CN103041840A - Macroporous fluid catalytic cracking catalysts and preparation method thereof - Google Patents
Macroporous fluid catalytic cracking catalysts and preparation method thereof Download PDFInfo
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- CN103041840A CN103041840A CN2012105688409A CN201210568840A CN103041840A CN 103041840 A CN103041840 A CN 103041840A CN 2012105688409 A CN2012105688409 A CN 2012105688409A CN 201210568840 A CN201210568840 A CN 201210568840A CN 103041840 A CN103041840 A CN 103041840A
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Abstract
The invention provides a macroporous fluid catalytic cracking catalyst which is synthesized by an ionic liquid and halloysite, and a preparation method thereof. The method comprises the following steps: mixing the ionic liquid, the halloysite, a catalytic agent and a molecular sieve; aging, forming and drying the mixture; and removing the ionic liquid, wherein the ionic liquid is used for controlling the assembly of the halloysite, the catalytic agent base material and the molecular sieve. The synthetic catalyst is high in cracking activity and good in gasoline/diesel oil selectivity, and is particularly suitable for being used as a heavy-oil catalytic cracking catalyst.
Description
Technical field
The present invention relates to the preparation of catalyst and catalyst, a kind of macropore fluidized catalytic cracking catalyst and preparation method thereof particularly, this catalyst is applicable to contain the catalyzed cracking processing of heavy distillate raw material.Specifically about a kind of assembling of using ionic liquid control galapectite, catalyst substrates and molecular sieve, the synthetic eurypyloue fluidized catalytic cracking catalyst of tool.
Background technology
Along with to the continuous growth of light-end products demand and the raising of feedstock oil price, catalytic cracking proportion in light materialization of heavy oil is increasing.Conventional catalyst Cracking catalyst aperture is less, reacts so that the macromolecular components in the heavy oil is difficult to enter the catalyst cavity inside, brings difficulty for the transmission of raw material and product molecule because large (〉 2.5 nm of the kinetic diameter of residual oil molecule).Therefore, increase the aperture of Cracking catalyst, not only be beneficial to the heavy oil solid tumor and enter the catalyst duct, also help product and diffuse out in time catalyst, reduce the formation of secondary cracking and coke, improve selectivity of product, significantly improve the cracking effect.The granular formworks such as CN100469447 patented technology employing polystyrene are macropore catalytic cracking catalyst synthesized, and macropore diameter is adjustable in the catalyst, has cracking activity height, good selective.But the granular formworks such as these organic polymers or carbon belong to a kind of pure mechanical mixture in catalyst preparation process, have that active force is strong, skewness, cause the shortcoming such as catalyst strength reduction after removing template.
Has the galapectite bore approximate range of tubular structure at 2 ~ 1000 nm, this natural large pore material chemical composition is similar to kaolinite, partly or completely replace kaolin to be used for catalyst for heavy oil catalytic cracking, wherein the tubulose duct is conducive to the macromolecular cracking of heavy oil.But in the preparation technology of ready-made catalytic cracking catalyst, the pipeline that catalyst substrates easily stops up galapectite causes its lower cracking activity.And novel ion liquid is as a kind of good organic and inorganic thing solvent, has been widely used in a plurality of fields such as organic, analysis, catalysis.If first ionic liquid is mixed with galapectite, ionic liquid can be effectively with the Adsorption generation bonding of galapectite, in the catalytic cracking catalyst preparation process, can stop catalyst substrates to occupy pipeline and the active sites thereof of galapectite, after high-temperature roasting or solvent are removed ionic liquid, the macroporous structure that has kept galapectite is conducive to the raising of cracking activity.
Summary of the invention
The purpose of this invention is to provide a kind of ionic liquid and synthetic macropore fluidized catalytic cracking catalyst and method thereof of galapectite utilized, macropore in its catalyst is that ionic liquid is with the Adsorption generation bonding of galapectite, effectively stoped binding agent etc. to occupy galapectite duct and active sites thereof, remove by roasting or dissolution with solvents behind shaping of catalyst that ionic liquid forms, this catalyst is significantly increased aspect catalytic activity.
The concrete technical scheme that realizes the object of the invention is:
A kind of macropore fluidized catalytic cracking catalyst, characteristics are: this catalyst is comprised of galapectite, catalyst substrates and molecular sieve, it comprise with ionic liquid, galapectite, catalyst substrates and molecular sieve mix, aging, moulding and drying, then remove the process of ionic liquid wherein, use the assembling of ionic liquid control galapectite, catalyst substrates and molecular sieve, obtain described macropore fluidized catalytic cracking catalyst; Described ionic liquid comprises the mixture of imidazoles, quaternary ammonium salt, pyridines, piperidines ionic liquid and above-mentioned substance; Described galapectite is natural or manually synthesizes galapectite.
(take the catalyst weight as benchmark) composed as follows of described catalyst: galapectite is 2 ~ 40%, and is preferred 4.5 ~ 25%, and catalyst substrates is 88-10 %, preferred 80.5-40 %, and molecular sieve is 10-50 %, preferred 15-35 %.
A kind of preparation method of above-mentioned catalyst, the method comprise following concrete steps:
The first step: ionic liquid, galapectite and water are mixed to get slurries A, and wherein, the ionic liquid consumption accounts for 0.3 ~ 500 % of galapectite weight, and the galapectite consumption accounts for 2 ~ 40 % of catalyst weight;
Second step: after molecular sieve, catalyst substrates and water mixed, drip dilute acid soln and regulate pH value to 2, obtain slurries B, wherein, the molecular sieve consumption accounts for 10 ~ 50 % of catalyst weight, and the catalyst substrates consumption accounts for 88 ~ 10% of catalyst weight, and diluted acid is rare nitric acid, watery hydrochloric acid or dilute sulfuric acid;
The 3rd step: slurries A and slurries B are mixed, sieve behind aging, spray shaping and get 60 ~ 400 purpose particles, 500 ℃ of lower roastings are 2 hours in air atmosphere, use NH
4NO
3Solution carries out after the ion-exchange again in 550 ℃ of roastings, repeats to obtain described macropore fluidized catalytic cracking catalyst after the exchange operations 3 times.
In catalyst preparation process, galapectite is elder generation and ionic liquid generation bonding before adding the synthetic colloidal sol of catalyst, can stop catalyst substrates to occupy pipeline and the active sites thereof of galapectite, after high-temperature roasting or solvent are removed ionic liquid, the macroporous structure that has kept galapectite is conducive to the raising of cracking activity.
In catalyst preparation process, ionic liquid plays protects the macroporous structure of galapectite not occupied.Therefore, the adding of ionic liquid not only makes catalyst produce macropore, has improved macropore volume and large pore specific surface area, and has improved mesopore and micropore specific area, thereby improved cracking activity and improve selective.
Galapectite used in the present invention is selected the galapectite of tubulose macroporous structure, and galapectite bore scope is at 2 ~ 1000 nm, can be natural galapectite or artificial synthetic galapectite.
Catalyst substrates used in the present invention does not have particular determination, but preferably include various amorphous aluminum silicates, aluminium oxide, silica etc., wherein amorphous aluminum silicate, aluminium oxide, silica can be bought from the market, also can with the compound that contains Si, Al, synthesize such as sodium metasilicate, waterglass, aluminum sulfate, aluminum nitrate, sodium metaaluminate, Ludox and aluminium colloidal sol etc.
Ionic liquid used in the present invention is commercially available imidazoles, quaternary ammonium salt, pyridines, the mixture of piperidines ionic liquid and above-mentioned substance, preferred triethyl ammonium villaumite ([HNEt3] [Cl]), triethyl ammonium nitrate ([HNEt3] [NO3]), N-butyl-pyridinium tetrafluoroborate ([BPy] [BF4]), N-ethylpyridine bromine salt ([EPy] [Br]), 1-butyl-3-methylimidazole villaumite ([BMIM] [Cl]), 1-butyl-3-methylimidazole bromine salt ([BMIM] [Br]), 1-butyl-3-methylimidazole acetate ([BMIM] [OAc]), 1-butyl-1-crassitude villaumite ([BMPr] [Cl]), 1-butyl-1-methyl piperidine villaumite ([BMPi] [Cl]), wherein, the ionic liquid consumption accounts for 0.3 ~ 500 % of galapectite weight, preferred 1 ~ 200 %.
Molecular sieve used in the present invention is Y zeolite or the Y zeolite after modification, preferred HY, RE-HY, REY and USY etc., and above-mentioned molecular sieve can be bought from the market, also can be with the compou nd synthesis that contains Si, Al.
Macropore fluidized catalytic cracking catalyst of the present invention can be used for the catalytic cracking reaction of petroleum heavy oil, i.e. boiling point〉350
oThe petroleum distillate of C, for example catalytic cracking of vacuum distillate, wax tailings, reduced crude and decompression residuum.
The present invention adopts ionic liquid to occupy pipeline and the Adsorption of galapectite in preparation process, then has macropore by making in the final catalyst except the deionization special body size.Catalyst and the prior art main distinction synthetic according to the inventive method are, macropore in the catalyst is that ionic liquid is with the Adsorption generation bonding of galapectite, effectively stoped binding agent etc. to occupy galapectite duct and active sites thereof, remove by roasting or dissolution with solvents behind shaping of catalyst that ionic liquid forms, and the catalyst of compared with prior art, preparing is significantly increased aspect catalytic activity.
Description of drawings
Fig. 1 is the SEM figure with tubulose macroporous structure galapectite;
Fig. 2 is the SEM figure of catalyst of the present invention.
The specific embodiment
Below introduce in detail realization of the present invention and the beneficial effect that has by specific embodiment, understand better novelty essence of the present invention place to help the reader, but but do not consist of restriction to the present invention's practical range.
Embodiment 1 ~ 4 ionic liquid method synthetic catalyst C-1, C-2, C-3, C-4
The first step: 114.2 milliliters in ionic liquid [BMIM] [Cl] 5 gram, galapectite 50 grams and water is mixed to get slurries A;
Second step: with USY molecular sieve 50 grams, boehmite 28.19 grams, H
3PO
444.55 after gram, 181.67 milliliters in water mix, under stirring, drip dilute nitric acid solution and regulate pH value to 2, obtain slurries B;
The 3rd step: slurries A and slurries B are mixed, sieve behind aging, spray shaping and get 60 ~ 400 purpose particles, 500 ℃ of lower roastings are 2 hours in air atmosphere, use NH
4NO
3Solution carries out after the ion-exchange again in 550 ℃ of roastings, repeats to obtain fluidized catalytic cracking catalyst C-1 after the exchange operations 3 times.
Except ionic liquid [BMIM] [Cl] is replaced by respectively ionic liquid [HNEt3] [NO
3], [BPy] [BF
4], [BMPi] [Cl], press step Kaolinite Preparation of Catalyst C-2, C-3, the C-4 of synthetic catalyst C-1.
Embodiment 5 ionic liquid method synthetic catalyst C-5
The first step: 64.2 milliliters in ionic liquid [BMIM] [Cl] 2.5 gram, galapectite 25 grams and water is mixed to get slurries A;
Second step: with USY molecular sieve 50 grams, kaolin 25 grams, boehmite 28.19 grams, H
3PO
444.55 after gram, 231.67 milliliters in water mix, under stirring, drip dilute nitric acid solution and regulate pH value to 2, obtain slurries B;
The 3rd step: slurries A and slurries B are mixed, sieve behind aging, spray shaping and get 60 ~ 400 purpose particles, 500 ℃ of lower roastings are 2 hours in air atmosphere, use NH
4NO
3Solution carries out after the ion-exchange again in 550 ℃ of roastings, repeats to obtain fluidized catalytic cracking catalyst C-5 after the exchange operations 3 times.
Embodiment 6 synthetic reference catalyst R-1
The first step: 114.2 milliliters in galapectite 50 gram and water is mixed to get slurries A;
Second step: with USY molecular sieve 50 grams, boehmite 28.19 grams, H
3PO
444.55 after gram, 181.67 milliliters in water mix, under stirring, drip dilute nitric acid solution and regulate pH value to 2, obtain slurries B;
The 3rd step: slurries A and slurries B are mixed, sieve behind aging, spray shaping and get 60 ~ 400 purpose particles, 500 ℃ of lower roastings are 2 hours in air atmosphere, use NH
4NO
3Solution carries out after the ion-exchange again in 550 ℃ of roastings, repeats to obtain reference catalyst R-1 after the exchange operations 3 times.
Embodiment 7 sucrose template are synthesized control sample catalyst D-1
The first step: 114.2 milliliters in sucrose 5 gram, galapectite 50 grams and water is mixed to get slurries A;
Second step: with USY molecular sieve 50 grams, boehmite 28.19 grams, H
3PO
444.55 after gram, 181.67 milliliters in water mix, under stirring, drip dilute nitric acid solution and regulate pH value to 2, obtain slurries B;
The 3rd step: slurries A and slurries B are mixed, sieve behind aging, spray shaping and get 60 ~ 400 purpose particles, 500 ℃ of lower roastings are 2 hours in air atmosphere, use NH
4NO
3Solution carries out after the ion-exchange again in 550 ℃ of roastings, repeats to obtain control sample catalyst D-1 after the exchange operations 3 times.
Embodiment 8 polystyrene moulding methods are synthesized control sample catalyst D-2
The first step: 114.2 milliliters in polystyrene 5 gram, galapectite 50 grams and water is mixed to get slurries A;
Second step: with USY molecular sieve 50 grams, boehmite 28.19 grams, H
3PO
444.55 after gram, 181.67 milliliters in water mix, under stirring, drip dilute nitric acid solution and regulate pH value to 2, obtain slurries B;
The 3rd step: slurries A and slurries B are mixed, sieve behind aging, spray shaping and get 60 ~ 400 purpose particles, 500 ℃ of lower roastings are 2 hours in air atmosphere, use NH
4NO
3Solution carries out after the ion-exchange again in 550 ℃ of roastings, repeats to obtain control sample catalyst D-2 after the exchange operations 3 times.
The mensuration of embodiment 9 catalyst reaction performances
Ionic liquid method synthetic catalyst and reference, control sample catalyst are carried out the mensuration of catalyst reaction performance after aging 17 hours in 800 ℃ of lower 100% steam.
The evaluation method of catalyst: select Jinan Refinery fluid catalytic cracking (FCC) device feedstock oil and FCC poising agent, measure the activity of catalyst at the senior catalytic cracking unit of the ACE-MODEL R+MM of U.S. Kayser company design.Main operating condition is as follows: 530 ℃ or 500 ℃ of reaction temperatures, oil ratio 6, feedstock oil charging rate 1.2 g/min, catalyst amount 9 g.The raw material oil properties is as shown in table 1.
The physical property of table 1 Jinan FCC feedstock oil
Ionic liquid method synthetic catalyst and reference, the reaction result of control sample catalyst under 530 ℃ see Table 2 on the ACE-MODEL R+ MM device.
Table 2
530 ℃ of reaction temperatures, oil ratio 6, feedstock oil charging rate 1.2 g/min, catalyst amount 9 g; * add 90% poising agent.
Table 2 explanation, under identical reaction condition, the homostasis agent is compared, and outside reference, control sample catalyst carbon remover amount slightly reduced, other did not have significant change.And in catalyst preparation process, allow first ionic liquid be mixed into slurries and synthetic catalyst with the galapectite of tubulose macroporous structure, under 530 ℃ of cracking temperature, compare with reference, FCC feedstock oil conversion ratio and gasoline/diesel productive rate significantly improve, the mink cell focus productive rate obviously reduces, especially on the poising agent that contains 10% catalyst C-3, conversion ratio and gasoline yield improve respectively 1.99 wt% and 1.42 wt%, and the mink cell focus productive rate reduces by 1.37 wt%.
Adopt ionic liquid method synthetic catalyst and the reaction result of reference catalyst under 500 ℃ to see Table 3 on the ACE-MODEL R+ MM device.
Table 3
500 ℃ of reaction temperatures, oil ratio 6, feedstock oil charging rate 1.2 g/min, catalyst amount 9 g; * the poising agent that adds 90 wt%, * * add 80 wt% poising agents.
Table 3 explanation, under the low cracking temperature, the catalyst that the ionic liquid method is synthetic, its reactivity and selectively also all significantly improving than reference catalyst.
Claims (4)
1. macropore fluidized catalytic cracking catalyst, it is characterized in that this catalyst is comprised of galapectite, catalyst substrates and molecular sieve, it comprise with ionic liquid, galapectite, catalyst substrates and molecular sieve mix, aging, moulding and drying, then remove the process of ionic liquid wherein, use the assembling of ionic liquid control galapectite, catalyst substrates and molecular sieve, obtain described macropore fluidized catalytic cracking catalyst; Described ionic liquid comprises the mixture of imidazoles, quaternary ammonium salt, pyridines, piperidines ionic liquid and above-mentioned substance; Described galapectite is natural or manually synthesizes galapectite.
2. the preparation method of the described catalyst of claim 1 is characterized in that the method comprises following concrete steps:
The first step: ionic liquid, galapectite and water are mixed to get slurries A, and wherein, the ionic liquid consumption accounts for 0.3 ~ 500 % of galapectite weight, and the galapectite consumption accounts for 2 ~ 40 % of catalyst weight;
Second step: after molecular sieve, catalyst substrates and water mixed, drip dilute acid soln and regulate pH value to 2, obtain slurries B, wherein, the molecular sieve consumption accounts for 10 ~ 50 % of catalyst weight, and the catalyst substrates consumption accounts for 88 ~ 10% of catalyst weight, and diluted acid is rare nitric acid, watery hydrochloric acid or dilute sulfuric acid;
The 3rd step: slurries A and slurries B are mixed, sieve behind aging, spray shaping and get 60 ~ 400 purpose particles, 500 ℃ of lower roastings are 2 hours in air atmosphere, use NH
4NO
3Solution carries out after the ion-exchange again in 550 ℃ of roastings, repeats to obtain described macropore fluidized catalytic cracking catalyst after the exchange operations 3 times.
3. preparation method according to claim 2 is characterized in that described catalyst substrates is amorphous aluminum silicate, aluminium oxide, silica, clay or their mixture.
4. preparation method according to claim 2 is characterized in that described molecular sieve is Y zeolite or the Y zeolite after modification.
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| CN109304148A (en) * | 2017-11-16 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of oil spilling adsorption production based on catalytic cracking spent catalyst |
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| US20050215693A1 (en) * | 2004-03-29 | 2005-09-29 | Xiaorong Wang | Clay modified rubber composition and a method for manufacturing same |
| CN102019207A (en) * | 2009-09-16 | 2011-04-20 | 住友化学株式会社 | Photocatalyst composite and photocatalytic functional product using the same |
| CN102548899A (en) * | 2009-08-26 | 2012-07-04 | 株式会社巴川制纸所 | Clay dispersion liquid, method for producing the clay dispersion liquid, clay film, method for producing the clay film, and transparent material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050215693A1 (en) * | 2004-03-29 | 2005-09-29 | Xiaorong Wang | Clay modified rubber composition and a method for manufacturing same |
| CN102548899A (en) * | 2009-08-26 | 2012-07-04 | 株式会社巴川制纸所 | Clay dispersion liquid, method for producing the clay dispersion liquid, clay film, method for producing the clay film, and transparent material |
| CN102019207A (en) * | 2009-09-16 | 2011-04-20 | 住友化学株式会社 | Photocatalyst composite and photocatalytic functional product using the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109304148A (en) * | 2017-11-16 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of oil spilling adsorption production based on catalytic cracking spent catalyst |
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