CN1270984A - Preparation of fluidifying and cracking catalyst - Google Patents

Abstract

A method for preparing a fluidized catalytic cracking catalyst comprises drying the aqueous slurry containing catalytic cracking catalyst components and/or its precursors, and recovering the prepared catalyst, wherein, before drying, adding a An auxiliary agent, wherein the auxiliary agent is selected from one or more of soluble polyphosphates and hydrates thereof, and the auxiliary agent accounts for 0.005-3% by weight of the solid content of the water slurry. By using this method, the viscosity of the water slurry can be reduced, and at the same time, the activity of the catalyst can be significantly improved and the appearance of the catalyst microspheres can be improved.

Description

Preparation method of fluidized catalytic cracking catalyst

The invention relates to a preparation method of a catalyst containing molecular sieves, more specifically to a preparation method of a fluidized catalytic cracking catalyst containing aluminosilicate zeolite.

The commonly used preparation method of FCC catalyst includes mixing binder (and clay) and molecular sieve in a certain ratio to form a water slurry, and then drying or spray-drying to form solid catalyst particles. The improvement of the solid content in the preparation process has at least two advantages, that is, reducing the energy consumption in the drying process and improving the use efficiency of the drying equipment. The main factor that hinders the increase of solid content is the viscosity of the water slurry. If the viscosity of the water slurry is too high, it will not only be difficult to transport, but the solid content of the water slurry has to be reduced, and it is easy to block the turntable and nozzle of the spray dryer.

In the prior art, a method of adding a specific viscosity reducer to the water slurry to reduce the viscosity of the water slurry and increase the solid content of the water slurry has been reported. For example, US4,443,553 discloses a method for preparing a fluid catalytic cracking catalyst, which method includes spray drying an aqueous slurry containing a Y-type zeolite, an aluminum-containing binder and a silica A source of silicon selected from natural and synthetic silicon-containing materials and mixtures thereof. The improvement includes adding a viscosity reducer to the slurry, the general formula of the viscosity reducer is [Al ₂ (OH) _6-y Cl _y ] _x , wherein x is 1-6, y is 1-2 , based on alumina, the added amount of the viscosity reducer is 0.5-2.5% by weight of the solids in the slurry, and the catalyst particles substantially free of water are recovered. The method can increase the solid content of the slurry by more than 20%.

US 4,476,239 discloses a process for preparing a fluid catalytic cracking catalyst from a mixture of zeolite particles, clay, aluminum binder and silicon source, said mixture being dispersed in a slurry, the process comprising drying said slurry, which The improvement includes adding a viscosity reducer to the slurry, the general formula of the viscosity reducer is Al ₂ (OH) ₅ NO ₃ , and the addition amount of the viscosity reducer is 1% of the solid in the slurry in terms of alumina. 0.2 to 2.5% by weight, after adding the viscosity reducer, the viscosity of the slurry drops to a lower level from the viscosity level without adding the viscosity reducer, and adding another catalytic cracking catalyst component with the same weight ratio increases the viscosity of the slurry To the viscosity when no viscosity reducer is added, the slurry with increased solid content is dried to obtain fluidized catalytic cracking catalyst particles. By adopting the method, the solid content of the water slurry can be increased from 20-25% by weight to 30% by weight without increasing the viscosity of the water slurry.

CN1,032,498A discloses a method for preparing a fluidized catalytic cracking catalyst, wherein. Before spray drying, add polypropylene with a molecular weight of 2.5 to 5 million units, accounting for 0.005 to 0.30% by weight of solid content in the slurry, to the water slurry prepared by mixing molecular sieves, clay and silica sol or aluminum sol or silica-alumina gel Phenylamines act as viscosity reducers. By adopting the method, the viscosity of the catalyst slurry can be reduced by 10-50%.

Although the above-mentioned prior art can reduce the viscosity of the water slurry and improve the solid content of the water slurry, there are respective shortcomings: as using the method described in US4,443,553, part of the chloride ions contained in the viscosity reducer remains in the catalyst In the particles, these chloride ions will have an adverse effect on the catalytic performance of the catalyst and the subsequent catalytic cracking operation. US4,476,239, CN1,032,498A disclosed method does not have good influence on the catalytic performance of catalyzer, and, CN1,032, the viscosity reducer used in the disclosed method of 498A is a kind of high polymer, because the consistency of high polymer itself is relatively Large, not easy to disperse evenly and affect its viscosity-reducing effect.

The purpose of the present invention is to provide a method for preparing a fluidized catalytic cracking catalyst that can greatly reduce the viscosity of the water slurry, improve the appearance of the catalyst microspheres, and improve the catalytic activity of the catalyst.

The preparation method of the fluidized catalytic cracking catalyst provided by the present invention comprises drying the aqueous slurry containing the catalytic cracking catalyst component and/or its precursor, and reclaiming the prepared catalyst, wherein, before drying, in the aqueous slurry An auxiliary agent is added, and the auxiliary agent is selected from one or more kinds of soluble polyphosphates and hydrates thereof, and the auxiliary agent accounts for 0.001-5% by weight of the solid content of the water slurry.

According to the method provided by the present invention, the auxiliary soluble polyphosphate refers to a soluble salt of polyphosphoric acid formed by condensation of two or more phosphoric acid molecules. The soluble polyphosphate is preferably one or more of soluble pyrophosphate, polymetaphosphate and polyphosphate.

Commonly used soluble pyrophosphates can be selected from one or more of the pyrophosphates and ammonium pyrophosphates of Group IA metals in the periodic table of elements, among which, sodium pyrophosphate, lithium pyrophosphate, and potassium pyrophosphate are preferred. One or more, more preferably sodium pyrophosphate.

Commonly used soluble polymetaphosphate such as can be the trimetaphosphate of Group IA metal in the periodic table of elements, one or more in hexametaphosphate, wherein, preferably sodium trimetaphosphate, potassium trimetaphosphate, hexametaphosphate One or more of sodium metaphosphate, lithium hexametaphosphate, potassium hexametaphosphate, more preferably sodium hexametaphosphate.

Commonly used soluble polyphosphates can be one or more of tripolyphosphates and ammonium tripolyphosphates of Group IA metals in the periodic table of elements, wherein sodium tripolyphosphate, lithium tripolyphosphate, and tripolyphosphate are preferred. One or more of potassium polyphosphate, more preferably sodium tripolyphosphate.

The added amount of the auxiliary agent is preferably 0.005-3% by weight.

The catalytically active component and/or its precursor in the aqueous slurry contains at least one aluminosilicate zeolite and one binder and/or its precursor.

The aluminosilicate zeolite is selected from one or more of various aluminosilicate zeolites that can be used as active components of catalytic cracking catalysts, such as one of faujasite, MFI zeolite, mordenite, and BETA zeolite. species or several. The preferred aluminosilicate zeolite is selected from one or more of X-type zeolite, Y-type zeolite and ZSM-5 zeolite. The X-type zeolite is preferably one or more of hydrogen-type X zeolite, rare earth type X zeolite, and rare-earth hydrogen type X zeolite. The Y-type zeolite is preferably one or more of hydrogen-type Y zeolite, rare earth-type Y zeolite, rare-earth hydrogen-type zeolite, ultra-stable Y-type zeolite, rare-earth-type ultra-stable Y zeolite, and dealuminated Y-zeolite. The amount of the aluminosilicate zeolite added is such that the final catalyst contains 5-90% by weight of the aluminosilicate zeolite, preferably 15-85% by weight.

The binder and/or its precursors are selected from one or more of silicon oxide and its precursors, aluminum oxide and its precursors, silicon oxide-alumina and its precursors. The precursors of silica, alumina and silica-alumina may be one or more of silica sol, alumina sol, pseudo-boehmite, silica-alumina sol and silica-alumina gel. The added amount of the binder and/or its precursor is such that the binder in the final catalyst contains 10-95% by weight, preferably 15-85% by weight.

The catalyst active component and/or its precursor in the water slurry can also contain clay, and the clay includes commonly used various clays, such as kaolin, halloysite, montmorillonite, diatomaceous earth, bentonite, seafoam One or several kinds of stones, preferably kaolin. The clay is added in such an amount that the final catalyst contains 0-75% by weight of clay, preferably 0-65% by weight.

When one or more clays are contained in the water slurry, the addition of the zeolite, binding agent and clay is more preferably such that the final catalyst contains 5-50% by weight of zeolite, preferably 15-45% by weight, 10-40% by weight of binder, preferably 15-35% by weight, 25-75% by weight of clay, preferably 35-65% by weight.

According to the method provided by the present invention, the method for drying the water slurry may adopt a conventional drying method, such as a drying method or a spray drying method. The drying temperature can be from room temperature to 800°C, and the commonly used drying temperature is from room temperature to 650°C.

Compared with the prior art, the method provided by the invention has better viscosity-reducing effect, and at the same time, the activity of the catalyst prepared by the method provided by the invention is obviously improved. For example, adopt the method provided by the present invention to prepare the catalyst with the water slurry containing rare earth Y-type zeolite, kaolin, and buffered silica sol with a solid content of 26.2% by weight, and add the auxiliary hexametasulfuric acid of the present invention that accounts for 0.01% by weight of the solid content Sodium reduces the viscosity of the water slurry by 24.2% compared with that without additives, and the light oil micro-reactivity of the prepared catalyst increases by 6.5%. And adopt the disclosed method of CN1,032,498A to prepare catalyst with the same water slurry, the difference is only adding 0.01 weight % viscosity reducer polyacrylamide, compared with when not adding viscosity reducer, the viscosity of water slurry has only reduced 20.8 %, the light oil micro-reaction activity of the catalyst is basically unchanged.

Because the auxiliary agent used in the method provided by the invention can improve the activity of the catalyst, therefore, compared with the prior art, the method provided by the invention can greatly increase the amount of auxiliary agent, so better visbreaking effect can be achieved, and simultaneously the The catalytic activity of the catalyst is further improved. For example, the method provided by the present invention is used to prepare a catalyst with a water slurry containing rare earth type ultrastable Y zeolite, kaolin, pseudo-boehmite and aluminum sol with a solid content of 30.0% by weight, and the 1.5% by weight of the solid content of the present invention is added. The additive sodium hexametaphosphate, compared with no additive, reduces the viscosity of the water slurry by 86.7%, and the light oil micro-reaction activity of the prepared catalyst is increased by 20.7%, and the heavy oil micro-reaction activity is increased by 12.9%. . This is unmatched by the prior art.

In addition, the preparation of the catalyst by the method provided by the present invention can significantly improve the appearance of the microspheres of the finished catalyst, make the particles of the finished catalyst more uniform, and reduce the breakage rate, which can be clearly seen from the comparison of the catalyst optical microscope photos of Fig. 1 and Fig. 2 see clearly.

The following examples will further illustrate the present invention, but do not thereby limit the present invention.

Instances 1 to 5

The following examples illustrate the methods provided by the present invention and the catalytic activity of the resulting catalysts.

Take by weighing 5 parts of 120 grams of kaolin (dry basis weight, produced by Suzhou Kaolin Industry Company), make kaolin slurry with 449 milliliters of deionized water respectively, add 6 milliliters of concentrated hydrochloric acid of 36% by weight and pseudo-boehmite (to oxidize Aluminum meter, produced by Shandong Aluminum Works) 33 grams, stir, slurry is mixed evenly, then add respectively 11 grams of aluminum sols (in terms of alumina, produced by Qilu Petrochemical Company Catalyst Factory), add respectively 55 grams of rare earth ultra-stable molecular sieves REUSY ( Dry basis weight, unit cell constant is 2.446 nanometers, rare earth oxide content is 1.8% by weight, produced by catalyst factory of Qilu Petrochemical Company) and stirred evenly. In the above five parts of slurry, add sodium hexametaphosphate (analytical pure, produced by Nankai University Chemical Factory) accounting for 0.02% by weight, 0.04% by weight, 0.12% by weight, 0.4% by weight and 1% by weight of the solid content of the slurry, and stir evenly , and the resulting slurries were denoted as A, B, C, D and E in sequence. HAAKE ROTOVISCO RV20 rotational viscometer (produced by HAAKE, Germany) was used to measure the viscosity value of the slurry at 75 revolutions per second, and the results are listed in Table 1. Dry the above slurry at 110°C to obtain catalysts C ₁ , C ₂ , C ₃ , C ₄ , and C ₅ prepared by the method provided by the present invention. The compositions of catalysts C ₁ , C ₂ , C ₃ , C ₄ , and C ₅ are listed in Table 2.

Wherein, the content of each component in the catalyst is obtained by calculation. The sodium oxide in the table only refers to the sodium oxide brought in due to the addition of additives, and does not include the sodium oxide contained in zeolite, binder and clay. The content of sodium oxide contained in zeolite, binder and clay is not separately Calculation, but included in the zeolite, binder and clay content; rare earth oxide content is included in the zeolite, not listed separately. The situations in the following examples are the same, and no further description is given.

Aging catalysts C ₁ , C ₂ , C ₃ , C ₄ , and C ₅ in 100% water vapor at 800°C for 4 hours, crushing them into particles with a particle diameter of 420-841 microns, and using a small fixed-bed reactor Evaluate its light oil micro-reactivity, the catalyst loading is 5.0 grams, the reaction raw material is straight-run light oil oil (density at 20 ℃ is 0.8419 g/cm ³ ) with a distillation range of 235 to 337 ° C, and the reaction condition is a reaction temperature of 460 °C. ℃, the weight hourly space velocity is 16 hours ^-1 , and the weight ratio of agent to oil is 3.2. Table 3 shows the slightly inactive light oil activity of catalysts C ₁ , C ₂ , C ₃ , C ₄ , and C ₅ . The product composition was analyzed by gas chromatography, and the light oil microreactivity was calculated according to the product composition.

Light oil micro-reactivity = (gasoline yield + gas yield + coke yield below 204°C in the product)/total amount of feed × 100% = gasoline yield + gas yield + coke in the product below 204°C Yield.

Comparative example 1

This comparative example illustrates the preparation method of the comparative catalyst and the catalytic activity of the obtained catalyst.

Catalyst slurry and catalyst were prepared according to the methods of Examples 1-5, except that sodium hexametaphosphate was not added to obtain slurry F and catalyst C ₆ . The viscosity values of Slurry F are listed in Table 1 and the catalyst composition is listed in Table 2. Aged catalyst _C6 according to the method of Examples 1-5 and evaluated the light oil micro-reactivity of aged catalyst _C6 , and the results are listed in Table 3.

Table 1 instance number Serum number Addition amount of sodium hexametaphosphate, weight % Viscosity, mPa·s Viscosity reduction, % 1 A 0.02 1061 24.7 2 B 0.04 950.0 32.6 3 C 0.12 915.4 40.5 4 D. 0.4 570.9 59.5 5 E. 1 447.5 68.2 Comparative example 1 f 0 1409 -

Table 2 instance number Catalyst number Catalyst composition, wt% REUSY Kaolin Aluminum oxide P ₂ O ₅ Na ₂ O 1 C ₁ 25.11 54.78 20.09 0.01 0.01 2 C ₂ 25.11 54.77 20.08 0.03 0.01 3 C ₃ 25.08 54.73 20.07 0.08 0.04 4 C ₄ 25.01 54.58 20.01 0.28 0.12 5 C ₅ 24.86 54.25 19.89 0.70 0.30 Comparative example 1 C ₆ 25.12 54.79 20.09 - -

table 3 instance number Catalyst number light oil slightly reactive 1 C ₁ 66.2 2 C ₂ 67.5 3 C ₃ 68.2 4 C ₄ 69.0 5 C ₅ 73.4 Comparative example 1 C ₆ 62.0

Instances 6-9

The following examples illustrate the methods provided by the present invention and the catalytic activity of the resulting catalysts.

Take by weighing 4 parts of 120 grams of kaolin (same example 1), make kaolin slurry with 536 milliliters, 441 milliliters, 300 milliliters and 281 milliliters of deionized water respectively, add 10 milliliters of concentrated hydrochloric acid of 36% by weight and pseudoboehmous aluminum respectively Stone (with example 1) 48 grams, stir, make slurry mix uniformly, add sodium hexametaphosphate respectively and make it account for 0.6 weight % of final slurry solid content, then add respectively 55 grams of rare earth type ultra-stable molecular sieves REUSY (with example 1) , stirred evenly, and the obtained slurry was recorded as G, H, I and J in sequence. The viscosity values of slurries G, H, I and J were measured in the same manner as in Example 1. The solids content and viscosity values for slurries G, H, I and J are listed in Table 4. Dry the above slurry at 110°C to obtain catalysts C ₇ , C ₈ , C ₉ and C ₁₀ prepared by the method provided by the present invention. The compositions of catalysts C ₇ , C ₈ , C ₉ and C ₁₀ are listed in Table 5.

Aging catalysts C ₇ , C ₈ , C ₉ and C ₁₀ according to the method of examples 1 to 5 and evaluating the light oil micro-reactivity of catalysts C ₇ , C ₈ , C ₉ and C ₁₀ after aging, the results are listed in Table 6 .

Comparative example 2

This comparative example illustrates the preparation method of the comparative catalyst and the catalytic activity of the obtained catalyst.

Catalyst slurry and catalyst were prepared according to the method of Example 6, except that sodium hexametaphosphate was not added to obtain slurry K and catalyst C ₁₁ . The solid content and viscosity values of slurry K are listed in Table 4, and the catalyst composition is listed in Table 5. Aged catalyst _C11 according to the method of Examples 1-5 and evaluated the light oil micro-reactivity of aged catalyst _C11 , the results are listed in Table 6.

Table 4 instance number Serum number Slurry solid content, wt% Viscosity, mPa·s reduced viscosity, Solid content increase, % 6 G 25 838.0 68.1 - 7 h 28 1837 30.1 12 8 I 34 2072 21.2 36 9 J 35 2512 4.5 40 Comparative example 2 K 25 2629 - -

table 5 instance number Catalyst number Catalyst composition, wt% REUSY Kaolin Aluminum oxide P ₂ O ₅ Na ₂ O 6 C ₇ 24.52 53.49 21.39 0.42 0.18 7 C ₈ 24.52 53.49 21.39 0.42 0.18 8 C ₉ 24.52 53.49 21.39 0.42 0.18 9 C ₁₀ 24.52 53.49 21.39 0.42 0.18 Comparative example 2 C ₁₁ 24.66 53.81 21.53 - -

Table 6 instance number Catalyst number light oil slightly reactive 6 C ₇ 70.3 7 C ₈ 70.5 8 C ₉ 71.2 9 C ₁₀ 71.2 Comparative example 2 C ₁₁ 62.2

Example 10

This example illustrates the method provided by the invention and the catalytic activity of the resulting catalyst.

Take by weighing 135 grams of 20 weight percent sulfuric acid and 20 grams of aluminum sulfate containing 7 weight percent of alumina (chemically pure, produced by Qilu Petrochemical Company Catalyst Factory) solution and mix uniformly to make a buffer solution. Water glass (produced by Beijing Red Star Chemical Factory, modulus is 3.0～3.2) is mixed with above-mentioned buffer solution to make buffer silica sol; Then add 120 grams of kaolin (same as example 1) and 30 grams of rare earth Y-type molecular sieves (unit cell constant is 2.467 Nanometer, rare earth oxide content is 17.2% by weight, produced by Zhoucun Catalyst Factory of Qilu Petrochemical Company) Stir evenly, add sodium hexametaphosphate accounting for 0.01% by weight of slurry solid content, to obtain slurry L. The results of measuring the viscosity of L by the same method as Example 1 are listed in Table 7. The above slurry was dried at 110°C to obtain catalyst C ₁₂ prepared by the method provided by the present invention. The composition of Catalyst _C12 is listed in Table 8.

Aged catalyst _C12 according to the method of examples 1-5 and evaluated the light oil micro-reactivity of aged catalyst _C12 , the results are listed in Table 9.

Comparative example 3

This comparative example illustrates the preparation method of the comparative catalyst and the catalytic activity of the obtained catalyst.

Prepare the slurry and the catalyst according to the method of Example 10, except that the method disclosed in CN1,032,498A is used to prepare, that is, polyacrylamide (produced by Dalian Tongde Chemical Factory, powdery, hydrolyzed, Molecular weight 3 to 5 million units) to replace sodium hexametaphosphate accounting for 0.01% by weight of the solid content of the slurry to obtain slurry M and catalyst C ₁₃ . The solids content and viscosity values of slurry M are listed in Table 7. The composition of catalyst C ₁₃ is listed in Table 8.

Aged catalyst _C13 according to the method of Examples 1-5 and evaluated the light oil micro-reactivity of aged catalyst _C13 , the results are listed in Table 9.

Comparative example 4

This comparative example illustrates the preparation method of the comparative catalyst and the catalytic activity of the obtained catalyst.

The slurry and catalyst were prepared according to the method of Example 10 except that sodium hexametaphosphate was not added to obtain slurry N and catalyst C ₁₄ . The solids content and viscosity values of Slurry N are listed in Table 7. The composition of catalyst C ₁₄ is listed in Table 8.

Aged catalyst _C14 according to the method of examples 1-5 and evaluated the slightly inactive light oil activity of catalyst _C14 after aging, and the results are listed in Table 9.

Table 7 instance number Serum number Slurry solid content, wt% Viscosity value, mPa·s Viscosity reduction, % 10 L 26.2 1503 24.2 Comparative example 3 N 26.2 1570 20.8 Comparative example 4 m 26.2 1982 -

Table 8 instance number Catalyst number Catalyst composition, wt% REY Kaolin Silicon oxide Aluminum oxide P ₂ O ₅ Na ₂ O 10 L 14.90 59.57 24.83 0.69 0.003 0.007 Comparative example 3 m 14.91 59.57 24.83 0.69 - - Comparative example 4 N 14.91 59.57 24.83 0.69 - -

Table 9 instance number Catalyst number light oil slightly reactive 10 C ₁₂ 72.5 Comparative example 3 C ₁₃ 68.3 Comparative example 4 C ₁₄ 68.1

Example 11

This example illustrates the method provided by the invention and the catalytic activity of the resulting catalyst.

Take by weighing 120 grams of kaolin (same as example 1) and make kaolin slurry with 281 milliliters of deionized water, add 9 milliliters of concentrated hydrochloric acid and 33 grams of pseudo-boehmite (in terms of alumina, produced by Shandong Aluminum Plant) of 36% by weight And aluminum sol (same example 1) 11 grams, stir, make the slurry mix uniformly, add ultra-stable molecular sieve REUSY 55 grams (same example 1), add and account for the sodium hexametaphosphate of 0.6 weight % of slurry solid content, stir, obtain slurry O. The viscosity value of the slurry O was measured in the same manner as in Example 1. The solid content and viscosity values of the slurry are listed in Table 10. Dry the above slurry at 110°C to obtain the catalyst C ₁₅ prepared by the method provided by the present invention. The composition of Catalyst _C15 is listed in Table 11.

Aged catalyst _C15 according to the method of Examples 1-5 and evaluated the light oil micro-reactivity of aged catalyst _C15 , the results are listed in Table 13.

Be that the decompression wax oil of 227～475 ℃ with the distillation range is the heavy oil micro-reaction of the catalyst C ₁₅ (catalyst particle size is 420～841 micron) after evaluating on the small fixed-bed reactor by the method aging of example 1～5 Activity, catalyst loading 4.0g, reaction conditions: reaction temperature 482°C, weight hourly space velocity 16 hours ^-1 , agent-oil weight ratio 5.0. The properties of the heavy oil are listed in Table 12, and the heavy oil microreactivity of catalyst _C15 is listed in Table 13. in,

Heavy oil micro-reaction activity = (gas output below C ₅ + gasoline output at C ₅ ~ 221°C + coke output) / total amount of feed × 100% = gas yield below C ₅ + gasoline output at C ₅ ~ 221°C + coke output Rate.

Comparative example 5

This comparative example illustrates the preparation method of the comparative catalyst and the catalytic activity of the obtained catalyst.

The slurry and catalyst were prepared according to the method of Example 11, except that sodium hexametaphosphate was not added to obtain slurry P and catalyst C ₁₆ . The solids content and viscosity values of slurry P are listed in Table 10. The composition of catalyst _C16 is listed in Table 11.

According to the method aging catalyst C ₁₆ of example 11 and evaluate the light oil slight inversion activity and the heavy oil inactivity of the catalyst C ₁₆ after aging, the results are listed in table 13.

Table 10 instance number Serum number Slurry solid content, wt% Viscosity value, mPa·s Viscosity reduction, % 11 o 34.2 1536 38.2 Comparative example 5 P 34.2 2484 -

Table 11 instance number Catalyst number Catalyst composition, wt% REUSY Kaolin Aluminum oxide P ₂ O ₅ Na ₂ O 11 o 24.96 54.47 19.97 0.42 0.18 Comparative example 5 P 25.12 54.79 20.09 - -

Table 12 Raw oil name Decompression wax oil Density (20℃), g/ ^cm3 0.8652 Viscosity, ^mm2 /sec 14.58 Asphaltene content, weight % 0.686 Kang's residual carbon, weight % 0.04 Distillation range, ℃ initial boiling point 227 10% 289 50% 389 90% 446 95% 458 do it 475

Table 13 instance number Catalyst number light oil slightly reactive Heavy oil micro-reactivity 11 C ₁₅ 69.7 85.7 Comparative example 5 C ₁₆ 62.2 79.1

Instances 12～13

The following examples illustrate the methods provided by the present invention and the catalytic activity of the resulting catalysts.

Take by weighing 120 grams of kaolin (same as example 1) respectively, make kaolin slurry with 419 milliliters and 281 milliliters of deionized water respectively, add 9 milliliters and 10 milliliters of concentrated hydrochloric acid of 36% by weight respectively, add pseudo-boehmite ( With example 1) 33 grams and aluminum sol (same example 1) 11 grams, stir, slurry is mixed homogeneously, add REUSY 44 grams (same example 1) and ZSM-5 zeolite (silicon-aluminum ratio is 60, Qilu Petrochemical Company Catalyst Factory) 11 grams were added into 0.6% by weight and 1% by weight of sodium hexametaphosphate accounting for the solid content of the slurry, and stirred evenly to obtain slurries Q and R. The viscosity values of slurries Q and R were measured in the same manner as in Example 1. The solid content and viscosity values of the slurry are listed in Table 14. Dry the above slurry at 120°C to obtain catalysts C ₁₇ and C ₁₈ prepared by the method provided by the present invention. The compositions of catalysts C ₁₇ and C ₁₈ are listed in Table 15.

According to the method aging catalyst C ₁₇ and C ₁₈ of example 11 and the light oil slight inversion activity and the heavy oil inversion activity of the catalyst C ₁₇ and C ₁₈ after the evaluation aging, the results are listed in table 16.

Comparative example 6

This comparative example illustrates the preparation method of the comparative catalyst and the catalytic activity of the obtained catalyst.

The slurry and catalyst were prepared according to the method of Example 12, except that sodium hexametaphosphate was not added to obtain slurry S and catalyst C ₁₉ . The solids content and viscosity values of Slurry S are listed in Table 14. The composition of catalyst _C19 is listed in Table 15.

According to the method aging catalyst C ₁₉ of example 11 and evaluate the light oil slightly reverse activity and the heavy oil slightly reverse activity of the catalyst C ₁₉ after aging, the results are listed in table 16.

Table 14 instance number Serum number Slurry solid content, wt% Viscosity, mPa·s 12 Q 28.0 520.5 13 R 34.0 1607 Comparative example 6 S 28.0 1625

Table 15 instance number Catalyst number Catalyst composition, wt% REUSY+ZSM-5 Kaolin Aluminum oxide P ₂ O ₅ Na ₂ O 12 C ₁₇ 24.96 54.47 19.97 0.42 0.18 13 C ₁₈ 24.86 54.25 19.89 0.70 0.30 Comparative example 6 C ₁₉ 25.12 54.79 20.09 - -

Table 16 instance number Catalyst number light oil slightly reactive Heavy oil micro-reactivity 12 C ₁₇ 67.0 83.4 13 C ₁₈ 70.2 86.2 Comparative example 6 C ₁₉ 57.1 75.6

Example 14

This example illustrates the method provided by the invention, the catalytic activity of the catalyst prepared by the method and the appearance of the catalyst microspheres.

Take by weighing 22.4 kilograms of kaolin (same as example 1) and 64.4 kilograms of deionized water to make kaolin slurry, add 1.2 liters of 36% by weight of concentrated hydrochloric acid, add 3.0 kilograms of pseudo-boehmite (dry weight, produced by Shandong Aluminum Factory) and 2.8 kg of aluminum sol (dry basis weight, produced by Qilu Petrochemical Company Catalyst Factory), stirred to make the slurry evenly mixed, adding 9.4 kg of REUSY molecular sieves (dry basis weight, produced by Qilu Petrochemical Company Catalyst Factory), and adding 1.5 wt. % sodium hexametaphosphate, stirred evenly to obtain slurry T. The viscosity value of the slurry T was measured in the same manner as in Example 1. The solid content and viscosity values of the slurry are listed in Table 17. The above slurry was spray-dried at 600° C. to obtain the catalyst C ₂₀ prepared by the method provided by the present invention. The composition of Catalyst _C20 is listed in Table 18. The 400-fold optical microscope photo of catalyst _C20 obtained on the XTL-1 stereo microscope is shown in Figure 1.

According to the method aging catalyst C ₂₀ of example 11 and evaluate the catalyst C ₂₀ after aging light, heavy oil micro-reactive, the result is listed in table 19.

Comparative Example 7

This comparative example illustrates the preparation method of the comparative catalyst, the catalytic activity of the obtained catalyst and the appearance of the catalyst microspheres.

Catalyst slurry and catalyst were prepared according to the method of Example 14, except that sodium hexametaphosphate was not added to obtain slurry U and catalyst C ₂₁ . The solid content and viscosity values of slurry U are listed in Table 17, and the catalyst composition is listed in Table 18. According to the method aging catalyst C ₂₁ of example 11 and evaluate the light and heavy oil micro-reactivity of catalyst C ₂₁ after aging, the result is listed in table 19. The photomicrograph of catalyst C ₂₁ magnified 400 times is shown in Fig. 2 .

Table 17 instance number Serum number Slurry solid content, wt% Viscosity, mPa·s Viscosity reduction, % 14 T 30.0 259.0 86.7 Comparative example 7 u 30.0 1947 -

Table 18 instance number Catalyst number Catalyst composition, wt% REUSY Kaolin Aluminum oxide P ₂ O ₅ Na ₂ O 14 C ₂₀ 24.63 58.69 15.19 1.04 0.45 Comparative example 7 C ₂₁ 25.00 59.57 15.43 - -

Table 19 instance number Catalyst number light oil slightly reactive Heavy oil micro-reactivity 14 C ₂₀ 74.2 88.3 Comparative example 7 C ₂₁ 61.5 78.2

Example 15-17

This example illustrates the method provided by the invention and the catalytic activity of the resulting catalyst.

Catalyst is prepared by the method for example 5, and difference just changes sodium hexametaphosphate into potassium hexametaphosphate (analytical pure, Tianjin Nankai Chemical Plant produces), sodium pyrophosphate (analytical pure, Tianjin Chemical Reagent Factory produces) and trimeric Sodium phosphate (analytical pure, produced by Tianjin Chemical Reagent Factory), REUSY is changed into HY zeolite (produced by Qilu Petrochemical Company Catalyst Factory) with a unit cell constant of 2.454 nanometers respectively, and the slurry obtained is denoted as V, W and X successively, and the obtained Catalysts are recorded as C ₂₂ , C ₂₃ , and C ₂₄ in sequence. Table 20 gives the solid content and viscosity values of slurries V, W and X, and Table 21 gives the compositions of catalysts C ₂₂ , C ₂₃ , and C ₂₄ . Catalysts C ₂₂ , C ₂₃ , and C ₂₄ were aged according to the methods of Examples 1-5, and the light oil inversion activity of the aged catalysts C ₂₂ , C ₂₃ , and C ₂₄ was evaluated. The results are listed in Table 22.

Comparative example 8

This comparative example illustrates the preparation method of the comparative catalyst and the catalytic activity of the obtained catalyst.

Catalyst slurry and catalyst were prepared according to the methods of Examples 15-17, except that potassium hexametaphosphate, sodium pyrophosphate or sodium tripolyphosphate were not added to obtain slurry Z and catalyst C ₂₅ . The solids content and viscosity values of Slurry Z are listed in Table 20 and the composition of Catalyst C ₂₅ is listed in Table 21. Aging catalyst C ₂₅ according to the method of Examples 1-5 and evaluating the light oil micro-reactivity of the aging catalyst C ₂₅ , the results are listed in Table 22.

Table 20 instance number Serum number Slurry solid content, wt% Viscosity, mPa·s 15 V 27.0 451.0 16 W 27.0 520.0 17 x 27.0 542.4 Comparative example 8 Z 27.0 1409.0

Table 21 instance number Catalyst number Catalyst composition, wt% HY Kaolin Aluminum oxide P ₂ O ₅ Na ₂ O 15 C ₂₂ 24.87 54.25 19.88 0.60 0.40 16 C ₂₃ 24.87 54.25 19.88 0.47 0.53 17 C ₂₄ 24.87 54.25 19.88 0.42 0.58 Comparative example 8 C ₂₅ 25.12 54.79 20.09 - -

Table 22 instance number Catalyst number light oil slightly reactive 15 C ₂₂ 67.4 16 C ₂₃ 64.2 17 C ₂₄ 63.0 Comparative example 8 C ₂₅ 57.5

Claims (24)

1. A preparation method of a fluid catalytic cracking catalyst comprises the steps of drying an aqueous slurry containing a catalytic cracking catalyst component and/or a precursor thereof, and recovering the prepared catalyst, and is characterized in that before drying, an auxiliary agent is added into the aqueous slurry, wherein the auxiliary agent is selected from one or more of soluble polyphosphate and hydrate thereof, and accounts for 0.001-5 wt% of the solid content of the aqueous slurry.

2. The method of claim 1, wherein the soluble polyphosphate is one or more of soluble pyrophosphate, polymetaphosphate and polyphosphate

3. The method according to claim 2, wherein the soluble pyrophosphate is selected from one or more of pyrophosphate of metals in group IA of the periodic table of elements and ammonium pyrophosphate; the soluble polymetaphosphate is selected from one or more than one polymetaphosphate of metals in the IA group of the periodic table of elements; the soluble polyphosphate is one or more selected from tripolyphosphate and ammonium tripolyphosphate of metals in the IA group of the periodic table.

4. The method according to claim 3, wherein the soluble pyrophosphate is selected from one or more of sodium pyrophosphate, lithium pyrophosphate and potassium pyrophosphate.

5. The method of claim 4, wherein the soluble pyrophosphate salt is sodium pyrophosphate.

6. The method according to claim 3, wherein the soluble polymetaphosphate salt is selected from one or more of trimetaphosphate salts and hexametaphosphate salts of metals in group IA of the periodic Table of elements.

7. The method according to claim 6, wherein the soluble polymetaphosphate is selected from one or more of sodium trimetaphosphate, potassium trimetaphosphate, sodium hexametaphosphate, lithium hexametaphosphate and potassium hexametaphosphate.

8. The method of claim 7, wherein the soluble polymetaphosphate salt is sodium hexametaphosphate.

9. The method according to claim 3, wherein the soluble polyphosphate is selected from one or more of sodium tripolyphosphate, lithium tripolyphosphate and potassium tripolyphosphate.

10. The method of claim 9, wherein the soluble polyphosphate salt is sodium tripolyphosphate.

11. The method according to claim 1, wherein the addition amount of the auxiliary is 0.005 to 3 wt%.

12. The process of claim 1 wherein the catalytically active component and/or precursor thereof in the aqueous slurry comprises at least one aluminosilicate zeolite and a binder or precursor thereof; the addition amount of the aluminosilicate zeolite enables the aluminosilicate zeolite in the final catalyst to be 5-90 wt%; the binder and/or the precursor thereof is added in an amount such that the final catalyst contains 10 to 95 wt% of the binder.

13. The process of claim 12 wherein the aluminosilicate zeolite is added in an amount from 15 to 85 weight percent of the aluminosilicate zeolite in the final catalyst; the binder and/or the precursor thereof is added in an amount such that the final catalyst contains 15-85 wt% of the binder.

14. A method according to claim 12 or 13, wherein the binder and/or its precursors are selected from one or more of silica, alumina, silica-alumina and their precursors.

15. The method according to claim 14, wherein the silica, alumina, silica-alumina precursor is selected from one or more of silica sol, alumina sol, pseudo-boehmite, silica-alumina sol and silica-alumina gel.

16. The process of claim 12 wherein the catalyst active component and/or its precursor in the aqueous slurry further comprises clay, said clay being added in an amount to provide a clay content of from 0 to 75 wt% in the final catalyst.

17. The process of claim 16 wherein the clay is added in an amount to provide a clay content in the final catalyst of from 0 to 65 wt%.

18. The process of claim 1 wherein the catalyst active component and/or precursor thereof in the aqueous slurry comprises an aluminosilicate zeolite, a binder and/or precursor thereof, and clay, wherein the zeolite, binder and/or precursor thereof, and clay are added in amounts such that the final catalyst comprises 5 to 50 wt% aluminosilicate zeolite, 10 to 40 wt% binder, and 25 to 75 wt% clay.

19. The process of claim 18 wherein the aluminosilicate zeolite, binder and/or precursor thereof, and clay are added in amounts such that the final catalyst comprises 15 to 45 wt% aluminosilicate zeolite, 15 to 35 wt% binder, and 35 to 65 wt% clay.

20. The process according to any one of claims 12, 13, 18 and 19, wherein the aluminosilicate zeolite is selected from one or more of faujasite, MFI zeolite, mordenite, BETA zeolite.

21. The method of claim 20, wherein the aluminosilicate zeolite is selected from one or more of X-type zeolite, Y-type zeolite, ZSM-5 zeolite.

22. The method of claim 21, wherein the Y-type zeolite is selected from one or more of hydrogen-type Y zeolite, rare-earth type hydrogen Y zeolite, ultrastable Y zeolite, rare-earth type ultrastable Y zeolite, and dealuminized Y zeolite.

23. The method according to any one of claims 16 to 19, wherein the clay is selected from one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, bentonite and sepiolite.

24. The method of claim 23, wherein the clay is kaolin.

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