CN102451754A - 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 the particle and their preparation method that contain the molecular sieve active component and a kind of and 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 chemical material, to the very vigorous and continuous growth of its demand.Ethene, the propylene of existing market more than 95% produced the low-carbon alkene technology by naphtha steam cracking and heavy-oil catalytic and provided.Heavy-oil catalytic is produced the low-carbon alkene operator and is utilized catalytic pyrolysis technology, and energy consumption is low, and ingredient requirement is low, and the product profile adjustment is flexible, has bigger development prospect satisfying on the ever-increasing demand in future market.But, utilize riser reactor in the prior art, the technology 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 harsh more to the requirement of its supporting catalyst.
What heavy oil catalytic pyrolysis produced that the process of ethene pursues is some intermediate products in a series of consecutives and the parallel reaction; Belong to irreversible complex reaction network; There are competition in thermal response and catalytic reaction on the reaction time and the extent of reaction; Finally can generate such as 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 with the secondary response type; Need the side reaction of inhibition also different, degree and selectivity how to control thermal response and catalytic reaction are most important, and catalyst should fully take into account the balance of these two types of reactions in the preparation process.
For example, CN1031029A discloses a kind of cracking catalyst of clay molecular sieve with layer structure.Preparing the used sodium type lamellar clay of this catalyst is with sodium-chloride water solution and the exchange of natural calcium type soil, makes through filtration, drip washing; Or mix in water with highly acid polystyrene sodium type cationic ion-exchange resin and natural calcium type soil and to stir exchange 8 hours, hold over night gets that upper strata particles suspended diameter processes less than 2 microns clay.Though using the little anti-initial activity of light oil of this catalyst of calcium type lamellar clay preparation is 46%, the catalytic cracking light oil microactivity after 800 ℃ of water vapour deactivations are handled 4 hours has only 28%, can not satisfy the requirement of industry to catalyst stability.
And for example; CN1031489A discloses a kind of complex carrier or Preparation of catalysts method that contains clay molecular sieve with layer structure; Be each component raw material with this complex carrier or catalyst: the lamellar clay of montomorillonite class or regular interbed mineral structure, zeolite molecular sieve, refractory oxide, clay are by required mixed moulding; Carry out cross-linking reaction with crosslinking agent then, and steps such as warp is aging, roasting are processed required carrier or catalyst.
For another example, CN1211470A points out to adopt 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 the production, strengthens the agent consumption, could keep required activity of such catalysts requirement.
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; Provide a kind of combination of molecular sieve and a kind of to 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, provide 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, said preparation of compositions method comprises that the zeolite with the MFI structure contacts with the mixing of organic amine solution, 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, This method comprises provides a kind of mixture, isolates solid in the said mixture and dry, and the solid that drying obtains is pulled an oar with clay and Ludox; With slurry dried that obtains and roasting, the combination of molecular sieve that said 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 obtains according to the method for the invention.
The present invention further provides a kind of catalytic cracking catalyst; Said catalytic cracking catalyst contains particle a and particle b; Said particle b contains rectorite and heat-resistant inorganic oxide matrix; Wherein, the particle of said 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; Through from combination of molecular sieve of the present invention, isolating solid and dry; Solid that drying is obtained and clay and Ludox making beating; Slurry dried that obtains and roasting can be obtained, promptly through in the combination of molecular sieve building-up process, introducing organic amine, make the particle that contains the molecular sieve active component of the present invention more existing directly with zeolite and binding agent (like 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 that heavy oil cracking ability by particle a that contains the molecular sieve active component provided by the invention and the catalyst of the particle b that contains clay and heat-resistant inorganic oxide matrix is strong, the high feedstock oil of blending ratio is had heavy oil conversion performance preferably, make the particularly productive rate height of ethene of low-carbon olefines high-output.
The specific embodiment
According to the present invention, said preparation of compositions method comprises that the zeolite with the MFI structure contacts with the mixing of organic amine solution, 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 inventor of the present invention finds; When the weight ratio of the zeolite of said organic amine and MFI structure is 0.2-7: 1, be preferably 0.2-5: 1, the weight ratio of the zeolite of said y-type zeolite and MFI structure is 0.01-1: 1; Be preferably 0.1-0.75: 1, the particle that contains the molecular sieve active component that is synthesized by the combination of molecular sieve that obtains has outstanding advantages such as catalytic activity is higher, performance is more stable.
The present invention does not limit the concentration of said organic amine solution is special, as long as guarantee to make the organic amine in the solution of organic amine to contact with the zeolite with MFI structure.Under the preferable case, more effective with contacting of the zeolite with MFI structure in order to make organic amine, the concentration of said organic amine solution is generally 0.05-15 weight %, is preferably 0.1-10 weight %.Under the preferable case, the weight ratio of the zeolite of the said MFI of having structure and organic amine solution is 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 weight % of the weight of organic amine solution.
According to the present invention, the kind of said 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 said polyvinylamine can be 1000-10000, is preferably 1000-5000, further is preferably 1000-3000; The number-average molecular weight of said polymine can be 1000-10000, is preferably 1000-5000, further is preferably 1000-3000.To said N, the carbon number of the alkyl in the N-dimethyl alkylamine is not special to be limited, and can be the straight or branched alkyl of 1-15 for carbon number generally, for example; N, N-dimethyl methylamine, N, N-dimethyl amine, N, N-dimethyl n propylamine, N; N-dimethyl butylamine, N, N-dimethyl cyclopentamine, N, 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 the N-dimethyl pentadecyl amine.The solvent that forms organic amine aqueous solution also can be preferably water for the solvent of various routines known in the field.
According to the present invention, the zeolite that will have a MFI structure and organic amine solution mix the condition that contact and generally comprise the time that the temperature of mixing contact contacts with mixing.The temperature of said mixing contact can be selected in wider temperature range; For example, the zeolite of the said MFI of having structure mixes the temperature that contacts with organic amine solution can be 20-80 ℃, is preferably 40-70 ℃; The prolongation that mixes time of contact helps said 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, and generally speaking; The time of said mixing contact can be 30-60 minute, is preferably 35-50 minute.
The present invention contacts the mixture that obtains and mixes the not special qualification of the mode that contacts with y-type zeolite with the mixing of organic amine solution to the zeolite with MFI structure; As long as the mixture that obtains is mixed with y-type zeolite to be contacted; But inventor of the present invention finds, y-type zeolite is joined in the said 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 the said mixture in batches, and under the preferable case, the addition of every batch of y-type zeolite is at most 80 weight % of the total consumption of y-type zeolite; Be preferably 30-70 weight %; Also comprise the time interval between the step of adjacent two batch mixed, the said time interval can be 5-120 minute, is preferably 15-60 minute.
According to the present invention; The zeolite of the said 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 the further preferable case, said 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, said y-type zeolite can be for well known to a person skilled in the art various y-type zeolites, for example, can be selected from REY, REHY, USY, HY, REUSY, PREY, the PREHY zeolite one or more.
According to the present invention; The said preparation method who contains the particle of molecular sieve active component comprises provides a kind of mixture; And the solid of isolating in the said mixture is also dry; With the solid that obtains and clay and Ludox making beating, with slurry dried that obtains and roasting, the combination of molecular sieve of said mixture for making by preceding method of the present invention.
Among 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, the weight ratio of the mixture of the said solid that obtains and clay and Ludox not had specific (special) requirements; Generally speaking; The weight ratio of the mixture of solid that obtains and clay and Ludox can be 1: 0.2-10 is preferably 1: 0.5-6, and the solid content of gained mixture is 3-40 weight % after mixing usually.
The selectable range broad of the weight ratio of said clay and Ludox, but under the preferable case, the weight ratio of said clay and Ludox can be 0.01-10: 1, further be preferably 0.1-4: 1.
Wherein, the weight of said clay is in its butt weight, and the weight of said Ludox is with SiO
2Meter.
Said Ludox can be purchased acquisition and also can prepare according to method known in those skilled in the art for this area Ludox commonly used.
Under the preferable case, the step of the solid that obtains and clay and Ludox making beating can also be comprised the adding rare earth compound, be benchmark with the gross weight of the particle that contains the molecular sieve active component that obtains, with RE
2O
3Meter, the consumption of said rare earth compound makes the said content that contains the particle middle rare earth oxide of molecular sieve active component be no more than 8 weight %.Wherein, RE representes rare earth element.
Wherein, said clay can this area conventional various clays, for example, can be selected from rectorite, kaolin, imvite, diatomite, galapectite, saponite, sepiolite, attapulgite, hydrotalcite and the bentonite one or more.
Said rare earth compound can be the conventional various rare earth compounds in this area; For example; Can be in chloride, bromide and the nitrate of rare earth one or more; In addition, can be a kind of salt of rare earth element, also can be the mixed rare earth compound that comprises multiple rare earth element commonly used in the catalyst preparation process.Said rare earth element is preferably selected from one or more in the lanthanide series.Said 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 said rare earth compound generally can be 20-60 weight %.
According to the present invention; The method of said 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 air dry, vacuum drying and the spray-drying; Be preferably spray-drying, the condition of said drying generally comprises dry temperature can be 100-200 ℃, and the dry time can 1-10 hour.
The method of said 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, said 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 organic amine solution (mass percent concentration is 0.05-15 weight %), stirs 30-60 minute;
(2) divide the many batches of mixtures that obtain with step (1) to mix y-type zeolite, the addition of every batch of y-type zeolite is at most 80 weight % of the total consumption of y-type zeolite, is preferably 30-70 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 said Ludox can prepare according to conventional method, for example, and can be with water glass solution (SiO
2Concentration is preferably 15-40 weight %, and modulus of water glass is 3-3.5) join in the sulfuric acid (the preferred mass percent concentration is 15-50%), add soon earlier, and stir, add half back and slowly add, and stop to stir, 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 in its butt weight, 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 the solid content that mixes back gained mixture usually is 3-40 weight %); Stir spray drying forming, roasting.
According to the present invention, said catalytic cracking catalyst contains particle a and particle b, and said particle b contains rectorite and heat-resistant inorganic oxide matrix, and wherein, said particle a is the particle of prepared in accordance with the method for the present invention.
According to the present invention; The selectable range broad of the weight ratio of said particle a and particle b; Generally speaking, can be according to the demand flexible 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 said particle a and particle b can be 0.5-15: 1, be preferably 1-10: 1.
Under the optimum condition, among the said 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 said heat-resistant inorganic oxide matrix can adopt this area heat-resistant inorganic oxide matrix commonly used.For example, said heat-resistant inorganic oxide matrix can be selected from one or more in silica, gama-alumina, magnesia, silica-alumina and the aluminium oxide-phosphorous oxide, is preferably silica.
Said 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 the preferable case, said heat-resistant inorganic oxide matrix contains silica, and the preparation method of said particle b comprises: sulfuric acid is mixed with waterglass, obtain the slurries of pH value for 1-3, rectorite is mixed with the slurries that obtain, dry and roasting.
The adjustable extent broad of said rectorite and the weight ratio of the slurries that obtain; Contain rectorite and heat-resistant inorganic oxide matrix as long as guarantee among the said 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 speaking, said rectorite can be 1 with the weight ratio of the slurries that obtain: 1.5-50.
The method and the condition of said drying, roasting detail in preamble, repeat no more at this.
According to the present invention, can also contain rare earth compound in the said catalyst, for example, can contain rare earth compound among said particle a and/or the particle b.Said rare earth compound can be introduced (the for example method of dipping) through existing variety of way, as long as make catalyst of the present invention contain rare earth element.Under the preferable case, in the process of preparation particle b, introduce rare earth compound (being that particle b contains rare earth compound), specifically, can before drying, rectorite be mixed with rare earth compound with the mixture of the slurries that obtain.Gross weight with catalyst is a benchmark, with RE
2O
3Meter, the consumption of said rare earth compound makes the content of catalyst middle rare earth oxide be no more than 8 weight %.
Except providing according to method of the present invention particle a and the particle b, catalyst of the present invention can be after with particle a that makes respectively and particle b moulding, with 0.5-15: 1, be preferably 1-10: 1 weight ratio mixes and can make.
To further specify the present invention through specific embodiment below, but therefore not limit the present invention.
In each embodiment and Comparative Examples, Na in the 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 industry analytical method " (RIPP experimental technique), volumes such as Yang Cuiding].
800 ℃/4h active (MA) is defined as: 800 ℃ of activity datas of being surveyed after 4 hours with 100% steam aging down, MA method are measured referring to [" petrochemical industry analytical method " (RIPP experimental technique), volumes such as Yang Cuiding, Science Press, nineteen ninety publication].
Embodiment 1
Present embodiment is used to explain the preparation of catalytic cracking catalyst.
A: preparation combination of molecular sieve and particle a
(1) under 30 ℃; With 14kg ZSP-3 molecular sieve (catalyst Shandong branch company of China Petrochemical Industry product; ZSP-3 silica alumina ratio=40), mix with the 100kg polyvinylamine aqueous solution (number-average molecular weight of polyvinylamine is 1800 (available from westernization appearance (Beijing) Science and Technology Ltd.s), and the mass percent concentration of the polyvinylamine aqueous solution is 3%); Stirred 40 minutes, and obtained slurries 114kg;
(2) under 40 ℃, 4kg DASY2.0 molecular sieve (catalyst Shandong branch company of China Petrochemical Industry 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 ℃, again 4kg DASY2.0 molecular sieve (catalyst Shandong branch company of China Petrochemical Industry 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 dries 5 hours down in 120 ℃, obtains solid 22.2kg;
(5) preparation of Ludox: with 20kg decationized Y sieve water and 35kg waterglass (SiO
2Content 28.4 weight %, modulus of water glass 3.1) mix, join the H of 30kg
2SO
4In the solution (mass percent concentration is 30 weight %), the speed of adding is 60kg/ hour, and the Ludox slurries 85kg that stirring obtains pH=1.6 is (with SiO
2Meter, Ludox is 9.9kg);
(6) 19kg halloysite (Suzhou china clay company industrial products, solid content 72.3 weight %) is mixed with the slurries that step (5) obtains, stirred 30 minutes, obtain the mixture 104kg (solid content of mixture is 22.7 weight %) of kaolin and Ludox slurries;
(7) in the kaolin that 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 weight %, modulus 3.1) mix, join the H of 10kg
2SO
4In the solution (mass percent concentration is 50%), the speed of adding is 60kg/ hour, stirs the slurries 38kg that obtains pH=1.6;
(2) with 15kg rectorite (Zhongxiang City, Hubei rectorite, solid content 87 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: Preparation of Catalyst
Particle a and particle b were mixed by weight 10: 1, after the roasting (sintering temperature is 550 ℃, and roasting time is 2 hours), spend deionised water and remove free Na
+Ion, dry (baking temperature is 150 ℃, and be 2 hours drying time) obtains catalyst 1.
Embodiment 2
Present embodiment is used to explain the preparation of catalytic cracking catalyst.
Method according to embodiment 1 prepares catalyst; 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 replaced by 20kg ZRP (catalyst Shandong branch company of China Petrochemical Industry product, silica alumina ratio is 60); The consumption of DASY2.0 molecular sieve is 3kg (catalyst Shandong branch company of a China Petrochemical Industry product; Silica alumina ratio is 4.9) (in step (2) and (3), adding 1kg and 2kg respectively), simultaneously particle a and particle b were mixed by weight 5: 1, obtain catalyst 2.
Embodiment 3
Present embodiment is used to explain the preparation of catalytic cracking catalyst.
Method according to embodiment 1 prepares catalyst, and different is to 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 (catalyst Shandong branch company of the China Petrochemical Industry product of 10kg; Silica alumina ratio is 45), the consumption of DASY2.0 molecular sieve (catalyst Shandong branch company of China Petrochemical Industry product, silica alumina ratio is 3.6) is 7.5kg (in step (2) and (3), adding 5kg and 2.5kg respectively); Simultaneously particle a and particle b were mixed by weight 15: 1, obtain catalyst 3.
Embodiment 4
Present embodiment is used to explain the preparation of catalytic cracking catalyst.
Method according to embodiment 1 prepares catalyst, and different is that particle a and particle b are obtained by weight mixing in 1: 1.Obtain catalyst 4.
Embodiment 5
Present embodiment is used to explain the preparation of catalytic cracking catalyst.
Method according to embodiment 1 prepares catalyst, and different is, with DASY2.0 molecular sieve disposable adding in step (2) of 8kg.Obtain catalyst 5.
Embodiment 6
Present embodiment is used to explain the preparation of catalytic cracking catalyst.
Method according to embodiment 1 prepares catalyst, and 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 weight %, and rare earth new material Co., Ltd in Gansu produces, La in the rare earth oxide
2O
3Account for 23 weight %, CeO
2Account for 46 weight %, other rare earth oxide content is 31 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 to explain the reference preparation method of catalytic cracking catalyst.
The method that provides according to embodiment among the CN1353012A 1 prepares Cracking catalyst, obtains comparative catalyst D1.
Comparative Examples 2
This Comparative Examples is used to explain the reference preparation method of catalytic cracking catalyst.
The method that provides according to embodiment among the CN101210187A 1 prepares Cracking catalyst, obtains contrast medium D2.
EXPERIMENTAL EXAMPLE 1-6
Present embodiment is used to explain the performance test of catalytic cracking catalyst.
The catalyst that will be made by embodiment 1-6 respectively earlier is that 100% water vapour contacts 17 hours in 800 ℃ with content; Carry out preliminary treatment, then, in the presence of the process 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 weight %, character are seen table 1) of mixing refining 15 weight % decompression residuum, and reaction temperature is 640 ℃, WHSV=4h
-1, agent weight of oil ratio is 15.Evaluation result is seen table 2.
Experiment Comparative Examples 1-2
Present embodiment is used to explain the performance test of 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 is seen table 2.
Table 1
Table 2
Result by table 2 can find 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 the productive rate that can guarantee propylene does not simultaneously reduce even be higher.
Claims (20)
1. the preparation method of a combination of molecular sieve is characterized in that, said preparation of compositions method comprises that the zeolite with the MFI structure contacts with the mixing of organic amine solution, mixes the mixture that obtains contacting with y-type zeolite.
2. method according to claim 1, wherein, the weight ratio of the zeolite of said organic amine and MFI structure is 0.2-7: 1, the weight ratio of the zeolite of said y-type zeolite and MFI structure is 0.01-1: 1.
3. method according to claim 2, wherein, the weight ratio of the zeolite of said organic amine and MFI structure is 0.2-5: 1, the weight ratio of the zeolite of said y-type zeolite and MFI structure is 0.1-0.75: 1.
4. method according to claim 1, wherein, the concentration of said organic amine solution is 0.05-15 weight %.
5. according to any described method among the claim 1-4, wherein, said organic amine is selected from polyvinylamine, polymine and N, one or more in the N-dimethyl alkylamine.
6. method according to claim 1; Wherein, the zeolite of said MFI structure mixes temperature 20-80 ℃ that contacts with organic amine solution, and the time is 30-60 minute; The mixture that obtains is mixed temperature 40-80 ℃ that contacts with y-type zeolite, and the time is 60-120 minute.
7. according to claim 1 or 6 described methods, wherein, the mixture that obtains and y-type zeolite are mixed the method that contacts comprise y-type zeolite is joined in the said mixture in batches.
8. method according to claim 7, wherein, the addition of every batch of y-type zeolite is at most 80 weight % of the total consumption of y-type zeolite, also comprises the time interval between the step of adjacent two batch mixed, and the said time interval is 5-120 minute.
9. one kind by any combination of molecular sieve that described method makes among the claim 1-8.
10. preparation method who contains the particle of molecular sieve active component; It is characterized in that; This method comprises provides a kind of mixture, isolates solid in the said mixture and dry, and the solid that drying obtains is pulled an oar with clay and Ludox; With slurry dried that obtains and roasting, said mixture is by any combination of molecular sieve that described method makes among the claim 1-8.
11. method according to claim 10, wherein, said clay is selected from one or more in kaolin, imvite, diatomite, galapectite, saponite, sepiolite, attapulgite, hydrotalcite and the bentonite.
12. method according to claim 10 wherein, also comprises the adding rare earth compound with the step of the solid that obtains and clay and Ludox making beating, is benchmark with the said gross weight that contains the particle of molecular sieve active component, with RE
2O
3Meter, the consumption of said rare earth compound makes the said content that contains the particle middle rare earth oxide of molecular sieve active component be no more than 8 weight %.
13. method according to claim 10, wherein, the temperature of roasting is 400-650 ℃, and the time of roasting is 0.5-6 hour.
14. particle that contains the molecular sieve active component that obtains by any described method among the claim 10-13.
15. catalytic cracking catalyst; It is characterized in that; Said catalytic cracking catalyst contains particle a and particle b, and said particle b contains rectorite and heat-resistant inorganic oxide matrix, and said particle a is according to any particle that described method makes among the claim 10-13.
16. catalyst according to claim 15, wherein, by weight, the ratio of said particle a and particle b is 0.5-15: 1.
17. catalyst according to claim 16, wherein, by weight, the ratio of said particle a and particle b is 1-10: 1.
18. catalyst according to claim 15, wherein, said particle a and/or particle b also contain rare earth compound, are benchmark with the gross weight of catalyst, with RE
2O
3Meter, the consumption of said rare earth compound makes the content of catalyst middle rare earth oxide be no more than 8 weight %.
19. catalyst according to claim 15, wherein, said heat-resistant inorganic oxide matrix contains silica; The preparation method of said particle b comprises sulfuric acid is mixed with waterglass; Obtain the slurries of pH value, rectorite is mixed contacting with the slurries that obtain, dry and roasting for 1-3.
20. according to claim 15 or 19 described catalyst, wherein, the basal spacing d of said rectorite
001Value be 2.7-5.0nm, the BET specific area is 100-300m
2/ g.
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| CN113952978A (en) * | 2020-07-20 | 2022-01-21 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
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| 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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| 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 |
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| CN113952978A (en) * | 2020-07-20 | 2022-01-21 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN113952978B (en) * | 2020-07-20 | 2023-07-14 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method and application thereof |
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