SA05260221B1 - Cracking catalyst and process for its preparation - Google Patents

Abstract

A hydrocarbon cracking catalyst contains eta-alumina and/or x- alumina or the mixture of said alumina (0.5-50 Wt %) and gamma-alumina (0-50), the mixture of Y zeolite (30-90) and MFI zeolite (10-70), clay (0-75) and P(0.1-8). Its advantage is high quality of gasoline and liquefied gas.

Description

Y_ — cracking catalyst and process for its preparation Full description

“a 1” except a 1 a

The present invention relates to a cracking catalyst used in petroleum refining and process

To prepare that catalyst.

The catalytic cracking process feed ores tending to become heavier and heavier sharply led to

oe Increase the need for Jef cracking capacity of cracking catalysts in the fracking process to achieve the goal of

In the production of lighter oil (gasoline, diesel oil and liquefied petroleum gas)

liquefied petroleum gas

For the fluidized catalytic cracking (FCC) process, benzene

Isoparaffins, isoparaffins, aromatic aromatics, J gall, olefins, and olefins of gasoline, however, the lack of octane number content are the main substances involved in the octane number 0

The olefin in FCC gasoline is one of the things required for environmental protection.

To compensate for the decrease in the octane number due to the decrease in the olefin content; It is necessary

Increasing the content of isoparaffin and aromatic compounds in gasoline.

therefore; There is a dala to develop a cracking catalyst and a cracking process so that 1 can produce gasoline with a low olefin content but characterized by a dle content of

Aromatic compounds and isoparaffins.

—- YF~

Meanwhile; The quality of diesel oil produced by catalytic cracking also needs to be improved, because diesel oil produced using the current cracking catalyst and from the current cracking process has a low aniline point, high density, and a lower cetane number. number. Hence; There is a dala to develop a cracking catalyst and a cracking process 0 to achieve high cracking capacity for heavy oil and there is a possibility to reduce the density of diesel oil.

Increasing the aniline point and its cetane number. Furthermore it. The light olefins and isobutane inside the liquefied petroleum gas as a result of the catalytic cracking process are considered feedstocks for the basic organic chemical industries. Currently, the demand for the supply of light olefins (particularly propylene 0) and isobutane is declining. However, the content of light olefins (particularly propylene) and isobutane (HU sa) It is lower in liquefied petroleum gas products than existing cracking catalysts and processes.Therefore, there is dala for developing a new cracking catalyst and cracking method that can be used to produce cracking products containing lighter olefins (particularly propylene

. liquefied petroleum gas in liquefied petroleum gas isobutane and isobutane ( 0 zy cracking catalyst for cracking catalyst 001477801 Chinese patent No. reveals the ratio of catalyst in which more than © to © carbon atoms. The catalyst contains olefins olefins characterized by a unit cell size less than or equal to 786 zeolite by weight 7-zeolite 01 ranging from the element element to be selected from 2534-5 nanometer zeolite and from ? to 7450 0 zeolite

The group consisting of P, 805, 11, and from Ye to 245 by weight is a semi-synthetic block made of kaolin and an alumina binder. Chinese Patent No. 001585701 discloses gly cracking catalyst More isoolefins 015-150 and benzene The catalyst consists of oo ratio oo to 7760 alumina based compound alumina bond; alec is made using pseudo-boehmite and a colloidal alumina solution with a ratio by weight of 1 : 9 to 4 : aged © to 775 by weight of clay and of YY .75 . By weight, a molecular sieve. Where the aforementioned molecular sieve is a mixture consisting of a ratio ranging from 15 to 787 by weight 577- Le zeolite. The rest is a zeolite 0 with high silica with pentasil containing rare earth elements; This zeolite contains a percentage ranging from zero to 701 phosphorus (measured in HZSM-5 zeolite and/or POs). Image Chinese Patent No. -0177700 discloses Catalyst for the conversion of octane hydrocarbons with an octane number of light gasoline and gasoline olefins to produce olefins hydrocarbons

LE to 7460 by weight of 01 percent ranging from catalyst high. The catalyst consists of number 00 types of zeolite “these are zeolite 2534-5, zeolite REY zeolite, zeolite (Je Y zeolite), silica, and the remainder of the manufactured or semi-finished mold containing a percentage of Ranging from 01 to TE by weight silica and/or alumina binder where 2534-5 zeolite quantity ranges from ? to 786 by weight and SREY zeolite quantities 0 Y zeolite High silica zeolite ranging from 11 to 7975 by weight each.

Gen. Chinese Patent No. 01888705-A discloses a hydrocarbon conversion catalyst to produce propylene, butene 501606, and gasoline with a high octane number. The catalyst consists of a percentage ranging from 01 to 0 by weight of ADB types of zeolite “ZRP zeolite, REY zeolite © and Je 7 zeolite silica silica and the remainder of the manufactured or semi-finished mold containing a percentage ranging from 10 to 748 by weight of silica and/or alumina binder. The amount of ZRP zeolite ranges from 7506 JY by weight and the quantities of REY zeolite and high silica Y zeolite 68 range from 11 to 11 Yo by weight each.

phosphorus for a catalyst containing phosphorus Lyall No. 17789446 The patent reveals 0 to 01 of a ratio ranging from 85 catalysts to crack hydrocarbons The catalyst has a zeolite structure with Y zeolite or of 7 zeolite by weight of 0 2160 zeolite to 01 of clay Jib of zero to 7975 by weight of zeolite and/or MFI phosphorus zeolite by weight of ZY to 1.1 phosphorus alumina by weight from two types of alumina and from zero to 778 by weight rare earth elements measured as POs measured as No pseudo-boehmite from Boehmite Zav alumina these two types of alumina are made. RE;03 It has a high colloidal catalyst ability; Respectively. Although the alumina catalyst and the alumina solution are low in the olefin gasoline yield to convert heavy oil and make the broken olefin content catalytic and diesel oil cannot, the use of the catalyst 4 does not improve the quality of diesel oil petrol isobutane Light isobutane olefins that increase the olefins content

. liquefied petroleum gas

0.0

Chinese Patent No. 1-074 discloses a cracking catalyst: a catalyst for the production of gasoline rich in isoparaffins, propylene and isobutane The catalyst contains a ratio of zero to 770 by weight clay baby and from © to 7950 by weight inorganic oxides and from 1 e to Joo by weight molecular sieve; Where the molecular sieve is a mixture containing (1) from 01 to ve by weight zeolite 7 high silica 11168 having a ratio of ALO; [SiO; © to VO and a content of rare earth elements ranges from A to 770 wt measured as 185:0 and (7) from 01 to 797/5 wt zeolite 7 high silica having a ratio of 5:0/ALO; it is 6 to 0 and a rare earth element content ranging from 0 * to ZV by weight measured as REO; and (©) from 1 to 750 by weight 8 zeolite, mordenite, or ZRP zeolite Se alumina zeolite is generally included in the formation of cracking catalysts.In the previous art, the alumina is mostly alumina from alumina monohydrate and colloidal alumina solution, where the alumina trihydrate contains boehmite boehmite and Vo psendo- boehmite during calcification in catalyst preparation; boehmite, pseudo- boehmite and colloidal alumina solution are converted to —y alumina alumina, and therefore, the alumina included in the Glad catalysts mentioned in the previous art are all considered alumina Lie sf —y. Alumina can also be composed of alumina trihydrate. 00 Alumina trihydrate contains “alumina trihydrate”

d - trihydrate and 8 - lise of (Bayerite) alumina trihydrate and Nordstrandite. during catalyst preparation; Alumina trihydrate is converted into -alumina and B-alumina trihydrate is converted into #- alumina. Nordstrandite is the only form found in 0 nature; But there is no way to get it synthetically. Asal Patent No. 1,788,715 discloses a process for preparing fluid cracking catalysts by drying a mixture of cracking catalyst components containing clay, alumina, and molecular sieve, where that catalyst contains a ratio of 1, 0 to 700 by weight alumina from 8- alumina trihydrate. Although the aforementioned catalyst 0 is characterized by high cracking activity in heavy oil and better selectivity for light oil; it cannot reduce the olefin content in gasoline; It cannot improve the catalytic quality of diesel oil Jl and increase the content of light olefins ro isobutane in heavy petroleum gas. General description of the invention The present invention aims to provide a new catalyst for the cracking of hydrocarbons. Said catalyst has a higher ability to crack heavy oil; It gives cracking products with a low content of olefins in gasoline; And higher quality of diesel oil and higher contents of light olefins and isobutane in liquefied petroleum gas. YoYo

M - Although there are some examples in the previous art in which alumina trihydrate is introduced in the preparation of the cracking catalyst; It is simply used to increase the cracking ability of the catalyst without affecting the quality of gasoline, diesel oil, and liquefied petroleum gas in the cracking products. The owner of the current invention, oo, unexpectedly discovered that when inserting alumina formed with alumina trihydrate; Especially 8-Alumina trihydrate, Alumina trihydrate; And phosphorus “A-0 alumina and phosphorus at the same time to the cracking catalyst creates a special synergistic phenomenon which not only makes the catalyst cracking capacity increased but also improves the quality of gasoline and diesel oil Diesel oil and liquefied petroleum gas are largely used in cracking products.

The catalyst according to the present invention contains alumina, phosphorus and a molecular sieve with or without clay jib. Where the said alumina is Nn alumina or a mixture of -alumina, -alumina and/or -y-alumina; Whereas the catalyst contains on the basis of 1 its total quantity an amount ranging from 0.0 to 750 by weight of =n alumina and from zero to 7576 by weight =x alumina and / or —y alumina alumina » and from 01 to IV by weight molecular sieve Suis sieve and from zero to 7975 by weight baby clay and from 0.1 to

7A by weight phosphorus ; Size in photo and 0.5.

‎YoY.

F- The aforementioned molecular sieve is one or more selected from the group consisting of zeolite and non-zeolite molecular sieves as an active ingredient in the cracking catalyst. The aforementioned molecular sieves, whether of zeolite or others, are known to those with experience in this field. The aforementioned zeolite shall preferably be one or more selected from large pore zeolite and medium pore zeolite. A zeolite with large pores is that zeolite that contains a porous structure having an open ring pore diameter of 1.17 nm on Je 0 JY one or more zeolites selected from the group consisting of faujasite, zeolite, B = zeolite, and cmordenite, especially zeolite. Y zeolite contains 0 and one or more elements selected from phosphorus, iron, rare earth elements, and zeolite. Ultrastable zeolite -Y The ultrastable zeolite contains one or more elements selected from phosphorus, iron, rare earth elements, and zeolite-8. A medium-porous zeolite is a zeolite that contains a porous structure with an open ring pore diameter ranging from greater than 4.07 nanometers to less than 1.7 nanometers 0.-meter; Such as one or more selected zeolites having MFI structure (eg zeolite “(ZSM-5) zeolite and MFI JS zeolite containing one or more elements selected from iron and other elements Rare earths (eg ZSM-5 zeolite containing phosphorus, iron and/or rare earth elements; and MFT zeolite containing phosphorus are disclosed in Chinese Patent 0 No.)-1941781

And 1 Non-zeolite molecular sieve mentioned refers to one or more molecular sieves in which part or all of aluminum and/or silicon is replaced by other elements such as phosphorus titanium And gallium and germanium. Examples of these molecular sieves contain one or more selected types of silicate that differ in the percentage of ALO; [SiO] in which (for example; metal silicate and titanosilicates) and metalloaluminates (such as germanium aluminate 5 germanium) and mineral phosphates of its capacity: 2061100 and aluminophosphates and aluminophosphates Alumino-phosphate metalloaluminophosphates and silicoaluminophosphates integrated with metal (MeAPSO). SAPO one or more selected from the group consisting of a SAPO- 11 molecular sieve, a SAPO-34 molecular sieve, and a SAPO-37 molecular sieve. Preferably, one or more such molecular sieves shall be selected Of the group constituent “VO” of “Y- zeolite” and the “Y” zeolite contains phosphorus and/or iron df rare earth elements and 7a- super stable zeolite; and the “Y-” zeolite contains zeolite superstable to phosphorus, iron and/or rare earth elements, zeolite -8 and zeolite with frame 1; A zeolite having an MFI structure contains phosphorus and/or iron 08TZ and/or rare earth elements; And a molecular sieve, SAPO molecular sieve 0, YoYo

11- The most preferred molecular sieve is a zeolite mixture containing Y-zeolite and zeolite having a MFI structure. The Y-zeolite content is from *1 to .795. By weight, the zeolite content of the MFT structure ranges from 01 to 770 by weight based on the total weight of the zeolite mixture. 77 by weight rare earth metals (measured as oxides) The method for preparing the catalyst according to the present invention comprises drying of a slurry containing an aluminum compound, a molecular sieve, and water with a clay Jib or without it, where the aforementioned aluminum compound is that component capable of forming 0 alumina; or a mixture of an aluminum compound capable of forming - alumina and an aluminum compound capable of forming =x alumina and/or Liesl —y alumina, then calcining the slurry after adding an additional amount of a phosphorous compound. Each compound is used in an amount that makes the (Aled) catalyst contain based on The total weight of the catalyst varies from 1.9 to 756 by weight = m alumina and from zero to ve 7806 by weight x alumina and / or - alumina 0 alumina and from 01 to 770 wt. of a molecular sieve; and from zero to 7975 by weight clay and from 1,1 to (sls ZA) phosphorus; measured in the form of P,05. The catalyst according to the present invention is not only characterized by high cracking activity, but It also greatly improves the quality of gasoline, diesel oil and liquefied petroleum gas Cus liquefied petroleum gas 0 led to the provision of gasoline 43 low content of 1.0

11- Olefins, with a higher content of aromatic compounds and isoparaffins, and Say diesel oil with a lower density and higher octane number; LPG with a high content of 8e_light olefins; Especially the content of propylene and isobutane. The catalyst also has other advantages such as the ability to crack oo heavy oil and the ability to produce more light oils (gasoline, diesel oil and liquefied petroleum gas). Detailed description: The catalyst 41 produced according to the process of the present invention contains alumina, phosphorus, and a molecular sieve sa with clay Jib or cass, wherein the said alumina 0 is - alumina. alumina or a mixture of =n alumina ys alumina - alumina and/or —y alumina ¢ and where the ely catalyst has a total weight ratio of 1.5 To Zor by weight, preferably from © to 745 by weight, from 0-alumina by weight, and from zero to 7500 by weight, preferably from zero to +74 by weight, from - alumina —y Sis alumina, 1 alumina, and from ‎ 01 to 776 sll, preferably from 010 to 280 ve by weight of a molecular sieve; from zero to 7975 by weight, preferably from zero to AT by weight. Jib about; and from 0.1 to 74 wt.; preferably from .0 to 76 wt. of phosphorus measured as P05. Preferably from 1.7 to TVA by weight rare earth metals (measured as oxides 0 YY.

DSG -

The aforementioned molecular sieve is one or more selected from the group consisting of zeolite and non-zeolite molecular sieves as an active ingredient in the cracking catalyst. The aforementioned molecular sieves, whether of zeolite or others, are known to those with experience in this field.

It is preferable that the aforementioned zeolite be one or more selected from the zeolite

0 large pores and zeolite medium pores.

A large pore zeolite is that zeolite that contains a porous structure having an open ring pore diameter of at least 1.7 nm 0 such as one or more zeolites selected from the constituent group of faujasite, zeolite-8, mordenite and particularly one or more selected from zeolite 77; It contains

0 zeolite 7 contains one or more elements selected from phosphorus, iron, rare earth elements, and no- zeolite is ultra-stable. The ultra-stable zeolite contains one or more elements that are selected from phosphorus Iron, rare earth elements and zeolite (HY zeolite) The HY zeolite contains one or more elements selected from phosphorus, iron, rare earth elements and zeolite -8.

1 A medium-porous zeolite is a zeolite that contains a porous structure with an open annular pore diameter ranging from greater than 0.07 nanometers to less than 1.7 nanometers such as one or more selected from a zeolite having an MFI structure (eg ZSM-5 zeolite) A zeolite with an MFI structure contains one or more elements selected from iron and rare earth elements (eg zeolite is detected

zeolite 0 2514-5 contains phosphorus, iron and/or rare earth elements; And

ys — - zeolite with MFT structure containing phosphorus in patent Annal No. 11941481 - a). Said non-zeolite molecular sieve refers to one or more molecular sieves in which part or all of aluminum and/or silicon is replaced by other elements such as phosphorus and titanium. No to gallium and germanium. Examples of these molecular sieves contain one or more selected types of silicates with a ratio of 5102/1203m (for example, metal silicate and titanosilicates) and mineral aluminates (fis). metalloaluminate germanium aluminates and metallophosphates and alumino-0 phosphates aluminophosphates and alumino-metalloaluminophosphates and silico-alumino-phosphates integrated with metal (ELAPSO MeAPSO) and siliclo Alumino-phosphate (Jai) silicoaluminophosphates (SAPO molecular sieve) and gallo-germanates (gallogermanates) preferably a SAPO molecular sieve such as one or more selected from the group consisting of a SAPO-11 molecular sieve and a SAPO-34 molecular sieve molecular sieve eo and SAPO- 37 molecular sieve uy. Preferably, the aforementioned molecular sieve shall be one or more selected from the group consisting of ¢Y- zeolite and zeolite 77 contains phosphorus and/or iron and/or rare earth elements and 77a-superstable zeolite; The ultra-stable Y-zeolite contains phosphorus, iron and/or rare earth elements; And zeolite |0 - 8 and zeolite al zeolite “MFI” structure, and zeolite that has an MFI structure contains

1 - phosphorus and/or iron and/or rare earth elements; and a molecular sieve SAPO. Preferably, the mentioned molecular sieve consists of one or more that are selected from the group consisting of “Y- zeolite” and the zeolite-Y contains one or more that are selected 0 .of phosphorus and/or iron and/or rare earth elements; f-57 is an ultrastable zeolite; Whereas, the ultrastable CY zeolite contains one or more selected phosphorus, iron, and/or rare earth elements; and zeolite -117; zeolite-117 contains one or more alys selected from phosphorus, iron, and rare earth elements; The fp zeolite and the zeolite have an MFI structure. The 3 zeolite with the MFI structure contains one or more selected from phosphorus, iron, rare earth elements, and a molecular sieve (SAPO molecule). sieve It is more preferable that the molecular sieve contains a zeolite mixture of zeolite Y and a zeolite having a structure (MFI-) where the content of 577- zeolite ranges from Ye to 790 wt., preferably from 40 to 788 wt.; the content of zeolite ae with structure 1081 ranges from .01 to 790 wt.; preferably from 15 to 710 wt.; based on the total weight of the zeolite mixture The said clay is represented by one or more selected from the types of clay used as an active ingredient in the cracking catalyst, such as one or more selected from: kaolin, halloysite, montmorillonite, kieselguhr, allokite, soapstone, rectorite, sepiolite , atiapuleus, hydrotalcite, and bentonite 7

It is more preferable that the clay child be one or more to be chosen from: kaolin, montmorillonite, kieselguhr, rectorite, sepiolite and attapulgus, and these types are well known to those with experience in this field. The catalyst according to the present invention may contain a refractory inorganic oxide 0 other than alumina. A refractory inorganic non-alumina oxide is one or more selected from the group of refractory inorganic oxides other than alumina used as a template from the cracking catalyst; Jie silica or amorphous silica-alumina or: zirconia or titania or boric oxides or oxides of alkaline earth metal 0 . It is preferred; To be one or more selected from the group consisting of silica and amorphous silica - alumina, zirconia and titania Ws magnesia oxide and calcium oxide thereon "H . The refractory organic oxides are well known to those with experience in this field. Based on the total weight of the catalyst, the content of refractory inorganic oxide 1 other than alumina “Nestle_mentioned” ranges from zero to 701 by weight; Preferably from zero to 75 by weight. In the process of preparing the catalyst according to the present invention, the aluminum compound mentioned is the compound capable of forming –n alumina –alumina and the aluminum compound capable of forming alumina Lie off –y and/or alumina Lie si —y . YY

- 117 -

The aforementioned aluminum compound capable of forming =n alumina can be any aluminum compound capable of forming “-alumina” during the preparation of the catalyst 40, preferably 8-alumina trihydrate. That the aforementioned aluminum compound be capable of forming –y alumina, that is, an aluminum compound capable of forming “m”-alumina during the preparation of the catalyst; Preferably »- Alumina Tri Sas.

Alumina trihydrate jus that the aforementioned aluminum compound be capable of forming –y alumina –alumina any aluminum compound capable of forming –y alumina –alumina in the preparation of the catalyst ¢ preferably boehmite and/or False Boehmite

pseudo-boehmite and/or colloidal alumina solution.

0 - The aforementioned phosphorus compound can be added at any step before roasting; For example ; It can be added to mortar containing aluminum compound and “clay molecular sieve” with or without clay jib. Or, the phosphorus compound can be introduced by impregnating the solids obtained after drying the slurry containing the aluminum compound, the molecular sieve, and water; with or without water; Then roast the product

1 drinker. In the catalyst of the present invention, the mentioned phosphorus content is exclusive to the phosphorus content normally in the molecular sieve. The aforementioned phosphorus compound contains different compounds of phosphorus; For example; One or more is selected from the group consisting of phosphoric acid and phosphate compounds 5 phosphorous acid and

0 phosphites 5 pyrophosphoric acid and compounds

-VA-

Pyrophosphates, polyphosphoric acids, polyphosphate 85, metaphosphoric acid, and Lue metaphosphate compounds. To be one or more selected from the group consisting of Diammonium hydrogen phosphate ammonium phosphate 5 phosphoric acid

ammonium dihydrogen phosphates© and phosphorous acid and phosphorous acid and potassium pyrophosphate s sodium pyrophosphate s ammonium phosphite and sodium tripolyphosphate and potassium tripolyphosphate and sodium hexametaphosphate

and .potassium hexametaphosphate. It is more preferable 0 to be one or more selected from

The group consisting of:

phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium \ dihydrogen phosphate, phosphorous acid, ammonium phosphite, sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate.

Each component is used in a specific amount that makes the catalyst (led) catalyst contain a total weight of it at a ratio ranging from 1.9 to 7960 nm by weight alumina; And from zero to 750

1 wt = alumina alumina and/or —y alumina ¢ alumina and from 01 to ye es molecular sieve zero to 797/5 wt clay Jib from 1 wt 1, to 748 by weight phosphorus; measured in the image and 220. It is preferable that each component be used in a certain quantity so that the final catalyst contains in its total weight a ratio ranging from * to 745 by weight 1- Lie ol refractory and from zero to 60 7 by weight “- alumina and/or b”

1.0

and 1 - alumina 0 alumina and from 01 to 780 molecular sieve n> Jase from zero to Zhe by weight clay and from 1.9 to 77 by weight phosphorus ; Measured in the form of P,0s If the catalyst also contains inorganic oxides 85 other than alumina ¢, those mentioned oxides or the substance producing them can be added to the slurry gd slurry 0 Contains aluminum compound, molecular sieve and water. With or without clay child The material producing the aforementioned non-alumina inorganic oxide refers to a material capable of forming the aforementioned inorganic non-alumina oxide during the preparation of the catalyst 41 » Those of gall producing these 165 oxides are well known For those with experience in this field. For example; The silica precursor can be Soe silica solution and/or silica gel and/or sodium silicate and the silica precursor can be amorphous silica-alumina a colloidal silica-alumina solution and/or silica-alumina gel; The material produced for zirconia and titania is boric oxide and the oxides of 5 alkaline earth metals are the hydroxide for each of them. The aforementioned inorganic non-alumina 0 oxide and/or its precursor shall be used in such an amount that the final catalyst contains from zero to 708 by weight and preferably from zero to 75 by weight of non-alumina inorganic oxide . The said drying and roasting conditions are eg conventional drying and roasting of cracking catalysts; The drying temperature ranges from room temperature to 7010°C; 0 preferably 8 to VAY m; The roasting temperature ranges from greater than

L." - mouth to Vor and preferably from Te to 000m 0 and the roasting time is 1.1 hours on CJR and preferably from 1.1 to 10 hours; preferably from 1.7 to ; hours.As a drying method, various drying methods can be used, such as oven drying, air drying, or spray drying; oven drying or spray drying is preferred.

0 The catalyst according to the present invention is suitable for the catalytic cracking of petroleum and its various fractions; Particularly suitable for catalytic cracking of petroleum and its various fractions having a boiling point higher than 0 m Jha one or more selected from atmospheric distillation residue or vacuum distillation residue or vacuum distillation gas oil; or atmospheric distillation gas oil or direct operation gas oil or light or heavy de-asphalt oils from the solvent de-asphalt process and oil

0 Cooking gas to produce high quality gasoline, diesel oil and liquefied petroleum oil. One of the preferred catalysts in the present invention. The catalyst contains alumina, phosphorus, and a molecular sieve; With or without clay baby. Said alumina is =m alumina ¢ alumina or a mixture of = alumina 1 alumina”-alumina and/or —y-alumina

75. based on its total weight; At a ratio ranging from 0.0 to “catalyst” and the catalyst contains . 1 75. and from zero to alumina alumina = m by weight; preferably from © to 748 by weight from zero alumina and/or / alumina alumina = x alumina and preferably from zero to 7460 by weight 0.1 to 78; and from clay Jib by weight AT to 775; Preferably from zero to 01 in size in the image and 3720 and from phosphorus to 776 by weight phosphorus 1.9 and preferably from

Jail is considered. molecular sieve by weight Tow molecular sieve to 01 preferably from AVe 0

- For 1

The aforementioned molecule is a zeolite mixture that contains –Y zeolite and a zeolite that has a structure (MFI) as the content of 7-zeolite ranges from Ye to 7498 by weight, preferably from 0 to AO by weight and content of zeolite which has a MEL structure ranges from 01 to 776

Preferably from Ve to 770 by weight based on the total weight of the aforementioned zeolite mixture.

0 The process of preparing the preferred catalyst is as follows: The process includes drying the slurry containing an aluminum compound and sieve iia “slay molecular sieve with or without Fa child” where the aforementioned aluminum compound is that compound capable of forming — alumina; or a mixture of an aluminum compound capable of forming –n-alumina; and an aluminum compound capable of forming =x alumina—y s/s alumina. Then calcining the slurry and then adding the phosphorus compound again. Each component is used in such quantity that the final catalyst includes; Based on the total weight of that cone catalyst 0+ to 700 wt.; Preferably from © to 7465 by weight of wm alumina and from zero to 750 by weight and preferably from zero to 740 by weight = x isl alumina and/or /- alumina and from zero to 7975 1 by weight, preferably from zero to 7550 by weight; and from 1.1 to TA by weight and preferably from 1.9 to 75 by weight phosphorus “measuring in photo 205©; And from 01 to 2760 by weight, preferably from 01 to Tow by weight, a molecular sieve. The aforementioned molecular sieve (dads) is considered a zeolite containing 57- zeolite and a zeolite having a Cus MFI structure. The content of 7- zeolite ranges from 0 to 7460 by weight 0 Preferably from 00 to 788 _ by weight and the content of zeolite that has a MFI structure ranges from 0.0 seolite to 710 by weight based on the total weight of the zeolite mixture 11 to 7770 and preferably from the mentioned 0. The aforementioned zeolite mixture also contains zeolite -8 with a content ranging from zero to 72700 by weight and preferably from zero to 770 by weight based on the total weight of the aforementioned zeolite mixture. The catalyst greatly improves the quality of gasoline and liquefied petroleum gas in cracking products. The second preferred sisal catalyst according to the present invention, the catalyst contains alumina, phosphorus, rare earth metal 0 and a molecular sieve “with or without clay jib”. The said alumina — alumina “or a mixture of - alumina — y 5” alumina is alumina and/or b alumina. The catalyst contains 3 based on its total weight; on a ratio of 0.5 to Zoe by weight; Preferably from © to 745 by weight from =n alumina alumina and from zero to alumina and/r (- alumina by weight) and preferably from zero to 7460 of - alumina 0

IA; from + ) to clay Jib and from 0 to 775; Preferably from zero to 7750 by weight Ve by weight, preferably from 1.5 to 77 by weight phosphorus measured in form and 1270 and from 1 to 77 by weight, preferably from 1.7 to 71.8 by weight a rare earth metal Measured in the form of oxide 0 and from 01 to Ye, preferably from 01 to 756 by weight. Molecular sieve ua The molecular sieve is a Jade molecular sieve of zeolite - 7.

yy - - The preferred catalyst preparation process is as follows: The process comprises drying of an aluminum-containing slurry and an “elas molecular sieve” with or without clay jib; Where the said aluminum compound is that compound that is capable of forming “- alumina alumina ¢ or a mixture of 0 aluminum compound capable of forming “- alumina and an aluminum compound capable of forming –y alumina and/or —y alumina; Then calcining the slurry slurry and then adding another phosphorus 550 compound and a rare earth metal compound. Each component is used in this amount contained in the catalyst (Sled) based on the total weight of that catalyst; from 1.9 to 796 by weight; preferably from © to 745 by weight of =n lumina alumina and from zero to 780 by weight and preferably from zero to 746 by weight = x alumina by weight and/or —y alumina alumina and from zero to 775 by weight preferably from zero to 710 by weight baby clay and from 11 to ZA by weight, preferably from 1.5 to 77 by weight phosphorus measured in 205 and from 1.1 to 77 by weight, preferably from 0.7 to 71.8 by weight Rare earth metal measured as oxide and from 01 to 7970 by weight, preferably from 01 to 1 foe by weight. Zeolite The aforementioned rare earth metal compound is one or more selected from the group consisting of rare earth chloride and rare earth nitrate.

D — The catalyst is characterized by a high ability to break down heavy oil, and therefore it can be used in the production of more light oils (gasoline and diesel oil) and liquefied petroleum gas.

The conditions for using the catalyst according to the present invention are those of the conventional cracking reaction conditions. generally; The mentioned cracking conditions include a reaction temperature ranging from Te to cp Vou preferably from 001 to 100 °C and a catalyst-oil ratio (ratio by weight between catalyst

1_ and hydrocarbon oil) is from 1 to 10 and who is preferred? to No

The following are examples for the purpose of further illustrating the present invention. in examples; The alumina content in the –B-0 alumina trihydrate used is 7164 by weight (the trihydrate is manufactured by the Institute of ¢ (ShanDong Aluminum Corp) and the alumina content is In boehmite a9 Hl pseudo- boehmite (manufactured by (Shan Dong Aluminum Corp) 777 by weight and the alumina content is colloidal alumina (manufactured by: 2YY,1 (Qilu Catalyst Factory) ¢ and the silica content is silica In colloidal silica solution (manufactured by Beijing D Z\Y (Changhong Chemical Plant) by weight and the content of solid kaolin (manufactured by (China Kaolin Corp) is 727/76_ by weight and the content of solid montmornonite (factory By “sls ZA (Hubei Zhongxiang City Iron Ore Factory) the compound containing phosphorus is of chemical purity; the rare earth element chloride solution (prepared in the laboratory at a concentration of 719 grams of rare earth element oxide per liter and in which it is 0 and vy.87.7 of rare-earth element oxide is CeO, 717 of rare earth oxide

— Y m —

It is rare and amounts to 0,0 Prg 797 _ of the rare earth element oxide and amounts to 1120 ZY 0A of oxide

Rare Earth Element ' Solid Rare Earth Element Chloride is manufactured by Inner

Mongolia Baotou Rare Earth Factory

in examples; Molecular sieve SAPO-11 was prepared according to the process disclosed in Example 1.

201,646 in Chinese Patent No. o

In the examples, the compositions of the different zeolite forms are as follows, in order:

A HY zeolite (with a NayO content of 71.5 by weight and a ratio of 0.510 to

117,5 (with a content of 0 NaY zeolite is 5,7) ion exchange zeolite ALO;

by weight) and a ratio of SiO to ALO of 0 (manufactured by Qilu Catalyst Factory at 0 Av C for 1 hour with a ratio by weight of tele zeolite: NaY zeolite chloride ammonium

ammonium chloride is a solid of 0 I, then filtration and roasting at .00 . for a duration

Two hours, then exchange again by repeating the aforementioned steps, then filtering and roasting;

REY zeolite is a 57- zeolite containing earth elements.

Rare (the oxide content of the rare earth element YA,© is 7 by weight ¢ in which La; Os; is 7 07 by weight of that rare earth oxide in which J0© is 717 of that rare earth oxide in which

Prg On 217_by weight of that rare earth oxide in which NagOs is 770.8 by weight of that

Rare earth oxide, Nas content of 71.7 by weight, SiO to ALO ratio of 0.0¢

The unit cell size is 7,474 nm and the zeolite is manufactured by Qilu Catalyst.

(Factory

Y.Y.

yn - - REHY zeolite is a –-Y zeolite containing rare earth malic (the rare earth element oxide content is 7485 by weight; in it and 0 d1 is 757.7 by weight of that earth oxide of rare-earth oxide containing VY CeO; to ALO; of 0.1 and a unit cell size of 7.11 nanometers zeolite is manufactured by Qilu Catalyst (Factory MOY zeolite is —Y Zeolite contains phosphorus and rare earth elements (the oxide content of the rare earth element is TA by weight; 0 in it and 0 fa is 787.7 _ by weight of that rare earth oxide and has CeOp 717 of that oxide Rare earth and in it Op: 8 777 by weight of that rare earth oxide and in which 09s ZY +A NayOs of that rare earth oxide and content of 11.0 is 71.7 by weight and the content of phosphorus is 71.1 by weight measured as phosphorus elemental phosphorus. The ratio of SiO to ALO is 5.7 and the unit cell size is 7,477 cyte gli 0 zeolite is manufactured by Qilu Catalyst Factory DASY 0.0 zeolite is no - zeolite (ZY NayO content by weight; SiO content; to VLA ALO; EET unit cell size is nano-jie; zeolite is manufactured by Qilu Catalyst Factory). The DASY 2.0 zeolite is an ultra-stable Y-0 zeolite (RAE oxide content is 71.8 by weight; it has Lay Os YoY.

aly 57,7 by weight of that rare earth oxide in which VY CeO of that rare earth oxide in which is Pre Onn 7717 by weight of that rare earth oxide in which N2;03 4 27_ by weight of that rare earth oxide and content 18 : 0 by weight, SiO to ALO ratio of TA, unit cell size of 7.471 nm; The ZSM-5 zeolite is manufactured by Qilu Catalyst Factory. The ZSM-5 zeolite is an MFI structure zeolite (with a NayO content of 7 by weight and a SiOz to 01 ratio). ALO zeolite is manufactured by Qilu (Catalyst Factory) zeolite ZSP-1 is 41 MFI- structure containing phosphorus and iron (0 11 NagO content / wt. Ratio of 5:02 to Yo ALOs with a content of 0.17 O 71.5 by weight and a phosphorus content of 71.7 by weight; measured as elemental phosphorus; zeolite is manufactured by Qilu Catalyst Factory The p= zeolite has a NaO content of 77.7 by weight and a SiO; to ALO; ratio of YA. The zeolite is manufactured by Qilu Catalyst Factory 1. All ratios of SiO to ALO refer to the molecular ratio of silica and alumina EXAMPLES (1) through (1) The following examples illustrate the Baka catalysts of the present invention and a process for their preparation.

| M7 - Cp -,0 catalysts were obtained according to the present invention by mixing and alloying 8- alumina trihydrate, a mixture of -B alumina trihydrate, alumina trihydrate, pseudo- boehmite and a molecular sieve. molecular sieve, phosphorus compound, and sparkling water or without clay. The resulting slurry is dried by spraying into particles whose diameter ranges from 0-0 to 1501 microns, then roasting the resulting particles. The amount of 8- alumina trihydrate is clarified “ai 3) boehmite 5 alumina trihydrate used, the type and quantity of clay used, the type and quantity of molecular sieve, and the type and quantity of phosphorous compound used, respectively, in tables from 1 to 4. The spray drying temperature, roasting temperature, and its time are shown in the table 8. The compositions of the catalysts, Cs catalysts -,©, are shown in Table A

:)1( Comparative example - 0 and the phosphorus-free reference catalyst process This comparative example illustrates the catalyst with the CBI reference catalyst process. The catalyst was prepared Prepare that catalyst And using a different amount of phosphorus, except for not adding phosphorus 1 similar to the example a 30 and boehmite alumina trihydrate. The amount of 8- alumina trihydrate clay is clarified

pseudo- boehmite 0 used, the type and quantity of clay used, and the type and quantity of molecular sieve used, respectively, in tables from 1 to ? The spray drying temperature and roasting temperature and time are shown in the © table, and the reference catalyst composition is indicated.

1 in Table 1. Comparative example (?): YoYo

Yq - - This comparative example illustrates the reference catalyst free of =n alumina and the process for preparing that reference catalyst. The reference catalyst 032 was prepared by a process similar to Example 1 except that pseudo- bochmite was used instead of 8-alumina trihydrate. The quantity of 8-alumina trihydrate 0 and pseudo- boehmite used, the type and quantity of clay used, and the type and quantity of molecular sieve used, respectively, are shown in the tables from 1 to €, and the spray drying temperature is clarified The roasting temperature and time are in Table © and the composition of the reference catalyst 031 is shown in Table 1. Example No. (7): 0 This example shows the catalyst according to the present invention and a process for its preparation. The catalyst 67 was obtained by mixing and alloying 97.8 kg P=alumina trihydrate, 0.1/7 kg pseudo- boehmite, and 4 kg Te 5 «DASY molecular sieve 2.0 molecular sieve kg ZRP-1 molecular sieve and 1 kg molecular sieve pas 1 Y1,¥ 5 SAPO- 11 molecular sieve kaolin 5 +0 kg vo silica colloidal solution clay was deionized and the Al slurry was spray dried at 8681°C into particles ranging in diameter from Ee to 1560 µm and impregnation of Yoo kg (weight on dry basis) of the dried solids using aa FFA solution of 71.7 by weight ammonium dihydrogen phosphate, then calcining the resulting solids at a temperature of 00 C for two hours. The catalyst composition, © , is shown in Table 1 x. Example No. (A) YoYo

This example illustrates the catalyst according to the present invention and a process for its preparation. The C8 catalyst was obtained according to the present invention by the same process given in the same example 1 except using 5.4 kg Vo colloidal alumina solution of Caf pseudo- boehmite mentioned. The composition of the catalyst 8© is shown in the table. ° Table (1) example number Amount of boehmite 4S | Alumina trihydrate p- 3 8 < used; kg alumina colloidal solution used; kg atta TT en vm ow we Table (Y) Example No. Types of Molecular Sieve Molecular Sieve Quantity eed | = e um 1.0

1s l a l table (") type of child clay amount of child clay used; kg re ow | ew |e table (£) example number types of phosphorus «S je amount of compound phosphorus used; kg phosphate Tas phosphate ET phosphate YF, vy — phosphate (0) table (lela) example number temperature temperature | roasting time drying m | roasting m bee bone fy] ee ne Dae] ee ne [rg] eee Le py ee ee

Te Te Math (1) Table P,0s | Molecular Sieve | Child oy - Example No. 7 1 clay by weight 7 alumina | alumina | Catalyst wt 1 wt / wt Z| catalys by weight t ve |v [ov | | ha m | 1 Vee of | A vee Jom [1 Comparative proverb ve | ©» of [re | [om | vod oo [ree] sn [vee] ee Ja) ov le mln er rll eo Jv lr Jes] oe

- Sah _ Note: - 7 * 7 by weight is the silica content. Examples (3) through (1): The following examples illustrate the catalytic performance of the catalysts provided by the present invention. The C;- Cg catalysts were retarded with ARE water vapor at Ave m for A hours; The catalytic cracking of feedstock oil No. 1 was carried out as shown in Table 1 in the ACE unit using 3 g of stock from each aged catalyst (CC). (A) Where conversion - dry gas yield + yield of liquefied petroleum gas + yield of gasoline + yield of Coke; and total liquid product yield -< yield of 0 liquefied petroleum gas gas + benzene yield + diesel oil yield Here, the expression “gasoline” refers to a fraction of ©, which is a fraction at a distillation point of 1177 °C, so diesel oil (LCO) diesel refers to a fraction at a boiling point YY) ga m to yey 0 m. LPG liquefied petroleum gas denotes 3 ¢ C4-y. Dry gas is Ho-Cp part 1 comparison examples ( ©) and (;): The following comparison examples illustrate the catalytic performance of reference catalysts. YY

Deuce by following the same process as in Example (3); The catalysts were aged and the catalytic cracking of the same feedstock oil was carried out under the same conditions; Except that the used catalyst was from the reference catalysts CBI and 082 that were prepared in comparative example (1) and comparative example (7), respectively. The reaction conditions and results are shown in Table (A) ° Table (Y) of vacuum distillation and vacuum distillation residues.

- Dos (A) table catalyst oY + | EA £7 oY. LAR 0 reaction temperature m: qaq: ivory ow r 1 17 | all [YAY | Cloves 3 5 01 Ts WHSV v Work | YY, | YY, | YEA | YA] TA | widow | YY, / conversion » 1 4 wt Aa kH | Ya | AY | Tarafah | 4 Ve | 74.9 | The outcome of the products

A 9 J Total liquid by weight Ng Li | YY, Tech | Yee | YLT YALE LPG 1 ¢ £¥ a | SA, | £Y, | Yo,0 | £0) The F | EVA gasoline ¥1

VEY Ye we were [AY [vey | “L oar ka a LCO

Y

YA, LYE | for aE LY | Ya | Yoh YY Retarded q Yoo | Ya, | YE OL R YAA YY ¥1,)ve olefins ¢ A 1.0

vA — _ ee | No Aaa Qa D ‎Yo,Y | isoparaffins | MK 17 ARCHA 1 Matt 1 YA, LYE, LD Haralal. . 50 m) g/cm point ¥),Y | Initia] | Rama YA Ara | 1 | YA, | YAY | aniline film « m y cetane count YA FYE 1 fl TA | kk | vv | vo, | YY, Y 8 content 1,0 o,A 8 7 ft Ae 1 | Rala read propylene « / wt content 1 0,1 8 Ye | an | 4) Rala A Butene / wt. 31 4 go | 7 | 4, | 6X Isobutane / by weight Examples (11) and (11): The following examples illustrate the catalytic performance of the catalysts provided by the present invention. C7- C8 catalysts were aged at Ave m using 0 Water vapor for 0 elu VY time, respectively.The catalytic cracking of feedstock oil No. ?as shown in Table (3) was carried out in the FFB unit on a bench scale using 960 g of each aged catalyst 07-08. Clarification of reaction conditions and results in Table (01) vy — (3) Table Cl todas

Cl meas ame

December 01

I.E.Tr

I am deaf

I finished

sosum -

catalysts note that; In comparison with the stimuli (A) of the results presented in Table (Say

reference; The use of the catalyst according to the present invention performs the catalytic cracking of the same

Feed Crude Oil; Not only to a significant increase in the conversion of feedstock and liquid production yield

RASH, but Lad leads to a significant decrease in the olefin content in gasoline and an increase in

© in the content of aromatic compounds and isoparaffins in gasoline and decreases

density, aniline point increase, and gil cetane number 1.00; and more

Large in the content of light olefins (especially propylene, isobutane 5 ) propylene

In LPG, the results shown in Table (01) similarly indicate ead compared to what was stated in the previous art;

The catalyst according to the present invention not only has elle cracking activity but also leads to higher Ve quality of gasoline and 1.00 LPG in cracking products.

Examples are (VY) through (YY).

The following examples illustrate the first type of catalysts preferred according to the present invention

process for its preparation.

©Cor catalysts were obtained according to the present invention by mixing and alloying =p alumina trihydrate or a mixture of –B alumina trihydrate with

pseudo- boehmite, molecular sieve, phosphorous compound, and water

(with or without clay Jibs) and the slurry, El shury, is spray dried into particles ranging from

diameter from 56 to 100 microns and then roasting the resulting particles. The catalyst was obtained

catalyst 014 according to the example process YY using a colloidal alumina solution instead of 0 pseudo- boehmite In example (V1) the amount of 8-alumina trihydrate is shown

And — alumina trihydrate and pseudo- boehmite (or alumina colloidal solution) used, the type and quantity of clay used, the type and quantity of the molecular sieve, and the type and quantity of the phosphorus phosphorus used, respectively, in the tables from 11 to RE, then the temperature of the drying time and the temperature and time of roasting are shown in this table, NO, and the compositions of the catalysts are illustrated by © - and in the table AT

Comparative Example (5): This comparative example shows the phosphorus-free reference catalyst and the process of preparing that reference catalyst. The reference catalyst 683 was prepared with a process similar to Example 117 except that no addition was made.

0 phosphorus, and use a different amount of baby clay. The amount of 8-alumina trihydrate and pseudo- boehmite used and the type and quantity of the child are clarified

gre p

The clay used, the type and quantity of the molecular sieve used, respectively, in Tables 11 to 0, and the spray drying temperature and roasting temperature and time are indicated in the Vo table, and the reference catalyst arrangement 033 is indicated in the AT table ‏

: (1) Comparative example vo and alumina process Alumina —n-free reference catalyst This comparative example illustrates the reference catalyst. The catalyst prepares that catalyst except for the use of Bohmet 17 reference 4e By a process similar to the example catalyst, the catalyst was prepared. Alumina trihydrate from 8-alumina trihydrate False Yay pseudo- boehmite

The quantity of 8- alumina trihydrate, alumina trihydrate and pseudo- boehmite used, the type and quantity of clay used, and the type and quantity of sieve sal used, respectively, in tables from 11 to VE, and the drying temperature is clarified The spray, roasting temperature and time are in Table V0, and the arrangement of the reference catalyst, CBA, is clarified in Table E 1 Table (VY) Example No. Alumina —P quantity Boehmite pseudo monohydrate / solution alumina used; kg colloid used; kg aaa ee ema yg [rasa op table (VY) Example No. Types of molecular sieve Amount of molecular sieve used kg Actual Comparative Example 7 851121 Comparative Example REHY-+ZRP-1 0452 :4025 MOY +ZSM-5+ZRP-

Table (11) kg Table (Ve) Example No. Types of phosphorus compound Amount of phosphorus compound used; how much fea |

- Das (Yo) table m roasting m | (hours) ee ow

Co te ten feos

Ce ne rosea

Te te te rte te te

Ce eee |e (V1) Table «P05 Example | Catalyst - Sieve / Molecular Clay | child | alumina | alumina | catalyst (No. Apollozen 1.0) 260 re | 7160| weight number | by weight | by weight | By weight “a.| © | mf | grate | © [wv

YY Ye YA CB3 Example © Comparative M 8 YA CB4 | Jud Comparative A On the NLA

Examples (TY) through (18): The following examples illustrate the catalytic performance of the catalysts according to the present invention. Co-Cig catalysts were aged using 0 water vapor at Ave C for A hours, respectively. Catalytic cracking of Feed Crude Oil No. 1 was carried out as shown in Table 1 in 0 ACE units using 4 g of stock of each 0,4-Fine 0.4 catalyst. The reaction conditions and results are shown in Table (OY), where the conversion- dry gas yield + liquefied petroleum gas yield + gasoline yield + Coke yield; And the total liquid product yield - the proceeds of liquefied petroleum gas + the proceeds of gasoline + the proceeds of 100. 0 Here, the expression indicates gasoline, part Cs, which is a part at a distillation point of 221 m. 100 denotes a fraction at a boiling point of 171 C to VEY C. LPG stands for Cr Coen and dry gas is part:©-.11. Comparative Examples (7) and (+): The following comparative examples illustrate the catalytic performance of reference catalysts. vo following the same process as in Example (77); The catalysts were aged and the catalytic cracking of the same feedstock oil was carried out under the same conditions; Except that the catalyst used was one of the reference catalysts CB3 and 54 Y 0 7 0

oo — _ which is then prepared in a comparative example (0) and a comparative example (1) respectively. The reaction conditions and results are shown in Table (OY) Table (VY) Example Example Example No. ? 1 for comparator | for comparator | YA vv | Yn] ve | ve for A catlyst sind Reaction temperature number 0 oY” (0 .) 0 ov. oy 0 . oe [ole] co Ameya Mi Ba Water V1 "os 7 1 1 | number | 1 YAY "raha 7 vo, | vi, transform 7 wt | vey [view | Rala | Arla | vor except Y 1 result gl) #7 wt m vq for “bm mt | EYE | YVY | Gasoline Gasoline aS 7 wt. Ye, YY YY, A "97 Yat vee YEN 975 olefins A

— $4 — DTT ae | isoparaffi ,1m | Ya Yoo | YV,Y | YAY | YrY | vey ns ° propylene content ' except 1,0 AY 01 1 oA no Y 7# by weight Butene content / lara 0,4 0,1 qv ara LA Ao ml By weight Content of lb,A o 1 0 5 51 71 lb,4 7 Isobutane by weight From the results presented in table (VV) it is possible to note cal in comparison with the results obtained using the reference catalysts; The use of the catalyst according to the present invention to implement the catalytic cracking of the same feed crude oil leads to a significant decrease in the content of olefins in gasoline, and an increase in the content of aromatic compounds and isoparaffins in gasoline, and a clear increase in the content of olefins. Light olefins (particularly propylene isobutane s ( propylene) in LPG This indicates that the lak catalyst of the present invention clearly improves the quality of LPG gasoline in 0 products Examples from (5?) to (( YE).

La of the invention Lik's favorite catalysts The following examples show the second type of catalysts and a process for their preparation. A mixture of 8]- alumina trihydrate, alumina trihydrate hydrate, a phosphorous compound, a molecular sieve, and a molecular sieve pseudo- boehmite © produced by slurry and the slurry is dried (clay, rare earth mineral, and water (With or without kid to 580 microns and then roasting the resulting particles. And with Er to particles ranging in diameter from alumina Wie sll in example 74 using a solution of 020 catalyst that; the catalyst was obtained The amount of 8 is shown - Alumina FY in the example of pseudo-boehmite from Yay colloidal pseudo-boehmite used and the type of pseudo-boehmite af) boehmite alumina trihydrate trihydrate 0 used and the type and quantity of the molecular sieve and the type and quantity of the phosphorous compound clay, the amount of clay, rare earth metal used, and the amount of chloride solution of the rare earth metal, phosphorus. The spray drying temperature, YY, used, respectively, is shown in tables from + to catalysts. The catalyst compositions, TY, and the roasting temperature and time, are clarified. in the table

YE ware -E© in Table Vo:4) Comparative example phosphorus This comparative example shows the reference catalyst 1 free of phosphorus, rare earth metals and the process of preparing that catalyst No addition of olin ul 74 By a process similar to the example CBS reference catalyst the catalyst was prepared and a rare earth metal solution was prepared and a different amount of phosphorus was used.

- $A -

boehmite a3) and boehmite alumina trihydrate Lisa —B quantitative clarification

-286000 used, the type and quantity of clay used, and the type and quantity of molecular sieve used

In order, in Tables 18 to YY, the spray drying temperature and the degree of

The roasting temperature and time are shown in the YY table, and the reference catalyst arrangement 085 is shown in

Eh YE table

Comparative example: (01).

This comparative example illustrates the reference catalyst free of =n alumina and the

Prepare that reference catalyst.

The reference catalyst 086 was prepared by a process similar to the YA example except using pseudo-boehmite instead of 8-alumina trihydrate. is spelled out

8-alumina trihydrate and pseudo- boehmite quantity

User, type and quantity of clay used, type and quantity of molecular sieve used and type

And the amount of phosphorus compound used and the amount of rare earth metal chloride solution

rare earth metal, respectively, in Tables 18 to VY, and the temperature of 1 spray drying and the roasting temperature and time are shown in Table YY, and the catalyst arrangement is clarified

Yi reference 036 in the catalyst table

PP

(YA) Table [<5 3 boehmite amount B —example number Amount of alumina colloids Alumina trihydrate solution used; kg kg ee Le es] seg rT Messi (V4) table (01) user table; kg

Coen rn (YY) Table of the amount of phosphorus compound Example No. of the types of phosphorus compound used; kg Except (YY) Table Example No. Amount of Rare Earth Element Chloride Solution ee | 2 l soya eee

1e - table (YY) f drying m roasting m hours for Lee 301 | seas | Ed the proverb for a store as 0 31 | Ma A Tn here aa aa aa ee Te »for Te Te Table (Y€) Example No. 4 | for example | for example | YY | 1 | 1 cm | Comparative Eas | Comparative 4 01 [fer ©” | amine | | | Wadah ele [a molecular aya | 4 | © | The | oreo |

the mom

Examples (TO) through (40):

The following examples illustrate the catalytic performance of the catalysts provided by the present invention.

The Wu-Worn catalysts were aged using ZY water vapor at Ave m for A

hours; respectively. The catalytic cracking of feed crude oil No. LY shown in M Table 8 was carried out in the ACE unit using 4 g (stock) of each aged catalyst Y0-Z0. Complete

Clarification of reaction conditions and results in Table (16).

Where conversion is -< dry gas proceeds + liquefied petroleum gas proceeds

+ the proceeds of gasoline + the proceeds of Coke ; And the total liquid product yield - outcome

liquefied petroleum gas + toll of gasoline + toll of 100.

0 Here, the term “gasoline” refers to the © fraction, which is a fraction at a distillation point of 221 °C. LCO denotes a fraction with a boiling point of 771 C to VEY C. LPG stands for Cy Caen and dry gas is the Hp-Cy fraction Comparison Examples (VY) (VY) The following comparison examples illustrate the catalytic performance of reference catalysts.

1 Following the same process as in the example (Yo); The catalysts were aged and the catalytic cracking of the same feedstock oil was carried out under the same conditions; Except that the used catalyst was from the reference catalysts CBS and 086 All prepared in comparative example (4) and comparative example (Ye), respectively. The reaction conditions and results are explained in Table (1). Y .

- ov (Yo) table of TLE and residuals from vacuum distillation of MSA and “eT”

N - Table (Y1) Example No. Yo Example | example | 1 v4 YA | TY VY 11 [emia sim on l l l a l a (oo foe [tere [A] oe pe [oe |] ©6© | Product tally AVY Al AT DRILL NO. 1 AAT 1 Vio | ferment by weight olefins "rk | FEA" ra [YT] done | thinning over | las a n cle aromatic compounds YY,4 | Yo," 7.01410 | Karah Hara | YLY 1 Te a Is YA | YAY |Y.

Yo,A YoY | YAY isoparaffins | Orla YAS 1 cE (Say) from the results presented in Table (V1) Note that, in comparison with the results obtained using the reference catalysts, the use of the catalyst according to the invention 0 The current implementation of the catalytic cracking of the same feed crude oil leads to a significant decrease in the content of olefins in gasoline and an increase in the content of aromatic compounds and isoparaffins Y 0 Y 0

oo — - isoparaffins in gasoline . This indicates that the catalyst according to the process of the present invention is not only characterized by high cracking activity; i.e. a high production yield of oil and 1350 in cracking products; But also significantly improves the quality of gasoline in cracking products.

Claims (1)

1E Claims_1 -1 a cracking catalyst containing alumina, phosphorus and a molecular sieve with or without clay; where 3 said alumina is -alumina ¢ or a mixture ¢ of =n alumina —y 5 ¢ alumina alumina and/or —y alumina ; © and where the catalyst is contained based on its total weight; On:- 0 1 from 0 to 780 by weight =n alumina s ¢ for 0 from zero to 780 cols alumina and/or 7-alumina alumina A; and 0 9 from 01 to 7970 wt. dade molecular sieve ¢ Ya 0 from zero to 7978 wt. baby clay; and 1 in 1,1 to ZA by weight phosphorus ; Size in photo .P,0s VY ) = the catalyst according to Claim No. (1); where the catalyst Y contains on the basis of its total weight:- 0 7 from © to 745 by weight = m alumina alumina; 0 ¢ from 0 to 746 wt. From zero to 760 by weight stclay baby YoYo _ 7 0 — 0 A from 59 to 75 by weight phosphorus ; Size in the picture P,0s5 5 . 1 *- The catalyst according to Claim No. (1) or Cua oY number) The catalyst Y contains an earth metal ls and where the content of that metal ranges from “- rare earth 1 1. Oe rare earth metal to 77 by weight; measured in the form of 1 oxide. from 1.7 to 71.8 by weight; size Y in the form of oxide 1 #- catalyst of claim No. (1) or No. (1); where The aforementioned molecular sieve one or more is selected from the group consisting of and molecular sieves of zeolite and others, which is used as an active component ¢ in the cracking catalyst. catalyst according to claim No. (5), where the aforementioned molecular sieve is one or more selected from the group consisting of YF molecular sieves of large-porous and medium-porous zeolite materials. and so oA - - - 1 7- The catalyst according to Claim No. (1) where the zeolite Y is the aforementioned pore one or more to be selected from group 1 of faujasite and zeolite p— zeolite and mordenite .mordenite 1 +- the catalyst according to claim number oY) where the zeolite Y means “2_ the aforementioned macropore one or more to be selected from the constituent group Y | of <- zeolite and zeolite 7 contains one or more elements ¢ selected from phosphorus, iron and rare earth elements; f-57- zeolite ° ultrastable and –Y zeolite ultrastable zeolite contains one or more element 0s selected from phosphorus, iron and the earth elements of dab and zeolite –1177; Zeolite -117 contains one or more element A selected from phosphorus, iron and rare earth elements; And 9 zeolite -8. 1 +- The catalyst according to Claim No. (1) where the zeolite is bau gia zeolite Y pore one or more to be selected from the group of 7 zeolites [4 MFI structure and containing zeolite It has an MFI structure on an element; - one or more selected from phosphorus, iron and rare earth elements ° 0 - 1 catalyst according to claim No. (1) or oY) where is Y The aforementioned molecular sieve one or more is selected from the group consisting of 1 7- zeolite, and zeolite 7 contains one or more elements. Duh - his choice of phosphorus shud, iron and rare earth elements; the ultra-stable 57-zeolite 8; The ultra-stable zeolite-57 contains one or more element 7s selected from phosphorus, iron, and rare earth elements; zeolite 117 and zeolite -117 contains one or more element A selected from phosphorus, iron and earth elements 4 5330 zeolites “f— zeolite having MFI structure and containing zeolite 4d zeolite > 0 MFT structure on one or more elements selected from phosphorus | 11, iron and rare earth elements. -11-1 The catalyst according to Claim No. (1) or oY, where the aforementioned molecular sieve contains a mixture of 7-zeolite and zeolite 1 having an MFT structure and ranging from The content of the –Y zeolite zeolite ranges from 01 3 to Za by weight and the content of zeolite with MFI structure ranges from 0 01 to 727750 by weight based on the total weight of the zeolite mixture mentioned. 1? From 11 to 770 based on the total weight of the said ¢ zeolite mixture. -1” 1 catalyst according to Claim No. (11), where the mixture of Y Lad Sa zeolite contains pm zeolite and where YF zeolite content ranges from zero to 28 8 7700 based on the total weight of y mixture - +). ¢ The aforementioned zeolite. VE) the catalyst according to Claim No. 61, where the Y zeolite content ranges from 0;_ from zero to ZY by weight based on the total weight of the said 3 zeolite mixture. —Vo 1 Gh catalyst of claimant (1) or (VY) where the clay is lastly 7 or more chosen from the group consisting of Kaolin 7, halloysite and montmorillonite, kieselguhr ¢, allokite, soapstone, rectorite °, sepiolite, attapulgus, hydrotalcite 1, and bentonite 1 7- A process for preparing the catalyst according to claim (1); comprising:- 0 Y Drying a slurry containing an aluminum compound and a molecular sieve “elas molecular sieve 7” with clay or without it; and then 0 ¢ Roasting slurry Adding another amount of phosphorus ° ¢ 1 where an aluminum compound is that compound capable of forming mV alumina or a mixture of an aluminum compound capable of forming “-alumina A ¢ and an aluminum compound capable of forming —x alumina alumina and/or –y 9 alumina alumina ¢ and where each component is used in such an amount that the final catalyst Ye contains, based on its total weight, “on:- a” ¢ alumina —n to 756 by weight v0 from 11 0 for 0 from zero to 7560 wt = x alumina and/or —y alumina VY alumina; And ¢ molecular sieve to 7970 wt. molecular sieve 01 of 0 1 st clay dik 3s IYO LY aga 8 10 1 0 of 1.1 to ZA by weight phosphorus ; Size in photo VY 05 . de -17 1 to prepare the catalyst according to the oF claim) comprising:- 0 Y drying slurry containing aluminum compound and molecular sieve for slay sieve with or without clay ; and then ¢ e roasting slurry and then adding another amount of phosphorus o; a rare earth metal complex; 1 where an aluminum compound is that compound capable of forming 1 - -- alumina or a mixture of an aluminum compound capable of forming 1 alumina A ¢ and an aluminum compound capable of forming — y alumina 5 and/or (-alumina ¢ and where each component is used in such an amount that the final 4 01 catalyst contains, based on its total weight”:- ¢ alumina = n by weight 780 to 0.5 of 1 0 0 VY from zero to 756 by weight —y alumina and/or 7-alumina 7 ¢ and ¢ molecular sieve to 79760 wt. Molecular Sieve 01 of 0" 1 0; clay Jib from 0 to 797/8 wt. 0 Vo 1 0 from 1.1 to 728 by weight phosphorus ; Size in image P,05 VY = VA 1 Process for preparing the catalyst according to protection circuit (1) Y includes: 0 ¥ Drying slurry containing aluminum compound and eles molecular sieve ¢ with or without clay; and then 0” 0 Calcination of the slurry Adding another amount of phosphorus 1 ¢ No, where the aluminum compound is that compound that is capable of forming A - alumina alumina or a mixture of an aluminum compound that is capable of forming q - alumina and an aluminum compound that is capable of formation of “- alumina 01 and/or –y alumina ¢ and where each component is used in an amount such that the final catalyst 11 contains, based on its total weight,” the following: ¢ alumina alumina —n from 4.0 to 756 by weight 0 VY alumina —y o/s alumina alumina = x from 0 to 786 by weight 0 \¥ and ¢ alumina Y¢ ¢ molecular sieve to 7970 wt. molecular sieve 01 ao 1 5 8 zero to 7975 wt clay Jib ; and VY from 1.1 to ZA by weight phosphorus ; Measured in picture P05 YA where the aforementioned molecular sieve is a zeolite mixture containing -Y 4 zeolite and a zeolite having an MFI structure and where the content ranges from —Y to Ye Zeolite from Ye to 7960 by weight and the zeolite content ranges Das YY which has an MFI structure of 01 to 7970 by weight based on the total weight of the said zeolite YY mixture. -11-1 Process according to Claim No. (11) or (17) or (VA) where Y the said aluminum compound capable of forming alumina Lie sl =n is —B Alumina trihydrate, and the aforementioned aluminum ¢ compound capable of forming “-alumina” is: ° “- alumina trihydrate” and the aforementioned aluminum 1 compound capable of forming –y alumina alumina is boehmite and/or pseudo-boehmite and/or alumina A colloidal solution. or (17) or (VA) where Y is one or more LsS3dl phosphorus compounds selected from group 7 of: phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphoric ¢ acid , pyrophosphate, polyphosphoric acid, polyphosphate, © metaphosphoric acid, and metaphosphate. phosphoric acid, ammonium phosphate, diammonium hydrogen ¥ v phosphate, ammonium dihydrogen phosphate, phosphorous acid, ¢ and - ammonium phosphite, sodium pyrophosphate, sodium tripolyphosphate © and sodium hexametaphosphate. 1 YY process according to Claim No. (17) whereby each component is used in such quantity Y that the final catalyst contains, based on its total weight, “: – 0 v from * to 745 by weight = m alumina “0 ¢ from 0 to 746 wt = x alumina and/or —y alumina °¢ and 1 ye to 786 wt. sieve ¢ for ge 0 zero to 7780 wt s¢clay child A. 0 to 77 wt phosphorus; measured as [P05 YY] Process according to claim No. ( VY) where the "rare earth metal" is one or more selected from the group consisting of rare earth chloride and rare earth nitrate © .