CN103041840B - 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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- CN103041840B CN103041840B CN201210568840.9A CN201210568840A CN103041840B CN 103041840 B CN103041840 B CN 103041840B CN 201210568840 A CN201210568840 A CN 201210568840A CN 103041840 B CN103041840 B CN 103041840B
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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, particularly a kind of macropore fluidized catalytic cracking catalyst and preparation method thereof, this catalyst is applicable to the catalyzed cracking processing containing heavy distillate raw material.Specifically, about a kind of assembling that uses ionic liquid control galapectite, catalyst substrates and molecular sieve, synthesize the eurypyloue fluidized catalytic cracking catalyst of tool.
Background technology
Along with the raising of the continuous growth to light-end products demand and feedstock oil price, catalytic cracking proportion in light materialization of heavy oil is increasing.Due to large (the >2.5 nm) of kinetic diameter of residual oil molecule, conventional catalyst Cracking catalyst aperture is less, make macromolecular components in heavy oil be difficult to enter catalyst cavity inside and react, bring difficulty to the transmission of raw material and product molecule.Therefore, increase the aperture of Cracking catalyst, be not only beneficial to heavy oil solid tumor and enter 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 cracking effect.CN100469447 patented technology adopts the granular formwork such as polystyrene macropore catalytic cracking catalyst synthesized, and in catalyst, macropore diameter is adjustable, has that cracking activity is high, good selective.But the granular formworks such as these organic polymers or carbon, in catalyst preparation process, belong to a kind of pure mechanical mixture, have that active force is strong, skewness, after template, cause the shortcomings such as catalyst strength reduction removing.
There is 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 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, multiple fields such as organic, analysis, catalysis are widely used in.If first ionic liquid is mixed with galapectite, ionic liquid can be effectively with the Adsorption generation bonding of galapectite, in catalytic cracking catalyst preparation process, can stop catalyst substrates to occupy pipeline and the active sites thereof of galapectite, remove after ionic liquid in high-temperature roasting or solvent, retain the macroporous structure of galapectite, be conducive to the raising of cracking activity.
Summary of the invention
The object 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 the Adsorption generation bonding of ionic liquid with galapectite, effectively stop binding agent etc. to occupy galapectite duct and active sites thereof, after shaping of catalyst, remove by roasting or dissolution with solvents 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, feature is: this catalyst is made up of galapectite, catalyst substrates and molecular sieve, it comprises ionic liquid, galapectite, catalyst substrates and molecular sieve mixing, aging, moulding and dry, 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.
(taking the catalyst weight as benchmark) composed as follows of described catalyst: galapectite is 2 ~ 40%, preferably 4.5 ~ 25%, catalyst substrates is 88-10 %, preferably 80.5-40 %, molecular sieve is 10-50 %, preferably 15-35 %.
A preparation method for above-mentioned catalyst, the method comprises following concrete steps:
The first step: ionic liquid, galapectite and water are mixed to get to slurries A, and wherein, ionic liquid consumption accounts for 0.3 ~ 500 % of galapectite weight, and galapectite consumption accounts for 2 ~ 40 % of catalyst weight;
Second step: after molecular sieve, catalyst substrates and water are mixed, drip dilute acid soln and regulate pH value to 2, obtain slurries B, wherein, molecular sieve consumption accounts for 10 ~ 50 % of catalyst weight, and 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, then 60 ~ 400 object particles are got in screening after aging, spray shaping, roasting 2 hours at 500 DEG C, uses NH in air atmosphere
4nO
3solution carries out after ion-exchange again in 550 DEG C of roastings, repeats to obtain described macropore fluidized catalytic cracking catalyst after exchange operations 3 times.
In catalyst preparation process, galapectite is first and ionic liquid generation bonding before adding catalyst to synthesize colloidal sol, can stop catalyst substrates to occupy pipeline and the active sites thereof of galapectite, remove after ionic liquid in high-temperature roasting or solvent, retain the macroporous structure of galapectite, be conducive to the raising of cracking activity.
In catalyst preparation process, ionic liquid plays protects the macroporous structure of galapectite not occupied.Therefore, 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 is not particularly limited, 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 use the compound containing Si, Al, such as sodium metasilicate, waterglass, aluminum sulfate, aluminum nitrate, sodium metaaluminate, Ludox and aluminium colloidal sol etc. are synthetic.
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, preferably 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, ionic liquid consumption accounts for 0.3 ~ 500 % of galapectite weight, preferably 1 ~ 200 %.
Molecular sieve used in the present invention is Y zeolite or the Y zeolite after modification, preferably HY, RE-HY, REY and USY etc., and above-mentioned molecular sieve can be bought from the market, also can use the compou nd synthesis containing 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 makes to have macropore in final catalyst by removing deionization special body size.Be according to the synthetic catalyst of the inventive method and the prior art main distinction, macropore in catalyst is the Adsorption generation bonding of ionic liquid with galapectite, effectively stop binding agent etc. to occupy galapectite duct and active sites thereof, after shaping of catalyst, remove by roasting or dissolution with solvents that ionic liquid forms, and the catalyst of compared with prior art, preparing is significantly increased aspect catalytic activity.
Brief description of the drawings
Fig. 1 is the SEM figure with tubulose macroporous structure galapectite;
Fig. 2 is the SEM figure of catalyst of the present invention.
Detailed description of the invention
Introduce in detail realization of the present invention and the beneficial effect that has by specific embodiment below, to help reader to understand better novelty essence of the present invention place, but do not form can practical range to the present invention restriction.
Embodiment 1 ~ 4 ionic liquid method synthetic catalyst C-1, C-2, C-3, C-4
The first step: 114.2 milliliters, 5 grams of ionic liquids [BMIM] [Cl], 50 grams of galapectites and water is mixed to get to slurries A;
Second step: by 50 grams, USY molecular sieve, 28.19 grams of boehmites, H
3pO
4after 181.67 milliliters of 44.55 grams, 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, then 60 ~ 400 object particles are got in screening after aging, spray shaping, roasting 2 hours at 500 DEG C, uses NH in air atmosphere
4nO
3solution carries out after ion-exchange again in 550 DEG C of roastings, repeats to obtain fluidized catalytic cracking catalyst C-1 after exchange operations 3 times.
Except ionic liquid [BMIM] [Cl] is replaced by respectively to ionic liquid [HNEt3] [NO
3], [BPy] [BF
4], [BMPi] [Cl], by 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, 2.5 grams of ionic liquids [BMIM] [Cl], 25 grams of galapectites and water is mixed to get to slurries A;
Second step: by 50 grams, USY molecular sieve, 25 grams of kaolin, 28.19 grams of boehmites, H
3pO
4after 231.67 milliliters of 44.55 grams, 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, then 60 ~ 400 object particles are got in screening after aging, spray shaping, roasting 2 hours at 500 DEG C, uses NH in air atmosphere
4nO
3solution carries out after ion-exchange again in 550 DEG C of roastings, repeats to obtain fluidized catalytic cracking catalyst C-5 after exchange operations 3 times.
The synthetic reference catalyst R-1 of embodiment 6
The first step: 50 grams of galapectites are mixed to get to slurries A with 114.2 milliliters, water;
Second step: by 50 grams, USY molecular sieve, 28.19 grams of boehmites, H
3pO
4after 181.67 milliliters of 44.55 grams, 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, then 60 ~ 400 object particles are got in screening after aging, spray shaping, roasting 2 hours at 500 DEG C, uses NH in air atmosphere
4nO
3solution carries out after ion-exchange again in 550 DEG C of roastings, repeats to obtain reference catalyst R-1 after exchange operations 3 times.
Embodiment 7 sucrose template are synthesized control sample catalyst D-1
The first step: 114.2 milliliters, 5 grams of sucrose, 50 grams of galapectites and water is mixed to get to slurries A;
Second step: by 50 grams, USY molecular sieve, 28.19 grams of boehmites, H
3pO
4after 181.67 milliliters of 44.55 grams, 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, then 60 ~ 400 object particles are got in screening after aging, spray shaping, roasting 2 hours at 500 DEG C, uses NH in air atmosphere
4nO
3solution carries out after ion-exchange again in 550 DEG C of roastings, repeats to obtain control sample catalyst D-1 after exchange operations 3 times.
Embodiment 8 polystyrene moulding methods are synthesized control sample catalyst D-2
The first step: 114.2 milliliters, 5 grams of polystyrene, 50 grams of galapectites and water is mixed to get to slurries A;
Second step: by 50 grams, USY molecular sieve, 28.19 grams of boehmites, H
3pO
4after 181.67 milliliters of 44.55 grams, 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, then 60 ~ 400 object particles are got in screening after aging, spray shaping, roasting 2 hours at 500 DEG C, uses NH in air atmosphere
4nO
3solution carries out after ion-exchange again in 550 DEG C of roastings, repeats to obtain control sample catalyst D-2 after 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 at 800 DEG C to the mensuration of catalyst reaction performance in 100% steam after aging 17 hours.
The evaluation method of catalyst: select Jinan Refinery fluid catalytic cracking (FCC) device feedstock oil and FCC poising agent, measure the activity of catalyst on the senior catalytic cracking unit of ACE-MODEL R+MM of Kayser company of U.S. design.Main operating condition is as follows: 530 DEG C or 500 DEG C of reaction temperatures, oil ratio 6, feedstock oil charging rate 1.2 g/min, catalyst amount 9 g.Raw material oil properties is as shown in table 1.
The physical property of table 1 Jinan FCC feedstock oil
On ACE-MODEL R+ MM device, ionic liquid method synthetic catalyst and reference, the reaction result of control sample catalyst at 530 DEG C are in table 2.
Table 2
530 DEG C of reaction temperatures, oil ratio 6, feedstock oil charging rate 1.2 g/min, catalyst amount 9 g; * add 90% poising agent.
Table 2 illustrates, under identical reaction condition, homostasis agent is compared, and outside reference, control sample catalyst carbon remover amount slightly reduce, other does not have significant change.And in catalyst preparation process, first allow ionic liquid be mixed into slurries and synthetic catalyst with the galapectite of tubulose macroporous structure, at 530 DEG C of cracking temperature, compare with reference, FCC feedstock oil conversion ratio and gasoline/diesel productive rate significantly improve, mink cell focus productive rate obviously reduces, especially containing on the poising agent of 10% catalyst C-3, conversion ratio and gasoline yield improve respectively 1.99 wt% and 1.42 wt%, and mink cell focus productive rate reduces by 1.37 wt%.
On ACE-MODEL R+ MM device, adopt ionic liquid method synthetic catalyst and the reaction result of reference catalyst at 500 DEG C in table 3.
Table 3
500 DEG C of reaction temperatures, oil ratio 6, feedstock oil charging rate 1.2 g/min, catalyst amount 9 g; * add the poising agent of 90 wt%, * * adds 80 wt% poising agents.
Table 3 illustrates, at lower cracking temperature, and the catalyst that ionic liquid method is synthetic, its reactivity and selectively also all significantly improving than reference catalyst.
Claims (4)
1. a macropore fluidized catalytic cracking catalyst, it is characterized in that this catalyst is made up of galapectite, catalyst substrates and molecular sieve, it comprises ionic liquid, galapectite, catalyst substrates and molecular sieve mixing, aging, moulding and dry, 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. a preparation method for catalyst described in claim 1, is characterized in that the method comprises following concrete steps:
The first step: ionic liquid, galapectite and water are mixed to get to slurries A, and wherein, ionic liquid consumption accounts for 0.3 ~ 500 % of galapectite weight, and galapectite consumption accounts for 2 ~ 40 % of catalyst weight;
Second step: after molecular sieve, catalyst substrates and water are mixed, drip dilute acid soln and regulate pH value to 2, obtain slurries B, wherein, molecular sieve consumption accounts for 10 ~ 50 % of catalyst weight, and 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, then 60 ~ 400 object particles are got in screening after aging, spray shaping, roasting 2 hours at 500 DEG C, uses NH in air atmosphere
4nO
3solution carries out after ion-exchange again in 550 DEG C of roastings, repeats to obtain described macropore fluidized catalytic cracking catalyst after 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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