention, can be found in a small private fixed fluidized bed apparatus (ACE). Upon decomposition of the reduced pressure gas oil, it exhibits a substantially different coke selectivity. Figure 4-a is: For the Base Case Comparative Catalyst The catalyst of the present invention]: is a graph showing the Kokumeku (430 ° ^F -) + Kokumeku ^- (221 ° C.)]. FIG. 4-b shows that the catalyst of the present invention is more coke selective than the average coke selectivity seen from the commercially available prepared catalyst.

  FIG. 4-a is similar in that the catalysts of the present invention (Examples 4 and 5) produce less coke than other catalysts made with ammonium phosphate for a given conversion level. It shows that it is different from the comparative catalyst. In FIG. 5, the same data is normalized to conversion. Thereby, the gradient with respect to [coke: conversion rate] seen in FIG. 4 is removed.

If light hydrocarbon moieties (such as methyl groups) associated with heavy polycyclic aromatics in coke are decomposed as a result of high temperatures, the coke yield can drop, while light gas yields Rises. Since either coke or light gas constrains the operation of the device, it is not an obvious success to trade coke with light gas. For the catalyst of the present invention, both coke and light gas appear to be lower than the base case comparative catalyst. This is shown in FIG. 6-a, which is a plot of [dry gas make: (430 ° F. ⁻ (221 ° C. ⁻ ) + coke make)]. FIG. 6-b shows that the catalyst of the present invention produces less dry gas than the commercially available prepared catalyst.

  FIG. 7-a shows that the catalyst of the present invention produces propene that is more valuable than a similar base case comparative catalyst in achieving the same conversion. FIG. 7-b shows that the catalyst of the present invention produces more propene than the prepared catalyst in a commercially available state.

FIG. 8-a shows that the catalysts of the present invention (Examples 4 and 5) differ from similar base case comparative catalysts in the following respects. That is,
1. The maximum in the plot of [dV / dD: pore diameter] appears for pore diameters greater than 50 angstroms for the catalyst of the present invention;
2. For the steaming catalyst of the present invention, the tangent to the [dV / dD: pore diameter] curve of less than 50 angstroms is positive and intersects the pore diameter axis (dV / dD = 0) more than 10 angstroms. 2. and The catalyst of the present invention is that it is made of sodium silicate, urea, and sodium salt of phosphoric acid, as well as faujasite and alumina.

  FIG. 8-b shows that the commercially available prepared catalyst has a local maximum in the dV / dD plot below 60 angstroms (50 angstroms), regardless of steaming severity; And above 60 Angstroms indicate that more than one maximum is in the 60-200 Angstrom range.

  FIG. 8-c shows the locality in the dV / dD plot when a commercially available prepared catalyst was mixed with other catalysts from the same manufacturer, regardless of the severity of the steaming. [DV / dD: pore diameter] plot showing maximum value less than 60 angstroms.

  FIG. 8-d is a plot of [dV / dD: pore diameter] showing that the catalyst of the present invention has a maximum value in the dV / dD plot greater than 60 angstroms and less than 80 angstroms. This has a local maximum in the dV / dD plot below 60 Angstroms, regardless of the severity of the steaming, but is commercially available that may have one or more maxima above 80 Angstroms This is different from the prepared catalyst.

FIG. 4 is a plot of [differential mercury pore volume (dV / dD): pore diameter] for a catalyst matrix of 40 to 10,000 angstroms. It is a plot of [integrated differential mercury pore volume: 40-500 angstrom pore diameter] about the catalyst matrix. It is a plot of [dV / dD: pore diameter] showing an extrapolated value of pore volume for pores in the range of 10 to 40 angstroms. About: Base Case Comparative Catalyst The catalyst of the present invention],: ^- is a plot showing a comparison of [Kokumeku (221 ° C. + Kokumeku). Information: [commercially available catalyst catalysts of the present invention],: ^- is a plot showing a comparison of [Kokumeku (221 ° C. + Kokumeku). About: Base Case Comparative Catalyst The catalyst of the present invention, [(standardized coke yield to eliminate the effect of conversion) :( 221 ° C. ^- + Kokumeku) is a plot showing a comparison of. About: Base Case Comparative Catalyst The catalyst of the present invention, [dry Gasumeku: (221 ° C. ^- + Kokumeku) is a plot showing a comparison of. Information: [commercially available catalyst catalysts of the present invention, [dry Gasumeku: (221 ° C. ^- + Kokumeku) is a plot showing a comparison of. Catalyst of the present invention: Base Case Comparative Catalyst for: ^- a plot showing the comparison of the propene make (221 ° C. + coke) conversion. Information: [commercially available catalyst catalysts of the present invention],: ^- is a plot showing a comparison of the propene make (221 ° C. + coke) conversion. [DV / dD: pore diameter] plot showing that the catalyst of the present invention has a maximum value appearing at a pore diameter of more than 50 angstroms. [DV / dD: pore diameter] plot showing that the commercially available catalyst has a local maximum of dV / dD plot below 60 angstroms, regardless of steaming severity. . When a commercially available catalyst is mixed with other commercially available catalysts from the same manufacturer, the locality of the dV / dD plot is below 60 angstroms, regardless of the severity of the steaming. It is a plot of [dV / dD: pore diameter] which shows having a maximum value. FIG. 8-d is a plot [dV / dD: pore diameter] showing that the catalyst of the present invention has a maximum dV / dD plot above 60 angstroms and below 80 angstroms. This differs from commercially available catalysts that may have local maxima below 60 angstroms in all cases, and in some cases local maxima above 80 angstroms. To do.

Claims (19)

A fluid catalytic cracking (FCC) catalyst composition or catalyst comprising at least one amorphous porous matrix comprising:
The catalyst composition is part of a cracking catalyst and includes a silica-alumina matrix and at least one molecular sieve,
The matrix includes at least one clay, at least one aluminum hydroxide or aluminum oxyhydroxide, and a binder colloid, and each matrix has pores with a diameter in the range of 1 to 10 mm and a diameter of 40 mm. Fluidized catalytic cracking, characterized by having a single maximum value in the differential pore volume distribution in the range of 50 Å to 250 有 し for pores in the range of ˜500 、, and for pores in the range of 50 Å to 250 Å FCC) Catalyst composition or catalyst. 2. The fluid catalytic cracking (FCC) catalyst composition or catalyst according to claim 1 , wherein the molecular sieve is a zeolite that is at least one of a large pore zeolite and a shape selective zeolite. The aluminum hydroxide is alumina, the alumina is gibbsite, the clay fluid catalytic cracking (FCC) catalyst composition or catalyst according to claim 1, characterized in that the kaolin. The fluid catalytic cracking (FCC) catalyst composition or catalyst according to claim 1 , wherein the binder colloid is an alkaline silicate, and the alkaline silicate is sodium silicate. The fluid catalytic cracking (FCC) catalyst composition or catalyst according to any one of claims 1 to 4 , wherein the amount of the base material is 5 to 100% by weight, based on the total weight of the catalyst. The zeolite content of the cracking catalyst, based on the weight of the catalyst, the fluidized catalytic cracking (FCC) catalyst composition according to any one of claims 1 to 5, characterized in that in the range of 5 to 92% by weight or catalyst. Integration maximum pore volume to the volume of the preform pores with diameters 40Å~500Å is according to any one of claims 1 to 6, characterized in that in the range of 0.06cc / g~0.12cc / g Fluid catalytic cracking (FCC) catalyst composition or catalyst. The large pore zeolites are zeolite zeolite Y or zeolite Y and isostructural, the zeolite is any of claims 2-7, characterized by having a pore diameter in the range of 3 to 15 Angstroms A fluid catalytic cracking (FCC) catalyst composition or catalyst according to claim 1. The matrix is a single amorphous body or a mixture of two or more separate amorphous matrices, each matrix individually meeting the requirements for differential pore volume distribution. fluid catalytic cracking according to any one of claims 1 to 8, wherein (FCC) catalyst composition or catalyst. A process for producing a cracked catalyst precursor for a fluid catalytic cracking (FCC) catalyst composition or catalyst comprising the steps of:
(A) water, at least one molecular sieve, at least one aluminum hydroxide or aluminum oxyhydroxide, at least one clay,

Where R ₁ , R ₂ , R ₃ and R ₄ are independently H or C ₁ -C ₄ alkyl, and X is sulfur or oxygen.
Combining at least one urea compound having: and at least one alkali metal phosphate to form a first mixture;
(B) combining the first mixture with a sufficient amount of an aqueous alkaline silicate solution to form a slurry having a pH sufficient to prevent gelation of the aqueous alkaline silicate solution;
(C) drying the slurry at a drying temperature sufficient to remove moisture and form a first solid; and (d) the first solid with water and an ion exchange composition. Combining to form a catalyst precursor comprising:
The ion exchange composition includes at least one selected from the group consisting of mineral acids, aluminum salts of mineral acids, and salts of mineral acids,
The manufacturing method characterized by including the process by which the said catalyst precursor is ion-exchanged and has a lower density | concentration alkali metal compared with said 1st solid content. Combining the ion-exchanged catalyst precursor from step (d) with water and an independently selected second ion-exchange composition, the first solids and the first ion-exchanged Forming a second ion-exchanged catalyst precursor having a low concentration of alkali metal compared to the catalyst precursor,
The method according to claim 10 , wherein the independently selected second ion exchange composition contains at least one selected from the group consisting of sulfuric acid, aluminum sulfate, and ammonium sulfate. The method for producing a cracking catalyst precursor according to claim 10 or 11 , wherein in the urea compound, R ₁ , R ₂ , R ₃ and R ₄ are independently H and X is oxygen. . The method according to any one of claims 10 to 12 , wherein the phosphate is at least one water-soluble primary, secondary or tertiary phosphate. The alkali metal phosphate is sodium phosphate, the mineral acid is sulfuric acid, the aluminum salt of sulfuric acid is aluminum sulfate, and the salt of the mineral acid is at least one of aluminum sulfate or ammonium sulfate, or a mixture thereof. the process according to any one of claims 10 to 13, characterized in that. The first solids ammonium silicate, alkaline silicates and alkaline carbonates, urea compounds, clay, at least one of aluminum hydroxide or aluminum oxyhydroxide, and claims 10 to, characterized in that it comprises a molecular sieve 14 The manufacturing method in any one of. Any of claims 10 to 15, characterized in that it is adapted to produce a cracking catalyst precursor for fluid catalytic cracking (FCC) catalyst composition or catalyst of any of claims 1-9 The manufacturing method as described in. A process for producing a fluid catalytic cracking (FCC) catalyst composition or catalyst comprising:
Producing a cracking catalyst precursor according to any of claims 10 to 15 ;
(E) calcining the ion-exchanged catalyst precursor at a temperature in the range of 250 ° C. to 850 ° C. for a calcining time for producing an ion-exchanged catalyst precursor; and (f) the above A process comprising contacting the calcined and ion-exchanged catalyst precursor with steam at a temperature in the range of 650 ° C. to 850 ° C. for a steaming time for producing the catalyst. A fluid catalytic cracking (FCC) catalyst composition according to any one of claims 1 to 9 , wherein the hydrocarbon feedstock is brought into contact with a catalytically effective amount of a cracking catalyst under catalytic conversion conditions. Alternatively, a fluid catalytic cracking (FCC) method comprising a step including a catalyst. The catalytic conversion conditions are as follows: temperature 450 ° C. to 700 ° C., hydrocarbon partial pressure 10 to 40 psia (69 to 276 kPa), cracking catalyst / raw material ratio (weight / weight) (the weight of the cracking catalyst is the total weight of the catalyst) The fluid catalytic cracking (FCC) process according to claim 18 , characterized in that it comprises a pressure in the range of 3 to 100, atmospheric pressure to 45 psig (411 kPa) and a residence time of the raw material of 0.1 to 20 seconds. .

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