SA110320053B1 - Additive For Fluid Catalytic Cracking Catalysts - Google Patents

Abstract

Abstract: The present invention provides an additive for a fluid catalytic cracking catalyst, which is able to effectively increase the cracking of the heavy oil fraction and reduce the increase in coke yield rate. The invention specifically provides an additive for the catalytic fracturing catalyst that can be obtained by drying a mixed slurry comprising binder and spray alumina-silica, and this additive has a specific surface area ranging from 100 to 400 m2/g, It has a total amount of solid acid not less than 0.10 mmol/g but less than 50 mmol/g. It is preferred that the ratio of the amount of strong acid to the amount of the total solid acid not exceed 20%. It is also preferable that the percentage of alumina-silica in the mixed slurry is not less than 20% by mass and less than 80% by mass, and that the silica content in the alumina-silica mixture is more than zero% by mass and less than 10% by mass. Number of protection elements (6)

Description

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An additive for catalysts for catalytic fracturing

Additive for fluid catalytic cracking catalysts Full description BACKGROUND The present invention relates to an additive for fluid catalytic cracking catalysts 1010 catalytic cracking catalysts intended to be added to a fluid cracking catalyst (FCC 0 catalyst) and used in a catalytic cracking unit Fluid catalytic cracking unit (FCC) especially for cracking the heavy oil fraction (bottom product) of the feedstock to obtain a light fraction (particularly; gasoline). feedstock sale using a fluid cracking catalyst catalyst to produce light oil e. However, due to the high price of crude oil ah crude the heavier feedstock Ce (resid) was processed to crack this heavy oil fraction (such as residual oil. (heavy oil fraction) 0

Sli effectively using a catalyst fracturing (©00); The amount of active ingredient is increased, however, any increase in alumina or alumina zeolite Jia zeolite (FCC) catalytic fracturing causes problems that lead to a decrease (FCC) in the active ingredient ratio in the catalyst fracturing catalyst Catalyst strength, for example, and thus the decomposition of physical properties. In addition to that; In the process of cracking the heavy oil fraction 1 of the feedstock in the catalytic fracturing unit to produce light oil; There are problems that lead to an increase in the amount of coke as the process of cracking the heavy oil fraction progresses.” Also, the combustion of the resulting coke is accompanied by a rise in temperature and the formation of steam; and poor quality of the FCC catalyst. In order to solve these problems; The following additives have been developed as co-catalysts for FCC catalysts (Froidic Cracking Catalyst Additives (FCC) Y. JU patent document 1 discloses an additive for catalyst fracturing catalysts comprising a mixture Granular mixture of silica calumina Lue gli-silica cclay clay and silica The mixture of silica alumina Lies silica contains a percentage of 77 v silicon by weight and the mixture contains a percentage of silicon 00 to 01 ranges from silica silica (810; 810 to 770 by weight (calculated based on 01 ranges from silica catalyst additive includes 1 patent document discloses silica 811168. article includes cclay calumina Luasl-silica on a mixture of silica to 770 by weight 01 ranges from silicon added to particles having a total silicon content of 0 01 ranges from specific surface area specific surface area Lely ¢(SiO;) (calculated on the basis of mL/g. 0.46 to 0.04 ranging from total pore volume plows and aif capacity to 60 μm angstrom Te moreover; the capacity of pores having a radius of not more than 0.05 mL/g; The total amount of acid 86:0 ranges from 07 to 00565 mmol/g per mcd. | 0 And the patent document reveals? For an additive for catalytic fracturing catalysts, this material includes silica and silica “clay clay” 006181 oxide, a compound of metal oxide, with a total pore capacity ranging from mg m’ / g Av to 1 The additive has a specific surface area ranging from 10 to 10 ml/g. In addition to that; The capacity of pores having a diameter of 1.45 to 4 angstrom 0 is not less than 745 based on the total pore capacity. You oo The patent document discloses; About an additive for heavy oil cracking catalyst” that includes silica 511168. This additive has cclay metal oxide, a compound of metal oxide to 0207, and the total acid amount ranges from otf 80 m HY The specific surface area ranges from mmol/g.In addition, the percentage of the strong acid content varies on the basis of the amount 0A

Joe to 10 total acid 0 to 4; 1 and in additives disclosed in patent documents ranges by weight and ranges from 0 77 to 1 0 of alumina Gee sN silica in silica mixture silica content to 7710 by weight; The specific surface area ranges from 10 in the mixture of silica content to 06 mmol/g. 1.7 to 80 m"/g; the total amount of acid ranges from 0 [related technical documents ] ve [Patent Documents] SPECIFICATION VEVAVAY Japanese Patent No. :]1 [Patent Document [Patent Document “]: Japanese Patent No. 4977508 ?; Specifications

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¢ [PATENT DOCUMENT ?]: JAPANESE PATENT NO. ¢YVEYALY SPECIFICATION [PATENT DOCUMENT 4]: JAPANESE PATENT NO. YAY ATT SPECIFICATION GENERAL DESCRIPTION OF THE INVENTION [Problems that the invention solves] ° Although the materials Conventional additives are fairly effective in breaking down heavy oil fractions; However, there is a need to increase the cracking efficiency of the heavy oil fraction further. and when the heavy oil fraction is subjected to catalytic fracturing with such an additive; The coke production rate increases as the heavy oil fraction cracking process progresses. Jia, this increase in coke production rate raises the temperature in the catalyst regenerator in the FCC unit.

FCC Because of the high temperature or steam formation during the burning of the coke; The quality of catalysts is declining 0 The invention has been accomplished based on the above background. The objective of the invention is to provide an additive for fluid cracking catalysts (imal) that is capable of increasing the cracking efficiency of the heavy oil fraction and limiting the increase in the rate of coke production. [problem-solving methods] yo for the above mentioned objective the catalytic fracturing catalyst additive according to the invention is a catalytic fracturing catalyst additive; It can be obtained by drying a mixed slurry comprising sale binder and spray-silica alumina characterized by having a specific surface area ranging from 001 to 5060 m'/g; It has a total amount of solid acid not less than ©0010 mmol/g but less than 150 mmol/g. a and in the catalyst fracturing additive according to the invention; Preferably, the ratio of the amount of strong acid to the amount of total solid acid should not be more than IX and in the catalytic fracturing catalyst additive according to the invention; The mixed slurry preferably comprises porous silica or zeolite and in the catalyst fracturing additive according to the invention; It is preferable that the Yo ratio of alumina admixed-silica 11108 in the mixed slurry is not less than 771 by mass, Oly less than 7/80 by mass. mo

and in the catalytic fracturing additive according to the invention; The silica content of the silica \Slui-alumina mixture should preferably be greater than zero 7 by mass and less than 0 by mass. In the additive for catalyst fracturing according to the invention, “it is preferred that the binder be a silica compound or an aluminum compound. [Feature of the invention] The additive according to the invention has a specific surface area ranging from 001 to 400 m /gloom; It has a total amount of solid acid ranging from 0500 mmol/g to 1.50 mmol/g. Accordingly; When compared with conventional additives; The additive according to the invention has an increased efficiency 0 and provides a reduced production rate of re-refined heavy oil “(HCO) Heavy Cycle Oil, an increased production rate of gasoline and a relative production rate of coke. This may be due to the following reasons: due to the increase in the specific surface area and the total amount of solid acid in the additive compared to the conventional additive; There is an increased contact area between the feedstock and the additive; Plus there is an increasing number of active spots and as a result Vo; FCC catalyst efficiency increases while the re-refined Heavy Cycle Oil (HCO) Oil (HCO) production rate decreases as well as “ld” due to a decrease in the ratio of strong acid to solid acid JS of 7718 or less; The over-cracking reaction is minimized” thus increasing the production rates of Gasoline and Light Cycle Oil (LCO) recycled in the FCC unit. The increase in coke production rate is limited. 0 DETAIL DESCRIPTION [METHOD OF PROCEDURE OF THE INVENTION] The following describes an additive for catalytic fracturing catalysts according to one embodiment of the invention. The catalytic fracturing catalyst additive according to the invention (vo sometimes simply referred to as 'sald') is an additive 'additive' to a fracturing catalyst formed from an inorganic oxide porous body comprising It is based on zeolite and is used in the Hae fluid cracking unit (FCC unit) in particular to crack the heavy oil fraction (bottom product) of a feedstock containing a light fraction.

+ The additive according to the invention is obtained by spray-drying a mixed slurry comprising a binder and a silica sylu—alumina under known conditions. The additive has a specific surface area ranging from 1001 to 500 m'/gm as measured by the Brunauer-Emmett-Teller (BET) method (JIS Z8830), preferably from 1001 to 80 m/ swoon preferably from 000 to You m"/g; and having a total amount of solid acid (the amount of ammonia adsorbed using a heat of adsorption of 101 kJ/mol or greater) of not less than 10 mmol/g but less than 1,500 mmol/g as measured by ammonia adsorption calorimetry (see JP No. 4807 370; the actual measurement method was performed according to the method described in Example 1) Preferably 0 ranges from Ye to 1.45 mmol/g, and better than Er YO mmol/g. When the specific surface area of the additive is less than 001 m/g, then This leads to a decrease in the number of reaction sites in the additive with the feedstock, which reduces the effectiveness of cracking the oil fraction (Jul), but when it exceeds 400 m / g, the bulk density and sala strength of the additive decrease. The solid acid in the additive is more than 0500 mmol/g; the cracking efficiency of the oil fraction (JE) is less but when it is not less than 050 mmol/g; the heavy oil fraction is over-cracked, which increases the production rate And coke The used binder may be a silica compound or an aluminum compound, and as an example of a silica compound, water glass, a solution of silicic acid, or something else can be used. more like. As an example of compound 1 of aluminum Y., for example, basic aluminum chloride can be used in a cboehmite alumina peptized sol or similar. and as a mixture of hussein alumina “T1H-silica” 511108; A product obtained by mixing a silica compound with a pseudo-boehmite gel or boehmite big cgel may be used as an optional aging step. Yo and preferably dada alumina msn1ah-silica have a silica content greater than iia 7 by mass and less than 7101 by mass; It preferably ranges from 1 to 74 by mass. and when the silica content of 511168 in the silica Kaluli-alumina mixture is not less than 701 by mass; This leads to a decrease in the specific surface area and the amount of acid.

The mixed slurry may contain the cclay mineral cporous silica and zeolite. Examples of clay minerals include ckaolin, montmorillonite, dolomite, and calcite. Porous silicas Wet silica Wet silica Dry silica Examples include zeolites © zeolites Ultrastabilized Y-type zeolite Y ZSM-5 RE-USY (RE-Y “NH4-Y) and mordenite. By adding porous silica or zeolite, the specific surface area of the additive can be adjusted (increased); this also contributes to improving the effectiveness. It is preferable that The percentage of alumina “synthesized”: for him-silica in the mixed slury is not less than 0 770 oly REG less than 780 by mass; it is preferable to range from 0 © to 7770 by mass. Depending on the percentage of alumina –alumina silica The specific surface area of the additive and the amount of solid acid in it can be controlled, and when the ratio of alumina alumina 1m-silica in the mixed slurry is less than 770 by mass; The amount of active rectifier is not sufficient to crack gia the heavy oil” so it becomes difficult to crack the heavy oil part dle ly and when the ratio is not less than 1 780 by mass; This leads to a decrease in the strength of the added material and its volumetric density. Even when such an additive is used as an additive for catalysts, the fluidity decreases or dusting occurs, making it difficult to operate the catalytic fracturing unit. The concentration of the binder in the mixed slurry ranges from about 01 to about ve by mass and the solid matter content of the mixed shurry ranges from about 11 to about -77 by mass. The percentage of the amount of strong acid (the amount of ammonia adsorbed by the heat of adsorption that is not less than 101 kJ/mol) in the ammonia adsorption calorimeter does not increase depending on the total amount of solid acid In the added material, more than 7710, preferably not more than 0, and it is better not to exceed 0, and when the amount of strong acid exceeds 01 PE Yo, which is likely to cause excessive cracking reaction, which leads to an increase in the rate of Production of coke [Examples] The invention will be described in more detail with reference to examples and comparative examples.However, the invention is not limited thereto.Mo

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effect of the amount of solid acid) 1 : test Jb) [1 additive : 1 JG] by mass of alumina 717.0 g include 71400 weigh boehmite to boehmite slurry add g of alumina solution (alumina) 0001 g of alumina (containing (ALO) alumina of To i.e. containing silica by mass of silica 701 (including silica sol) © included on water glass prepared by adjusting the pH of water glass (silica) using 72725 by mass of 1.6 solution to a value of (SiO) silica by mass of silica 21.5 and the pH was adjusted The acidity of the resulting mixture was reduced to an aqueous sulfuric acid value of sodium sulfuric acid using 747 by mass of an aqueous solution of 01.8 sodium hydroxide for an hour (degrees centigrade (°C) and was also aged at 2790 ( Hydroxide | 0 degrees Celsius contains 77 by mass of silica one, so he obtained an alumina grout: his-silica

Kolul-alumina in alumina silica and silica alumina slurry, and the total concentration of alumina silica by mass was 712 silica, and moreover; The pH of water glass comprising 7197.5 by mass (hereinafter referred to as 717.5 by mass water glass) was adjusted to a value of (9:02) silica 10 to obtain a silica solution of 11168b. Concentration of sulfuric acid using sulfuric acid 1 (silica is an example of a binder from the silica compound ag) of which silica is 717.5 by mass silica g of 071 silica alumina grout and after adjusting the pH By using 4.0 in the amount of dad to silica (gm) of alumina binder “Dallah-silica 001” (containing a gram of silica solution 1168 and B (containing 0010) to which csulfuric acid was added. Sulfuric acid (Yo) and the same applies later). The resulting mixture was sprayed under the following conditions: inlet temperature 418 "C; exit temperature min (same applies to the following examples); and from 01 residence time Gd) and time PARE

ZX + by ammonium sulfate to ammonium 1 to salts by washing (1 sulfate was added and then Yo sulfuric acid A was removed) and then calkali was done by mass on the basis of dry catalyst to remove the alkali aqueous by 0 )¢ 7 The same applies in the examples, ammonia using sulfuric acid 101 average particle diameter is the following 1) and obtained an additive E771

micrometer. Table 1 shows the composition of the additive 1. Moreover; The specific surface area and bulk density of the additive 1 were measured by the Brunauer-Emmett-Teller (BET) method and the Universal Oil Products (UOP) 10-4 method by mounting (the same applies in the following examples). Table 1 shows the properties of the additive oo 1. (Method of measuring the amount of solid acid) The amount of solid acid in the resulting additive 1 was measured as follows. Al 0.7 g of additive 1 was heated at 0 6 “C for 1 hour” and then heat treated under reduced pressure (13,377 kilopascal 701 XV) torr At 0-0 400 "C for hours. After that, ammonia gas was adsorbed on it. The heat of adsorption generated in this way was detected and the total amount of solid acid was calculated. For measurement, a 'calorimeter' manufactured by a company was used. TOKYO RIKOSHA. The amount of ammonia adsorbed was determined by the heat of adsorption not less than Vo kJ/mol 101/0001 asl the amount of the total solid acid; the amount of ammonia adsorbed was determined by the heat of adsorption whose Ve is not less than 011 kJ/mol 0001/11 as the amount of strong acid (the measurement was carried out in the same way as in the following examples).Table 1 shows the results of measuring the amount of solid acid in the additive 1. [Example oY additive?] The pH of YAT g 00 g silica-alumina slurry (containing 500 g silica \Slul-alumina) was adjusted to a value of 4 0, using sulfuric acid, to which 01600 g of ABA silica 511168 b (containing Yoo gm of silica) was added to it, then 4060 g of kaolin was added to it and the resulting mixture was mixed properly. homogeneous. The resulting mixture was spray dried; Then, the salts were removed by washing, and a sale additive 1 was obtained with an average particle diameter of Te micrometer. Table 1 Yo shows the composition and properties of the additive CY [example?: additive?] The pH of 95000 gm of alumina-silica slurry (containing 01 gm of synthesized alumina 1e-silica) was adjusted to a value of 54.0 using a pH.

1 silica 511168 b (containing ADS 0601 g of silica and sulfuric acid was added to it and kaolin 001 gm of kaolin was mixed and then added to it (silica) 0601 g of silica The resulting mixture was spray-dried, then the salts were removed by washing, and 1 micrometer was obtained. £ Additive: 1 [comparison example a silica g of recycled-silica-alumina grout 011 pH adjusted using 4.0 to a value of (silica \Siludi~alumina 1510 grams of alumina (containing 511168 grams of silica solution B) (containing 06001) and sulfuric acid was added to it and kaolin mixed 650 grams of kaolin and then (silica) was added to it 0 grams of silica You, then the salts were removed by washing, and the resulting “ly” was obtained homogeneously. The resulting mixture was dried 1 micrometer The table shows 0 micrometer on an additive, with an average particle diameter of 4. Composition and properties of the additive [0 [Comparison example?: additive silica gm of silica-silica grade alumina ©5101 The pH of Yo was adjusted using 5.0 to a value of ( silica sululi-alumina (containing 800 gm of alumina) gm of silica solution 511:68b (containing 0601 to which csulfuric acid was added, and after homogeneous mixing, the resulting mixture was spray dried; And who. (silica) 001 grams of silica on 01, then the salts were removed by washing, and an additive was obtained with an average particle diameter of # . Composition and properties of the additive 1. The table shows micrometer . Efficiency [pi] to ©; the effect of the amount of solid acid in substance 1 was evaluated using the additives from the additive on its effectiveness. A Rotating Fluidized Bed (ARCO) manufactured by ARC O Yo in which the catalyst is iteratively and repeatedly subjected to a reaction step and a regeneration step “circulating fluidized bed” for use on an FCC scale during its circulation in the device and was modeled after a unit regeneration 10:18 at a mass ratio of FCC to © with a commercial 1st equilibrium catalyst.

11 desulfurized atmospheric desulfurized (goa kg). and by using 1.7 kg residual oil: VA) as feedstock; The reactor temperature was set at 187"C and the temperature of the regenerator at (DSAR) residing at 1g of feedstock in 1g of catalyst per 1"C and the adjustment was made so that there was ©g or the device. Then the catalytic cracking reaction was carried out; The reaction product and residues (product liquid, gas: 1:8 H: M), were analyzed. Then, the gas produced in the reactor was analyzed by gas chromatography liquor 0 manufactured by Shimadzu Micro GC using an E3000 chromatography device to; 1 Atoms and compounds with hydrogen Measuring hydrogen production rates 249 “SHIMADZU” and carbon dioxide (CO) carbon (1© to 4©). And at that time; The carbon monoxide produced in the infrared was analyzed by an infrared absorption gas analyzer (Coy) “SHIMADZU type 7000-17 manufactured by Shimadze Corporation absorption gas analyzer | 0 and the coke production rate was calculated. Furthermore; The product liquid was analyzed by gas chromatography

GC System 1106890 using a device of the type distillation gas chromatography by distillation and then measuring the resulting amounts of the gasoline fraction “Hewlett Packard” manufactured by Hewlett Packard (1.00); Light Cycle Oil Recycled Light Cycle Oil “gasoline” to © in 1% steam and before reaction; Additives have been processed. (HCO) Heavy Cycle Oil Extended evaluation results. In terms of conversion; 1 hour. Table 11 shows that at 08 o'clock for 0 the measurement results were used from a sample that did not contain an additive as a standard sample; And “gasoline” expressed the differences from the standard body as the results of the evaluation. as well; Regarding the results of measuring gasoline

Heavy Cycle Recycled Heavy Oil (LCO) Light Cycle Oil Use an additive-free volume as a standard; express coke and coke (HCO) 001 “©” the difference of this calculated amount Assuming that the conversion rate is constant, compared to the standard sample, as the results of the evaluation

Al This evaluation was carried out in the same way as in Examples 0.4 to 1 and as shown in Table 1; When the amount of solid acid ranged from mmol/g; With the increase in the amount of solid acid, the efficiency of cracking the heavy oil fraction increased and decreased, which gave excellent results. Change “(HCO) Heavy Cycle Oil to the amount of the re-refined heavy oil fraction Yo mmol/g; The efficiency of cracking the oil fraction decreased by 1.06 that when the amount of solid acid reached “(HCO) Heavy Cycle Oil”, which led to an increase in the amount of the re-refined heavy oil fraction, the amount of solid acid reached 9 mmol / g; The amount of coke produced increased; Although Laie, but

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Heavy fraction from the increased efficiency of breaking the heavy fraction and the decrease in the amount of the re-refined heavy oil fraction - (HCO) Cycle Oil

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7 3 a 2 aq! 3&4 3 Fla =| 3 1 3 2 23 3 8 3 1335736

IJ |g) =H 7 3 3 = -— 7 abm = “1d ol Ds dah dl OY -_ ee | & _ QQ 4 Old n a l 28 8 ol 3 e 3 rm c || 5 ". 1 slo oi 4 2 er 2 = 3 4 3 6 kl - Q

R= 2 Q £ al § 73 9 = 215 543 S| = = 3 9 33 7 3 SY P addage « ¥ 5 Q 2 A 3 Q == < A 9 = 3 "| mt © b 7 = 00 ° & 3 n > 2 3 oO = = 2 3 % l = a k 3 g 4 EE EE ggg 4 [ a a a a a a a a a a a mm 499 the 133 deg a 883 8 # 8 g1 BE oO + 4 3 ¥ k ) 5 5 3 =| 3 the 5 JL].

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3 =| +3 DL Jot. wi oo. | ++] +! A a qa 0 TC so 3 35 2 a + . +] +| + 1 | +

EINER EEE YR EE 04+ 3 +: 3 3. 33 —| 2 lol o. o < + H + +H 31 AH 1 PH 4 HY] + 7 : 7 B 3 =| = . . ~ . +1 + + + 37 I FE 41 A + [2] No 2 . So. . . 7 1 f

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(Test example?: Effect of specific surface area) [1 [Example;: Additive

I silica The pH of 78710 gm of alumina slurry was adjusted using 0.6 dad to silica Sluli-alumina (containing 4080 gm of alumina) gm of silica solution 8 Henzel B (containing 16001) and sulfuric acid was added to it, sulfuric acid © Yoo gkaolin gm 001 gm of kaolin, and then added to it “silica 001 gm of silica on ultra-stable zeolite from Type 7 (dry weight”; the same applies later) and the product was mixed homogeneously. The resulting mixture was spray dried, then the salts were removed by washing, and a substance was obtained. Additive is 1 A and properties of the additive are 0 [V [Comparison example?: Additive]

I silica grout of alumina slurry 0430, then adjust the pH using 5.0 dad to silica solid-alumina 001 g of alumina (containing b) The content of silica is 01601 grams of silica lysate p:: 18 AH, and sulfuric acid 5000 grams of kaolin and 001 grams of kaolin were added to it, and then silica 001 grams of silica was added to it. on Vo of type 7 superstable zeolite and the product was mixed homogeneously. The resulting mixture was spray dried with an average particle diameter of 1, then the salts were removed by washing to obtain an additive of 17 µm: ©0010 :07761. The table shows the composition and properties of the additive 0 [efficacy evaluation] 7 additive ; additive oF using additive 1; additive XY.

Y and Added Article 7; The effect of specific surface area on efficacy was evaluated. The table shows the results of the evaluation. Additive 7 had a low volumetric density and its use in the practical unit was difficult; Therefore, it was not possible to evaluate its effectiveness. To 001 shown in the table?; When the specific surface area ranged from LS m"/gm, the number of reaction sites increased with the heavy oil fraction, and thus the Yoo Yo oil production rate decreased, which gave excellent results. However, when it reached "(HCO) Heavy Cycle Oil Sill Reduction in m / g; there was a small number of reaction sites »and therefore the AC increased the specific surface area, but when the area reached ((HCO) Heavy Cycle Oil the rate of production of heavy oil re-refined m

\e m '/gm; Although it is expected that there will be a large number of reaction sites, where heavy oil can be effectively 408 qualitative surfactants; However, this additive had a low bulk density and therefore ea cracking was an impractical additive. 7-5

37 slam) Rl or wa Hajja 2 Halal =] 5 ed 30 3333333 1334331313 13 333 235 AH for 33 3d ge 2 p 38 a EES 139% 9; =| Qf i.e. 8 ' . El 0 £| 38 4 = 0 ol 3 kaj 1 l 3 r 8

J 2 3 gy 3 I 2 a =| 0 l — 3 2 3 1 3 8 h 8 = | 2 3 |= 2 | 8 + 0

A 8 ~ > a = we] se] se = «| «| « > 4 = 21 3 = yum oa 5 PY 5 1991 yay 949 8 |4

BBE Wf ye ¥ > > 3

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Jou. ah.| . + | + + J 513 [5] |= HAE 4 FE 5 JA? A 3 3 3| 2 pt 0 Lo. + +] + | | S513 Dadma Fal A] [HY 5 + 3

Ym 3 3 3] 5 of «| of A |. | e © + + + 4 +

S| owe | FRE THOT Fl 3 9 == . < oH + LH 313 vomit eA EYE] + 7 7 > | in 3 s 3 ya ET “lolz for a3 | > m

(Example test 3?: Effect of silica content in a non-synthetic alumina-silica mixture (silica [example to additive [A] to 76490 g of boehmite slurry comprising 717, 0 by mass of alumina 06 g of silica solution A (containing 0 5 g of silica ©) was added and the pH of the resulting mixture was adjusted to Ve,0 using 748 by mass of solution aqueous sodium hydroxide; Lad was aged at 2°40 for one hour and obtained a manufactured alumina-silica slurry "b" containing 75 by mass of silica and the total concentration of alumina and silica was In alumina-silica slurry 11168 and 719 b by mass.Ye, the pH of 0/5417 g of slull-silica 511168 b (containing 7000 g of silica slull-alumina) was adjusted to a value of 4.0 using sulfuric acid and 060 gm of silica solution (containing 100 gm of silica 511168) was added to it, and then 100 gm of kaolin was added to it and mixed output homogeneously. The resulting mixture was spray dried; Then, the salts were removed by washing, and No obtained an additive, A, with an average particle diameter of 01 ily micrometer. The table shows? Composition and properties of additive A [Comparative example: Additive 4] 57/5 g of boehmite slurry comprising 717.0 by mass of alumina (containing Veo g of alumina) was seized. To a value of 0.4 using sulfuric acid, to which 06001 grams of silica lysate (containing 100 grams of silica) was added, and then 0100 was added to it. grams of kaolin, and the resulting mixture was mixed homogeneously.The resulting mixture was spray-dried, then the salts were removed by washing, and additive 4 was obtained with an average particle diameter of 10 micrometers.Table 1 shows the composition and properties of the material. Additive A Yo Comparison so Additive [01 pH 0 719 g of boehmite slurry comprising 7130 by mass alumina and 7171*, by mass glass AL to a value of 0.6 using csulfuric acid to which 0701 g of silica lysate 11:68a (containing

on VY g of silica and the pH of the resulting mixture was adjusted to #01 using 8 by mass of aqueous sodium hydroxide solution; it was also aged at ado for 1 de Lu time and obtained Manmade alumina slurry: a-silica containing 711 by mass of silica, and the total concentration of alumina and silica was 511168 in a row of alumina © #Sandalah-Silica 711 “a silica by mass. 47116 gm of alumina slurry “a silica Sludl-alumina” (containing 0 gm of alumina sludl-silica to dad of 4.0 using sulfuric acid and 0601 was added to it 100 grams of ADA silica 811168b (containing 100 grams of silica), then 100 grams of kaolin was added to it and the resulting mixture was mixed homogeneously. The resulting mixture was spray dried; Then the salts were removed by washing and an additive 01 was obtained with an average particle diameter of 01 µm ©0010:001600 The table shows the composition and properties of the additive 01. [Evaluation of effectiveness] using the additive oF Additive (A) Additive 4 and Additive 01 0. The effect of the silica content of the 0n:l-silica alumina slurry on the effectiveness is evaluated. shows the table? Evaluation results. LS shown in Table oF The rate of production of Heavy Refined Heavy Oil (HCO) Cycle Oil decreased with the increase of silica content in the silica Sabull-alumina slurry, which gave excellent results. However, when the silica content reached zero / by mass; The amount of “0 solid acid was small; Heavy Cycle Oil (HCO) production decreased slightly; And when the silica content reached 7271 silica by mass; The coke production rate increased. M

Agaj Gao Jawa 322344333 4 A a = 3 3 a 3 3 3 d ao a aa 5 a 2583 9c 1359 right 38 b n) 873 2 4 3 3 413 5 ' ' + l 3 ka ag dla) = 271 5 3 3 da 3 2 4 dz 4 S|of 3 ME 3 3 3 = 5 = 2 d 8 . 5 3 _— 8 59 2 a HIE 2 2 na a 2 bh Ol 5 8 5 = 5 3 ol © 33 QO = q 3 with ad ad ah l ad adad | To ‎[UY AH AGAG ADAG 138 8 » A 43333 4 9 3 + 1 4 81 A A

7 Soe]. A - - Fl +] +| || l 7 5) | W 3 DA w 4 HEH A cla . . Jose

3 3 + || ]++ + - m |« dol]. = 3 a wi wi ~ |> - akh a> “2s 3) 3 a at at at . . |« < a I I I . da. RE 2c | — Su Su Ser Yakhai 4 + EA EE 312 JI we LL + ]+++ M |= -— ]4 | 3 |= Q3 | > |> | 3a> > lee a —- > |~— |> 1 3 0 Loo] : a iF - 0

Y. (Test example;: Effect of solid acid amount) [VY [Example +: Additive B base comprising aluminum chloride g of aluminum chloride solution AoA to a concentration of 777.7 by mass (It is an example of a binder prepared from the ALO alumina compound; 00 g of kaolin (alumina 001 g of alumina) was added to kaolin and it contains ¢ alumina g of alumina slurry: it has a silica-fat A (containing 11406 and then added to it, its acidity was adjusted to a value of Ally (silica Sluli-alumina) grams of alumina Yoo and the resulting mixture was mixed homogeneously. The sulfuric acid mixture was dried using sulfuric acid 0, with an average diameter of 11, produced by spraying, then the salts were removed by washing, and an additive was obtained. Table 4 shows the composition and properties of the additive.

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[VY] [Example 7: Basic additive B (content aluminum chloride 0 g of aluminum chloride solution AOA to and then kaolin was added to it 0 g of kaolin was added (alumina g of alumina 001 on a gram of alumina 0000 g of alumina slurry "Leh-Silica 11168a" (containing Tove 1) adjusted to a pH of £.0 using silica 1H-silica was synthesized and the resulting mixture was mixed homogeneously.The resulting mixture was spray-dried, and then sulfuric acid 20 with an average particle diameter of 11.The salts were removed by washing and an additive was obtained.

AY The table shows; Composition and properties of the additive micrometer micrometer [VY Additive A [Example 0. Basic B (containing aluminum chloride 0 g of aluminum chloride solution AOA to and then kaolin 0 g of kaolin was added to it) alumina 001 g of alumina was added to a g of alumina 7010 Tsilica (containing) 0 gm synthesized alumina slurry whose pH was adjusted to a value of 4.6 using synthesized silica acid and the resulting mixture was mixed homogeneously. The resulting mixture was spray dried; Hence sulfuric acid sulfuric Yo

Te with an average particle diameter of 11. The salts were removed by washing and an additive was obtained

AT micrometer:©0010000061. Table 4 shows the composition and properties of the additive [1 4 [Comparative Example 21 Additive].

Ya

Base B (containing aluminum chloride 1g of aluminum chloride solution AOA to and then kaolin 01gm of kaolin was added to it (alumina) You added a gram of alumina to a gram of alumina 001 (containing silica Saludi-alumina) of VET alumina slurry using acid 4.0 whose pH was adjusted to a value of silica and the product was mixed homogeneously. The mixture produced by spraying, and then sulfuric acid esulfuric © 11 with an average particle diameter of 04, the salts were removed by washing, and an additive was obtained.

NE The table shows; Composition and properties of the additive micrometer [Vo] additive oy [base comparison example B (content) aluminum chloride g of aluminum chloride solution AOA to g of alumina sand 2 sand-silica OY) + alumina (gm) of alumina 001 was added to 0 to which the degree of silica (containing 800 gm of alumina and silica 0150:16) was set, and after homogeneous mixing acid its acidity to a value of 0, using sulfuric acid, the resulting mixture was spray-dried, then the salts were removed by washing, and an additive was obtained.

Jo Additive Yo [Evaluation of Efficacy] The effect of the amount of solid acid was evaluated in 15 to 11 using additives from the additive on efficacy. The table shows; Evaluation results. As shown in Table 4; In the case where a binder of a ssilica solution of synthetic alumina is used; As in the case of using a 0 mmol/g silica binder; With the increase in the amount of acid from 1.4 to 1.1 when the amount of solid acid ranged from gia solid oil, the cracking efficiency of the heavy oil fraction increased; The amount decreased, which gave excellent results. However, when the amount of solid acid “(HCO) Heavy Cycle Oil reached mmol / g; The cracking efficiency of the heavy oil fraction is increased; The amount of the heavy oil fraction increased by 0.11 mmol/g;

_ for a [oa]. [as = A 1922237 831137473258 1 l 3 43 »5 gl 9 3 az th d AH = vould els 4 d god a4 or jah da for ST Bll _1 8 5 3 B E 4 SY 9 214913 97 |= ' _ g = = : QL b aj £753 |H1 E45] 5 8 5 2039/4 s 8 8 8 2 © pat a 35 qa = q = edag 1 gly and 5 = I 3 3 x y 3 3 © -" 3 = 8 g 2 - |g = 2 5 Bh o 3 = = — 32 > > 4 m a J ie 3 3 3 4 41> 3 Yua Mj e1 : D Eh ~ -4 L 2 3 2 3 21 31 » 60 ohms 333 S|a 20 9191 9 El Sl | 3 8 8 8 3 3 |_ H a + |+a|+ ... 315 <i "|= A 27 = ed 1 > 2 514 BE .. Kk = > r 3 1" 8 A S13 0 . 5 +| + Aya EE A gm 33 and Pippa 3 [4 f 5 4 # 2 ya ! ha ls] acad [EE 44 4 4 Fa Aya Maaa 11 3 to

sq (Test Example ©: Effect of Specific Surface Area) [Example 4: Additive] 11 to AoA g basic aluminum chloride solution B (containing Yoo g alumina 0 gm of kaolin 180110 was added. Then oo 181.0 gm of Tsilica solid-alumina slurry (containing 50860 gm of alumina: 1m-silica) was added to it, the pH of which was adjusted to a value of 54.0 using sulfuric acid and 1000 grams of ultra-stable zeolite type 7 and mixing the product homogeneously, and the resulting mixture was spray dried, then the salts were removed by washing, and an added Bale 11 was obtained. with an average particle diameter of 0 micrometer. Table © shows the composition of 0 and the properties of the additive AT [Comparative Example 8: Additive [VV] to AoA 1 g of aluminum chloride solution Basic aluminum chloride B (containing 100 grams of alumina) 100 grams of Kaolin was added, and then VET was added to it. Tsilica Slodi-alumina slurry (containing 001 gm of alumina “Yo” silica whose pH was adjusted to a value of 4.0 using sulfuric acid and 9060 gm of super stable zeolite type 7 and mixing the resulting uniformly. The resulting mixture was spray dried; Then, the salts were removed by washing, and an additive, VY, was obtained, with an average particle diameter of 0 micrometer. Table 0 shows the composition and properties of the additive [AY [aus] | 0 Efficiency] using additive 11 additive VY additive 04 additive 7 and additive Y 0) The effect of specific area area on effectiveness was evaluated. Table © shows the results of the evaluation. The additive 117 had a low volumetric density and its use in the practical unit was difficult and therefore it was not possible to evaluate its effectiveness. Yo and as shown in Table 0, when the specific surface area ranged from 001 to 0 m "/gm, the number of reaction sites increased with the heavy oil fraction, and thus the rate of production of re-refined heavy oil ((HCO) Heavy) decreased Cycle Oil, which gave excellent results, except that Lovie had a specific surface area of 0 m / g, there were a small number of reaction sites, and thus increased

Y ¢ But when the surface area ((HCO) Heavy Cycle Oil reached the rate of production of heavy oil re-refined m / g, and despite the expectation of a large number of reaction sites, where the specific surface 401 can crack the oil fraction Heavy effectively, but this additive had a low volumetric density and was therefore an impractical additive.‎ 71 15

= =, =| al 4 . A 9 Rl d d or ah 0 321 31 Al A 3 13333 +833 85 3 4 31 a a: = a dg tool 33 2 except “2% a 4 0 3 8 5 p 11 = J 45 7 Elo 1 4 g| 0 a 8 s 14 ERIE: 5 EEE 5 3 2 3 a a 84 3 y 41 2 g 0 2 = 9 = 8 = 2 8 5 © s v3 : g ss c 3 > © wn = =| 8 i © 3 33 2 2 _ Slo 9, a] = iwaim - xd a - w his «|| «af «| Duck EEE EES Oh “AD 1333 +8 EEE 8 ’ so | | sf ew | ; . | . . +++] || 7 2 -— » 1 <| * 4 aaaaa. 1 . J a at at 2 3 3 1 3 = Jou, |. . + +] +] || + = 1 | ~| = “| £ lim 4 Q | Wi >| >I > 2 ; : SET ct 3 3 1 —_ 25 3 = NE 0. + ol . . + | + | + + {ERE EEE Aja Hse «| 3 sl 3 8 3 A. elu] 3 1 i *]1 * bd - 4 mi — | — 2 ho | rr > - =o ; 4 A

P| 3 ad w

S03 2) q = 3 rl oe . 3 Sos of ZI = i.e

Be

as described above; The catalyzed fracturing additive Lady of the invention enables the heavy oil fraction of the feedstock to be efficiently broken; It also inhibits the production of and coke; This enables high production rates of gasoline and recycled Light Cycle Oil (00.]). This may be due to the following reasons, as the additive is characterized by its high surface area; So is the decrease in the percentage of strong acid on a total solid acid basis. and in general; when the percentage of strong acid is high; The reaction efficiency is high; However, there is a problem that the cracking reaction is too advanced” which results in excessive coke and and production. Accordingly; When the percentage of strong acid is reduced based on the amount of total solid acid in the additive; And also when the specific surface area is increased to reduce the amount of solid acid per unit area

0 surface; The increase in coke production rate caused by excessive crushing of the feed ore can be reduced.

Claims (1)

No: Fluid catalytic cracking catalysts for catalysts for catalytic cracking additive Additive 1-1 binder comprising a binder mixed slurry that can be obtained by drying a mixed slurry Y Cus by spraying; silica Kalualumina and alumina ¥ 1 The catalytic fracturing catalyst additive has a specific surface area ° ranging from 001 to Eve m/g p; It has a total amount of Y solid acid less than 101 mmol/g and less than 0.00 mmol/g. fluid catalytic cracking for catalytic fluid cracking catalysts additive additive —Y 1 on strong acid do not exceed the percentage of strong acid ll according to claim 1; The catalysts Y .771 total solid acid basis are distinguished from the ¥ fluid catalytic cracking of catalytic fracturing catalysts additive additive —Y 1 0 5 According to claim 1 is characterized by the mixed slurry comprising 1 porous silica or zeolite fluid catalytic cracking for catalytic fracturing additive additive —¢ 1 according to element protection 1; It is characterized by the fact that the proportion of synthetic alumina-silica 511168 in catalysts Y 7080 but less than by mass 7701 is not less than mixed slurry 1 by mass. ¢ fluid catalytic cracking for catalytic fluid cracking catalysts additive additive —o 1 for alumina 1 in a silica mixture of claim 1; Characterized by the fact that the silica content of the catalysts is 1 by mass. 701 and less than by mass more than zero / by mass Synthetic silica Y YA fluid catalytic cracking for catalytic cracking catalysts additive Additive - 1 is a binder compound of claim 1; It is distinguished by the fact that the binder material is 7 -aluminum catalysts or an aluminum compound silica 1 m