CN102451754B - Molecular sieve composition, molecular sieve active component-containing particle, and their preparation methods as well as catalytic cracking catalyst - Google Patents
Molecular sieve composition, molecular sieve active component-containing particle, and their preparation methods as well as catalytic cracking catalyst Download PDFInfo
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Abstract
The invention relates to a molecular sieve composition and its preparation method. Specifically, the preparation method of the composition comprises: mixing and contacting an MFI structured zeolite with an organic amine solution, then mixing and contacting the obtained mixture with a Y-type zeolite. The invention also provides a molecular sieve active component-containing particle, and its preparation method as well as a catalytic cracking catalyst. The method consists of: mixing and contacting an MFI structured zeolite with an organic amine solution; mixing and contacting the obtained mixture with a Y-type zeolite, separating a solid from the obtained mixture and drying the solid, beating the dried solid with clay and a silica sol, then drying and roasting the obtained slurry. The catalytic cracking catalyst provided in the invention has strong heavy oil cracking capacity, so that the yield of light olefins, especially ethylene can be high.
Description
Technical field
The present invention relates to a kind of combination of molecular sieve and contain the particle of molecular sieve active component and their preparation method and a kind ofly contain the catalytic cracking catalyst that contains the particle of molecular sieve active component of the present invention.
Background technology
Ethene and propylene are important industrial chemicals, the very vigorous and continuous growth to its demand.Ethene, the propylene of existing market more than 95% provided by naphtha steam cracking and heavy-oil catalytic preparing low-carbon olefins technology.Heavy-oil catalytic preparing low-carbon olefins operator utilizes the catalytic pyrolysis technology, and energy consumption is low, and ingredient requirement is low, and the product profile adjustment is flexible, has larger development prospect satisfying on the ever-increasing demand in future market.But, utilize riser reactor in prior art, the technique ubiquity ethylene yield of processing heavy oil producing light olefins is not high, the problem that coke yield is high.
In addition, raw material becomes gradually and heavily becomes bad in recent years, and the refinery requires to improve the ability of catalyst cracked fuel oil, improves the particularly productive rate of ethene of low-carbon alkene, and is in addition, also harsher to the requirement of its supporting catalyst.
The process of heavy oil catalytic pyrolysis preparing ethylene is pursued is some intermediate products in a series of consecutives and parallel reaction, belong to irreversible complex reaction network, there are competition in thermal response and catalytic reaction on reaction time and the extent of reaction, finally can generate non-target products such as coke, methane, H2, side reaction is many, and inactivation is fast.Compare with DCC with FCC, the catalytic thermal cracking catalyst primary first-order equation is different from the secondary response type, the side reaction that need to suppress is also different, how to control the degree of thermal response and catalytic reaction and selectively most important, and catalyst should fully take into account the balance of this two classes reaction in preparation process.
For example, CN1031029A discloses a kind of cracking catalyst of clay molecular sieve with layer structure.Prepare this catalyst sodium type lamellar clay used and be with sodium-chloride water solution and natural calcium type soil and exchange, after filtration, drip washing makes; Or with the mix and blend exchange 8 hours in water of highly acid polystyrene sodium type cationic ion-exchange resin and natural calcium type soil, hold over night gets that particle diameter that the upper strata suspends makes less than the clay of 2 microns.Although preparing the little anti-initial activity of light oil of this catalyst with calcium type lamellar clay is 46%, the catalytic cracking light oil microactivity after 800 ℃ of water vapour deactivations are processed 4 hours only has 28%, can not satisfy industry to the requirement of catalyst stability.
And for example, CN1031489A discloses a kind of preparation method who contains complex carrier or the catalyst of clay molecular sieve with layer structure, be each component raw material with this complex carrier or catalyst: the lamellar clay of montomorillonite class or regularly interstratified mineral structure, zeolite molecular sieve, refractory oxide, clay are in required ratio mixed-forming, then carry out cross-linking reaction with crosslinking agent, and make required carrier or catalyst through steps such as aging, roastings.
For another example, CN1211470A points out to adopt the modified molecular screen increases such as alkaline earth metals calcium, magnesium to select the shaped reaction performance.But catalyst activity is still on the low side, must strengthen the catalyst use amount in production, strengthens the agent consumption, the active requirement that could keep required catalyst.
Summary of the invention
The objective of the invention is to overcome the lower defective of catalytic activity of the catalytic cracking catalyst of prior art, a kind of combination of molecular sieve be provided and a kind ofly have the particle that contains the molecular sieve active component that contains this combination of molecular sieve of higher catalytic activity and their preparation method, providing simultaneously and contained the catalytic cracking catalyst that this contains the particle of molecular sieve active component.
The invention provides a kind of preparation method of combination of molecular sieve, wherein, the preparation method of described composition comprises that the zeolite with the MFI structure contacts with the By Amine Solutions mixing, mixes the mixture that obtains contacting with y-type zeolite.
The invention provides the combination of molecular sieve of prepared in accordance with the method for the present invention.
The invention provides a kind of preparation method who contains the particle of molecular sieve active component, wherein, the method comprises provides a kind of mixture, isolate solid and drying in described mixture, the solid that drying is obtained and clay and Ludox making beating, with slurry dried and the roasting that obtains, the combination of molecular sieve that described mixture is served as reasons and adopted method of the present invention to make.
The invention provides the particle that contains the molecular sieve active component that the method according to this invention obtains.
The present invention further provides a kind of catalytic cracking catalyst, described catalytic cracking catalyst contains particle a and particle b, described particle b contains rectorite and heat-resistant inorganic oxide matrix, wherein, the particle of described particle a for making according to the preparation method who contains the particle of molecular sieve active component provided by the invention.
Preparation of the present invention contains the method for the particle of molecular sieve active component, by isolate solid and dry from combination of molecular sieve of the present invention, the solid that drying is obtained and clay and Ludox making beating, the slurry dried and the roasting that obtain can be obtained, namely by introduce organic amine in the combination of molecular sieve building-up process, make the particle that contains the molecular sieve active component of the present invention more existing directly with zeolite and binding agent (as Al
2O
3) particle that obtains of sintering has especially ethylene selectivity of higher activity, selectivity of light olefin, and have lower coke yield.Therefore, make by the particle a that contains the molecular sieve active component provided by the invention and contain the heavy oil cracking ability of catalyst of particle b of clay and heat-resistant inorganic oxide matrix strong, the high feedstock oil of blending ratio is had heavy oil conversion performance preferably, particularly the productive rate of ethene is high to make low-carbon olefines high-output.
The specific embodiment
According to the present invention, the preparation method of described composition comprises that the zeolite with the MFI structure contacts with the By Amine Solutions mixing, mixes the mixture that obtains contacting with y-type zeolite.
Although as long as can obtain combination of molecular sieve according to method of the present invention, but the present inventor finds, when the weight ratio of the zeolite of described organic amine and MFI structure is 0.2-7: 1, be preferably 0.2-5: 1, the weight ratio of the zeolite of described y-type zeolite and MFI structure is 0.01-1: 1, be preferably 0.1-0.75: 1, it is outstanding that the particle that contains the molecular sieve active component that is synthesized by the combination of molecular sieve that obtains has advantages of that catalytic activity is higher, performance is more stable etc.
The present invention is not particularly limited the concentration of described By Amine Solutions, as long as guarantee to make the organic amine in the solution of organic amine to contact with the zeolite with MFI structure.Under preferable case, more effective with contacting of the zeolite with MFI structure in order to make organic amine, the concentration of described By Amine Solutions is generally the 0.05-15 % by weight, is preferably the 0.1-10 % by weight.Under preferable case, the zeolite of the described MFI of having structure and the weight ratio of By Amine Solutions are 1-60: 100, and 5-30 more preferably: 100.In addition, preferred y-type zeolite and the gross weight with zeolite of MFI structure are no more than 60 % by weight of the weight of By Amine Solutions.
According to the present invention, the kind of described organic amine can be various organic amines known in the field, for example, can be selected from polyvinylamine, polymine and N, one or more in the N-dimethyl alkylamine.Wherein, the number-average molecular weight of described polyvinylamine can be 1000-10000, is preferably 1000-5000, more preferably 1000-3000; The number-average molecular weight of described polymine can be 1000-10000, is preferably 1000-5000, more preferably 1000-3000.to described N, the carbon number of the alkyl in the N-dimethyl alkylamine is not particularly limited, can be generally the straight or branched alkyl of 1-15 for carbon number, for example, N, N-dimethyl methylamine, N, the N-dimethyl amine, N, N-dimethyl n propylamine, N, the N-dimethyl butylamine, N, N-dimethyl cyclopentamine, N, the N-dimethylhexylamine, N, N-dimethyl octylame, N, N-dimethyl nonyl amine, N, N-dimethyl decyl amine, N, N-dimethyl undecyl amine, N, N-dimethyl lauryl amine, N, N-dimethyl tetradecylamine and N, at least a in N-dimethyl pentadecyl amine.The solvent that forms By Amine Solutions also can for the solvent of various routines known in the field, be preferably water.
According to the present invention, the zeolite that will have a MFI structure and By Amine Solutions mix the condition that contact and generally comprise the time that the temperature of mixing contact contacts with mixing.The temperature of described mixing contact can be selected in wider temperature range, for example, the zeolite of the described MFI of having structure mixes with By Amine Solutions the temperature that contacts can be 20-80 ℃, be preferably 40-70 ℃, the prolongation that mixes time of contact is conducive to described combination of molecular sieve and by the further raising of the performance of its particle that contains the molecular sieve active component that makes, but mixing long increase rate to their performances time of contact is also not obvious, therefore, generally, the time of described mixing contact can be 30-60 minute, is preferably 35-50 minute.
the present invention contacts to the zeolite with MFI structure the mixture that obtains and is not particularly limited with the mode that the y-type zeolite mixing contacts with the By Amine Solutions mixing, as long as the mixture that obtains is mixed with y-type zeolite to be contacted, but the present inventor finds, y-type zeolite is joined in described mixture in batches, resulting combination of molecular sieve and have better ethylene selectivity by the particle that contains the molecular sieve active component that this combination of molecular sieve makes, has better heavy oil conversion performance, therefore the present invention preferably joins y-type zeolite in described mixture in batches, under preferable case, the addition of every batch of y-type zeolite is at most 80 % by weight of the total consumption of y-type zeolite, be preferably the 30-70 % by weight, also comprise the time interval between the step of adjacent two batch mixed, the described time interval can be 5-120 minute, be preferably 15-60 minute.
According to the present invention, the zeolite of the described MFI of having structure can be various zeolites with MFI structure known in those skilled in the art, be preferably HZSM-5 zeolite and/or element modified ZSM zeolite, for example, one or more in the ZSM-5 zeolite of the ZSM-5 zeolite of phosphorus modification, phosphorus and rare earth modified ZSM-5, phosphorus and iron modification, in the ZSP zeolite of the ZRP zeolite of phosphorus modification and phosphorus modification, under further preferable case, described silica alumina ratio (SiO with zeolite of MFI structure
2/ Al
2O
3) being preferably 15-300, silica alumina ratio especially is preferably 30-200.
According to the present invention, the various y-type zeolites that described y-type zeolite can be known to the skilled person for example, can be selected from one or more in REY, REHY, USY, HY, REUSY, PREY, PREHY zeolite.
According to the present invention, the described preparation method who contains the particle of molecular sieve active component comprises provides a kind of mixture, and the solid of isolating in described mixture is also dry, with solid and clay and the Ludox making beating that obtains, with slurry dried and the roasting that obtains, the combination of molecular sieve of described mixture for being made by preceding method of the present invention.
In the present invention; the method of the solid that obtains and clay and Ludox making beating can be the methods of beating of routine known in the field; therefore; weight ratio to the mixture of the described solid that obtains and clay and Ludox does not have specific (special) requirements; generally; the weight ratio of the mixture of the solid that obtains and clay and Ludox can be 1: 0.2-10 is preferably 1: 0.5-6, and after usually mixing, the solid content of gained mixture is the 3-40 % by weight.
The selectable range of the weight ratio of described clay and Ludox is wider, but under preferable case, the weight ratio of described clay and Ludox can be 0.01-10: 1, and 0.1-4 more preferably: 1.
Wherein, the weight of described clay is with its butt weighing scale, and the weight of described Ludox is with SiO
2Meter.
Described Ludox can for this area Ludox commonly used, can commercially availablely also can prepare according to method known in those skilled in the art.
Under preferable case, the step of the solid that obtains and clay and Ludox making beating can also be comprised add rare earth compound, take the gross weight of the particle that contains the molecular sieve active component that obtains as benchmark, with RE
2O
3Meter, the consumption of described rare earth compound makes the described content that contains the particle middle rare earth of molecular sieve active component be no more than 8 % by weight.Wherein, RE represents rare earth element.
Wherein, the various clays that described clay can this area routine for example, can be selected from one or more in rectorite, kaolin, imvite, diatomite, galapectite, saponite, sepiolite, attapulgite, hydrotalcite and bentonite.
Described rare earth compound can be the various rare earth compounds of this area routine, for example, can be one or more in chloride, bromide and the nitrate of rare earth, in addition, can be a kind of salt of rare earth element, can be also the mixed rare earth compound that comprises multiple rare earth element commonly used in catalyst preparation process.Described rare earth element is preferably selected from one or more in lanthanide series.Described rare earth compound can add with solid form or with the form of the aqueous solution of rare earth compound, and the concentration of the aqueous solution of described rare earth compound generally can be the 20-60 % by weight.
According to the present invention, the method of described drying can adopt the drying means of various routines known in the field, its operating condition also can be carried out according to condition known in those skilled in the art, for example, and one or more in natural drying, vacuum drying and spray-drying; Be preferably spray-drying, the condition of described drying generally comprises dry temperature can be 100-200 ℃, and the dry time can 1-10 hour.
The method of described roasting can adopt the method for various routines known in the field, and its operating condition also can be carried out according to condition known in those skilled in the art, as long as organic amine is removed.For example, the temperature of roasting can be 400-650 ℃, and the time of roasting can be 0.5-6 hour.
According to a kind of concrete embodiment of the present invention, described combination of molecular sieve and the preparation method who contains the particle of molecular sieve active component comprise following concrete steps:
(1) zeolite with the MFI structure mixes with By Amine Solutions (mass percent concentration is the 0.05-15 % by weight), stirs 30-60 minute;
(2) y-type zeolite is divided the many batches of mixtures that obtain with step (1) mix, the addition of every batch of y-type zeolite is at most 80 % by weight of the total consumption of y-type zeolite, is preferably the 30-70 % by weight, and the time interval is 5-120 minute, and stirs 60-120 minute; Obtain combination of molecular sieve;
(3) combination of molecular sieve that step (2) is obtained filters, dries, obtains solid;
(4) preparation pH value is the Ludox of 1-3, and the preparation method of described Ludox can prepare according to conventional method, for example, and can be with water glass solution (SiO
2Concentration is preferably the 15-40 % by weight, and modulus of water glass is 3-3.5) join in sulfuric acid (the preferred mass percent concentration is 15-50%), first add soon, and stir, slowly add after adding half, and stop stirring, the maintenance slurry pH value is 1-3;
(5) clay is mixed with the Ludox that step (4) obtains, obtain containing clay and Ludox mixture (weight ratio of clay and Ludox is 0.1-10: 1, the weight of clay is with its butt weighing scale, the weight of Ludox is with SiO
2Meter);
(6) solid that step (3) is obtained mixes with the mixture of Ludox with the clay that step (5) obtains that (weight ratio of the solid that step (3) obtains and the mixture of clay and Ludox is 1: 0.2-10; and after usually mixing, the solid content of gained mixture is the 3-40 % by weight); stir, spray drying forming, roasting.
According to the present invention, described catalytic cracking catalyst contains particle a and particle b, and described particle b contains rectorite and heat-resistant inorganic oxide matrix, and wherein, described particle a is the particle of prepared in accordance with the method for the present invention.
According to the present invention, the selectable range of the weight ratio of described particle a and particle b is wider, generally, can be according to the demand flexible modulation particle a of catalytic cracking reaction and the weight ratio of particle b, in order to obtain better catalytic cracking effect, the weight ratio of described particle a and particle b can be 0.5-15: 1, be preferably 1-10: 1.
Under optimum condition, in described particle b, the weight ratio 0.5-15 of rectorite and heat-resistant inorganic oxide matrix: 1, be preferably 1-10: 1.
According to the present invention, the kind of described heat-resistant inorganic oxide matrix can adopt this area heat-resistant inorganic oxide matrix commonly used.For example, described heat-resistant inorganic oxide matrix can be selected from one or more in silica, gama-alumina, magnesia, silica-alumina and aluminium oxide-phosphorous oxide, is preferably silica.
Described rectorite is preferably basal spacing d
001Value be 2.7-5.0nm, the BET specific area is 100-300m
2The rectorite of/g.
According to the present invention, under preferable case, described heat-resistant inorganic oxide matrix contains silica, and the preparation method of described particle b comprises: sulfuric acid is mixed with waterglass, obtain the pH value for the slurries of 1-3, rectorite is mixed with the slurries that obtain, dry and roasting.
Described rectorite is wider with the adjustable extent of the weight ratio of the slurries that obtain, contain rectorite and heat-resistant inorganic oxide matrix as long as guarantee in described particle b, and preferably make the weight ratio 0.5-15 of rectorite and heat-resistant inorganic oxide matrix: 1, be preferably 1-10: 1.Therefore, generally, described rectorite can be 1 with the weight ratio of the slurries that obtain: 1.5-50.
Method and the condition of described drying, roasting describe in detail in preamble, do not repeat them here.
According to the present invention, can also contain rare earth compound in described catalyst, for example, can contain rare earth compound in described particle a and/or particle b.Described rare earth compound can be introduced by existing variety of way (for example method of dipping), as long as make catalyst of the present invention contain rare earth element.Under preferable case, introduce rare earth compound (being that particle b contains rare earth compound) in the process of preparation particle b, specifically, can before drying, rectorite be mixed with rare earth compound with the mixture of the slurries that obtain.Take the gross weight of catalyst as benchmark, with RE
2O
3Meter, the consumption of described rare earth compound makes the content of Rare Earths in Catalyst oxide be no more than 8 % by weight.
Except providing according to method of the present invention particle a and particle b, catalyst of the present invention can be after the particle a that will make respectively and particle b moulding, with 0.5-15: 1, be preferably 1-10: 1 weight ratio mixes and can make.
The below will be described in further detail the present invention by specific embodiment, but not thereby limiting the invention.
In each embodiment and Comparative Examples, Na in zeolite
2O, Fe
2O
3, NiO, Al
2O
3, SiO
2The content mensuration that adopts x-ray fluorescence method mensuration, micro-activity and abrasion index (AI) referring to [Science Press, nineteen ninety publishes for " Petrochemical Engineering Analysis method " (RIPP experimental technique), the volumes such as Yang Cuiding].
800 ℃/4h active (MA) is defined as: the activity data of surveying after 4 hours with 100% steam aging under 800 ℃, the MA method is measured referring to [" Petrochemical Engineering Analysis method " (RIPP experimental technique), Yang Cui waits volume surely, Science Press, nineteen ninety publishes].
Embodiment 1
The present embodiment is used for the preparation of explanation catalytic cracking catalyst.
A: preparation combination of molecular sieve and particle a
(1) under 30 ℃, with 14kg ZSP-3 molecular sieve (China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, ZSP-3 silica alumina ratio=40), (number-average molecular weight of polyvinylamine is 1800 (available from westernization instrument (Beijing) Science and Technology Ltd.s) with the 100kg polyvinylamine aqueous solution, the mass percent concentration of the polyvinylamine aqueous solution is 3%) mix, stirred 40 minutes, and obtained slurries 114kg;
(2) under 40 ℃, 4kg DASY2.0 molecular sieve (China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, silica alumina ratio is 5.6) is mixed with the slurries that step (1) obtains, stir and obtained slurries 118kg in 40 minutes;
(3) under 40 ℃, then 4kg DASY2.0 molecular sieve (China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, silica alumina ratio is 5.6) is mixed with the slurries that step (2) obtains, stir and obtained slurries 122kg in 20 minutes, obtain combination of molecular sieve;
(4) combination of molecular sieve that step (3) is obtained filters, and oven dry is 5 hours under 120 ℃, obtains solid 22.2kg;
(5) preparation of Ludox: with 20kg decationized Y sieve water and 35kg waterglass (SiO
2Content 28.4 % by weight, modulus of water glass 3.1) mix, join the H of 30kg
2SO
4In solution (mass percent concentration is 30 % by weight), the speed that adds is 60kg/ hour, stirs and obtains the Ludox slurries 85kg of pH=1.6 (with SiO
2Meter, Ludox is 9.9kg);
(6) with 19kg halloysite (Suzhou china clay company industrial products, solid content 72.3 % by weight) mix with the slurries that step (5) obtains, stirred 30 minutes, and obtained the mixture 104kg (solid content of mixture is 22.7 % by weight) of kaolin and Ludox slurries;
(7) in the kaolin that the solid that step (4) is obtained and step (6) obtain and the mixture of Ludox slurries, stirred 20 minutes, (baking temperature is 120 ℃ to spray drying forming, be 3 hours drying time), roasting (sintering temperature is 550 ℃, and roasting time is 2 hours) obtains containing the particle a of molecular sieve active component.
B: preparation particle b
(1) with 10kg decationized Y sieve water and 18kg waterglass (SiO
2Content 28.4 % by weight, modulus 3.1) mix, join the H of 10kg
2SO
4In solution (mass percent concentration is 50%), the speed that adds is 60kg/ hour, stirs the slurries 38kg that obtains pH=1.6;
(2) with 15kg rectorite (From Zhongxiang Hubei rectorite, solid content 87 % by weight, basal spacing d
001Value be 4nm, specific area is 200m
2/ g) slurries with step (1) mix, and stirring and obtaining the pH value is 1.8 slurries, and spray-drying (baking temperature is 120 ℃, and be 3 hours drying time) obtains particle b.
C: catalyst preparation
Particle a and particle b were mixed by weight 10: 1, after roasting (sintering temperature is 550 ℃, and roasting time is 2 hours), remove free Na with the deionized water washing
+Ion, dry (baking temperature is 150 ℃, and be 2 hours drying time) obtains catalyst 1.
Embodiment 2
The present embodiment is used for the preparation of explanation catalytic cracking catalyst.
method Kaolinite Preparation of Catalyst according to embodiment 1, different is, in the step of preparation particle a: (number-average molecular weight of polymine is 3000 (available from the good companies of Beijing Cohan) to change the 100kg polyvinylamine solution into 280kg polyethyleneimine: amine aqueous solution, the mass percent concentration of polyethyleneimine: amine aqueous solution is 5%), the ZSP-3 molecular sieve of 14kg is by 20kg ZRP (China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, silica alumina ratio is 60) replace, the consumption of DASY2.0 molecular sieve is 3kg (China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, silica alumina ratio is 4.9) (adding 1kg and 2kg respectively in step (2) and (3)), simultaneously particle a and particle b were mixed by weight 5: 1, obtain catalyst 2.
Embodiment 3
The present embodiment is used for the preparation of explanation catalytic cracking catalyst.
method Kaolinite Preparation of Catalyst according to embodiment 1, different is, change the 100kg polyvinylamine solution into 500kg N, N-dimethyl dodecyl amine aqueous solution (N, N-dimethyl lauryl amine is available from Wuhan Yuancheng Technology Development Co., Ltd.), N, the mass percent concentration of N-dimethyl dodecyl amine aqueous solution is 10%), the ZSP-3 molecular sieve of 14kg is by HZSM-5 (China Petrochemical Industry's catalyst asphalt in Shenli Refinery product of 10kg, silica alumina ratio is 45), DASY2.0 molecular sieve (China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, silica alumina ratio is 3.6) consumption be 7.5kg (adding 5kg and 2.5kg respectively in step (2) and (3)), simultaneously particle a and particle b were mixed by weight 15: 1, obtain catalyst 3.
Embodiment 4
The present embodiment is used for the preparation of explanation catalytic cracking catalyst.
According to the method Kaolinite Preparation of Catalyst of embodiment 1, different is that particle a and particle b were mixed to get by weight 1: 1.Obtain catalyst 4.
Embodiment 5
The present embodiment is used for the preparation of explanation catalytic cracking catalyst.
According to the method Kaolinite Preparation of Catalyst of embodiment 1, different is, with DASY2.0 molecular sieve disposable adding in step (2) of 8kg.Obtain catalyst 5.
Embodiment 6
The present embodiment is used for the preparation of explanation catalytic cracking catalyst.
According to the method Kaolinite Preparation of Catalyst of embodiment 1, different is, in the step (2) of preparation particle b with the chlorination mixed rare earth solution of 0.4kg (with RE
2O
3The concentration of meter is 23.5 % by weight, and Gansu rare earth new material Co., Ltd produces, La in rare earth oxide
2O
3Account for 23 % by weight, CeO
2Account for 46 % by weight, other rare earth oxide content is 31 % by weight (other rare earth oxide comprises praseodymium oxide and rubidium oxide)) and rectorite join together in the slurries of step (1) of preparation particle b.Obtain catalyst 6.
Comparative Examples 1
This Comparative Examples is used for the reference preparation method of explanation catalytic cracking catalyst.
The method that provides according to embodiment in CN1353012A 1 prepares Cracking catalyst, obtains comparative catalyst D1.
Comparative Examples 2
This Comparative Examples is used for the reference preparation method of explanation catalytic cracking catalyst.
The method that provides according to embodiment in CN101210187A 1 prepares Cracking catalyst, obtains contrast medium D2.
EXPERIMENTAL EXAMPLE 1-6
The present embodiment is used for the performance test of explanation catalytic cracking catalyst.
The catalyst that first will be made by embodiment 1-6 respectively is that 100% water vapour contacts 17 hours in 800 ℃ with content, carry out pretreatment, then, under the process existence of pretreatment catalyst (the catalyst loading amount is 180 grams), on the small fixed flowing bed device, grand celebration VGO is carried out catalytic cracking reaction with the mixed material (water injection rate (accounting for raw material) 35 % by weight, character see Table 1) of mixing refining 15 % by weight decompression residuum, and reaction temperature is 640 ℃, WHSV=4h
-1, agent weight of oil ratio is 15.Evaluation result sees Table 2.
Experiment Comparative Examples 1-2
The present embodiment is used for the performance test of explanation catalytic cracking catalyst.
Method according to EXPERIMENTAL EXAMPLE 1-6 is carried out performance test to catalytic cracking catalyst, and different is, the catalyst of test is catalyst D1 and the D2 that the method by Comparative Examples 1 and Comparative Examples 2 makes.Evaluation result sees Table 2.
Table 1
Table 2
Result by table 2 can be found out, adopts catalyst provided by the invention, and liquefied gas yield improves, and coke yield reduces, and the productive rate of ethene is greatly improved, and can guarantee that the productive rate of propylene does not reduce even higher simultaneously.
Claims (2)
1. the preparation method of a combination of molecular sieve, it is characterized in that, the preparation method of described composition comprises that the zeolite with the MFI structure contacts with the By Amine Solutions mixing, the mixture that obtains is mixed with y-type zeolite contact, the weight ratio of the zeolite of described organic amine and MFI structure is 0.2-7:1, and the weight ratio of the zeolite of described y-type zeolite and MFI structure is 0.01-1:1; The zeolite of described MFI structure mixes temperature 20-80 ℃ that contacts with By Amine Solutions, and the time is 30-60 minute, and the mixture that obtains is mixed temperature 40-80 ℃ that contacts with y-type zeolite, and the time is 60-120 minute.
2. method according to claim 1, wherein, the weight ratio of the zeolite of described organic amine and MFI structure is 0.2-5:1, the weight ratio of the zeolite of described y-type zeolite and MFI structure is 0.1-0.75:1.
3, method according to claim 1, wherein, the concentration of described By Amine Solutions is the 0.05-15 % by weight.
4, the described method of any one according to claim 1-3, wherein, described organic amine is selected from polyvinylamine, polymine and N, one or more in the N-dimethyl alkylamine.
5, method according to claim 1 wherein, is mixed with the mixture that obtains and y-type zeolite the method that contacts and is comprised y-type zeolite is joined in described mixture in batches.
6, method according to claim 5, wherein, the addition of every batch of y-type zeolite is at most 80 % by weight of the total consumption of y-type zeolite, comprises also between the step of adjacent two batch mixed that the time interval, the described time interval are 5-120 minute.
7, a kind of combination of molecular sieve that is made by the described method of any one in claim 1-6.
8, a kind of preparation method who contains the particle of molecular sieve active component, it is characterized in that, the method comprises provides a kind of mixture, isolate solid and drying in described mixture, the solid that drying is obtained and clay and Ludox making beating, with slurry dried and the roasting that obtains, the combination of molecular sieve of described mixture for being made by the described method of any one in claim 1-6.
9, method according to claim 8, wherein, described clay is selected from one or more in kaolin, imvite, diatomite, galapectite, saponite, sepiolite, attapulgite, hydrotalcite and bentonite.
10, method according to claim 8 wherein, also comprises the step of the solid that obtains and clay and Ludox making beating adding rare earth compound, take the gross weight of the described particle that contains the molecular sieve active component as benchmark, with RE
2O
3Meter, the consumption of described rare earth compound makes the described content that contains the particle middle rare earth of molecular sieve active component be no more than 8 % by weight.
11, method according to claim 8, wherein, the temperature of roasting is 400-650 ℃, the time of roasting is 0.5-6 hour.
12, a kind of particle that contains the molecular sieve active component that is obtained by the described method of any one in claim 8-11.
13, a kind of catalytic cracking catalyst, it is characterized in that, described catalytic cracking catalyst contains particle a and particle b, and described particle b contains rectorite and heat-resistant inorganic oxide matrix, and described particle a is the particle that according to claim 8-11, the described method of any one makes.
14, catalyst according to claim 13, wherein, by weight, the ratio of described particle a and particle b is 0.5-15:1.
15, catalyst according to claim 14, wherein, by weight, the ratio of described particle a and particle b is 1-10:1.
16, catalyst according to claim 13, wherein, described particle a and/or particle b also contain rare earth compound, take the gross weight of catalyst as benchmark, with RE
2O
3Meter, the consumption of described rare earth compound makes the content of Rare Earths in Catalyst oxide be no more than 8 % by weight.
17, catalyst according to claim 13, wherein, described heat-resistant inorganic oxide matrix contains silica, the preparation method of described particle b comprises sulfuric acid is mixed with waterglass, obtain the pH value and be the slurries of 1-3, rectorite is mixed contacting with the slurries that obtain, dry and roasting.
18, according to the described catalyst of claim 13 or 17, wherein, the basal spacing d of described rectorite
001Value be 2.7-5.0nm, the BET specific area is 100-300m
2/ g.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5318696A (en) * | 1992-12-11 | 1994-06-07 | Mobil Oil Corporation | Catalytic conversion with improved catalyst catalytic cracking with a catalyst comprising a large-pore molecular sieve component and a ZSM-5 component |
| CN1421508A (en) * | 2001-11-29 | 2003-06-04 | 中国石油化工股份有限公司 | Catalytic cracking process of paraffin-base crude oil with mixed residual oil |
| CN1704163A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Molecular screen microspherical catalyst |
| CN101036892A (en) * | 2007-04-19 | 2007-09-19 | 复旦大学 | Zeolite catalyst with functions of amic (nitrogen) hybrid acid-alkali and the preparing method and the application |
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2010
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5318696A (en) * | 1992-12-11 | 1994-06-07 | Mobil Oil Corporation | Catalytic conversion with improved catalyst catalytic cracking with a catalyst comprising a large-pore molecular sieve component and a ZSM-5 component |
| CN1421508A (en) * | 2001-11-29 | 2003-06-04 | 中国石油化工股份有限公司 | Catalytic cracking process of paraffin-base crude oil with mixed residual oil |
| CN1704163A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Molecular screen microspherical catalyst |
| CN101036892A (en) * | 2007-04-19 | 2007-09-19 | 复旦大学 | Zeolite catalyst with functions of amic (nitrogen) hybrid acid-alkali and the preparing method and the application |
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