CN1270203A - Process for preparing cracking catalyst of petroleum hydrocarbons - Google Patents
Process for preparing cracking catalyst of petroleum hydrocarbons Download PDFInfo
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Abstract
A process for preparing cracking catalyst of petroleum hydrocarbons features that molecular sieve and/or aluminium sol are added before clay and inorganic acid, and the inorganic acid is added after aluminium sol and pseudo-boehmite. The grout of said catalyst contains a dethickening agent (0.1-2 wt.%), which may be ammonium phosphate, diammonium hydrogen phosphate, or ammonium bihydrogen phosphate, or their mixture. Its advantages are high solid content in catalyst grout before spray drying, short colloid-forming time, high productivity and low energy consumption and production cost.
Description
The present invention relates to the preparation method of the catalytic cracking catalyst that uses in a kind of petroleum refining process.
Because the heavy of stock oil and poor qualityization, present fluid catalytic cracking of heavy oil (FCC) catalyzer mostly adopt the semi-synthetic catalyzer of polymer sieve content (more than the 30 weight %).In order to guarantee the wear strength of catalyzer, in order to improve its reaction preference, must select suitable caking agent simultaneously.Caking agent used in the prior art mainly contains pseudo-boehmite caking agent, compound sial caking agent or the composite aluminum base caking agent be made up of aluminium colloidal sol and pseudo-boehmite etc.
A kind of cracking catalyst and preparation method thereof has been proposed, the composite aluminum base caking agent of forming by aluminium colloidal sol and pseudo-boehmite that wherein adopts among the CN1098130A.Pseudo-boehmite macromole cracking ability is strong, the sol bonded performance of aluminium is good and coke selectivity is good because the composite aluminum base binding agent combines, and domestic heavy oil FCC catalyzer great majority all adopt this composite aluminum base binding agent at present.The preparation method of the cracking catalyst of describing in this patent mixes making beating with clay and deionized water earlier, add hcl acidifying, add pseudo-boehmite then, again the gained slurries were worn out 0.5～2 hour at 50～80 ℃, after the cooling, add aluminium colloidal sol and molecular sieve pulp again, mix and spraying drying.The shortcoming of this method is that preparation time is longer owing to need to heat up agingly, and energy consumption is big, and the catalyst slurry fluid solid content before the spraying drying is lower, is generally less than 25 weight %, causes energy consumption height, production efficiency low, the production cost height.If the raising slurry solid content then can can't be carried greatly because of viscosity.
USP5, cracking catalyst that proposes in 547,564 and preparation method thereof is to replace pseudo-boehmite with bayerite and/or η-aluminum oxide, can improve the preventing from heavy metal ability and the coke selectivity of catalyzer.
Improve the production efficiency that the preceding FCC catalyst slurry fluid solid content of spraying drying can improve catalyzer, reduce spray-dired energy consumption, the exhaust gas emission that minimizing produces because of fuel combustion, can reduce simultaneously the consumption of deionized water, thereby the reduction catalyst production cost improves competitiveness of product.
U.S. Pat P4,476,239 and USP4,443, reported a kind of preparation method of cracking catalyst in 553, it is characterized in that in catalyst slurry, adding viscosity depressant aluminium chlorohydroxide or hydroxyl aluminum nitrate and reduce the catalyst slurry fluid viscosity and then improve the catalyst slurry fluid solid content.According to description wherein, the catalyst slurry that contains aluminium base caking agent, clay, silicon source and molecular sieve, the catalyst slurry maximum solids content is 20～25 weight % during not with viscosity depressant, adds the later catalyst slurry maximum solids content of said viscosity depressant and can reach 30 weight %.Its preparation flow is: the viscosity depressant Al of the poly ammonium silicate of the molecular sieve of the kaolin of the 1. pseudo-boehmite of water → 2. → 3. acid → 4. → 5. → 6. → 7.
2(OH)
5NO
3Or Al
2(OH)
5Cl, spray-dried and washing, drier and product.
For the FCC catalyzer that adopts pseudo-boehmite and aluminium colloidal sol composite aluminum base binding agent, the Production Flow Chart of patent report both at home and abroad all is to adopt adding acid to make the pseudo-boehmite peptization add the processing step of aluminium colloidal sol later on again (as CN1098130A, and USP5,547, embodiment 5 in 564), the catalyst slurry fluid viscosity is big, and solid content is low, even the slurry solid content before the adding viscosity depressant, spraying drying is generally all below 30 weight %.
The preparation method who the purpose of this invention is to provide a kind of cracking catalyst makes the solid content of the catalyst slurry before the spraying drying that by a relatively large margin raising can be arranged, thereby improves the production efficiency of catalyzer, reduces energy consumption and production costs.
The preparation method of cracking catalyst provided by the present invention comprises molecular sieve pulp, aluminium colloidal sol, pseudo-boehmite, clay and mineral acid making beating mixed and makes catalyst slurry, then spraying drying; It is characterized in that molecular sieve and/or aluminium colloidal sol added before clay and mineral acid, mineral acid adds after aluminium colloidal sol, preferably mineral acid adds after aluminium colloidal sol and pseudo-boehmite, the addition sequence of rest materials has no particular limits, and contains a kind of viscosity depressant in the said catalyst slurry; Wherein said viscosity depressant is ammonium phosphate, Secondary ammonium phosphate or primary ammonium phosphate, or their mixture, and the add-on of viscosity depressant is 0.1～2%, preferred 0.3～1.5% of a catalyzer butt weight; Al in said mineral acid and the pseudo-boehmite
2O
3Weight ratio be 0.02～0.25; The solid content of said catalyst slurry is 30～55 weight %.
Preferably earlier molecular sieve pulp, aluminium colloidal sol and pseudo-boehmite are mixed in any order and pull an oar among the preparation method of cracking catalyst provided by the present invention and mix; And then mix to wherein adding clay, mineral acid and viscosity depressant and pulling an oar in any order; Then with gained catalyst slurry spraying drying.
The preparation method of cracking catalyst provided by the present invention is characterized in that the addition sequence of each raw material and adds a kind of special viscosity depressant, and the composition of said catalyst slurry can decide according to the prescription of concrete catalyzer, and the present invention has no particular limits it.
Among the preparation method of cracking catalyst provided by the present invention in the said catalyst slurry each components contents (by butt weight) be preferably molecular sieve 10～50%, clay 15～70%, pseudo-boehmite and aluminium colloidal sol (are pressed Al
2O
3Meter) 10～35%; The Al of pseudo-boehmite and aluminium colloidal sol wherein
2O
3The ratio of weight is (6: 1)～(1: 10), the Al in mineral acid and the pseudo-boehmite
2O
3Weight ratio be 0.02～0.25, the solid content of slurries is 30～55 weight %.
One or more oxide compounds that are selected from rare earth oxide, silicon oxide, magnesium oxide, titanium oxide, phosphorus oxide, aluminum oxide-silicon oxide or its precursor that can also contain 0～10 weight % in the method provided by the invention in the said slurries; Wherein preferably rare earth oxide or silicon oxide or their precursor.
Said molecular sieve is the mixture of one of y-type zeolite or y-type zeolite and ZSM-5 zeolite, Omega zeolite, β zeolite in the method provided by the invention; The mixture of y-type zeolite or y-type zeolite and ZSM-5 zeolite preferably wherein.
Said clay is kaolin, halloysite, sepiolite, tired soil, polynite or their mixture of taking off in the method provided by the invention; Wherein preferably kaolin, halloysite, sepiolite or their mixture; Most preferred is kaolin.
Said pseudo-boehmite can use boehmite, gibbsite, bayerite or η-aluminum oxide to replace in the method provided by the invention.
Said mineral acid is hydrochloric acid or sulfuric acid in the method provided by the invention; Hydrochloric acid preferably wherein.
The concentration of said molecular sieve pulp is 250～550 grams per liters in the method provided by the invention.
Can also comprise the step that gained catalyzer after the spraying drying is carried out roasting or washing in the method provided by the invention.
Can also the scheme according to the invention beyond the such scheme among the preparation method of catalyst of cracking petroleum provided by the invention.
Fig. 1 is the viscosity of catalyst slurry when the catalyst slurry fluid solid content is about 50% and the relation of Secondary ammonium phosphate add-on (accounting for the percentage ratio of catalyzer butt gross weight).
The viscosity of catalyst slurry depends on the composition of catalyst slurry fluid solid content, catalyst slurry and the existence of each component.For the FCC catalyzer that adopts the composite aluminum base binding agent, topmost two factors that influence the catalyst slurry fluid viscosity are the solid content of catalyst slurry and the existence of pseudo-boehmite.
Will keep the catalyst slurry modest viscosity under the situation of high catalyst slurry solid content, the most effective means are existences of control pseudo-boehmite.
Key problem in technology of the present invention is that molecular sieve pulp and/or aluminium colloidal sol added before clay, and aluminium colloidal sol is added in before the acid.Thereby adding earlier molecular sieve pulp and/or aluminium colloidal sol can make full use of water in molecular sieve pulp and/or the aluminium colloidal sol and clay is pulled an oar guarantee that catalyst slurry has higher solid content, just must add big water gaging if earlier clay is pulled an oar, the water that must contain in molecular sieve pulp that adds after adding and the aluminium colloidal sol, then the solid content of catalyst slurry just is difficult to improve; Thereby aluminium colloidal sol is added in and can utilizes aluminium colloidal sol that the shock absorption of PH is guaranteed to add acid before the acid to be unlikely to make slurries PH to cross low not saboteur sieve, can change simultaneously the existence of pseudo-boehmite behind the peptization again, and the interaction between the change micelle, thereby slurry viscosity is reduced greatly; And, make gelation time shorten greatly because the inventive method does not need intensification aging, also can further reduce slurry viscosity simultaneously; On the other hand,, can further reduce slurry viscosity, improve slurry solid content, and the phosphorus ammonium salt also is new discovery of the present invention to the visbreaking performance of slurries owing to also contain phosphorus ammonium salt viscosity depressant in the catalyst slurry in the inventive method; About adopting solid content that the inventive method can make catalyst slurry up to 50 weight %, this is that prior art is beyond one's reach.The wear strength of the inventive method gained catalyzer and reactivity worth etc. are not compared with other method of prior art and are reduced in addition.Therefore, method provided by the invention is compared with the method for prior art, can improve the production efficiency of catalyzer greatly, and reduce energy consumption and production costs.
The following examples will the present invention is further illustrated, but protection scope of the present invention is not subjected to the restriction of these embodiment.
In each embodiment and Comparative Examples, adopt Cole Parmer 98936 rotating cylinder viscosimeters to measure slurry viscosity, the viscosity that provides is the result who uses the R4 rotating shaft to record under the 2.5rpm rotating speed; Water droplet pore volume, abrasion index and the micro-activity of gained catalyzer is respectively according to " petrochemical complex analytical procedure (RIPP test method) " (volume such as Yang Cuiding, Science Press, nineteen ninety publishes) in RIPP28-90, RIPP29-90 and RIPP92-90 standard method measure.
Embodiment 1～5
Add in the reactor with colloidal mill levigate to particle diameter be that (Chang Ling oil-refining chemical factory catalyst plant commerical prod is rare earth HY type molecular sieve, RE for the SRCY molecular sieve of 40 weight % less than 10 microns concentration
2O
3Content is 13 weight %, down with) 11.2 kilograms in slurries and the aluminium colloidal sol (commerical prod that obtains from Chang Ling oil-refining chemical factory catalyst plant, alumina content is 21 weight %, 14.2 kilograms down together), after stirring, under agitation to wherein adding 7.6 kilograms of pseudo-boehmite (Shandong Aluminum Plant's commerical prods, alumina content is 60 weight %, down together), making beating was stirred after 30 minutes, added 25.4 kilograms of kaolin (Suzhou kaolin company commerical prod, igloss 29 weight %, down together), making beating was stirred after 45 minutes, added Secondary ammonium phosphate, and the add-on of Secondary ammonium phosphate is 0.2% of a catalyzer butt gross weight, stir after 10 minutes, the hydrochloric acid that to add 0.3 kilogram of concentration again be 30 weight %, making beating was stirred after 30 minutes again, measured the viscosity of catalyst slurry, with gained catalyst slurry spraying drying, the product after the spraying drying is got catalyst A through 600 ℃ of roastings 20 minutes.Said catalyst slurry this moment thickness comparatively.
According to above-mentioned identical prescription and preparation process, just the add-on of Secondary ammonium phosphate is changed into 0.5%, 0.8%, 1.0% and 1.2% of catalyzer butt gross weight respectively, make catalyst B, C, D and E respectively.This moment, the viscosity of catalyst slurry obviously reduced with the increase of Secondary ammonium phosphate add-on, and the relation of the viscosity of catalyst slurry and Secondary ammonium phosphate add-on (accounting for the percentage ratio of catalyzer butt gross weight) is seen Fig. 1.
When the Secondary ammonium phosphate add-on was 0.3 kilogram (account for catalyzer butt gross weight 1.0%), gained catalyst slurry fluid solid content was 50.9 weight %, and slurry viscosity is 4900 centipoises; The abrasion index of gained catalyzer is 1.9.
Embodiment 6
Add in the reactor with colloidal mill levigate to particle diameter be SRY molecular sieve (the Chang Ling oil-refining chemical factory catalyst plant commodity of 24.8 weight % less than 10 microns concentration, igloss 2.6 weight %, be super-stable Y molecular sieves, lattice constant 2.455 nanometers, down together) 14.1 kilograms in slurries and aluminium colloidal sol are 2.9 kilograms, after stirring, under agitation to wherein adding 4.0 kilograms of pseudo-boehmites, making beating was stirred after 20 minutes, added 1.01 kilograms of hydrochloric acid that concentration is 21.5 weight %, added 4.9 kilograms of kaolin again, making beating was stirred after 45 minutes, add 0.1 kilogram of primary ammonium phosphate, stir after 10 minutes, gained catalyst slurry spraying drying.The spraying drying products obtained therefrom washed with water and through air stream drying and catalyzer F.
Slurry solid content before the catalyzer F spraying drying is 37 weight %, and viscosity is 2300 centipoises, and gained catalyst abrasion index is 1.8,0.35 milliliter/gram of water droplet method pore volume, and micro-activity is 72 (800 ℃/4 hours aging backs).
Embodiment 7
Get 1.05 kilograms of ZRP-1 molecular sieves (Qilu Petrochemical company Zhou village catalyst plant commodity, igloss 5.0 weight %, be type ZSM 5 molecular sieve, together following) and 1.54 kilograms of DASY molecular sieve (Qilu Petrochemical company Zhou village catalyst plant commodity, igloss 2.6 weight %, be super-stable Y molecular sieves, lattice constant 2.452 nanometers, mix down together), add 5.22 kilograms of deionized waters, later on join reactor less than 10 microns with colloidal mill is levigate to particle diameter, again to wherein adding the 2.9 kg aluminium colloidal sols (commerical prod that obtains from Qilu Petrochemical company Zhou village catalyst plant, alumina content is 21 weight %, down together), stir, in the process that stirs, add 3.5 kilograms of pseudo-boehmite (Shandong Aluminum Plant's commerical prods then, alumina content is 60 weight %, down together), stir and add 6.8 kilograms of kaolin (Suzhou kaolin company commerical prods after 15～30 minutes, igloss 29 weight %, down together) and 0.1 kilogram of Secondary ammonium phosphate, stir the hydrochloric acid that adds 0.85 kilogram of 21.5% weight % after 45 minutes, the spraying drying after 30 minutes of pulling an oar, with the product after the spraying drying through 600 ℃ of roastings 20 minutes and catalyzer G.
Slurry solid content before the catalyzer G spraying drying is 45.7 weight %, and viscosity is 3500 centipoises, and gained catalyst abrasion index is 1.5,0.33 milliliter/gram of water droplet method pore volume, and micro-activity is 62 (800 ℃/4 hours aging backs).
Comparative Examples 1
The explanation of this Comparative Examples prepares the effect of catalyzer according to the method for CN1098130A.
The water that adds 21.8 kilograms in the reactor, added 6.8 kilograms of kaolin and stirring to pulp again 90 minutes, add 3.5 kilograms of pseudo-boehmites then, stir the hydrochloric acid that adds 0.64 kilogram of 27.8 weight % after 10 minutes, pull an oar be warming up to after 30 minutes 65 ℃ aging 2 hours, equitemperature is reduced to the adding of back below 50 ℃ 2.9 kg aluminium colloidal sols, pull an oar and add the molecular sieve pulp (molecular sieve pulp is for adding the mixture that 5.22 kilograms of deionized waters are formed by 1.05 kilograms of ZRP-1 molecular sieves and 1.54 kilograms of DASY molecular sieves) that ground through colloidal mill after 25 minutes, the spraying drying after 30 minutes of pulling an oar, with the product after the spraying drying through 600 ℃ of roastings 20 minutes and catalyzer H.
Slurry solid content before the catalyzer H spraying drying is 23 weight %, and viscosity is 17920 centipoises, and gained catalyst abrasion index is 1.9,0.27 milliliter/gram of water droplet method pore volume, and micro-activity is 60 (800 ℃/4 hours aging backs).
Comparative Examples 2
The water that adds 11.6 kilograms in the reactor, add 6.8 kilograms of kaolin making beating 90 minutes again, add 3.5 kilograms of pseudo-boehmites then, stir the hydrochloric acid that adds 0.64 kilogram of 27.8 weight % after 10 minutes, pull an oar be warming up to after 30 minutes 65 ℃ aging 2 hours, equitemperature is reduced to the adding of back below 50 ℃ 2.9 kg aluminium colloidal sols, pull an oar and add the molecular sieve pulp (molecular sieve pulp is for adding the mixture that 5.22 kilograms of deionized waters are formed by 1.05 kilograms of ZRP-1 molecular sieves and 1.54 kilograms of DASY molecular sieves) that ground through colloidal mill after 25 minutes, pulled an oar 30 minutes and the slurries of catalyst I, the viscosity of these slurries is 84750 centipoises, can't spraying drying because viscosity is too big.
The slurry solid content of catalyst I is 30 weight %
Embodiment 8
Getting concentration is that 24.8 weight % and ground SRY molecular sieve pulp join in the glue reactor for 14.1 kilograms, under agitation add 3.0 kilograms of pseudo-boehmites, stir after 20 minutes, add 5.7 kg aluminium colloidal sols, restir adds 5.1 kilograms of halloysites (commerical prod that obtains from Chang Ling oil-refining chemical factory catalyst plant after 15 minutes, igloss 32 weight %) and 0.15 kilogram of Secondary ammonium phosphate, stir the hydrochloric acid that adds 0.670 kilogram of 21.5 weight % after 45 minutes, the spraying drying after 30 minutes of pulling an oar, the spraying drying products obtained therefrom washed with water and through air stream drying and catalyzer J.
Slurry solid content before the catalyzer J spraying drying is 35 weight %, and viscosity is 2150 centipoises, and gained catalyst abrasion index is 1.3,0.39 milliliter/gram of water droplet method pore volume, and micro-activity is 70 (800 ℃/4 hours aging backs).
Embodiment 9
Add concentration in the reactor and be 24.8 weight % and ground 14.1 kilograms of SRY molecular sieve pulps and 2.9 kg aluminium colloidal sols, under agitation to wherein adding 4.0 kilograms of pseudo-boehmites and 0.09 kilogram of primary ammonium phosphate, stir after 20 minutes, the hydrochloric acid that adds 1.01 kilogram of 21.5 weight %, restir adds 4.9 kilograms of kaolin after 20 minutes, restir adds 1.2 kilograms of silicon sol (Changhong chemical plant, Beijing commerical prod, SiO after 45 minutes
2Content is 25 weight %), the back spraying drying that stirs, the spraying drying products obtained therefrom washed with water and through air stream drying and catalyzer K.
Slurry solid content before the catalyzer K spraying drying is 37 weight %, and viscosity is 7530 centipoises, and gained catalyst abrasion index is 1.9,0.36 milliliter/gram of water droplet method pore volume, and micro-activity is 71 (800 ℃/4 hours aging backs).
Embodiment 10
Add the 7.1 kg aluminium colloidal sols (commerical prod that obtains from Chang Ling oil-refining chemical factory catalyst plant in the reactor, alumina content is 21 heavy %) and 3.2 kg water, when stirring, add 2.5 kilograms of pseudo-boehmite (Shandong Aluminum Plant's commerical prods, alumina content is 60 heavy %), pull an oar and add 4.7 kilograms of kaolin (Suzhou kaolin company commerical prods after 20 minutes, igloss 29 weighs %) and 0.12 kilogram of Secondary ammonium phosphate, 0.55 kilogram of concentration of adding was 22% hydrochloric acid after restir was pulled an oar 45 minutes, after pulling an oar again 30 minutes, add used colloidal mill levigate to particle diameter less than 10 microns, by 0.158 kilogram of ZRP-5 molecular sieve (Chang Ling oil-refining chemical factory catalyst plant commodity, igloss 5.1 heavy %, molecular sieve for the ZSM-5 structure type), 1.80 kilogram SRY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant commodity, igloss 2.6 heavy %, be super-stable Y molecular sieves, unit cell parameters 2.455 nanometers) and 1.79 kilograms of REUSY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant commodity, igloss 2.5 heavy %, be rare earth superstable Y-type molecular sieve, rare earth oxide content is 7 heavy %) and the molecular sieve pulp formed of 6.68 kg water, the spraying drying after 30 minutes of pulling an oar, with the product after the spraying drying through 600 ℃ of roastings 20 minutes and catalyzer L.
Slurry solid content before the catalyzer L spraying drying is 35%, and slurry viscosity is 9500 centipoises; Gained catalyst abrasion index is 1.7, water droplet method pore volume 0.36ml/g, and micro-activity is 75 (800 ℃/4 hours aging backs).
Claims (15)
1. the preparation method of a cracking catalyst, this method comprise molecular sieve pulp, aluminium colloidal sol, pseudo-boehmite, clay and mineral acid making beating mixed and make catalyst slurry, then spraying drying; It is characterized in that molecular sieve and/or aluminium colloidal sol added before clay and mineral acid, mineral acid adds after aluminium colloidal sol, and the addition sequence of rest materials has no particular limits, and contains a kind of viscosity depressant in the said catalyst slurry; Wherein said viscosity depressant is ammonium phosphate, Secondary ammonium phosphate or primary ammonium phosphate, or their mixture, and the add-on of viscosity depressant is 0.1～2% of a catalyzer butt weight; Al in said mineral acid and the pseudo-boehmite
2O
3Weight ratio be 0.02～0.25; The solid content of said catalyst slurry is 30～55 weight %.
2. according to the preparation method of claim 1, it is characterized in that mineral acid adds after aluminium colloidal sol and pseudo-boehmite.
3. according to the preparation method of claim 1, it is characterized in that this method comprises earlier molecular sieve pulp, aluminium colloidal sol and pseudo-boehmite being mixed in any order and pulling an oar to mix; And then mix to wherein adding clay, mineral acid and viscosity depressant and pulling an oar in any order; Then with gained catalyst slurry spraying drying.
4. according to the preparation method of claim 1, the content of molecular sieve, aluminium colloidal sol, pseudo-boehmite, clay in the wherein said catalyst slurry (all by butt weight) is respectively molecular sieve 10～50%, clay 15～70%, and pseudo-boehmite and aluminium colloidal sol (are pressed Al
2O
3Meter) 10～35%; The Al of pseudo-boehmite and aluminium colloidal sol wherein
2O
3The ratio of weight is (6: 1)～(1: 10).
5. according to claim 1,2,3 or 4 preparation method, also contain one or more oxide compounds that are selected from rare earth oxide, silicon oxide, magnesium oxide, titanium oxide, phosphorus oxide, aluminum oxide-silicon oxide or its precursor of 0～10 weight % in the wherein said slurries.
6. according to the preparation method of claim 5, also contain rare earth oxide or silicon oxide or their precursor of 0～10 weight % in the wherein said slurries.
7. according to the preparation method of claim 1, wherein said molecular sieve is the mixture of one of y-type zeolite or y-type zeolite and ZSM-5 zeolite, Omega zeolite, β zeolite.
8. according to the preparation method of claim 7, wherein said molecular sieve is the mixture of y-type zeolite or y-type zeolite and ZSM-5 zeolite.
9. according to the preparation method of claim 1, wherein said clay is kaolin, halloysite, sepiolite, tired soil, polynite or their mixture of taking off.
10. according to the preparation method of claim 9, wherein said clay is kaolin, halloysite, sepiolite or their mixture.
11. according to the preparation method of claim 10, wherein said clay is a kaolin.
12. according to the preparation method of claim 1, wherein said pseudo-boehmite replaces with boehmite, gibbsite, bayerite or η-aluminum oxide.
13. according to the preparation method of claim 1, wherein said mineral acid is hydrochloric acid or sulfuric acid.
14. according to the preparation method of claim 13, wherein said mineral acid is a hydrochloric acid.
15. according to the preparation method of claim 1, wherein the concentration of said molecular sieve pulp is 250～550 grams per liters.
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|---|---|---|---|
| CN 99103577 CN1119390C (en) | 1999-04-09 | 1999-04-09 | Process for preparing cracking catalyst of petroleum hydrocarbons |
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| CN 99103577 CN1119390C (en) | 1999-04-09 | 1999-04-09 | Process for preparing cracking catalyst of petroleum hydrocarbons |
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| CN105050715B (en) * | 2013-03-22 | 2017-08-08 | 克斯莫石油株式会社 | The manufacture method of the catalytic cracking catalyst of hydrocarbon ils |
| CN103861636A (en) * | 2014-03-07 | 2014-06-18 | 北京化工大学 | Heavy oil catalytic cracking catalyst for enhancing diesel oil yield and preparation method of catalyst |
| CN109304205A (en) * | 2017-07-28 | 2019-02-05 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst for improving coke selectivity and preparation method thereof |
| CN109304212A (en) * | 2017-07-28 | 2019-02-05 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN109304212B (en) * | 2017-07-28 | 2021-09-28 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN109304205B (en) * | 2017-07-28 | 2021-11-02 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst for improving coke selectivity and preparation method thereof |
| CN116408130A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method and application thereof |
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