CN1322928C - Cracking catalyst for reducing alkene content in catalytically cracked gasoline - Google Patents
Cracking catalyst for reducing alkene content in catalytically cracked gasoline Download PDFInfo
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- CN1322928C CN1322928C CNB2004100580906A CN200410058090A CN1322928C CN 1322928 C CN1322928 C CN 1322928C CN B2004100580906 A CNB2004100580906 A CN B2004100580906A CN 200410058090 A CN200410058090 A CN 200410058090A CN 1322928 C CN1322928 C CN 1322928C
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Abstract
The present invention discloses a cracking catalyst for lowering the olefinic content in catalytically cracked gasoline, which is characterized in that the catalyst comprises 10 to 50 wt% of CDY molecular sieves and 12 to 22 wt% of oxidized rare earth (measured by the content of rare earth), wherein the CDY molecular sieves are prepared by an exchanging method of liquid-solid combination, and all rare earth ions are positioned in the small cages of the molecular sieves. No peak occurs at 0 ppm chemical shift in a 27Al M AS NMR spectrogram. The catalyst is capable of greatly lowering the olefinic content in catalytically cracked gasoline, and simultaneously has the advantage of excellent conversion ability of heavy oil.
Description
Technical field
The invention relates to a kind of Cracking catalyst, the Cracking catalyst of further saying so and reducing catalytic cracking gasoline olefine content about a kind of.
Background technology
The quality of gasoline that environmental regulation is produced the FCC process has proposed the requirement of increasingly stringent, is≤20 volume % as world's fuel oil standard content of olefin in gasoline II class standard, and the III class standard is≤10 volume %.
In order to reduce catalytic cracking gasoline olefine content, at present extensively the strategy that adopts is to be active component with the Y zeolite that contains rare earth with high hydrogen transfer activity, as the said catalyst of CN1317547A is to be active component with REY and PREY, they all adopt two to hand over the technology of two roastings to prepare, and cause the molecular sieve cost higher.
I.Bresinska, K.J.Balkus, Jr. wait people [J.Phys.Chem.98 (1994) 12989～12994] to study to feed intake in the exchange of NaY and rare earth-iron-boron liquid phase the relation of rare earth and molecular sieve mol ratio and rare earth exchanged degree, discovery exchanges product middle rare earth/NaY mole and always is lower than the rare earth that feeds intake/NaY mol ratio.
The REY of a roasting is handed in CN1053808A preparation one, and its rare earth oxide that feeds intake/NaY mass ratio is 0.20, and rare earth oxide among the product REY/REY mass ratio is 0.14.
CN1069553C is equipped with REY through two friendships, two roastings, and its rare earth oxide that always feeds intake/NaY mass ratio is 0.23, and rare earth oxide among the product REY/REY mass ratio is 0.15.CN1069553C has proposed one and has handed over a wet method that bakes and will partly exchange the product of roasting circulation to prepare REY, at the rare earth oxide that feeds intake/NaY mass ratio is 0.20, and internal circulating load is that rare earth oxide among the product REY/REY mass ratio can reach 0.158 under 25% the situation.Tradition one hands over the REY molecular sieve of a roasting technology preparation to have quite a few rare earth ion to be in the Y zeolite supercage.CN1069553C and CN1026225C adopt one to hand over the method for a wet roasting, the rare earth ion after the exchange is positioned in the little cage more, but still has the part rare earth ion to be in the supercage.
The method rare earth utilization rate of industrial preparation REY molecular sieve is not too high at present, and rare earth ion liquid phase exchange back also has quite a few rare earth ion to stay in the exchange liquid, drains with filtrate after filtering.Even the preparation middle rare earth is excessive a lot, with the traditional REHY molecular sieve of handing over a roasting method to prepare of present employing, maximum oxidation content of rare earth generally is lower than 14m%; And its rare earth oxide content of REY that adopts part to exchange the method preparation of product of roasting circulation is not higher than 16m% yet.
CN1317547A discloses a kind of FCC catalyst that reduces content of olefin in gasoline, form by zeolite type active component, amorphous silicon aluminium oxide and kaolin, wherein active component is to be made up of 0.5～5% (accounting for the percentage by weight of FCC catalyst, down together) ZSM-5,0.5～15% rare earth exchanged Y zeolite, 20～40% phosphorus and the composite modified overstable gamma zeolite of rare earth.This catalyst is compared with conventional catalyst, is guaranteeing obviously to reduce the olefin(e) centent of gasoline under the prerequisite that other products distribute and octane number is constant substantially.
Summary of the invention
The purpose of this invention is to provide a kind of prior art that is better than, have the Cracking catalyst that reduces the catalytic cracking gasoline olefine content effect.
The Cracking catalyst of reduction catalytic cracking gasoline olefine content provided by the invention, it is characterized in that active component in this catalyst contains a kind of rare-earth Y molecular sieve of 10～50 heavy % (brief note is the CDY molecular sieve), the content of rare earth of this molecular sieve is counted 12～22 heavy % with rare earth oxide, rare earth ion all is positioned at the little cage of molecular sieve, its
27In the Al MAS NMR spectrogram, be that the 0ppm place does not have the peak to occur in chemical shift.
In the catalyst provided by the invention, the content of rare earth of said CDY molecular sieve is counted 12～22 heavy % with rare earth oxide, is preferably 13～20 heavy %, more preferably 14～18 weigh %, molecular sieve is after the ammonium exchange, and content of rare earth does not reduce, and sodium oxide content is 0.1～1.0 heavy %.
Said CDY molecular sieve, content of rare earth does not reduce after the ammonium exchange.Y zeolite has three kinds of cages, i.e. supercage, sodalite cage and hexagonal prism cage, and wherein supercage window diameter is 7.4 , and sodalite cage and hexagonal prism cage window diameter are 2.2 , sodalite cage and hexagonal prism generally are called little cage.In the process of ammonium exchange, the rare earth ion that is in the supercage can be changed in the solution by the ammonium ion reciprocal cross in the solution, and runs off in filtration subsequently, causes the reduction of ammonium exchange back molecular sieve content of rare earth.Rare-earth Y molecular sieve provided by the invention, there is not rare earth ion to exist in the supercage, its rare earth ion all is positioned at little cage, and the rare earth ion that is arranged in little cage can not exchange with the ammonium ion of solution, so the molecular sieve content of rare earth can not reduce after the CDY molecular sieve through ammonium exchange.
In addition, there is not non-framework aluminum in the CDY molecular sieve, shows it
27In the Al MAS NMR spectrum, be that the 0ppm place does not have the peak to occur in chemical shift, and XRD spectra show that the diffraction maximum that does not have free rare earth oxide exists.
Said CDY molecular sieve be with the NaY molecular sieve pulp with or with ammonium salt exchange after, with rare earth chloride according to NaY butt: RECl
3=1: 0.17～0.35 weight ratio is carried out ion-exchange under 5～100 ℃, pH=2.5～7.5, water and NaY weight ratio 3～50, use alkaline solution regulator solution pH to 8～11 then, stirring, filtration, washing, drying, again at 200～950 ℃, roasting is more than 0.1 hour under 0～100% steam, the molecular sieve of roasting is pressed the molecular sieve butt again: ammonium salt: the weight ratio of water=1: 0～1: 2～50 is handled down at 60～100 ℃, obtains through washing, filtration, drying.
Said CDY molecular sieve can also be with the NaY molecular sieve pulp with or not with ammonium salt exchange, again with rare earth chloride according to NaY butt: RECl
3=1: 0.17～0.35 weight ratio is carried out ion-exchange under 5～100 ℃, pH=2.5～7.5, water and NaY weight ratio 3～50, isolated molecule sieving cake, collect filtrate, in filtrate, add alkaline solution, regulator solution pH to 8～11, make the rare earth ion in the filtrate be precipitated as rare earth hydrate, again rare earth hydrate filter cake and the molecular sieve filter cake that obtains added the water making beating, filter, washing, dry, again at 200～950 ℃, roasting is more than 0.1 hour under 0～100% steam, and the molecular sieve of roasting is pressed the molecular sieve butt again: ammonium salt: the weight ratio of water=1: 0～1: 2～50 is handled down at 60～100 ℃, through washing, filter, drying obtains.
Catalyst provided by the invention except containing above-mentioned said CDY molecular sieve, can also contain other molecular sieve component in the active component, comprising 0～5 heavy %MFI structure shape-selective molecular sieve, USY molecular sieve and/or the REUSY molecular sieve of 0～20 heavy %.
Said catalyst can also contain conventional other included component of Cracking catalyst, as clay, inorganic oxide binder and rare earth oxide etc.Said clay is selected from one or more the mixture in kaolin, halloysite, imvite, diatomite, bentonite, attapulgite and the sepiolite, wherein preferred kaolin or halloysite; Said inorganic oxide binder is selected from one or more mixture of boehmite, aluminium colloidal sol, Ludox, Alusil and aluminum phosphate, wherein preferred boehmite and/or aluminium colloidal sol, the more preferably double aluminium binder of boehmite and aluminium colloidal sol; Said rare earth oxide is meant free rare earth oxide or free hydrogen rare earth oxide.
Catalyst provided by the invention preferably consists of the USY molecular sieve of inorganic oxide binder, 0～5 heavy %MFI structure shape-selective molecular sieve, 0～20 heavy % of CDY molecular sieve, 20～60 heavy % clays, 15～45 heavy % of 15～35 heavy % and/or REUSY molecular sieve and with RE
2O
3The rare earth oxide of meter 0～2 heavy %; More preferably the boehmite of the clay of the CDY molecular sieve of 20～28 heavy %, 40～55 heavy %, 15～20 heavy %, 3～9 weighs the aluminium colloidal sol of %, the free hydrogen rare earth oxide of the MFI structure shape-selective molecular sieve of 0.5～1.5 heavy %, the USY molecular sieve of 0～10 heavy % and 0～0.5 heavy %.
Catalyst provided by the invention can add molecular sieve pulp earlier in becoming the glue process, add binding agent, clay making beating then successively, adds sour peptization boehmite then, obtains finished catalyst through spray-drying, washing, pneumatic conveying drying again.
Catalyst provided by the invention owing to adopted a kind of novel rare-earth Y molecular sieve (CDY molecular sieve) in the active component, can reduce content of olefin in gasoline significantly, has excellent heavy oil conversion performance simultaneously.
Description of drawings
Fig. 1 is the CDY-1 sieve sample of embodiment 1 preparation
27Al MAS NMR spectrogram.
Fig. 2 is the XRD spectra of the CDY-1 sieve sample of embodiment 1 preparation.
The specific embodiment
The following examples will the present invention is further illustrated, but protection scope of the present invention is not subjected to the restriction of these embodiment.
In an embodiment,
27The assay method of Al MAS NMR spectrogram is: adopt Varian 300M NMR spectrometer with superconducting magnet, solid double resonance probe, 6mmZrO
2Rotor, magic angle rotating speed is 5KHz.
27The resonant frequency that Al detects nuclear is 78.162MHz, 0.02 second sampling time, pulsewidth 1.6 microseconds, 0.6 second circulation delay time.Data acquisition 4k point, accumulative frequency 800 times, probe temperature are room temperature.
In an embodiment, the assay method of XRD spectra is: Siemens D5005 type X-ray diffractometer, and experiment condition: the Cu target, the Ka radiation, tube voltage 30Kv, tube current 40mA, filter plate are Ni, 5 °≤2 θ≤50 °, 2 °/min of sweep speed.
Embodiment 1～6 explanation is as the preparation process of the CDY molecular sieve of active component.
Embodiment 1
Get 18.6 kilograms NaY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant, igloss 24.9 heavy %, silica alumina ratio is 5.2) and 140 kilograms of deionized waters join in the reactor, again to wherein adding 2.1 kilo sulfuric acid ammoniums, stir under 90 ℃ and use after 5 minutes between hydrochloric acid regulation system pH to 3.5～5.5, continue to stir filtration after 1 hour.Filter cake adds 140 kg water, adds 5.3 kilograms of solid lanthanum chlorides again, and 90 ℃ were stirred 2 hours down, added 1.5 kilograms of sodium aluminate solutions and 1.2 kilograms of ammoniacal liquor, stirred filtration after 5 minutes, and washing, the laggard roaster of pneumatic conveying drying, when weight space velocity 0.5
-1Following 550 ℃ of roastings of water vapour 1.5 hours, obtain molecular sieve after the cooling and be designated as CDY-1A, in molecular sieve: ammonium chloride: the ratio of water=1: 0.1: 10 was with 60 ℃ ammonium chloride solution washing 10 minutes, and drying obtains the finished product molecular sieve, is numbered CDY-1.
It is 15.9 heavy % that fluorescence method records CDY-1A lanthana content, and sodium oxide molybdena is 4.5 heavy %; CDY-1 lanthana content is 16.2 heavy %, and sodium oxide content is 0.6 heavy %, its
27Al MAS NMR spectrum is seen Fig. 1, in Fig. 1, is that the 0ppm place does not have the peak to occur in chemical shift.Fig. 2 is the XRD spectra of CDY-1, and Fig. 2 shows that CDY-1 does not have the diffraction maximum of free rare earth oxide to exist.
With CDY-1 once more with after the ammonium chloride solution exchange, the lanthana content that fluorescence method records wherein is 16.3 heavy %, the molecular sieve content of rare earth slightly increases, illustrate that rare earth ion is in little cage, rare earth ion in the little cage in the ammonium chloride exchange process can not with ammonium ion exchange, thereby total amount of rare earth is constant before and after the exchange, but the ammonium exchange can further reduce sodium oxide content in the molecular sieve, thereby causes molecular sieve middle rare earth content to increase.
Embodiment 2
Get 18.6 kilograms NaY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant, igloss 24.9 heavy %, silica alumina ratio is 5.2) and 140 kilograms of deionized waters join in the reactor, again to wherein adding 2.1 kilo sulfuric acid ammoniums, stir under 90 ℃ and use after 5 minutes between hydrochloric acid regulation system pH to 3.5～5.5, continue to stir filtration after 1 hour.Filter cake adds 140 kg water, (rare earth oxide concentration is 312 grams per liters to wherein adding 10.4 liters of re chlorides again, down together), stir under the room temperature after 5 minutes with between hydrochloric acid regulation system pH to 3.5～5.5, continue to stir after 1 hour, add 2.2 kg water glass solutions and 1.3 kilograms of ammoniacal liquor, stir after 5 minutes and filter, and washing, the laggard roaster of pneumatic conveying drying, 550 ℃ of roastings 1.5 hours obtain molecular sieve and are designated as CDY-2A after the cooling, again in molecular sieve: ammonium chloride: the ratio of water=1: 0.1: 10 was in 60 ℃ of ammonium chloride solutions washings 10 minutes, drying obtains finished product, and molecular sieve is numbered CDY-2.
It is 21.1 heavy % that fluorescence method records CDY-2A rare earth oxide content, and sodium oxide molybdena is 3.9 heavy %; Rare earth oxide content is 21.6 heavy % among the CDY-2, and sodium oxide content is 0.3 heavy %, its
27Al MAS NMR spectrum has the feature of Fig. 1, is that the 0ppm place does not have the peak to occur in chemical shift.
Once more with after the ammonium chloride solution exchange, the rare earth oxide content that fluorescence method records wherein is 21.6 heavy % with CDY-2, and content of rare earth does not reduce, and illustrates that rare earth ion is all in the little cage of molecular sieve.
Embodiment 3
Get 46.6 kilograms NaY molecular sieve pulp (Shandong catalyst plant, NaY concentration is 30.0 heavy %, the NaY silica alumina ratio is 5.1) and 80 kilograms of deionized waters join in the reactor, again to wherein adding 5.3 liters of re chlorides, 60 ℃ are stirred down after 5 minutes with between hydrochloric acid regulation system pH to 3.5～5.5, continue to stir after 1 hour, add 1.6 kilograms of ammoniacal liquor, stir after 5 minutes and to filter, and washing, the laggard roaster of pneumatic conveying drying, when weight space velocity 0.2
-1Following 600 ℃ of roastings of water vapour 1.5 hours, obtain molecular sieve after the cooling and be designated as CDY-3A, again in molecular sieve: ammonium chloride: the ratio of water=1: 0.1: 10 was with 90 ℃ of ammonium chloride solutions washings 10 minutes, and drying obtains the finished product molecular sieve, is numbered CDY-3.
It is 11.9 heavy % that fluorescence method records CDY-3A rare earth oxide content, and sodium oxide molybdena is 4.8 heavy %; Rare earth oxide content is 12.1 heavy % among the CDY-3, and sodium oxide content is 0.7 heavy %, its
27Al MAS NMR spectrum has the feature of Fig. 1, is that the 0ppm place does not have the peak to occur in chemical shift.
With after the ammonium chloride solution exchange, the rare earth oxide content that fluorescence method records wherein is 12.2 heavy % with CDY-3, and content of rare earth does not reduce, and illustrates that rare earth ion is all in the little cage of molecular sieve.
Embodiment 4
Get 18.6 kilograms NaY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant commodity, igloss 24.9 heavy %, silica alumina ratio is 5.2) and 110 kilograms of deionized waters join in the reactor, be warmed up to 90 ℃, again to the ammonium sulfate that wherein adds 3.5 kilograms, stir and use after 5 minutes between hydrochloric acid regulation system pH to 3.5～4.0, continue to stir after 1 hour, filter, the molecular sieve filter cake adds the making beating of 90 kg water, add 10.4 liters of re chlorides again, stir under the room temperature and use after 5 minutes between hydrochloric acid regulation system pH to 3.5～5.5, continue to stir after 1 hour, add 1.6 kilograms of ammoniacal liquor, stir after 5 minutes and filter, and washing, the laggard roaster of pneumatic conveying drying is when weight space velocity 0.1
-1Following 540 ℃ of roastings of water vapour 1.5 hours, obtain molecular sieve after the cooling and be designated as CDY-4A, again in molecular sieve: ammonium chloride: the ratio of water=1: 0.1: 10 was with 60 ℃ of ammonium chloride solutions washings 10 minutes, and drying obtains the finished product molecular sieve, is numbered CDY-4.
It is 21.2 heavy % that fluorescence method records CDY-4A rare earth oxide content, and sodium oxide molybdena is 3.9 heavy %; Rare earth oxide content is 21.6 heavy % among the CDY-4, and sodium oxide content is 0.2 heavy %, its
27Al MAS NMR spectrum has the feature of Fig. 1, is that the 0ppm place does not have the peak to occur in chemical shift.
Once more with after the ammonium chloride solution exchange, the rare earth oxide content that fluorescence method records wherein is 21.6 heavy % with CDY-4, and content of rare earth does not reduce, and illustrates that rare earth ion is all in the little cage of molecular sieve.
Embodiment 5
Get 18.6 kilograms NaY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant commodity, igloss 24.9 heavy %, silica alumina ratio is 5.2) and 110 kilograms of deionized waters join in the reactor, add 10.4 liters of re chlorides again, stir under the room temperature and use after 5 minutes between hydrochloric acid regulation system pH to 3.5～5.5, continue to stir after 1 hour and filter.Collect filtrate, add 1.5 kg of hydrogen sodium oxide molybdenas in the filtrate and make the rare earth ion in the filtrate be converted into the rare earth hydrate precipitation, filter, wash, again rare earth hydrate filter cake and the molecular sieve filter cake that obtains added the making beating of 80 kg water, filtration, the laggard roaster of pneumatic conveying drying are when weight space velocity 0.1
-1Following 540 ℃ of roastings of water vapour 2.5 hours, obtain molecular sieve after the cooling and be designated as CDY-5A, again in molecular sieve: ammonium chloride: the ratio of water=1: 0.1: 10 was with 80 ℃ of ammonium chloride solutions washings 10 minutes, and drying obtains the finished product molecular sieve, is numbered CDY-5.
It is 21.0 heavy % that fluorescence method records CDY-5A rare earth oxide content, and sodium oxide molybdena is 3.7 heavy %; Rare earth oxide content is 21.4 heavy % among the CDY-5, and sodium oxide content is 0.3 heavy %, its
27Al MAS NMR spectrum has the feature of Fig. 1, is that the 0ppm place does not have the peak to occur in chemical shift.
Once more with after the ammonium chloride solution exchange, the rare earth oxide content that fluorescence method records wherein is 21.4 heavy % with CDY-5, and content of rare earth does not reduce, and illustrates that rare earth ion is all in the little cage of molecular sieve.
Embodiment 6
Get 18.6 kilograms NaY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant, igloss 24.9 heavy %, silica alumina ratio is 5.2) and 140 kilograms of deionized waters join in the reactor, again to wherein adding 2.1 kilo sulfuric acid ammoniums, stir under 90 ℃ and use after 5 minutes between hydrochloric acid regulation system pH to 3.5～5.5, continue to stir filtration after 1 hour.Filter cake adds 140 kg water, add 5.3 kilograms of solid lanthanum chlorides again, 90 ℃ were stirred 2 hours down, added 1.5 kilograms of sodium aluminate solutions and 1.2 kilograms of ammoniacal liquor, stirred after 5 minutes and filtered, and directly advance roaster after the washing, pneumatic conveying drying, 650 ℃ of roastings are 1.5 hours under dry air, obtain molecular sieve after the cooling and are designated as CDY-6A, again with 10 times deionized water washing 10 minutes, drying obtains the finished product molecular sieve, is numbered CDY-6.
It is 15.9 heavy % that fluorescence method records CDY-6A lanthana content, and sodium oxide molybdena is 4.6 heavy %; Lanthana content is 16.2 heavy % among the CDY-6, and sodium oxide content is 0.7 heavy %, its
27Al MAS NMR spectrum has the feature of Fig. 1, is that the 0ppm place does not have the peak to occur in chemical shift.
With CDY-6 once more with after the ammonium chloride solution exchange, the lanthana content that fluorescence method records wherein is 16.3 heavy %, the molecular sieve content of rare earth slightly increases, illustrate that rare earth ion is in little cage, rare earth ion in the little cage in the ammonium chloride exchange process can not with ammonium ion exchange, thereby total amount of rare earth is constant before and after the exchange, but the ammonium exchange can further reduce the molecular sieve sodium oxide content, thereby causes molecular sieve middle rare earth content to increase.
Embodiment 7～14 explanations Preparation of catalysts process provided by the invention.
Embodiment 7
The CDY-1 molecular sieve pulp of getting concentration and be 30.0 heavy % joins in 20 liters of colloid generating kettles for 5.4 kilograms, add 2 kg water more successively, 66 gram RPSA (MFI structure shape-selective molecular sieves, long company product is built in the Hunan, down together), 2.5 kg aluminium colloidal sol (aluminium oxide 21.8 heavy %, down together), 2.0 kilogram boehmite (alumina content 56.6 heavy %, together following) and 3.1 kilograms of kaolin (commodity of China Kaolin Co., Ltd, igloss 15.8 heavy %, down together), stir the back and add 100 milliliters of hydrochloric acid, stir spray-drying after 2 minutes, again through washing, drying obtains catalyst CAT-1.
Catalyst CAT-1 consists of: the RPSA of 27 heavy %CDY-1,1 heavy %, 19 heavy % boehmites, 9 heavy % aluminium colloidal sols and 44 heavy % kaolin.
Embodiment 8
Get 1.24 kilograms of CDY-2 (igloss 3.20%) and 0.599 kilogram of super stable molecular sieve PSRY (Chang Ling catalyst plant industrial products, igloss 9.9%) and 5.0 kg water join and add 2 kg water, 66 gram RPSA, 2.5 kg aluminium colloidal sols, 2.0 kilograms of boehmites and 3.0 kilograms of kaolin in 20 liters of colloid generating kettles more successively, stir the back and add 100 milliliters of hydrochloric acid, stir spray-drying after 2 minutes, obtain catalyst CAT-2 through washing, drying again.
Catalyst CAT-2 consists of: the RPSA of 20 heavy %CDY-2,9.0 heavy %PSRY, 1.0 heavy %, 19 heavy % boehmites, 9 heavy % aluminium colloidal sols and 42 heavy % kaolin.
Embodiment 9
The CDY-3 molecular sieve pulp of getting concentration and be 30.0 heavy % joins in 20 liters of colloid generating kettles for 5.8 kilograms, add 2 kg water, 2.5 kg aluminium colloidal sols, 2.0 kilograms of boehmites and 3.0 gram kaolin more successively, stir the back and add 100 milliliters of hydrochloric acid, stir spray-drying after 2 minutes, obtain catalyst CAT-3 through washing, drying again.
Catalyst CAT-3 consists of: 29 heavy %CDY-3,19 heavy % boehmites, 9 heavy % aluminium colloidal sols and 43 heavy % kaolin.
Embodiment 10
Get 1.24 kilograms of CDY-4 (igloss 3.20%) and 0.599 kilogram of super stable molecular sieve PSRY (Chang Ling catalyst plant industrial products, igloss 9.9%, down with) and 5.0 kg water join and add 2 kg water, 66 in 20 liters of colloid generating kettles more successively and restrain RPSA, 2.5 kg aluminium colloidal sols, 2.0 kilograms of boehmites and 3.0 kilograms of kaolin, stir the back and add 100 milliliters of hydrochloric acid, stir spray-drying after 2 minutes, obtain catalyst CAT-4 through washing, drying again.
Catalyst CAT-4 consists of: 20 heavy %CDY-4,9 heavy %PSRY, 1.0 heavy %RPSA, 19 heavy % boehmites, 9 heavy % aluminium colloidal sols and 42 heavy % kaolin.
Embodiment 11
The CDY-5 molecular sieve pulp of getting concentration and be 30.0 heavy % joins in 20 liters of colloid generating kettles for 7.3 kilograms, add 3 kg water, 1.4 kg aluminium colloidal sols, 3.0 kilograms of boehmites and 7.4 gram halloysites (igloss 12.0 heavy %) more successively, stir the back and add 20 milliliters of hydrochloric acid, continue to stir spray-drying after 2 minutes, obtain catalyst CAT-5 through washing, drying again.
Catalyst CAT-5 consists of: 22 heavy %CDY-5,17 heavy % boehmites, 3 heavy % aluminium colloidal sols and 58 heavy % halloysites.
Embodiment 12
The CDY-6 molecular sieve pulp of getting concentration and be 30.0 heavy % joins in 20 liters of colloid generating kettles for 5.8 kilograms, add 2 kg water, 2.5 kg aluminium colloidal sols, 2.0 kilograms of boehmites and 3.1 gram kaolin more successively, stir the back and add 100 milliliters of hydrochloric acid, stir spray-drying after 2 minutes, obtain catalyst CAT-6 through washing, drying again.
Catalyst CAT-6 consists of: 29 heavy %CDY-6,19 heavy % boehmites, 9 heavy % aluminium colloidal sols and 43 heavy % kaolin.
Embodiment 13
The CDY-1 molecular sieve pulp of getting concentration and be 30.0 heavy % joins in 20 liters of colloid generating kettles for 5.4 kilograms, add 2 kg water more successively, 94 gram ZRP-5 (MFI structure shape-selective molecular sieves, long company product is built in the Hunan, igloss 4.0 heavy %), 2.5 kg aluminium colloidal sol, 2.0 kilogram boehmite and 3.1 kilograms of kaolin, stir the back and add 100 milliliters of hydrochloric acid, adding 96 milliliters of re chlorides in the container in addition, add 110 milliliters of ammoniacal liquor again, obtain the precipitation of rare earth hydrate, the precipitation of rare earth hydrate is joined in the colloid generating kettle, stir spray-drying after 2 minutes, again through washing, drying obtains catalyst CAT-7.
Catalyst CAT-7 consists of: 27 heavy %CDY-1,1.5 heavy %ZRP-5,0.5 heavy %RE
2O
3, 19 heavy % boehmites, 9 heavy % aluminium colloidal sols and 43 heavy % kaolin.
Embodiment 14
Getting 1.58 kilograms of CDY-3 (igloss 5.18%) and 0.666 kilogram of super stable molecular sieve PSRY and 5.0 kg water joins in 20 liters of colloid generating kettles, 66 restrain RPSA, 2.2 kg aluminium colloidal sols, 2.3 kilograms of boehmites and 2.4 kilograms of kaolin successively again, stir the back and add 100 milliliters of hydrochloric acid, stir spray-drying after 2 minutes, obtain catalyst CAT-8 through washing, drying again.
Catalyst CAT-8 consists of: 25 heavy %CDY-3,10 heavy %PSRY, 1.0 heavy %RPSA, 22 heavy % boehmites, 8 heavy % aluminium colloidal sols and 34 heavy % kaolin.
Comparative Examples 1
This Comparative Examples prepares olefine lowering catalyst with reference to the composition of catalyst F among the CN 1317547A, and wherein adopting active component is the MOY molecular sieve.
Getting concentration is MOY (the Shandong catalyst plant industrial products of 30.0 heavy %, rare earth oxide 9.1%, phosphorous oxide 3.3%) molecular sieve pulp joins in 20 liters of colloid generating kettles for 7.0 kilograms, add 2 kg water more successively, 66 gram RPSA, 2.5 kg aluminium colloidal sol, 2.0 kilogram boehmite and 2.5 kilograms of kaolin, stir the back and add 100 milliliters of hydrochloric acid, adding 96 milliliters of re chlorides in the container in addition, add 110 milliliters of ammoniacal liquor again, obtain the precipitation of rare earth hydrate, the precipitation of rare earth hydrate is joined in the colloid generating kettle, stir spray-drying after 2 minutes, again through washing, drying obtains comparative catalyst DB-1.
Comparative catalyst DB-1 consists of: 35 heavy %MOY, 1.0 heavy %RPSA, 0.5 heavy %RE
2O
3, 19 heavy % boehmites, 9 heavy % aluminium colloidal sols and 35.5 heavy % kaolin.
Comparative Examples 2
This Comparative Examples prepares olefine lowering catalyst with reference to the composition of catalyst F among the CN 1317547A, and wherein adopting active component is the PREY-2 molecular sieve.
Getting concentration is that 30.0 PREY-2 molecular sieve (method by patent CN 1317547A example 6 the prepares PREY-2) slurries that weigh % join in 20 liters of colloid generating kettles for 7.0 kilograms, add 66 gram RPSA more successively, 2.5 kg aluminium colloidal sol, 2.0 kilogram boehmite and 2.5 kilograms of kaolin, stir the back and add 100 milliliters of hydrochloric acid, adding 96 milliliters of re chlorides in the container in addition, add 110 milliliters of ammoniacal liquor again, obtain the precipitation of rare earth hydrate, the precipitation of rare earth hydrate is joined in the colloid generating kettle, stir spray-drying after 2 minutes, again through washing, drying obtains comparative catalyst DB-2.
Comparative catalyst DB-2 consists of: 35 heavy %PREY-2,1.0 heavy %RPSA, 0.5 heavy %RE
2O
3, 19 heavy % boehmites, 9 heavy % aluminium colloidal sols and 35.5 heavy % kaolin.
Comparative Examples 3
This Comparative Examples is with reference to the conventional olefine lowering catalyst of the composition preparation of embodiment 1.
Getting concentration is REY molecular sieve (the Shandong catalyst plant production of 30.0 heavy %, rare earth oxide 20.0 heavy %) 5.4 kilograms join in 20 liters of colloid generating kettles, add 2 kg water more successively, 66 gram RPSA, 2.5 kg aluminium colloidal sol, 2.0 kilogram boehmite and 3.1 kilograms of kaolin, stir the back and add 100 milliliters of hydrochloric acid, adding 96 milliliters of re chlorides in the container in addition, add 110 milliliters of ammoniacal liquor again, obtain the precipitation of rare earth hydrate, the precipitation of rare earth hydrate is joined in the colloid generating kettle, stir spray-drying after 2 minutes, again through washing, drying obtains comparative catalyst DB-3.
Comparative catalyst DB-3 consists of: 27 heavy %REY, 1.0 heavy %RPSA, 0.5 heavy %RE
2O
3, 19 heavy % boehmites, 9 heavy % aluminium colloidal sols and 43.5 heavy % kaolin.
The catalyst of the foregoing description and Comparative Examples preparation and the physico-chemical property of contrast medium see Table 1.
Table 1
| The catalyst numbering | RE 2O 3，m％ | Na 2O，m％ | P 2O 5，m％ | SA，m 2/g | Activity, (800 ℃/17h) |
| CAT-1 | 4.3 | 0.08 | 0 | 246 | 74 |
| CAT-2 | 4.3 | 0.11 | 0 | 251 | 68 |
| CAT-3 | 3.5 | 0.06 | 0 | 258 | 66 |
| CAT-4 | 4.3 | 0.12 | 0.1 | 253 | 65 |
| CAT-5 | 4.7 | 0.05 | 0 | 198 | 68 |
| CAT-6 | 4.6 | 0.07 | 0 | 262 | 74 |
| CAT-7 | 4.8 | 0.07 | 0 | 248 | 75 |
| CAT-8 | 3.0 | 0.12 | 0.1 | 240 | 64 |
| DB-1 | 3.7 | 0.22 | 1.2 | 273 | 56 |
| DB-2 | 3.3 | 0.25 | 2.7 | 282 | 56 |
| DB-3 | 5.9 | 0.24 | 0 | 227 | 55 |
Table 1 data show, adopting CDY is that the catalyst of active component preparation is compared with contrast medium and had excellent hydrothermal stability more.
Embodiment 15
Present embodiment illustrates the fixed fluidized bed evaluation result of catalyst provided by the invention.
Through aging 12 hours of 800 ℃, 100% steam, feedstock oil be military mixed three, 500 ℃ of reaction temperatures, air speed 30h before the evaluating catalyst
-1, oil ratio is 6.0.
The evaluation result of CAT-1 and contrast medium DB-1, DB-2 and DB-3 sees Table 2.
The evaluation result of CAT-2～CAT-8 sees Table 3.
Table 2
| Catalyst | CAT-1 | DB-1 | DB-2 | DB-3 |
| Dry gas | 1.9 | 2.2 | 2.0 | 2.4 |
| Liquefied gas | 13.9 | 14.1 | 12.6 | 14.6 |
| Gasoline | 48.1 | 44.3 | 43.5 | 45.1 |
| Diesel oil | 18.4 | 21.0 | 21.6 | 18.1 |
| Heavy oil | 8.4 | 10.3 | 12.2 | 9.6 |
| Coke | 9.3 | 8.1 | 8.1 | 10.2 |
| Conversion ratio | 73.2 | 68.7 | 66.2 | 72.3 |
| RON | 86.3 | 86.1 | 86.2 | 86.1 |
| MON | 81.4 | 81.8 | 81.3 | 81.3 |
| N-alkanes | 4.04 | 3.78 | 3.75 | 3.90 |
| Isomeric alkane | 37.93 | 37.90 | 37.55 | 38.03 |
| Alkene | 13.84 | 29.05 | 19.28 | 18.21 |
| Cycloalkane | 6.64 | 7.10 | 7.05 | 7.09 |
| Aromatic hydrocarbons | 37.47 | 32.00 | 32.22 | 32.69 |
Y zeolite content is 27 heavy % among Comparative Examples DB-3 and the Embodiment C AT-1, and Y zeolite content is 35 heavy % in Comparative Examples DB-1, the DB-2 catalyst.From the fixed fluidized bed evaluation result that table 2 provides, employing CDY is that the catalyst CAT-1 of active component compares with contrast medium, and gasoline olefin is minimum, gasoline aromatic hydrocarbons is the highest, heavy oil is minimum.
Table 3
| The catalyst numbering | CAT-2 | CAT-3 | CAT-4 | CAT-5 | CAT-6 | CAT-7 | CAT-8 |
| Dry gas | 1.9 | 2.0 | 2.0 | 1.9 | 1.9 | 1.8 | 1.9 |
| Liquefied gas | 13.2 | 12.3 | 13.0 | 12.1 | 13.5 | 13.4 | 13.5 |
| Gasoline | 47.7 | 48.1 | 47.5 | 48.6 | 47.6 | 48.5 | 48.1 |
| Diesel oil | 21.3 | 20.3 | 21.7 | 20.3 | 20.5 | 18.6 | 19.7 |
| Heavy oil | 8.0 | 9.2 | 8.0 | 9.1 | 8.6 | 8.4 | 9.1 |
| Coke | 7.9 | 8.1 | 7.8 | 8.0 | 7.9 | 9.3 | 7.7 |
| Conversion ratio | 71.2 | 70.5 | 70.3 | 71.2 | 71.2 | 73.2 | 71.2 |
| RON | 86.3 | 86.6 | 86.4 | 85.8 | 86.3 | 86.3 | 86.6 |
| MON | 81.4 | 81.6 | 81.4 | 81.0 | 81.4 | 81.4 | 81.3 |
| Alkene | 16.59 | 18.20 | 16.63 | 17.72 | 15.76 | 13.92 | 18.21 |
| Aromatic hydrocarbons | 34.03 | 33.28 | 34.31 | 33.30 | 35.72 | 36.49 | 32.33 |
Claims (10)
1, a kind of Cracking catalyst that reduces catalytic cracking gasoline olefine content, it is characterized in that this catalyst contains the CDY molecular sieve of 10～50 heavy %, the content of rare earth of said CDY molecular sieve is counted 12～22 heavy % with rare earth oxide, and rare earth ion all is positioned at the little cage of molecular sieve, its
27In the Al MAS NMR spectrogram, be that the 0ppm place does not have the peak to occur in chemical shift.
2, according to the catalyst of claim 1, said CDY molecular sieve content of rare earth is 13～20 heavy %.
3, according to the catalyst of claim 2, said CDY molecular sieve content of rare earth is 14～18 heavy %.
4, according to the catalyst of one of claim 1～3, the sodium oxide content of said CDY molecular sieve is 0.1～1.0 heavy %.
5,, it is characterized in that this catalyst is by the USY molecular sieve of the MFI structure shape-selective molecular sieve of the clay of the CDY molecular sieve of 15～35 heavy %, 20～60 heavy %, 15～45 heavy inorganic oxide binders, 0～5 heavy %, 0～20 heavy % and/or REUSY molecular sieve with RE according to the catalyst of claim 1
20
3The rare earth oxide of meter 0～2 heavy % is formed.
6, according to the catalyst of claim 5, said clay is selected from one or more the mixture in kaolin, halloysite, imvite, diatomite, bentonite, attapulgite and the sepiolite.
7, according to the catalyst of claim 5, said inorganic oxide binder is selected from one or more the mixture in boehmite, aluminium colloidal sol, Ludox, Alusil and the aluminum phosphate.
8, according to the catalyst of claim 7, said inorganic oxide binder is selected from boehmite and/or aluminium colloidal sol.
9, according to the catalyst of claim 5, said rare earth oxide is free rare earth oxide or free hydrogen rare earth oxide.
10,, it is characterized in that this catalyst is made up of the CDY molecular sieve of 20～28 heavy %, the clay of 40～55 heavy %, the boehmite of 15～20 heavy %, the aluminium colloidal sol of 3～9 heavy %, the MFI structure shape-selective molecular sieve of 0.5～1.5 heavy %, the USY molecular sieve of 0～10 heavy % and the free hydrogen rare earth oxide of 0～0.5 heavy % according to claim 5, one of 8 or 9 catalyst.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9844772B2 (en) | 2011-12-15 | 2017-12-19 | Petrochina Company Limited | Heavy oil catalytic cracking catalyst and preparation method therefor |
| US9889439B2 (en) | 2011-12-15 | 2018-02-13 | Petrochina Company Limited | High light received heavy oil catalytic cracking catalyst and preparation method therefor |
| US9968918B2 (en) | 2012-06-01 | 2018-05-15 | Petrochina Company Limited | Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof |
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| CN102233274B (en) * | 2010-04-28 | 2014-07-02 | 中国石油化工股份有限公司 | Catalyst for reducing alkene content in aromatic hydrocarbon, and a preparation method thereof |
| AU2013284234B2 (en) | 2012-06-27 | 2018-03-01 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst containing modified Y type molecular sieve and preparation method therefor |
| KR102109395B1 (en) | 2012-09-14 | 2020-05-28 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor |
| CN103657712B (en) * | 2012-09-14 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and preparation method thereof |
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| US9844772B2 (en) | 2011-12-15 | 2017-12-19 | Petrochina Company Limited | Heavy oil catalytic cracking catalyst and preparation method therefor |
| US9889439B2 (en) | 2011-12-15 | 2018-02-13 | Petrochina Company Limited | High light received heavy oil catalytic cracking catalyst and preparation method therefor |
| US9968918B2 (en) | 2012-06-01 | 2018-05-15 | Petrochina Company Limited | Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof |
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