CN101898146B - Catalytic thermal cracking catalyst and preparation method thereof - Google Patents
Catalytic thermal cracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalytic thermal cracking catalyst and a preparation method thereof. The catalyst comprises the following components by weight percent: 5-75% of aluminum bonding agent, 0.5-70% of zeolite with MFI structure and 3-25% of zirconium oxide substrate, wherein the weight of aluminum bonding agent is calculated according to aluminium oxide; the silicon-aluminium ratio of the zeolite with MFI structure is 15-300, and the diameter of the primary particles is 5-55mu m. The preparation method of the catalyst comprises the following steps: mixing zeolite with MFI structure, aluminium oxide bonding agent and zirconium oxide substrate, beating and drying, wherein in the beating process, zirconium oxide substrate is introduced in two steps. The catalyst of the invention is used for the catalytic thermal cracking of heavy oil, the conversion rate of the raw material is high, the low-carbon olefin selectivity is good; and by using the preparation method of the invention, the wear resistance of the catalyst can be improved and the thermal stability and hydrothermal stability of the catalyst can be increased.
Description
Technical field
The present invention relates to a kind of catalytic thermal cracking catalyst and preparation method thereof.
Background technology
Catalytic pyrolysis is that a kind of heavy oil that utilizes in the presence of catalyst is produced the double method of producing propylene of ethene, has energy consumption low, and ingredient requirement is low, and the product profile adjustment is characteristics flexibly.The reaction temperature of catalytic pyrolysis (CPP) technique is higher, can reach 600 ℃, therefore require catalyst system therefor to have good heat and hydrothermal stability, particularly heavily become bad along with cracking stock becomes, its operation harshness raising has proposed requirements at the higher level to catalytic thermal cracking catalyst.
CN1048428C discloses a kind of catalyst for the petroleum hydrocarbon preparing low-carbon olefin by conversion, this catalyst is comprised of the clay of 0～70 heavy %, the inorganic oxide of 5～90 heavy % and the zeolite of 10～35 heavy %, and its mesolite is comprised of the five-membered ring silica-rich zeolite of the phosphorous and rare earth of 20～75 heavy %, the Y-type high-Si zeolite of 20～75 heavy % and the y-type zeolite that contains rare earth of 1～25 heavy %.
CN1222558A discloses a kind of catalyst for catalytic thermal cracking process to prepare lower olefine, has following composition (in catalyst weight): 10～70% clay, 5～85% inorganic oxide and 1～50% zeolite, its mesolite is the phosphorous and aluminium of 0～25% y-type zeolite and 75～100% or the five-membered ring structure high-silicon zeolite of magnesium or calcium, this silica-rich zeolite is the ZSM-5 that contains the aluminium of 2～8% phosphorus and 0.3～3% or magnesium or calcium (in oxide) ,-8 or the zeolite of-11 types, and its silica alumina ratio is 15～60.
Yet above catalyst is used for catalytic pyrolysis, and its ethylene yield is not high enough.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of catalytic thermal cracking catalyst with higher ethylene yield, and the other technical problem that the present invention will solve provides the methods for making and using same of described catalyst.
The invention provides a kind of catalytic thermal cracking catalyst, described catalyst contains zeolite, al binder and the zirconium matrix with MFI structure, the silica alumina ratio of the zeolite of the wherein said MFI of having structure (mol ratio of silica and aluminium oxide) is 15～300, and the primary particle diameter is 5～55 μ m; Take the weight of catalyst as benchmark, described catalyst contains in aluminium oxide 5～75 % by weight al binders, and 0.5～70 % by weight has the zeolite of MFI structure, 3～25 % by weight zirconias.
The present invention also provides a kind of preparation method of catalytic thermal cracking catalyst provided by the invention, and the method may further comprise the steps:
(1) aqueous solution with zirconates mixes with ammoniacal liquor, and it is 9～12 that the consumption of ammoniacal liquor makes the pH value of resulting suspension, and then ageing, filtration, washing, drying, in 500～700 ℃ of roastings obtain Zirconium oxide powder;
(2) preparation al binder slurries;
The Zirconium oxide powder of the al binder slurries that (3) step (2) obtained and step (1) preparation mixes, pulls an oar, and take the gross weight of catalyst as benchmark, zirconia introducing amount is 2～10 % by weight;
(4) slurries that step (3) obtained mix with the zeolite with MFI structure, making beating; The silica alumina ratio of the zeolite of the described MFI of having structure (mol ratio of silica and aluminium oxide) is 15～300, and the primary particle diameter is 5～55 μ m;
(5) in the slurries that step (4) obtains, introduce the Zirconium oxide powder that step (2) prepares, making beating, the zirconia gross weight that introduce step (3) and (5) accounts for 3～25 % by weight of catalyst gross weight;
(6) add acid in the slurries that step (5) obtains, the pH value that the consumption of acid makes slurries is for being 2～5;
(7) slurry dried that step (6) is obtained.
The present invention further provides a kind of catalytic thermocracking process, be included in the step that under the catalytic pyrolysis condition hydrocarbon ils is contacted with catalyst, it is characterized in that, the catalyst that described catalyst provides for the invention described above.
Catalytic thermal cracking catalyst provided by the invention has good heat and hydrothermal stability, is used for heavy-oil catalytic thermal cracking, and heavy oil cracking ability is strong, and feed stock conversion is high, and ethylene yield, productivity of propylene, productivity of low carbon olefin hydrocarbon are high.Method for preparing catalyst provided by the invention can improve the anti-wear performance of catalyst, improves the catalyst spherical degree, makes catalyst have higher degree of crystallinity and hydrothermal aging post crystallization degree, and can improve the activity of catalyst and ethene, Propylene Selectivity.
The specific embodiment
In the catalytic thermal cracking catalyst provided by the invention, also can contain one or more in the Cracking catalyst such as clay, the inorganic oxide matrix commonly used, take the weight of catalyst as benchmark, the content of described clay is no more than 60 % by weight, and the content of inorganic oxide is no more than 60 % by weight.Described clay is selected from one or more in the Cracking catalyst clay commonly used, for example one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite.
Under the preferable case, in the catalytic thermal cracking catalyst provided by the invention, contain 10～40 % by weight al binders, the zeolite with MFI structure of 0.5～60 % by weight is no more than the clay of 60 % by weight, the zirconia of 3～25 % by weight; More preferably in the situation, in the catalyst provided by the invention, the content of al binder is 10～35 % by weight, and the content with MFI structural zeolite is 15～45 % by weight, and clay content is 3～55 % by weight, and zirconia content is 3～20 % by weight.
In the catalytic thermal cracking catalyst provided by the invention, the zeolite that can also contain Cracking catalyst other type commonly used, one or more in y-type zeolite, β zeolite and the modenite for example, described y-type zeolite are one or more in USY zeolite, REY zeolite, HY zeolite, REHY zeolite and the REUSY zeolite for example.Take the weight of catalyst as benchmark, the content of described other type zeolite is no more than 40 % by weight.
Among the catalytic thermal cracking catalyst preparation method provided by the present invention, in the step (1) aqueous solution of zirconates mixed with ammoniacal liquor and react, form suspension, then carry out ageing, digestion time is 10～48 hours, temperature for ageing does not have specific (special) requirements, preferred 15～50 ℃, more preferably 25～35 ℃, after the ageing sediment is separated with mother liquor, wash with water, extremely be detected (content≤0.1 % by weight without anion in the cleaning solution after the washing, described anion is the anion of used zirconates, for example is chlorion, sulfate ion or nitrate ion); Drying precipitate after the washing, roasting do not have specific (special) requirements to the condition of drying, and for example baking temperature can be 100～200 ℃, and be 15～48 hours drying time; The time of roasting is preferably 2～15 hours, more preferably 5～10 hours.Described zirconates is one or more in zirconium oxychloride, zirconyl nitrate, the zirconium sulfate for example.The concentration of the aqueous solution of described zirconates is 0.1～3.0mol/L, preferred 1.0～1.5mol/L; Described ammonia concn is 15～28 % by weight, is preferably 25～28 % by weight.
Among the catalytic thermal cracking catalyst preparation method provided by the invention, zirconia is introduced in two steps, and the zirconia amount of introducing in the step (3) is 2～10% of total catalyst weight, and all the other are introduced in step (5).The ratio of the zirconia weight of introducing in the zirconia of introducing in the preferred steps (3) and the step (5) is (0.4～5): 1.After introducing zirconia in step (3) and (5), making beating is not less than 15 minutes respectively, preferably pulls an oar 20～45 minutes.Preferably, described introducing makes that zirconic content is 3～20 % by weight in the catalyst.Step is mixed the al binder slurries in (3) with zirconia, preferably introduce Zirconium oxide powder in the al binder slurries.
Among the catalytic thermal cracking catalyst preparation method provided by the invention, step (6) is introduced acid in the slurries that step (5) obtains, and it is 2～5 that the consumption of acid makes the pH value of slurries, is preferably 2～4; Preferably pulled an oar at least 5 minutes after introducing acid, more preferably pulled an oar 10～30 minutes.After adding acid, preferably also wear out, aging temperature is room temperature～75 ℃, is preferably 40～70 ℃, ageing time 10～480 minutes.Described acid is one or more of inorganic acid, for example one or more in phosphoric acid, nitric acid, the hydrochloric acid.
Among the preparation method of catalyst provided by the present invention, the described preparation al binder of step (2) slurries, preparation method's preparation according to al binder slurries in the existing Cracking catalyst preparation process, comprise al binder is mixed with water, making beating, it is 2～4 that the step that adds acidifying, the consumption of preferred acid make the pH value of slurries, and described acid is for example one or more in hydrochloric acid, nitric acid and the phosphoric acid of acid commonly used in the Cracking catalyst preparation.Described al binder is selected from boehmite, has a diaspore structure hydrated alumina, has one or more in gibbsite structure hydrated alumina, the hydrated alumina with bayerite structure, gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, the aluminium colloidal sol.Take the weight of catalyst as benchmark, the alumina amount that described al binder slurries are introduced is 5～75 % by weight, is preferably 10～40 % by weight.
Among the catalytic thermal cracking catalyst preparation method provided by the invention, step (4) is introduced the zeolite with MFI structure, can introduce the solid zeolite powder, also can introduce zeolite slurry.Described zeolite slurry can for example mix water according to existing method preparation with zeolite, making beating, and beating time preferably is not less than 10 minutes, more preferably 15～60 minutes.Beating time is not less than 10 minutes, preferred 15～60 minutes after introducing zeolite.Described MFI structural zeolite is preferably for example one or more in the ZSM-5 zeolite, ZRP zeolite, ZSP zeolite of phosphorus modification of HZSM-5 zeolite, element modified ZSM zeolite, the mol ratio of its silica and aluminium oxide is 15-300, the primary particle diameter is 5～55 μ m, is preferably 8～15 μ m.Take the weight of catalyst as benchmark, introduce to have MFI structural zeolite amount be 0.5～60 % by weight, be preferably 15～45 % by weight.Described large crystal grain zeolite is commercially available or according to the preparation of existing method, for example according to EP0026962, EP0026963, EP0021674, CN1530322A or the preparation of " catalysis journal " method that Vol.15No.6P468 provided in 1994.
Among the catalytic thermal cracking catalyst preparation method provided by the invention, also can introduce other type zeolite, described other type zeolite is preferable in the step (4) and introduces, and can introduce at the same time or separately with the zeolite of MFI structure.Described introducing makes the content of other type zeolite in the catalyst that obtains be no more than 40 % by weight.
Among the catalytic thermal cracking catalyst preparation method provided by the invention, also can comprise the step of introducing Cracking catalyst matrix commonly used, described matrix in step (2), (3), (4), (5) or (6) any step or a few step in introduce, introduced after the matrix preferred making beating 15～60 minutes.Take the weight of catalyst as benchmark, be no more than 60% in the introducing amount of the described matrix of oxide.Described matrix is selected from one or more of clay, inorganic oxide and precursors of inorganic oxides, described clay is one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite for example, take the weight of catalyst as benchmark, in butt, the introducing amount of described clay is no more than 60 % by weight, be preferably 3～55 % by weight, described clay is preferable in the step (2) and introduces.Described inorganic oxide is rare earth oxide, silica, gama-alumina for example, and described precursors of inorganic oxides is salt, the waterglass of aluminium colloidal sol, rare earth for example.When introducing rare-earth salts, described rare-earth salts preferably after for the second time introducing zirconia, dry before in the introducing slurries, more preferably in the slurries of step (6), add earth solution, preferably take the weight of catalyst as benchmark, be no more than 0.5～2 % by weight in the introducing amount of oxide rare earth.
Among the catalytic thermal cracking catalyst preparation method provided by the invention, drying described in the step (7) is drying mode commonly used in the catalytic cracking catalyst, spray-drying for example, and the present invention does not have specific (special) requirements.
In the method for preparing catalyst provided by the invention, also can comprise the dried catalyst roasting of step (7).Roasting condition is roasting condition habitual in the catalytic cracking catalyst preparation process, and the temperature of preferred roasting is 400～700 ℃, and roasting time is 0.5～8 hour, and more preferably roasting time is 500～650 ℃, and roasting time is 0.5～5 hour.
In the catalytic cracking method provided by the invention, described hydrocarbon ils is contacted with catalyst, can according to existing method for example the method that provides of patent US20050020867A1 carry out.Preferably, described catalytic pyrolysis condition is: temperature 600-800 ℃, the agent weight of oil is than being 10-15, and air speed is 7-12h
-1Described heavy oil is reduced crude, decompression residuum, vacuum gas oil (VGO), AGO (atmospheric gas oil) for example.
Following example will be further described the present invention, but not thereby limiting the invention.In each example and Comparative Examples, catalyst abrasion Index A I, activity (MA), degree of crystallinity (ACR) are measured, referring to " Petrochemical Engineering Analysis method " (RIPP experimental technique), and the volumes such as Yang Cuiding, Science Press, nineteen ninety publishes.
Embodiment 1
(1) with the ZrOCl of 4Kg
2(zirconia 36 % by weight wherein, technical grade, Zibo ring is opened up chemical industry Co., Ltd) be mixed and made into the aqueous solution of concentration 1.0mol/L with decationized Y sieve water, under agitation add ammoniacal liquor (Beijing Chemical Plant, 25 % by weight) to the pH value be 9, then 25 ℃, stir under ageing 26 hours, filter to get ZrO (OH)
2Gel does not measure Cl with inspection in the cleaning solution of decationized Y sieve water washing after wash
-, 24 hours, 550 ℃ roastings of 120 ℃ of lower dryings 2 hours obtain Zirconium oxide powder;
(2) 20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63m%) are mixed, making beating, regulating its pH value with hydrochloric acid is 3;
(3) with 19Kg halloysite (Suzhou china clay company industrial products, solid content 72.3 % by weight) in the slurries that adding step (2) obtains, pulled an oar 5 minutes, and then added the Zirconium oxide powder 0.61Kg of step (1) preparation, pulled an oar 15 minutes;
(4) (the Qilu Petrochemical catalyst plant is produced, Al to add 10Kg aluminium colloidal sol in the slurries that step (3) obtains
2O
3Content is 21.7 % by weight), stirred 40 minutes, adding ZRP zeolite slurry 20Kg (wherein contain ZRP zeolite 8Kg, be China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, ZRP silica alumina ratio 40, the knot precision is 80, the primary particle diameter is 10 μ m), pulled an oar 15 minutes;
(5) in the slurries that step (4) obtains, add the Zirconium oxide powder that remaining step (1) prepares, pulled an oar 15 minutes, the pH value that adds hydrochloric acid adjusting slurries is 3, pulled an oar 5 minutes, and then left standstill in 65 ℃ and wore out 1.5 hours, then cool the temperature to 55 ℃, spray-drying, the flush away Na ion that dissociates, drying obtains catalyst A.
Embodiment 2
(1) 20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63m%) are mixed, making beating, regulating its pH value with hydrochloric acid is 2.5;
(2) with 14Kg ZrOCl
2(36 % by weight, technical grade, Zibo ring is opened up chemical industry Co., Ltd) mix with decationized Y sieve water, make the aqueous solution that concentration is 1.5mol/L, then be 9 in stirring lower to wherein adding ammoniacal liquor (Beijing Chemical Plant, 25 % by weight) to pH value, ageing is 16 hours under 30 ℃ of stirrings, filter, obtain ZrO (OH)
2Gel is used in the water after the decationized Y sieve water washing is extremely washed without Cl
-Detect, 115 ℃ lower dry 26 hours, 600 ℃ of roastings 5 hours obtain Zirconium oxide powder;
(3) with 18Kg halloysite (Suzhou china clay company industrial products, solid content 72.3 % by weight) mix in the slurries that adding step (1) obtains, pulled an oar 5 minutes, and then added the Zirconium oxide powder 3.21Kg of step (2) preparation, pulled an oar 15 minutes;
(4) (the Qilu Petrochemical catalyst plant is produced, Al to add 10Kg aluminium colloidal sol in the slurries that step (3) obtains
2O
3Content is 21.7 % by weight), stirred 40 minutes, adding ZRP zeolite slurry 30Kg (wherein contain ZRP zeolite 18Kg, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, ZRP silica alumina ratio 80, degree of crystallinity 76, the primary particle diameter is 15 μ m), pulled an oar 15 minutes;
(5) in the slurries that step (4) obtains, add the Zirconium oxide powder that remaining step (2) prepares, pulled an oar 15 minutes, the pH value that adds hydrochloric acid adjusting slurries is 4, then left standstill aging 1.5 hours at 65 ℃, cool the temperature to 55 ℃, spray-drying, the flush away Na ion that dissociates, drying obtains catalyst B.
Embodiment 3
(1) with the ZrOCl of 18Kg
2(36 % by weight, technical grade, Zibo ring is opened up chemical industry Co., Ltd) mix with water, make the aqueous solution that concentration is 1.0mol/L, then under agitation add ammoniacal liquor (Beijing Chemical Plant, 25 % by weight) to pH be 10, the sediment that obtains 35 ℃, stir under ageing 14 hours, filter to get ZrO (OH)
2Gel, with the decationized Y sieve water washing to the cleaning solution without Cl
-Detect, 130 ℃ of lower dry doing 20 hours, 650 ℃ of lower roastings 10 hours obtain Zirconium oxide powder;
(2) 20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63m%) are mixed, making beating, regulating its pH value with hydrochloric acid is 3.5;
(3) with 19Kg halloysite (Suzhou china clay company industrial products, solid content 72.3 % by weight) in the slurries that adding step (2) obtains, pulled an oar 5 minutes, and then added the Zirconium oxide powder 1.90Kg of step (1) preparation, pulled an oar 15 minutes;
(4) (the Qilu Petrochemical catalyst plant is produced, Al to add 10Kg aluminium colloidal sol in the slurries that step (3) obtains
2O
3Content is 21.7 % by weight), stirred 40 minutes, add zeolite slurry 40Kg, (ZRP zeolite 31Kg wherein, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, ZRP silica alumina ratio 120, degree of crystallinity is 82, the primary particle diameter is 8 μ m), pulled an oar 15 minutes;
(5) in the slurries that step (4) obtains, add the Zirconium oxide powder that remaining (1) prepares, pulled an oar 15 minutes, adding hydrochloric acid adjusting pH value is 3.2, pulled an oar 15 minutes, and then left standstill in 65 ℃ and wore out 1.5 hours, cool the temperature to 55 ℃, spray-drying, the flush away Na ion that dissociates, drying obtains catalyst C.
Comparative Examples 1
Method Kaolinite Preparation of Catalyst according to industrial catalyst.
With 20Kg decationized Y sieve water and 19Kg halloysite (Suzhou china clay company industrial products, solid content 72.3 % by weight) mix making beating, add again 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63m%), with hydrochloric acid its PH is transferred to 3, stir, left standstill under 65 ℃ aging 1 hour, keeping PH is 2～4, cools the temperature to 55 ℃, (the Qilu Petrochemical catalyst plant is produced, Al to add 10Kg aluminium colloidal sol
2O
3Content is 21.7 % by weight), stirred 40 minutes.Add zeolite slurry, ZRP zeolite (China Petrochemical Industry's catalyst asphalt in Shenli Refinery product) 31Kg wherein, ZRP silica alumina ratio 120, primary particle diameter are 8 μ m.Making beating, spray drying forming, the flush away Na ion that dissociates is drying to obtain contrast medium DB-1.
The intensity data of catalyst A, B, C, DB-1 and 800 ℃/17h (under 800 ℃, 100% water vapour atmosphere aging 17 hours) activity and crystallization reservation degree see Table 1.
Comparative Examples 2
According to catalyst formulation and the preparation process of embodiment 3, ZRP zeolite primary particle diameter is 3 μ m in the zeolite slurry that just adds, the silica alumina ratio 120 of ZRP zeolite, and degree of crystallinity is 83, obtains catalyst DB-2.
Embodiment 4～6
On the small fixed flowing bed device, take Daqing atmospheric residue (character sees Table 2) as raw material, A～C estimates to catalyst sample, and reaction temperature is 640 ℃, and agent weight of oil ratio is 20, air speed 10h
-1, water injection rate (accounting for raw material) 50%.Catalyst sample is in advance through 800 ℃, and 100% steam treatment 17 hours, loading amount are 180 grams.Evaluation result sees Table 3.
Embodiment 7
(1) 20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63m%) are mixed, making beating, regulating its pH value with hydrochloric acid is 3;
(2) in the slurries that 19Kg halloysite (Suzhou china clay company industrial products, solid content 72.3 % by weight) adding step (1) obtained, pulled an oar 5 minutes, then add the ZrOCl of 4Kg
2(Zibo ring is opened up chemical industry Co., Ltd for zirconia 36 % by weight wherein, technical grade) pulled an oar 15 minutes;
(3) (the Qilu Petrochemical catalyst plant is produced, Al to add 10Kg aluminium colloidal sol in the slurries that step (2) obtains
2O
3Content is 21.7 % by weight), stirred 40 minutes, adding zeolite slurry 20Kg (wherein ZRP zeolite 8Kg is China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, ZRP silica alumina ratio 40, and degree of crystallinity is 80, the primary particle diameter is 10 μ m), pulled an oar 15 minutes; Left standstill aging 1.5 hours in 65 ℃, then cool the temperature to 55 ℃, spray-drying, the flush away Na ion that dissociates, drying obtains catalyst D.
Method according to embodiment 4 is estimated catalyst D, the results are shown in Table 3.
Embodiment 8
(1) with the ZrOCl of 36Kg
2(36 % by weight, technical grade, Zibo ring is opened up chemical industry Co., Ltd) mix with water, compound concentration is the aqueous solution of 2.0mol/L, then under agitation to wherein adding ammoniacal liquor (Beijing Chemical Plant, 25 % by weight) to pH be 10, ZrO (OH) is filtered to get in the sediment that obtains ageing 14 hours under 35 ℃ of stirrings
2Gel, with the decationized Y sieve water washing to the cleaning solution without Cl
-Detect, 130 ℃ of lower dry doing 20 hours, 650 ℃ of lower roastings 10 hours obtain Zirconium oxide powder;
(2) 20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63m%) are mixed, making beating, regulating its pH value with hydrochloric acid is 3.5;
(3) in the slurries that 19Kg halloysite (Suzhou china clay company industrial products, solid content 72.3 % by weight) adding step (2) obtained, pulled an oar 5 minutes, then add the Zirconium oxide powder 4.0Kg of step (1) preparation, pulled an oar 15 minutes;
(4) (the Qilu Petrochemical catalyst plant is produced, Al to add 10Kg aluminium colloidal sol in the slurries that step (3) obtains
2O
3Content is 21.7 % by weight), stirred 40 minutes, add zeolite slurry 40Kg, (ZRP zeolite 15Kg wherein, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product; DASY2.0 zeolite 16Kg, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product; ZRP silica alumina ratio 120, degree of crystallinity are 82, and the primary particle diameter is 35 μ m), pulled an oar 15 minutes;
(5) in the slurries that step (4) obtains, add the Zirconium oxide powder for preparing in the remaining step (1), pulled an oar 15 minutes, adding hydrochloric acid adjusting pH value is 3.2, pulled an oar 5 minutes, and then left standstill in 65 ℃ and wore out 1.5 hours, cool the temperature to 55 ℃, spray-drying, the flush away Na ion that dissociates, drying obtains catalyst E.
Method according to embodiment 4 is estimated catalyst D, the results are shown in Table 3
Comparative Examples 3～4
Method according to embodiment 4 is estimated DB-1, DB-2 catalyst.Evaluation result sees Table 3.
By table 1 and as seen from Table 3, compare with the catalyst of existing method preparation, the Cracking catalyst of method preparation provided by the invention, activity stability is good, anti-wear performance is better, and degree of crystallinity is higher, is used for RFCC, conversion ratio is high, and olefine selective is good, and ethylene yield is high.
Table 1
| The embodiment numbering | Comparative Examples 1 | Comparative Examples 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 7 | Embodiment 8 |
| The catalyst numbering | DB-1 | DB-2 | A | B | C | D | E |
| AI，％ | 3.5 | 1.1 | 1.5 | 0.9 | 1.0 | 2.5 | 2.0 |
| 800 ℃/17h active (MA) | 65 | 70 | 71 | 72 | 74 | 66 | 71 |
| ACR, % (fresh dose) | 15.6 | 16.0 | 16.6 | 16.2 | 16.3 | 16.0 | 16.1 |
| ACR, % (after 800 ℃/17h is aging) | 11.4 | 12.9 | 13.8 | 13.2 | 13.3 | 12.2 | 13.2 |
Table 2
| Feedstock oil | Daqing atmospheric residue |
| Density (20 ℃), g/cm 3Carbon residue, m% hydrogen content, m% sulfur content, m% tenor, ppm Fe Ni V Na | 0.8938 4.6 12.89 0.13 4.9 4.3 0.2 5.2 |
Table 3
| The embodiment numbering | Comparative Examples 3 | Comparative Examples 4 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| The catalyst numbering | DB-1 | DB-2 | A | B | C | D | E |
| Products collection efficiency | |||||||
| Dry gas, % by weight | 22.04 | 21.62 | 24.20 | 24.56 | 23.57 | 22.31 | 23.42 |
| Liquefied gas, % by weight | 39.87 | 40.14 | 40.78 | 41.21 | 40.65 | 40.62 | 41.11 |
| Gasoline, % by weight | 16.32 | 16.16 | 15.62 | 14.36 | 15.41 | 16.04 | 15.53 |
| Diesel oil, % by weight | 7.33 | 7.05 | 4.85 | 5.15 | 6.22 | 5.94 | 5.31 |
| Heavy oil, % by weight | 5.40 | 5.14 | 3.41 | 3.88 | 4.12 | 4.14 | 3.58 |
| Coke, % by weight | 9.04 | 9.89 | 11.14 | 10.84 | 10.03 | 10.95 | 11.05 |
| Gas yield, % by weight | |||||||
| Ethene | 9.24 | 10.92 | 12.43 | 13.24 | 11.95 | 11.52 | 13.09 |
| Propylene | 19.02 | 19.49 | 19.33 | 20.54 | 19.44 | 19.26 | 20.47 |
Claims (11)
1. the preparation method of a catalytic thermal cracking catalyst, described catalytic cracking catalyst contains the zeolite with MFI structure of 0.5～70 % by weight, in the al binder of aluminium oxide 5～75 % by weight with in the zirconium matrix of zirconia 3～25 % by weight; Wherein, the silica alumina ratio of the zeolite of the described MFI of having structure is 15～300, and the primary particle diameter is 5～55 μ m, and described preparation method may further comprise the steps:
(1) aqueous solution with zirconates mixes with ammoniacal liquor, and it is 9～12 that the consumption of ammoniacal liquor makes the pH value of resulting suspension, and then ageing, filtration, washing, drying, in 500～700 ℃ of roastings obtain Zirconium oxide powder;
(2) preparation al binder slurries;
(3) the al binder slurries that step (2) obtained mix with the Zirconium oxide powder of step (1) preparation, making beating, and take total catalyst weight as benchmark, zirconia introducing amount is 2～10 % by weight;
(4) in the slurries that step (3) obtains, introduce the zeolite with MFI structure, making beating, the silica alumina ratio of the zeolite of the described MFI of having structure is 15～300, the primary particle diameter is 5～55 μ m;
(5) in the slurries that step (4) obtains, introduce the Zirconium oxide powder that step (1) prepares, making beating, the zirconia gross weight that introduce step (3) and (5) accounts for 3～25 % by weight of catalyst gross weight;
(6) add acid in the slurries that step (5) obtains, it is 2～5 that the consumption of acid makes the pH value of slurries;
(7) slurry dried that step (6) is obtained.
2. in accordance with the method for claim 1, it is characterized in that, digestion time is 10～48 hours in the step (1), and the temperature of ageing is 15～50 ℃, and the time of roasting is 2～15 hours.
3. according to claim 1 or 2 described methods, it is characterized in that, in the step (1), the concentration of described zirconium saline solution is 0.1～3mol/L, and ammonia concn is 15～28 % by weight.
4. in accordance with the method for claim 1, it is characterized in that, the ratio of the zirconia weight of introducing in the zirconia of introducing in the step (3) and the step (5) is (0.4～5): 1.
5. in accordance with the method for claim 1, it is characterized in that, described catalyst also contains clay, take the weight of catalyst as benchmark, the al binder that contains 10～40 % by weight in the described catalyst, 0.5 the zeolite with MFI structure of～60 % by weight is no more than the clay of 60 % by weight, the zirconia of 3～25 % by weight.
6. in accordance with the method for claim 5, it is characterized in that, contain 10～35 % by weight al binders in the described catalyst, the zeolite of 15～45 % by weight MFI structures, 3～55 % by weight clays, 3～20 % by weight zirconias.
7. in accordance with the method for claim 1, it is characterized in that, the primary particle diameter of the zeolite of the described MFI of having structure is 8～15 μ m.
8. catalytic thermocracking process, be included in the step that under the catalytic pyrolysis condition hydrocarbon ils is contacted with catalyst, it is characterized in that, described catalyst contains the zeolite with MFI structure of 0.5～70 % by weight, in the al binder of aluminium oxide 5～75 % by weight with in the zirconium matrix of zirconia 3～25 % by weight; Wherein, the silica alumina ratio of the zeolite of the described MFI of having structure is 15～300, and the primary particle diameter is 5～55 μ m.
9. in accordance with the method for claim 8, it is characterized in that, described catalyst also contains clay, take the weight of catalyst as benchmark, the al binder that contains 10～40 % by weight in the described catalyst, 0.5 the zeolite with MFI structure of～60 % by weight is no more than the clay of 60 % by weight, the zirconia of 3～25 % by weight.
10. in accordance with the method for claim 9, it is characterized in that, contain 10～35 % by weight al binders in the described catalyst, the zeolite of 15～45 % by weight MFI structures, 3～55 % by weight clays and 3～20 % by weight zirconias.
11. in accordance with the method for claim 8, it is characterized in that, the primary particle diameter of the zeolite of the described MFI of having structure is 8～15 μ m.
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| CN1098130A (en) * | 1993-07-29 | 1995-02-01 | 中国石油化工总公司 | A kind of cracking catalyst and preparation method thereof |
| CN1221015A (en) * | 1997-12-23 | 1999-06-30 | 中国石油化工总公司 | Layer-column clay catalyst for heavy-oil catalytic thermal cracking and its preparation |
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| CN1098130A (en) * | 1993-07-29 | 1995-02-01 | 中国石油化工总公司 | A kind of cracking catalyst and preparation method thereof |
| CN1221015A (en) * | 1997-12-23 | 1999-06-30 | 中国石油化工总公司 | Layer-column clay catalyst for heavy-oil catalytic thermal cracking and its preparation |
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