CN100496711C - Cracking catalyst and its preparing process - Google Patents
Cracking catalyst and its preparing process Download PDFInfo
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- CN100496711C CN100496711C CNB2006101125813A CN200610112581A CN100496711C CN 100496711 C CN100496711 C CN 100496711C CN B2006101125813 A CNB2006101125813 A CN B2006101125813A CN 200610112581 A CN200610112581 A CN 200610112581A CN 100496711 C CN100496711 C CN 100496711C
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Abstract
The invention discloses a cracking catalyst and making method, which comprises the following parts: 15wt%-50wt% clay, 1wt%-40wt% SiO2 from silicasol, 5wt%-30wt% Al2O3 from aluminium oxide and/or aluminium oxide predecessor, 5wt%-50wt% molecular sieve. The making method comprises the following steps: A. blending and beating the clay and silicasol; B. mixing and beating the slurry in the step A and aluminium oxide and/or aluminium oxide predecessor and molecular sieve; C. spraying and drying the slurry in the step B; washing; drying again; obtaining the product. The preparing course of the catalyst doesn't need surface activator, which improves the selection of heavy-oil catalyzed cracking petroleum.
Description
Technical field
The invention relates to a kind of Cracking catalyst and preparation method thereof.
Background technology
The continuous heaviness of catalytically cracked material and growing to the high-knock rating gasoline demand need the catalyst for cracking heavy oil that coke selectivity is low, gasoline selective is high.Generally speaking, with respect to the Cracking catalyst with aluminium base adhesive preparation, the Cracking catalyst coke yield that contains silica sol binder is low, the gasoline selective height.
1973, U.S. Grace company has proposed to contain the preparation method of the catalytic cracking catalyst of Ludox first in U.S. Pat 3867308, this method sulfuric acid is that the acidulant preparation contains the sodium Ludox, and use the Ludox of being produced to prepare catalytic cracking catalyst, this catalyst wear resistance is good, and is active high.In the U.S. Pat 3957689 the said firm to propose to adopt acidifying aluminum sulfate again be that acidulant preparation contains the sodium Ludox, the stability of Ludox is improved.But above-mentioned patent is not all mentioned and add activated alumina in catalyst, thereby prepared catalyst substrates activity is low, and heavy oil cracking ability is poor.
U.S. Pat 4946814 discloses the method for improving the catalytic cracking catalyst anti-wear performance that contains silica sol binder with surfactant, spray-drying prepares catalyst to adopt Ludox, kaolin oar liquid, molecular sieve pulp and four bursts of logistics of activated alumina slurries to mix then continuously, it is binding agent that this method only adopts Ludox, and must add expensive surfactant to guarantee the anti-wear performance of catalyst.
The 1980s, Chang Ling oil-refining chemical head factory is cooperated with Beijing Research Institute of Petro-Chemical Engineering, developed the catalyst for cracking heavy oil (trade names CHZ-1) that contains silica sol binder, in lab scale and Commercial application show that the coke selectivity of this agent is good, heavy oil conversion performance and anti-metal ability are strong.But this agent preparation condition harshness, production cycle are long, and very easily gelling of Ludox, cause the catalyst slurry poor stability, and the resting period is short, unstable product quality.
Chinese patent CN1552801A has announced a kind of catalytic cracking catalyst that contains silica sol binder and preparation method thereof, its preparation method is that Ludox, kaolin, boehmite and molecular sieve are made 2,3 or 4 bursts of logistics respectively, proportion of composing according to catalyst, each burst logistics is mixed, spray-dried, the washing, drying and other steps promptly gets catalyst again.In this method for preparing catalyst, two plume hybrid modes are: Ludox is a plume, and clay, boehmite and molecular sieve pulp are another plume; Three plume hybrid modes are: Ludox, molecular sieve respectively are a plume, the mixed serum of clay and boehmite is a plume, or Ludox, clay respectively are a plume, the mixed serum of boehmite and molecular sieve is a plume, or Ludox, boehmite slurries respectively be a plume, and the mixed serum of clay and molecular sieve is a plume; Four plume hybrid modes are: Ludox, molecular sieve pulp, clay slurry and boehmite slurries respectively are a plume.The big molecule cracking of the catalyst ability of this method preparation is strong, and anti-wear performance is good, but will use surfactant in the Preparation of catalysts, and gasoline selective needs further to improve.
Proposed to adopt the compound binding agent matrix that contains aluminium colloidal sol and boehmite composition to prepare catalytic cracking catalyst among the Chinese patent CN1098130A, the composite aluminum base binding agent that adopts aluminium colloidal sol and peptization boehmite to combine can integrate the peptization boehmite the characteristics of certain cracking activity and the advantage that the sol bonded performance of aluminium is good, the product coke is few, improved the selectivity of wearability, activity, gasoline yield and the STRENGTH ON COKE of catalyst, but the gasoline selective of catalyst and coke selectivity need still to improve.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, and high hydrocarbon cracking catalyzer of a kind of gasoline selective that contains Ludox newly and preparation method thereof is provided.
The invention provides a kind of preparation method of Cracking catalyst, may further comprise the steps:
A. clay is mixed making beating with Ludox;
B. steps A gained slurries and aluminium oxide and/or alumina precursor and molecular sieve are mixed making beating;
C. with step B gained slurries spray-drying, washing, drying obtains Cracking catalyst again;
Wherein the consumption of each component makes the clay that contains in the catalyst in butt 15 weight %～50 weight %, the SiO that is derived from Ludox of 1 weight %～40 weight %
2, the Al that is derived from aluminium oxide and/or alumina precursor of 5 weight %～30 weight %
2O
3, in the molecular sieve of butt 5 weight %～50 weight %.
The Cracking catalyst of the inventive method preparation, coke selectivity is low, and the gasoline selective height in the preparation process, does not need to add dispersant.For example the inventive method preparation contains SiO
219.8 weight %, kaolin 29.6 weight %, Al
2O
316.1 the catalyst of weight %, molecular sieve 34.6 weight %, with the miscella of vacuum gas oil (VGO) and reduced crude in the small fixed flowing bed evaluating apparatus, than being to react under 4 the condition, gasoline selective is 73.1 at 500 ℃, agent weight of oil, and coke selectivity is 7.5.And according to the catalyst of the same composition content of the method for CN1552801A preparation, under similarity condition, estimate, gasoline selective is 71.8, coke selectivity is 7.7.
The specific embodiment
In the Preparation of catalysts method of the present invention, clay is mixed making beating with Ludox, form uniform clay-Ludox slurries, the mode and the condition of making beating are well known to those skilled in the art, and preferably clay are mixed back making beating 10 minutes～300 minutes with Ludox.Described Ludox can be commercial or by prepared in various methods, for example, and by U.S. Pat 3957689, the described method preparation of US3867308.
Described clay is selected from as in the clay of Cracking catalyst component one or more, for example one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite.These clays are that those of ordinary skills are known.
The slurries that the making beating of clay and Ludox is formed of the present invention and aluminium oxide and/or alumina precursor and molecular sieve mix making beating, can pull an oar by any way mixing.Aluminium oxide and/or alumina precursor and the molecular sieve form with solid can be joined in clay-Ludox slurries, or aluminium oxide and/or alumina precursor and a kind of form with slurries of molecular sieve are added another form with solid add, then mixture is pulled an oar; Join in Ludox-clay slurry again after also molecular sieve and aluminium oxide and/or alumina precursor can being prepared into one or two strands of slurries, described one slurries that are prepared into are meant aluminium oxide and/or alumina precursor are mixed the resulting slurries of making beating with molecular sieves and water, described two strands of slurries are meant that molecular sieve is mixed making beating with water be prepared into one slurries, aluminium oxide and/or alumina precursor are mixed to pull an oar being prepared into one slurries with water.No matter take which kind of form to mix making beating, each component is mixed described mixture making beating after the mixing.Described aluminium oxide and/or alumina precursor slurries and molecular sieve pulp or slurries salic and/or alumina precursor and molecular sieve can be by existing method preparations, for example method preparation that provides according to CN1552801A.Mix making beating with clay-Ludox slurries again after preferably aluminium oxide and/or alumina precursor and molecular sieve being prepared into two strands of slurries.Clay-Ludox slurries are mixed making beating with molecular sieve pulp, aluminium oxide and/or alumina precursor slurries, both can adopt intermittent mode also can adopt the multiply logistics to become the mode of glue continuously.The precedence that various slurries mix does not require, for example, can with molecular sieve pulp with mix making beating with clay-Ludox slurries again after aluminium oxide and/or alumina precursor slurries mix, also can with molecular sieve pulp and aluminium oxide and/or alumina precursor slurries each as one logistics simultaneously or successively mix making beating with clay-Ludox slurries.
Aluminium oxide of the present invention or alumina precursor are selected from the Cracking catalyst usually aluminium oxide or in the alumina precursor one or more of employed various forms.For example, aluminium oxide is selected from one or more in gama-alumina, η-aluminium oxide, θ-aluminium oxide, the χ-aluminium oxide, preferred gama-alumina; Alumina precursor is selected from one or more in the hydrated alumina of (Pseudoboemite) structure that has boehmite, a diaspore (Boehmite) structure, gibbsite (Gibbsite) structure or bayerite (Bayerite) structure, is preferably the hydrated alumina that has structure of similar to thin diaspore and/or have the gibbsite structure.
Molecular screening of the present invention is from as the zeolite of active component of cracking catalyst and in the non-zeolite molecular sieve one or more.Described zeolite is preferably one or more in large pore zeolite and the mesopore zeolite.Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, as in faujasite, L zeolite, Beta zeolite, omega zeolite, modenite, the ZSM-18 zeolite one or more, the particularly overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, in the Beta zeolite one or more.Described mesopore zeolite is to have greater than the zeolite of 0.56 nanometer less than the cavernous structure of 0.7 nano-rings opening, for example has in the zeolite with MFI structure (the disclosed phosphorous zeolite with MFI structure of ZSM-5 zeolite, CN1194181A for example phosphorous and/or rare earth), ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, MCM-56 zeolite of the zeolite (for example ZSM-5 zeolite) of MFI structure, phosphorous and/or rare earth one or more.Described non-zeolite molecular sieve refers to that aluminium in the zeolite and/or silicon are partly or entirely by other element such as phosphorus, titanium, gallium, the molecular sieve of one or more replacements in the germanium comprises silicate with Different Silicon aluminum ratio (metal silicate metallosilicate for example, titan silicate titanosilicate), metal aluminate metalloaluminates (for example germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphate metalloaluminophosphates, the silicoaluminophosphate metal integratedsilicoaluminophosphates (MeAPSO) of metal combination, silicoaluminophosphate silicoaluminophosphates (SAPO), in the gallium germanate (gallogermanates) one or more.Preferred non-zeolite molecular sieve is one or more in SAPO-17 molecular sieve, SAPO-34 molecular sieve and the SAPO-37 molecular sieve.
Molecular sieve of the present invention is one or more in the zeolite with MFI structure of overstable gamma zeolite, Beta zeolite, the zeolite with MFI structure, the phosphorous and/or rare earth of y-type zeolite, overstable gamma zeolite, the phosphorous and/or rare earth of y-type zeolite, phosphorous and/or rare earth more preferably.
Under the preferable case, with described aluminium oxide and/or alumina precursor with before clay-Ludox slurries mix, also comprise step with described aluminium oxide and alumina precursor usefulness peptizing agent peptization, described peptization is a prior art, comprises peptizing agent is mixed making beating with the slurries of salic and/or alumina precursor.Form aluminium oxide and/or alumina precursor slurries if aluminium oxide and/or alumina precursor are pulled an oar separately, in aluminium oxide and/or alumina precursor slurries, add the peptizing agent peptization; If prepare slurries salic and/or alumina precursor and molecular sieve, then in preparation process, aluminium oxide and/or alumina precursor making beating back add the peptizing agent peptization.Described peptizing agent is one or more of acid, one or more of hydrochloric acid, nitric acid, formic acid, acetate, phosphoric acid for example, and preferable formic acid or hydrochloric acid, the consumption of peptizing agent makes acid and Al
2O
3Mol ratio be no more than 0.35, peptization time 10 minutes～5 hours; Better for the performance that makes catalyst, the consumption of preferred peptizing agent makes aluminium oxide and/or the complete peptization of alumina precursor, acid and Al
2O
3Mol ratio be 0.15～0.35, more preferably 0.18～0.24.
The method of the invention, preferably the consumption of each component makes the clay that contains in the catalyst in butt 20 weight %～35 weight %, the SiO that is derived from Ludox of 5 weight %～15 weight %
2, the Al that is derived from aluminium oxide and/or alumina precursor of 10 weight %～25 weight %
2O
3, in the molecular sieve of butt 25 weight %～40 weight %.
Rare earth metal, aluminium, alkaline-earth metal, titanium, phosphorus, zirconium, manganese are known in the art and are usually used in the adjuvant component of catalytic cracking catalyst, when described catalyst contains above component, according to method provided by the invention, also comprise the step of introducing described adjuvant component, weight with catalyst is benchmark, in oxide, described introducing makes the content of adjuvant component be no more than 5% weight (not comprising the component of the same race that molecular sieve is brought into).Described adjuvant component before spray-drying any preparation process or after spray-drying by the exchange or the deposition mode introduce.For example, when described adjuvant component is introduced before spray-drying, described adjuvant component can be joined in clay-Ludox slurries, and then mix with molecular sieve, aluminium oxide and/or alumina precursor; If aluminium oxide and/or alumina precursor and molecular sieve are prepared into one or two strands of slurries, described auxiliary agent can be in the aluminium oxide slurries, introduce in the molecular sieve pulp or in the slurries of salic and molecular sieve; Also can in the slurries of clay-Ludox, aluminium oxide and/or alumina precursor and molecular sieve mixing making beating formation, introduce adjuvant component.Preferred described adjuvant component is introduced by the method for exchange or deposition.The method of exchange or deposition aid component is existing method.The metal promoter of introducing can stem from one or more in the oxide, hydroxide, nitrate, chloride, phosphate of metal; The non-metal assistant component of being introduced can be derived from one or more in its oxide, oxyacid or the oxysalt, and for example phosphorus can be derived from one or more of phosphoric acid or phosphate, acid phosphate.Described adjuvant component is preferably rare earth metal.
The spray-drying condition of catalyst slurry is conventionally known to one of skill in the art in the inventive method, and the dryer export temperature of preferably spray drying is 100 ℃～700 ℃, more preferably 100 ℃～300 ℃.
The purpose of catalyst detergent is to make the content of sodium oxide molybdena in the final catalyst and other impurity be lower than the content value of permission in the inventive method, for example makes sodium oxide content be not more than 0.3 weight %.The method of washing is existing Cracking catalyst washing methods, for example according to US3867308 or the disclosed method washing of CN1552801A.
Drying of the present invention is any existing method, for example pneumatic conveying drying, dry, dry.Preferred dry temperature is a room temperature to 400 ℃, more preferably 100 ℃～350 ℃.
Catalyst of the present invention can be used as the hydrocarbon oil catalytic cracking catalyst, described hydrocarbon ils is selected from crude oil or its various distillates, for example reduced crude, decompression residuum, vacuum gas oil (VGO), AGO (atmospheric gas oil), straight run gas oil, propane is light/in heavy deasphalted oil and the coker gas oil one or more.
The following examples will the invention will be further described.
The abrasion index of catalyst is to measure according to the RIPP29-90 standard method in " petrochemical industry analytical method (RIPP test method) " (nineteen ninety publishes for volume such as Yang Cuiding, Science Press) in example and the Comparative Examples.
Gasoline selective method for expressing: the conversion ratio of the productive rate/feedstock oil of gasoline * 100.
Coke selectivity method for expressing: the conversion ratio of the productive rate/feedstock oil of coke * 100.
Embodiment 1
The explanation of this example prepares catalytic cracking catalyst according to method provided by the invention.
Ludox preparation: water glass solution and 1 liter of free acid that to prepare 2 liters of silica concentrations be 155g/l are 148g/l, Al
2O
3Content is the acidified aluminum sulfate solution of 20g/l, and above-mentioned two kinds of solution enter the flash mixer reaction simultaneously.
The preparation of kaolin-Ludox slurries: add 465 gram kaolin (Suzhou kaolin company product, solid content 80 weight %) in the Ludox of above-mentioned preparation, pulling an oar obtained kaolin-Ludox slurries in 1 hour.
The preparation of the mixed serum of boehmite and molecular sieve: contain Al
2O
3(Shandong Aluminum Plant produces the boehmite of 124 grams, Al
2O
3Content 33 weight %) and 450 gram deionized waters mix making beating 30 minutes, adding 25 ml concns then is hydrochloric acid (acid/Al of 31 weight %
2O
3Mol ratio is 0.20) peptization, continue making beating 2 hours, adding 1360 gram molecules sieve content then is that (the industrial trade mark of molecular sieve is DASY2.0 to the ground molecular sieve pulp of 32 weight %, the Shandong catalyst plant is produced, lattice constant is 24.45 dusts, the ultra-steady Y molecular sieve that contains rare earth, mixed rare-earth oxide content is 2.0 weight %, wherein, lanthana content is 0.7 weight %, and cerium oxide content is 1.1 weight %, and other rare earth oxide content is 0.2 weight %), pulled an oar 30 minutes, and obtained the mixed serum of boehmite and molecular sieve.
Preparation of catalysts: the kaolin-Ludox slurries of above-mentioned preparation are mixed making beating 10 minutes with the boehmite of above-mentioned preparation and the mixed serum of molecular sieve, obtain catalyst slurry, under 180 ℃ dryer export temperature with the slurries spray drying forming that obtains, obtaining diameter is 20～120 microns, silica content is 24.6 weight %, kaolin content is 29.5 weight %, alumina content is 11.4 weight %, molecular sieve content is the solid particle of 34.5 weight %, spending deionised water is not detected to there being sodium ion, filtering back adding 6L content is the earth solution exchanged rare earth of 0.5 weight %, filter back 150 ℃ of oven dry, obtain catalyst C1.Testing its abrasion index is 0.7.
Embodiment 2
The explanation of this example prepares catalytic cracking catalyst according to method provided by the invention.
The Ludox preparation is with example 1.
The preparation of kaolin and Ludox slurries: add 580 gram kaolin (with example 1) in the Ludox of above-mentioned preparation, pulling an oar obtained kaolin-Ludox slurries in 1 hour.
The preparation of the mixed serum of boehmite and molecular sieve: contain Al
2O
3The boehmite (with example 1) of 233 grams and 845 gram deionized waters mix making beating 30 minutes, and adding 47 ml concns then is 31 weight % hydrochloric acid (acid/Al
2O
3Mol ratio is 0.20) peptization, continue making beating 2 hours, adding the ground molecular sieve content of 1695 grams then is that (the industrial trade mark of molecular sieve is DASY0.0 for the molecular sieve pulp of 32 weight %, the Shandong catalyst plant is produced, lattice constant is 24.45 dusts, ultra-steady Y molecular sieve), pulled an oar 30 minutes, obtain the mixed serum of boehmite and molecular sieve.
Preparation of catalysts: the kaolin-Ludox slurries of above-mentioned preparation are mixed making beating 10 minutes with the boehmite of above-mentioned preparation and the mixed serum of molecular sieve, obtain catalyst slurry, under 180 ℃ temperature with the slurries spray drying forming that obtains, obtaining diameter is 20～120 microns, silica content is 19.7 weight %, kaolin content is 29.6 weight %, alumina content is 16.1 weight %, molecular sieve content is the solid particle of 34.6 weight %, spending deionised water is not detected to there being sodium ion, filtering back adding 7.5L content is the earth solution deposition of rare-earth of 0.5 weight %, filter back 150 ℃ of oven dry, obtain catalyst C2.Testing its abrasion index is 1.5.
Embodiment 3
The explanation of this example prepares catalytic cracking catalyst according to method provided by the invention.
The Ludox preparation is with example 1.
The preparation of kaolin and Ludox slurries: add 900 gram kaolin (with example 1) in the Ludox of above-mentioned preparation, pulling an oar obtained kaolin-Ludox slurries in 1 hour.
Boehmite slurry preparation: get and contain Al
2O
3The boehmite (with example 1) of 413 grams and 1640 gram deionized waters mix making beating 30 minutes, and adding 83 ml concns then is hydrochloric acid (acid/Al of 31 weight %
2O
3Mol ratio is 0.20) peptization, continue making beating 2 hours, obtain the boehmite slurries.
Molecular sieve pulp preparation: get molecular sieve (the Shandong catalyst plant product that the industrial trade mark of butt 620 grams is DASY6.0, lattice constant is 24.55 dusts, the ultra-steady Y molecular sieve that contains rare earth, mixed rare-earth oxide content is 6.0 weight %, wherein, lanthana content is 2.2 weight %, and cerium oxide content is 3.4 weight %, other rare earth oxide content is 0.4 weight %), add 1320 gram deionized water making beating 1 hour.Obtain molecular sieve pulp.
Preparation of catalysts: with the kaolin-Ludox slurries of above-mentioned preparation, boehmite slurries and molecular sieve pulp mix making beating 15 minutes, obtain catalyst slurry, under 180 ℃ temperature with the slurries spray drying forming that obtains, obtaining diameter is 20～120 microns, silica content is 14.9 weight %, kaolin content is 34.6 weight %, alumina content is 20.8 weight %, molecular sieve content is the solid particle of 29.8 weight %, spending deionised water is not detected to there being sodium ion, filtering back adding 10L content is the earth solution exchanged rare earth of 0.5 weight %, filter back 150 ℃ of oven dry, obtain catalyst C3.Testing its abrasion index is 2.0.
Comparative Examples 1
The explanation of this Comparative Examples prepares catalytic cracking catalyst according to the method for CN1552801A.
The Ludox preparation is with example 1.
The preparation of the mixed serum of kaolin, boehmite and molecular sieve: get 580 gram kaolin (with example 1) respectively, contain 24 gram Al
2O
3Aluminium colloidal sol (Shandong catalyst plant produce, alumina content 22 weight %), the ground molecular sieve content of 1695 grams is the molecular sieve pulp (the molecular sieve industry trade mark is DASY0.0, with example 2) of 32 weight %, contains Al
2O
3The boehmite (with example 1) of 233 grams and deionized water mix making beating 2 hours, and adding 26 ml concns then is hydrochloric acid (acid/Al of 31 weight %
2O
3Weight ratio is 0.04) peptization, it is standby after 30 minutes to continue making beating, and the solid content of mixed serum is 42 weight %.
Preparation of catalysts: in the mixing kettle that stirs fast with the Ludox of above-mentioned preparation and above the kaolin for preparing, the mixed serum of boehmite and molecular sieve mixes and obtains the catalyst precursor slurries, then under 180 ℃ temperature with the slurries spray drying forming that obtains, obtaining diameter is 20～120 microns, silica content is 19.5 weight %, kaolin content is 29.1 weight %, alumina content is 17.4 weight %, molecular sieve content is the solid particle of 34.0 weight %, be not detected to there being sodium ion with the washing of sulphur aqueous ammonium, 150 ℃ of oven dry, obtain catalyst D1, testing its abrasion index is 2.5.
Comparative Examples 2
The explanation of this Comparative Examples prepares catalytic cracking catalyst according to the method for CN1098130A.
Get 875 gram kaolin (with example 1), add 3000 gram deionized waters and mix the half an hour of pulling an oar, adding 92 ml concns is the hcl acidifying making beating half an hour of 31 weight %, adds 1210 gram boehmites (with example 1) and stirs half an hour, wore out 2 hours at 55 ± 5 ℃, add and contain 200 gram Al
2O
3Aluminium colloidal sol (with Comparative Examples 1) stirred 15 minutes, (the industrial trade mark is DASY2.0 to add the ground molecular sieve of 2190 grams, with example 1) content is the molecular sieve pulp of 32 weight %, continue to stir half an hour, making beating mixes, spray drying forming under 250 ℃ temperature, obtaining diameter and be 20～120 microns, kaolin content is that 35.0 weight %, alumina content are that 30.0 weight %, molecular sieve content are the solid particle of 35.0 weight %, spending deionised water is not detected to there being sodium ion, 150 ℃ of oven dry obtain catalyst D2.Testing its abrasion index is 2.2.
Embodiment 4～6
This example illustrates the performance of catalyst provided by the invention.
With the catalyst C1～C3 of example 1～3 preparation at 800 ℃, with aging 8 hours of 100% steam, the small fixed flowing bed device of packing into (the ACE Model R of U.S. KTI company production
+Micro-reactor) in the reactor, the catalyst loading amount is 10 grams, is 500 ℃ in reaction temperature, and agent weight of oil ratio is 4.0, condition under, feed the miscella of vacuum gas oil (VGO) shown in the table 1 and reduced crude, this miscella is carried out catalytic cracking, the result is as shown in table 2.
Comparative Examples 3～4
The catalytic performance of the catalyst of this Comparative Examples explanation reference method preparation.
Method according to example 4 is carried out catalytic cracking to same feedstock oil under similarity condition, different is that catalyst system therefor is catalyst D1, the D2 of Comparative Examples 1～2 preparation.The result is as shown in table 2.
Table 1
Table 2
| Example number | 4 | 5 | 6 | Comparative Examples 3 | Comparative Examples 4 |
| Catalyst | C1 | C2 | C3 | D1 | D2 |
| Conversion ratio, weight % | 69.0 | 76.4 | 70.0 | 71.9 | 70.5 |
| Gasoline selective | 74.1 | 73.1 | 72.8 | 71.8 | 71.9 |
| Coke selectivity | 7.4 | 7.5 | 7.6 | 7.7 | 7.8 |
From the result of table 2 as can be seen, compare with D2 with the reference catalyst D1 that adopts existing method preparation, catalyst C1 provided by the invention, C2, C3 obviously improve the selectivity of gasoline, coke selectivity descends, C1 is bigger to the selectivity increase rate of gasoline, and the selectivity of STRENGTH ON COKE descends more.
Claims (11)
1, a kind of preparation method of Cracking catalyst may further comprise the steps:
A. clay is mixed making beating with Ludox;
B. with steps A gained slurries, aluminium oxide and/or alumina precursor, molecular sieve and water mix the slurries that making beating forms, and mix making beating;
C. with step B gained slurries spray-drying, washing, drying obtains Cracking catalyst again;
Wherein the consumption of each component makes the clay that contains in the catalyst in butt 15 weight %～50 weight %, the SiO that is derived from Ludox of 1 weight %～40 weight %
2, the Al that is derived from aluminium oxide and/or alumina precursor of 5 weight %～30 weight %
2O
3, in the molecular sieve of butt 5 weight %～50 weight %.
2, method according to claim 1, it is characterized in that, aluminium oxide in the slurries that described aluminium oxide and/or alumina precursor, molecular sieve and water making beating form and/or alumina precursor are also through the peptizing agent peptization, and described peptizing agent is one or more of acid, acid and Al
2O
3Mol ratio be no more than 0.35, peptization time 10 minutes～5 hours.
3, method according to claim 2 is characterized in that, acid and Al
2O
3Mol ratio be 0.15～0.35.
4, method according to claim 3 is characterized in that, acid and Al
2O
3Mol ratio be 0.18～0.24.
5, method according to claim 1 is characterized in that, described clay is selected from one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite.
6, method according to claim 1 is characterized in that, described alumina precursor be selected from have structure of similar to thin diaspore, in the hydrated alumina of a diaspore structure, gibbsite structure or bayerite structure one or more; Described aluminium oxide is selected from one or more in gama-alumina, η-aluminium oxide, θ-aluminium oxide, the x-aluminium oxide.
7, method according to claim 1, it is characterized in that described molecular screening one or more in the zeolite with MFI structure of overstable gamma zeolite, the Beta zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, zeolite, phosphorous and/or rare earth with MFI structure.
8, method according to claim 1 is characterized in that, the consumption of each component makes the clay that contains in the catalyst in butt 20 weight %～35 weight %, the SiO that is derived from Ludox of 5 weight %～15 weight %
2, the Al that is derived from aluminium oxide and/or alumina precursor of 10 weight %～25 weight %
2O
3, in the molecular sieve of butt 25 weight %～40 weight %.
9, method according to claim 1, it is characterized in that, also comprise the step of introducing adjuvant component, described adjuvant component is selected from one or more of rare earth metal, aluminium, alkaline-earth metal, titanium, phosphorus, zirconium, manganese, weight with catalyst is benchmark, in oxide, described introducing makes the content of adjuvant component be no more than 5% weight.
10, method according to claim 1 is characterized in that, described adjuvant component is a rare earth metal.
11, a kind of catalytic cracking catalyst is characterized in that, this catalyst is by any described method preparation of claim 1～10.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101125813A CN100496711C (en) | 2006-08-24 | 2006-08-24 | Cracking catalyst and its preparing process |
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| CN101745416B (en) * | 2008-11-28 | 2012-07-18 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN101767028B (en) * | 2008-12-31 | 2012-02-22 | 中国石油化工股份有限公司 | Preparation method of fluid catalytic cracking catalyst |
| CN101767029B (en) * | 2008-12-31 | 2012-06-27 | 中国石油化工股份有限公司 | Heavy oil cracking catalyst and application thereof |
| CN101773845B (en) * | 2009-01-08 | 2012-08-01 | 中国石油化工股份有限公司 | Heavy-oil cracking catalyst and preparation and application method thereof |
| CN102430422B (en) * | 2010-09-29 | 2013-07-31 | 中国石油化工股份有限公司 | Catalytic cracking catalyst for producing low-carbon olefin and application thereof |
| CN103182304B (en) * | 2011-12-29 | 2015-01-14 | 中国石油化工股份有限公司 | Catalyst with cracking and gasification effects and its preparation method |
| CN103623858A (en) * | 2012-08-21 | 2014-03-12 | 湖北赛因化工有限公司 | Catalytic cracking catalyst and preparation method |
| CN107376986A (en) * | 2017-08-02 | 2017-11-24 | 上海润琦化工科技有限公司 | A kind of bottom of towe oil catalytic cracking cracking auxiliary agent and preparation method thereof |
| CN109718831B (en) * | 2017-10-31 | 2022-12-13 | 中国石油化工股份有限公司 | Process for preparing cracking catalyst and cracking catalyst |
| CN109718832A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | Prepare the method and Cracking catalyst of Cracking catalyst |
| CN112237909B (en) * | 2019-07-18 | 2022-09-27 | 中国石油化工股份有限公司 | Modified alumina and preparation method and application thereof |
| CN112808299B (en) * | 2019-11-18 | 2022-05-03 | 中国石油化工股份有限公司 | Solid acid alkylation catalyst and preparation method thereof |
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