CN1854252A - Petroleum hydrocabon cracking catalyst and its production - Google Patents
Petroleum hydrocabon cracking catalyst and its production Download PDFInfo
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Abstract
This invention is about a kind of petroleum hydrocarbon cracking catalyst, for dry basis weight, it includes 10-50% Y zeolite,0-5% Choosing Style zeolite,10-60% modified alumina combination,5-45% clay and 2-35% inorganic oxide agglomerant. It is detected by pyridine adsorption infra-red sepectrometry that there is only lewis acid in the surface acid center of the modified alumina combination, no Bronsted acid is detected, and silicon oxide is well-distributed in the alumina phase, the modified alumina combination is still keep the XRD derivant characteristic of the gamma-Al2O3 . The modified alumina combination in the catalyst which this invention mentioned, have good function for catalyzing isomerization of straight chain olefinic hydrocatbon. For this reason the cracking catalyst which this invention mentioned can reduce the contents of olefinic hydrocarbon in the catalytically cracked gasoline, and in the same time it can wide rangeincrease the contents of isoparaffin in the petrol.
Description
Technical field
The present invention relates to a kind of catalyst for cracking petroleum hydrocarbons, more particularly, is to be used to produce the cracking catalyst that is rich in isoparaffin gasoline about a kind of silicon oxide-containing modified alumina composition.
Background technology
Along with the specification of quality increasingly stringent of environment protection to gasoline products, gasoline develops into reformulated gasoline from white gasoline.Content to olefin component in the reformulated gasoline standard has had clearly restriction.Such as, the olefin(e) centent in world's fuel oil standard in the II class gasoline standard requirement gasoline component is below 20 volume %.The gasoline standard that China rose in Beijing on July 1st, 2002, carry out in Shanghai, three big cities, Guangzhou requires the olefin(e) centent in the gasoline component to be lower than 35 volume %.China's gasoline quality standard from now on also will further limit the content of olefin component in the gasoline.
Catalytic cracking is to produce one of major technique of motor spirit component, and catalytic gasoline is the main blend component of motor spirit.In China, catalytic gasoline accounts for more than 80% of motor spirit blend component especially.Since the 1980s, the unleaded catalytic cracking technology that forces of motor spirit develops to the direction of producing stop bracket gasoline.But catalytic cracking technology newly developed all is the octane value that increases gasoline with the olefin(e) centent in the raising gasoline component.At present olefin(e) centent is 35～65 heavy % in the gasoline component, and this and reformulated gasoline differ greatly to the requirement of olefin(e) centent.
Isoparaffin octane value height, susceptibility are low, are very good gasoline blend components.Therefore, reduce the more satisfactory approach of catalytic cracking gasoline olefine content and be to use the novel cracking catalytic that can increase isoparaffin content in the gasoline, in catalytic cracking process, make olefin component through isomerization reaction and hydrogen transfer reactions as much as possible, change into the higher isoparaffin component of octane value.
The cracking catalyst of this class raising catalytically cracked gasoline isoparaffin content is disclosed in the patents such as CN 1354223, CN 1325940, USP 5,366,948.As a whole, these technology mainly rely on the performance of improving zeolite component, the isomerization and the hydrogen transfer activity that improve cracking catalyst reduce content of olefin in gasoline, improve isoparaffin content, rather than improve the cracking catalyst isomerization performance by the performance of improving the catalyst substrates component.
US 4,806, disclose the preparation of the alumina composition of handling through the silicon oxide coating and with fluorochemicals on a kind of surface in 513.Among the JP09183609 public Ji a kind of on alumina particulate the porous silicon aluminium-mixed oxide composition of coated silica coating, contain the silicon oxide of 5～30 heavy % in the said composition, the aperture peak value is at 80～100 , specific surface area 〉=240m
2/ g, total pore volume 〉=0.65ml/g.Said composition is used for the transformation efficiency that carrier of cracking can improve catalyzer.Silicon oxide component in the disclosed composition of above patent is to be distributed in alumina surface with coating form, rather than forms homogeneous phase with aluminum oxide, thereby is unfavorable for improving the surface acidity of aluminum oxide.
Among the WO 9712011 public Ji a kind of catalyzer that is used for heavy oil cracking, contain a kind of its silicon oxide and aluminum oxide aluminosilicate composition in this catalyzer with molecularity combination.Said composition is the C by silicate compound and aluminium
2-C
20Alkoxide makes through chemical reaction.The XRD thing of this improved composition contains amorphous Si O in mutually
2-Al
2O
3, thereby its surface acid center that is recorded by the pyridine adsorption infrared spectroscopy should contain a large amount of Br nsted acid, makes its isomerization selectivity to straight chain hydrocarbon relatively poor.US 4,758, disclose a kind of silicon oxide-containing of hydrofining catalyst carrier and composition of aluminum oxide of being used as in 330, the preparation of said composition is to form the water-sol with a kind of aluminium salt and alkali metal aluminate earlier, adds alkalimetal silicate then in this water-sol.Disclose a kind of silica modified alumina composition as catalyst carrier for hydrgenating among the CN 1033285, this carrier is to be raw material with the sodium metaaluminate that mixes a certain amount of water glass, feeds CO
2And the control pH value reacts 10～12 and obtains, and silica content accounts for 2% of vehicle weight in the said composition.Composition in the above patent all is that the solution with alkali metal aluminate or alkali metal containing aluminate is raw material, therefore also will form Br nsted acid site in the composition, its isomerization selectivity to straight chain hydrocarbon is relatively poor, and the purpose of its invention is the preparation hydrofining catalyst carrier, rather than provides matrix components for cracking catalyst.
Summary of the invention
The invention provides a kind of catalyst for cracking petroleum hydrocarbons that is rich in isoparaffin gasoline that is used to produce.
The present invention also provides above-mentioned Preparation of catalysts method.
Catalyst for cracking petroleum hydrocarbons provided by the invention, by butt weight, contain the y-type zeolite of 10～50 heavy %, 0～5 heavy % selects the shape zeolite, the modified alumina composition of 10～60 heavy %, 5～45 heavy % the inorganic oxide of clay material and 2～35 weight %.
The surface acid center that described modified alumina composition is recorded by the pyridine adsorption infrared spectroscopy has only Lewis acid, does not have Br nsted acid, wherein the silicon oxide component be dispersed in alumina body mutually in, modified alumina composition still keeps γ-Al
2O
3XRD derivative phase character.The content of modified alumina composition in catalyzer is 10～60 heavy %, preferred 15～50 heavy %.
Described modified alumina composition by butt weight, contains the aluminum oxide of 80～99.5 heavy %, 0.5 the silicon oxide of～20 heavy %, the aluminum oxide that preferably contains 82～97 heavy %, the silicon oxide of 3～18 heavy % is 150～300m by the measured specific surface area of BET method
2/ g, preferred 150～240m
2/ g, pore volume are 0.40～0.70ml/g, preferred 0.40～0.65m
2/ g, most probable pore diameter range are 5～10nm, preferred 5～7nm.
Described y-type zeolite is the various y-type zeolites that generally adopt in the prior art, y-type zeolite as Hydrogen, ammonium type or rare-earth type, perhaps through the y-type zeolite of Hydrogen, ammonium type or the rare-earth type of phosphorus modification, or through the y-type zeolite of alkali-earth metal modified Hydrogen, ammonium type or rare-earth type, the perhaps ultrastable Y of handling through super stabilizing, or the combination of several above zeolites.The content of y-type zeolite in catalyzer is 10～50 heavy %, preferred 12～45 heavy %, most preferably 12～40 heavy %.
Described select the shape zeolite be the various ZSM-5 of comprising, the ZRP that generally adopt in the prior art, β zeolite, mordenite select the shape zeolite.Selecting the content of type zeolite in catalyzer is 0～5 heavy %, preferred 1～3 heavy %.
Described clay is the combination that generally adopt in the prior art various comprise one or more clay materials in kaolin, sepiolite, montmorillonite, the tired clay material that takes off stone etc.The content of described clay in catalyzer is 5～45 heavy %, preferred 10～40 heavy %, most preferably 12～30 heavy %.
Described inorganic oxide is generally to adopt silicon oxide, aluminum oxide or their mixture in the prior art, and the content in catalyzer is 2～35 heavy %, preferred 5～30 heavy %, most preferably 15～30 heavy %.Wherein the precursor of aluminum oxide is pseudo-boehmite or aluminium colloidal sol or their mixture.
The preparation method of catalyst for cracking petroleum hydrocarbons provided by the invention comprises:
(1) in the aqueous solution of aluminium salt, adds alkaline silicate solution, regulate the pH value, until forming gel;
(2) gel is warming up to 45～95 ℃, aging, to filter, washing removes sodium ion wherein, obtains silica modified alumina composition;
(3) described composition is mixed making beating with pseudo-boehmite, add the mineral acid acidifying, stir, obtain mixed serum;
(4) with zeolite with after clay material mixes, add the inorganic oxide binder making beating again, stir, obtain mixed serum;
(5) the described mixed serum of step (4) is mixed with the described mixed serum of step (3), continue to be stirred to evenly after, take out slurries, oven dry, roasting obtain containing the cracking catalyst of modified alumina composition.
Specifically, modified alumina composition provided by the invention can prepare in accordance with the following methods:
(1) add alkaline silicate solution in the aqueous solution of aluminium salt, thorough mixing, mixing temperature can be room temperatures, generally be 5～45 ℃, preferred 10～30 ℃, regulate pH value with alkaline matter, until forming gel, the pH value of this moment is general 3～9, is preferably 4～6; The solid content of gel slurries is 2～40 heavy %, preferably 7～15 heavy %.
Described alkaline matter can be ammoniacal liquor or alkaline ammonium salt, as volatile salt, bicarbonate of ammonia etc., and preferred ammoniacal liquor.
Described aluminium salt is to be selected from the water-soluble aluminum salt that interior aluminium element exists with cationic form one or more of aluminum chloride, Tai-Ace S 150 and aluminum nitrate, preferred aluminum chloride.
Described alkaline silicate is to be selected from interior water-soluble alkaline silicate one or more of water glass, water glass and Starso, preferably water glass.In the described water glass solution, SiO
2Content is 15～30 heavy %, preferred 20～29 heavy %.
(2) stirring rises to 45～95 ℃ with gel down, after being preferably 50～75 ℃ of temperature, stop to stir, aging 0.5～8 hour, preferred 1～2 hour, product is filtered, with products therefrom decationized Y sieve water reslurry, filtration, repetitive scrubbing removes sodium ion wherein for several times, promptly makes silica modified alumina composition.
The temperature of described decationized Y sieve water is 40～80 ℃, and preferred 50～70 ℃, described beating time is 0.2～4 hour, preferred 0.5～2 hour, and the Na of washing back final product
2O content is not higher than 0.3 heavy % (in butt weight), preferably is not higher than 0.1 heavy %.
(3) with described composition with after pseudo-boehmite mixes, add the making beating evenly of decationized Y sieve water after, add the mineral acid acidifying, stir.
Described mixed serum solid content is preferably 12～20 heavy % at 9～25 heavy %.
Described mineral acid is generally hydrochloric acid, can be nitric acid, phosphoric acid, sulfuric acid etc. also, and the technical indicator of described acidification step is conventionally known to one of skill in the art.
(4) with zeolite with after clay material mixes, add the inorganic oxide binder making beating again, stir.
The preferred aluminium colloidal sol of described inorganic oxide binder.
The solid content of described mixed serum is preferably 25～55 heavy % at 20～60 heavy %, and the median size of mixture is not higher than 5 μ m, preferably is not higher than 3.5 μ m.
(5) the described mixed serum of step (4) is mixed with the described mixed serum of step (3), preferably the described mixed serum of step (4) is joined in the described mixed serum of step (3), after continuing to be stirred to evenly, take out slurries, oven dry, roasting obtain containing the cracking catalyst of modified alumina composition.
Described bake out temperature is 110～150 ℃, and preferred 120～130 ℃, described maturing temperature is 400～800 ℃, preferred 500～650 ℃.
Modified alumina composition in the catalyzer provided by the present invention has good isomerizating straight-chain catalytic performance, therefore cracking catalyst provided by the present invention in the olefin(e) centent, can improve the content of isoparaffin in the gasoline greatly in reducing catalytically cracked gasoline.
Description of drawings
Fig. 1 is embodiment 1～4 and the XRD thing of the prepared composition of Comparative Examples 1～3 diffraction spectrogram mutually.
Fig. 2 is the pyridine adsorption infrared spectrogram of the prepared composition of embodiment 1～4 and Comparative Examples 1～3.
Embodiment
The following examples will give further instruction to the present invention, but be not therefore and restriction the present invention.The SiO of prepared composition among each embodiment and the comparative example
2, Al
2O
3And Na
2O content is by x-ray fluorescence spectrometry; Thing is measured by X-ray diffraction method (XRD).Adopt the BET method to measure specific surface, pore volume and pore distribution.
Adopt the surface acidity of pyridine adsorption infrared spectroscopic determination composition by Fourier infrared spectrograph: with the sample compressing tablet, be warming up to 350 ℃, be evacuated to 10
-3Pa keeps 1h, removes the sample surfaces gas molecule.Be chilled to room temperature, absorption pyridine 0.5h is warming up to 200 ℃, 10 after the adsorption equilibrium
-3Desorption 0.5h under the Pa scans 1400～1700cm after being chilled to room temperature
-1Wave-number range obtains the pyridine adsorption infrared spectra of sample through 200 ℃ of desorptions; Be warming up to 350 ℃ again, through the pyridine adsorption infrared spectra of same step acquisition through 350 ℃ of desorptions.According in the pyridine adsorption infrared spectra 1543 and 1456cm
-1The intensity of feature adsorption peak and desorption temperature obtain the relative quantity in B acid site and L acid site.
Embodiment 1
Silica modified alumina composition preparation provided by the present invention.
Stir down toward containing 500 gram decationized Y sieve water and 506.5 gram AlCl
36H
2Slowly drip 16.1 gram water glass solution (Shandong Aluminum Plant, SiO in the solution of O (Red Star chemical plant, Beijing, analytical pure)
2Content is 20.6%), reaction is 30 minutes under the room temperature, and the ammoniacal liquor (Beijing Chemical Plant, analytical pure) that dripped again 1: 1 is regulated pH value, and up to generating gel, its pH value is 4.5, after continuation is stirred and is warming up to 65 ℃, stops to stir and aging 1 hour vacuum filtration.Filter cake and 20 minutes final vacuums of 60 ℃ of decationized Y sieve water reslurries are filtered.So repetitive scrubbing is 3 times, obtains improved composition M
1The surface acidity that its chemical constitution, physico-chemical property and pyridine adsorption infrared spectroscopy record sees Table 1.
The preparation of silica modified alumina composition provided by the present invention.
Stir down toward containing 500 gram decationized Y sieve water and 475.2 gram AlCl
36H
2Slowly drip 48.2 gram water glass solutions in the solution of O, reaction is 25 minutes under the room temperature, and the ammoniacal liquor that dripped again 1: 1 is regulated pH value, and up to generating gel, its pH value is 4.8, after continuation is stirred and is warming up to 60 ℃, stops to stir and aging 1.5 hours vacuum filtration.Filter cake and 25 minutes final vacuums of 70 ℃ of decationized Y sieve water reslurries are filtered.So repetitive scrubbing is 3 times, obtains improved composition M
2The surface acidity that its chemical constitution, physico-chemical property and pyridine adsorption infrared spectroscopy record sees Table 1.
The preparation of silica modified alumina composition provided by the present invention.
Stir down toward containing 500 gram decationized Y sieve water and 454.5 gram AlCl
36H
2Slowly drip 69.6 gram water glass solutions in the solution of O, reaction is 30 minutes under the room temperature, and the ammoniacal liquor that dripped again 1: 1 is regulated pH value, and up to generating gel, its pH value is 5.5, after continuation is stirred and is warming up to 70 ℃, stops to stir and aging 1.5 hours vacuum filtration.Filter cake and 30 minutes final vacuums of 65 ℃ of decationized Y sieve water reslurries are filtered.So repetitive scrubbing is 3 times, obtains improved composition M
3The surface acidity that its chemical constitution, physico-chemical property and pyridine adsorption infrared spectroscopy record sees Table 1.
Embodiment 4
The preparation of silica modified alumina composition provided by the present invention.
Stir down toward containing 500 gram decationized Y sieve water and 432.2 gram AlCl
36H
2Slowly drip 90.8 gram water glass solutions in the solution of O, reaction is 35 minutes under the room temperature, and the ammoniacal liquor that dripped again 1: 1 is regulated pH value, and up to generating gel, its pH value is 4.5, after continuation is stirred and is warming up to 70 ℃, stops to stir and aging 2 hours vacuum filtration.Filter cake and 35 minutes final vacuums of 70 ℃ of decationized Y sieve water reslurries are filtered.So repetitive scrubbing is 3 times, obtains improved composition M
4The surface acidity that its chemical constitution, physico-chemical property and pyridine adsorption infrared spectroscopy record sees Table 1.
Comparative Examples 1
Prepare Comparative composition according to the method that provides among the CN 1033285.
With concentration is 40g Al
2O
3The sodium aluminate solution of/L places in the glue jar, 30 ℃ of controlled temperature, and feeding concentration is 40% CO
2Gas adds a certain amount of sodium silicate solution, makes carrier contain the SiO of 2 heavy %
2, according to the needs of preparation aluminum oxide, control stops into glue when reaching PH=10, and slurries wear out, and vacuum filtration with decationized Y sieve water washing, drying, obtains Comparative composition DBM
1The surface acidity that its chemical constitution, physico-chemical property and pyridine adsorption infrared spectroscopy record sees Table 1.
Comparative Examples 2
Prepare the amorphous aluminum silicate Comparative composition according to ordinary method in the prior art.
Stir down toward containing 200ml dilute sulphuric acid (Beijing Chemical Plant, analytical pure) and 100.5 gram Al
2(SO
4)
318H
2O (Beijing Chemical Plant, analytical pure) adds 800ml in the solution and be diluted to 1: 1 water glass solution with decationized Y sieve water, reaction is 30 minutes under the room temperature, drips 1: 1 hydrochloric acid (Beijing Chemical Plant, analytical pure) again, regulate pH value, up to generating gel, pH value is 8.0, stops to stir after continuing stirring and being warming up to 65 ℃, aging 1 hour, vacuum filtration.Filter cake and 20 minutes final vacuums of 60 ℃ of decationized Y sieve water reslurries are filtered.So repetitive scrubbing is 3 times, obtains butt Na
2The contrast amorphous silicic acid aluminum composition DBM of O content≤0.6%
2The surface acidity that its chemical constitution, physico-chemical property and pyridine adsorption infrared spectroscopy record sees Table 1.
Comparative Examples 3
Choose commercial γ-Al
2O
3(German Condex company produce) be DBM as a comparison case
3, the surface acidity that its chemical constitution, physico-chemical property and pyridine adsorption infrared spectroscopy record sees Table 1.
The chemical constitution of table 1 improved composition and main physical and chemical performance
| Sample | Chemical constitution, heavy % | The acid amount, A/g.cm -2 | Specific surface area (m 2/g) | Pore volume (ml/g) | Can several apertures (nm) | |||
| Na 2O | Al 2O 3 | SiO 2 | B acid | L acid | ||||
| M 1 M 2 M 3 M 4 DBM 1 DBM 2 DBM 3 | 0.020 0.026 0.048 0.060 0.065 0.094 0.038 | 96.8 90.7 87.1 82.6 97.7 11.0 99.1 | 3.0 9.2 12.8 17.2 2.2 88.0 0.8 | 0.0 0.0 0.0 0.0 0.4 1.0 0.0 | 2.9 3.2 3.7 4.4 3.1 4.1 2.5 | 160 176 187 220 204 320 141 | 0.45 0.47 0.50 0.55 0.45 0.71 0.32 | 5.5 6.0 5.5 5.5 5.0 5.0 6.0 |
As seen from Figure 1, silica modified alumina composition (M provided by the present invention
1-M
4) X-ray diffraction spectrum peak and γ-Al
2O
3(DBM
3) unanimity, Comparative Examples 1 and Comparative Examples 2 prepared silicon aluminium compositions then are metamict.By accompanying drawing 2 as seen, improved composition provided by the present invention does not have Br nsted acid characteristic peak, and two Comparative Examples resulting compositions all have B acid characteristic peak.By table 1 as seen, the Lewis acid site of modified alumina composition provided by the invention is apparently higher than γ-Al
2O
3(DBM
3).
Embodiment 5
Contain the cracking catalyst preparation of silica modified aluminum oxide provided by the present invention.
Get the prepared silica modified alumina composition M of 50 gram (butt) embodiment 1
1, add the making beating of 500m1 decationized Y sieve water, evenly after, add 40 gram (butt) pseudo-boehmites (Shandong Aluminum Plant produces, solid content 61 heavy %) again and continue making beating 45 minutes.Adding concentration is the hydrochloric acid 4.2ml of 36 heavy %, after stirring, is warming up to 60 ℃ and aging 1 hour.(the Qilu Petrochemical catalyst plant is produced to add 70 gram (butt) REUSY molecular sieves, commodity are called DM-4), (kaolin company in Suzhou produces 30 gram (butt) kaolin, solid content 78%) and 46.5 gram aluminium colloidal sols (Shandong Aluminum Plant produces, solid content 21.5 heavy %) in said mixture, after making beating mixes, oven dry.550 ℃ of following roastings 1 hour, make and contain 35 heavy %REUSY, 25 heavy %M
1, 15% heavy kaolin, 25 heavy %Al
2O
3Catalyzer C
1
Embodiment 6
Contain the cracking catalyst preparation of silica modified aluminum oxide provided by the present invention.
Get the prepared silica modified alumina composition M of 70 gram (butt) embodiment 2
2, add the making beating of 500ml decationized Y sieve water, evenly after, add 40 gram (butt) pseudo-boehmites again and continue making beating 45 minutes.Adding concentration is the hydrochloric acid 4.2ml of 36 heavy %, after stirring, is warming up to 60 ℃ and aging 1 hour.Add 50 gram (butt) REHY-7 molecular sieves (the Qilu Petrochemical catalyst plant is produced, and commodity are called REHY 7.0), 30 gram (butt) kaolin and 46.5 gram aluminium colloidal sols in said mixture, after making beating mixes, oven dry.550 ℃ of following roastings 1 hour, make and contain 25 heavy %REHY-7,35 heavy %M
2, on the 15% heavy high mountain range, 25 heavy %Al
2O
3Catalyzer C
2
Embodiment 7
Contain the cracking catalyst preparation of silica modified aluminum oxide provided by the present invention.
Get the prepared silica modified alumina composition M of 100 gram (butt) embodiment 3
3, add the making beating of 520ml decationized Y sieve water, evenly after, add 32 gram (butt) pseudo-boehmites again and continue making beating 35 minutes.The dilute hydrochloric acid 7.5ml that adds 1: 1 after stirring, is warming up to 65 ℃ and aging 1 hour.Add 30 gram (butt) REY molecular sieves (the Qilu Petrochemical catalyst plant is produced, and commodity are called REY), 30 gram (butt) kaolin and 37.2 gram aluminium colloidal sols in said mixture, after making beating mixes, oven dry.550 ℃ of following roastings 1 hour, make and contain 15 heavy %REY, 50 heavy %M
3, 15% heavy kaolin, 20 heavy %Al
2O
3Catalyzer C
3
Embodiment 8
Contain the cracking catalyst preparation of silica modified aluminum oxide provided by the present invention.
Get the prepared silica modified alumina composition M of 30 gram (butt) embodiment 4
4, add the making beating of 500ml decationized Y sieve water, evenly after, add 40 gram (butt) pseudo-boehmites again and continue making beating 45 minutes.Adding concentration is the hydrochloric acid 4.2ml of 36 heavy %, after stirring, is warming up to 60 ℃ and aging 1 hour.Add 70 gram (butt) REUSY molecular sieves, 50 gram (butt) kaolin and 46.5 gram aluminium colloidal sols in said mixture, after making beating mixes, oven dry.550 ℃ of following roastings 1 hour, make and contain 35 heavy %REUSY, 15 heavy %M
4, 25% heavy kaolin, 25 heavy %Al
2O
3Catalyzer C
4
Comparative Examples 4
Contain contrast silicon aluminium composition DBM
1Cracking catalyst preparation.
Get the prepared silicon aluminium composition DBM of 90 gram (butt) Comparative Examples 1
1, add the making beating of 500ml decationized Y sieve water, evenly after, add 40 gram (butt) pseudo-boehmites again and continue making beating 40 minutes.The dilute hydrochloric acid 7.5ml that adds 1: 1 after stirring, is warming up to 65 ℃ and aging 1.5 hours.Add 30 gram (butt) REY molecular sieves, 30 gram (butt) kaolin and 46.5 gram aluminium colloidal sols in said mixture, after making beating mixes, oven dry.550 ℃ of following roastings 1 hour, make and contain 15 heavy %REY, 45 heavy %DBM
1, 15% heavy kaolin, 25 heavy %Al
2O
3Catalyzer DBC
1
Comparative Examples 5
Contain contrast amorphous aluminum silicate DBM
2Cracking catalyst preparation.
Get the prepared silicon aluminium composition DBM of 40 gram (butt) Comparative Examples 2
2, add the making beating of 480ml decationized Y sieve water, evenly after, add 30 gram (butt) pseudo-boehmites again and continue making beating 35 minutes.The dilute hydrochloric acid 6.8ml that adds 1: 1 after stirring, is warming up to 60 ℃ and aging 1 hour.Add 70 gram (butt) REUSY molecular sieves, 40 gram (butt) kaolin and 93 gram aluminium colloidal sols in said mixture, after making beating mixes, oven dry.550 ℃ of following roastings 1 hour, make and contain 35 heavy %REUSY, 20 heavy %DBM
2, 20% heavy kaolin, 25 heavy %Al
2O
3Catalyzer DBC
2
Embodiment 9～12
Present embodiment illustrates the heavy oil conversion performance of the cracking catalyst of silicon oxide-containing modified alumina composition provided by the invention.
With catalyzer C
1, C
2, C
3And C
4Wore out 8 hours with 100% water vapour down at 800 ℃, at the catalytic performance of estimating the catalyzer after wearing out on the heavy oil microreactor.The catalyzer loading amount is 4 grams, and raw materials used oil properties is listed in table 2.Temperature of reaction is 482 ℃, and weight hourly space velocity is 16 hours
-1, agent-oil ratio is 4.Evaluation result is listed in table 3.Wherein:
The heavy % in transformation efficiency=(gas content+gasoline content+coke content)/inlet amount * 100;
Light oil yield=gasoline yield+diesel yield
Collect reacted liquid product, with PIONA (v%) value of gas chromatographic analysis gasoline.
Comparative Examples 6～7
This Comparative Examples explanation comparative catalyst's heavy-oil catalytic performance.
The method of pressing embodiment 9～12 is aging, the aging back of evaluation comparative catalyst DBC
1, DBC
2Catalytic performance.Evaluation result is listed in table 3.
The little anti-raw material oil properties of table 2 heavy oil
| Project | Index |
| Density (20 ℃), g/m 3 | 0.8652 |
| Kinematic viscosity, mm 2/s 50℃ 100℃ | 14.58 4.37 |
| Carbon residue, weight % | 0.04 |
| S, weight % | 0.42 |
| Boiling range, ℃ | 227 289 389 446 475 |
Table 3 heavy oil micro-inverse product distributes and gasoline is formed
| Sequence number | Embodiment 9 | | Embodiment 11 | Embodiment 12 | Comparative Examples 6 | Comparative Examples 7 |
| Catalyzer | C1 | C2 | C3 | C4 | DBC1 | DBC2 |
| Little work (800 ℃/8hr) | 71 | 69 | 70 | 73 | 69 | 71 |
| C/O | 4 | |||||
| Products distribution, m% gas coke gasoline, diesel heavy oil | 11.7 2.3 65.8 16.6 3.6 | 11.2 2.5 65.9 16.3 4.1 | 10.9 2.7 66.7 15.9 3.8 | 11.5 2.2 66.0 16.3 4.0 | 11.8 2.5 66.4 14.9 4.4 | 11.6 2.8 65.6 15.8 4.2 |
| Transformation efficiency, m% light oil yield, m% | 79.8 82.4 | 79.6 82.2 | 80.3 82.6 | 79.7 82.3 | 80.7 81.3 | 80.0 81.4 |
| Gasoline is formed, v% normal paraffin isoparaffin naphthenic hydrocarbon alkene aromatic hydrocarbons | 4.5 49.7 8.6 21.5 15.7 | 4.3 49.2 8.3 22.9 15.3 | 4.1 50.5 8.2 21.0 16.2 | 4.7 48.8 8.7 20.8 17.0 | 4.5 46.3 8.8 21.2 19.2 | 4.7 46.5 8.1 21.0 19.7 |
By table 3 as seen, the cracking catalyst heavy oil cracking ability and the comparative catalyst that contain improved composition provided by the present invention are suitable, and gas yield is close, and light oil yield is slightly high.Isoparaffin content is apparently higher than the comparative catalyst in its gasoline product.
Claims (21)
1. catalyst for cracking petroleum hydrocarbons, by butt weight, the y-type zeolite that contains 10～50 heavy %, 0～5 heavy % selects the shape zeolite, the modified alumina composition of 10～60 heavy %, 5～45 heavy % clay and the inorganic oxide binder of 2～35 heavy %, the surface acid center that described modified alumina composition is recorded by the pyridine adsorption infrared spectroscopy has only Lewis acid, there is not Br nsted acid, wherein the silicon oxide component be dispersed in alumina body mutually in, modified alumina composition still keeps γ-Al
2O
3XRD derivative phase character.
2. according to the described catalyzer of claim 1, it is characterized in that the content of modified alumina composition in catalyzer is 15～50 heavy %, the content of y-type zeolite is 12～45 heavy %, the content of clay is 10～40 heavy %, content 5～30 heavy % of inorganic oxide.
3. according to claim 1 or 2 described catalyzer, it is characterized in that the composition of described modified alumina composition contains the aluminum oxide of 80～99.5 heavy % by butt weight, 0.5 the silicon oxide of～20 heavy % is 150～300m by the measured specific surface area of BET method
2/ g, pore volume are 0.40～0.70ml/g, and the most probable pore diameter range is 5～10nm.
4. according to the described catalyzer of claim 3, it is characterized in that the composition of described modified alumina composition contains the aluminum oxide of 82～97 heavy % by butt weight, the silicon oxide of 3～18 heavy % is 150～240m by the measured specific surface area of BET method
2/ g, pore volume are 0.40～0.65m
2/ g, most probable pore diameter range 5～7nm.
5. according to claim 1 or 2 described catalyzer, it is characterized in that, described y-type zeolite is the y-type zeolite of Hydrogen, ammonium type or rare-earth type, perhaps through the y-type zeolite of Hydrogen, ammonium type or the rare-earth type of phosphorus modification, or through the y-type zeolite of alkali-earth metal modified Hydrogen, ammonium type or rare-earth type, the perhaps ultrastable Y of handling through super stabilizing, or the combination of several above zeolites.
6. according to claim 1 or 2 described catalyzer, it is characterized in that the content of y-type zeolite in catalyzer is 12～40 heavy %.
7. according to the described catalyzer of claim 1, it is characterized in that the described shape zeolite of selecting is to be selected from ZSM-5, ZRP, β zeolite, mordenite at the interior shape zeolite of selecting.
8. according to claim 1 or 2 described catalyzer, it is characterized in that described clay is to be selected from kaolin, sepiolite, montmorillonite, tired combination of taking off one or more clay materials of stone in interior clay material.
9. according to claim 1 or 2 described catalyzer, it is characterized in that the content of described clay in catalyzer is 12～30 heavy %.
10. according to claim 1 or 2 described catalyzer, it is characterized in that described inorganic oxide is silicon oxide, aluminum oxide or their mixture.
11., it is characterized in that content 15～30 heavy %s of described inorganic oxide in catalyzer according to claim 1 or 2 described catalyzer.
12. the preparation method of the described catalyst for cracking petroleum hydrocarbons of claim 1 comprises:
(1) in the aqueous solution of aluminium salt, adds alkaline silicate solution, regulate the pH value, until forming gel;
(2) gel is warming up to 45～95 ℃, aging, to filter, washing removes sodium ion wherein, obtains silica modified alumina composition;
(3) described composition is mixed making beating with pseudo-boehmite, add the mineral acid acidifying, stir, obtain mixed serum;
(4) with zeolite with after clay material mixes, add the inorganic oxide binder making beating again, stir, obtain mixed serum;
(5) the described mixed serum of step (4) is mixed with the described mixed serum of step (3), continue to be stirred to evenly after, take out slurries, oven dry, roasting obtain containing the cracking catalyst of modified alumina composition.
13., it is characterized in that the solid content that step (1) obtains the gel slurries is 2～40 heavy % according to the described Preparation of catalysts method of claim 12.
14., it is characterized in that the described aluminium salt of step (1) is aluminum chloride, Tai-Ace S 150 or aluminum nitrate according to the described Preparation of catalysts method of claim 12.
15., it is characterized in that the described alkaline silicate of step (1) is water glass, water glass or Starso according to the described Preparation of catalysts method of claim 12,
16. according to the described Preparation of catalysts method of claim 15, it is characterized in that, in the described water glass solution, SiO
2Content is 15～30 heavy %.
17. according to the described Preparation of catalysts method of claim 12, it is characterized in that, step (2) is after under agitation gel being risen to 50～75 ℃ of temperature, stop to stir, aging 0.5～8 hour, filter, with products therefrom decationized Y sieve water reslurry, filtration, washing, wherein the temperature of decationized Y sieve water is 40～80 ℃, described beating time is 0.2～4 hour.
18., it is characterized in that the described mixed serum solid content of step (3) is 9～25 heavy % according to the described Preparation of catalysts method of claim 12.
19., it is characterized in that the solid content of the described mixed serum of step (4) is 20～60 heavy % according to the described Preparation of catalysts method of claim 12.
20., it is characterized in that the described inorganic oxide binder of step (4) is an aluminium colloidal sol according to the described Preparation of catalysts method of claim 12.
21., it is characterized in that the described bake out temperature of step (5) is 110～150 ℃ according to the described Preparation of catalysts method of claim 12, maturing temperature is 400～800 ℃.
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| CN112237909A (en) * | 2019-07-18 | 2021-01-19 | 中国石油化工股份有限公司 | Modified alumina and preparation method and application thereof |
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| CN100443883C (en) * | 2006-11-20 | 2008-12-17 | 扬子石油化工股份有限公司 | Method for detecting hydrgenated tail-oil paraffin composition using near-infrared spectrum |
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| CN101310858B (en) * | 2007-05-21 | 2010-07-28 | 北京化工大学 | Heavy oil catalytic cracking catalyst |
| CN101241074B (en) * | 2008-03-12 | 2010-06-02 | 江南大学 | Fish meat petroleum hydrocarbon content determination method |
| CN101745373B (en) * | 2008-11-28 | 2012-05-23 | 中国石油化工股份有限公司 | Catalytic cracking additive |
| CN112237943A (en) * | 2012-12-21 | 2021-01-19 | 阿尔比马尔欧洲有限公司 | Improved Y-zeolite/ZSM-5 catalyst for increasing propylene yield |
| CN110286106A (en) * | 2019-06-13 | 2019-09-27 | 中国石油集团渤海钻探工程有限公司 | 3-D quantitative fluorescence index for oiliness calculation method |
| CN112237909A (en) * | 2019-07-18 | 2021-01-19 | 中国石油化工股份有限公司 | Modified alumina and preparation method and application thereof |
| 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 |
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