CN102430422B - Catalytic cracking catalyst for producing low-carbon olefin and application thereof - Google Patents
Catalytic cracking catalyst for producing low-carbon olefin and application thereof Download PDFInfo
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- CN102430422B CN102430422B CN2010102960500A CN201010296050A CN102430422B CN 102430422 B CN102430422 B CN 102430422B CN 2010102960500 A CN2010102960500 A CN 2010102960500A CN 201010296050 A CN201010296050 A CN 201010296050A CN 102430422 B CN102430422 B CN 102430422B
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Abstract
The invention discloses a catalytic cracking catalyst for producing low-carbon olefin. The catalyst consists of 0.5-15 parts by weight of particles A and 1 part by weight of particles B, wherein the particles A include 10-85 percent by weight of aluminum binder, 15-60 percent by weight of molecular sieve and 0-75 percent by weight of clay based on the total weight of the particles A; the molecular sieve is MFI zeolite or MFI zeolite and Y type zeolite; the clay is one or more of montmorillonoid, diatomite, halloysite, soapstone, sepiolite, attapulgite, hydrotalcite and bentonite; and the particles B include 20-80 percent by weight of rectorite and 20-80 percent by weight of silicon oxide binder in terms of silicon oxide based on the total weight of the particles B. The catalyst provided by the invention has high olefin yield and excellent wear resistance.
Description
Technical field
The present invention relates to a kind of heavy oil catalytic pyrolysis and produce catalyst and the preparation and the application of low-carbon alkene.
Background technology
Ethene and propylene are important chemical material, 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.In recent years, heavily become bad along with petroleum becomes gradually, heavy-oil catalytic produces that the low-carbon alkene technology is low because of energy consumption, ingredient requirement is low, the product profile adjustment obtains large development flexibly, has bigger development prospect satisfying on the ever-increasing demand in future market.
Rectorite is dioctahedron paragonite and montmorillonite rule interbed mineral, montmorillonite layer wherein has cation exchange and dilatancy, mica layer does not then have this character, after it is carried out crosslinked or modification with inorganic polymer, can between montmorillonite layer, generate " layer post " shape structure, and non-bloating mica layer has formed fixing top and bottom bottom, makes it have heavy oil conversion performance preferably, thereby can be used for preparing the catalyst of producing low-carbon alkene by catalytically cracking.
CN1107080A discloses a kind of layered molecular sieve catalyst of producing in high-yield olefin, and its component and content are: the layered molecular sieve of (1) 10-50m%; (2) 4-30m% is selected from the ZSM-5 zeolite with H, Mg, RE, Zn, P modification; (3) 0-15m% is selected from a kind of zeolite among beta-zeolite, modenite, the USY zeolite; (4) natural clay of 10-70m%; (5) inorganic oxide of 10-35m%.This Preparation of catalysts method is: carrier pulp is mixed making beating with layered molecular sieve and other molecular sieve, carry out moulding, drying then, promptly get product.This catalyst also can make with the back cross-linking method.This catalyst is to C
3 =-C
5 =, iC particularly
4 =And iC
5 =Selectivity is preferably arranged, simultaneously can also coproduction gasoline and diesel oil.Yet this catalyst is used for residual oil cracking, and ethylene selectivity is not high, and catalyst strength (wear resistance) is relatively poor.
CN1160743A has disclosed a kind of laminated clay column catalyst of polyvinyl alcohol modification of producing in high-yield olefin, it is laminated clay column active component by 20～90 heavy % polyvinyl alcohol modifications, 0～40 heavy % is selected from the auxiliary element of the silica-rich zeolite, ZSM-5, β zeolite or the y-type zeolite that contain rare-earth five-membered ring structure, and 0～50 heavy % is selected from the carrier component of kaolin etc. and 10～40 heavy % and is selected from by the friendship stick component of the inorganic oxides such as aluminium oxide of polyvinyl alcohol modification and forms.Its preparation method is: in the presence of polyvinyl alcohol, said components is mixed,, steps such as ammonification aging, drying, roasting dried through the making beating spray make.This catalyst is fit to the cracking heavy raw oil, the producing in high-yield olefin parallel connection oil that steams.Yet this catalyst ethylene selectivity is not high, and catalyst strength is relatively poor.
CN1353012A discloses a kind of preparation method of laminated clay column catalyst, it is characterized in that this method is after calcium type lamellar clay is disperseed in water with a kind of dispersant, other each component raw material with catalyst mixes again, and cross-linking reaction, aging and roasting are carried out in moulding then again.This method need not directly to adopt calcium type lamellar clay prepared layer clay column catalyst through the ion-exchanged process, however the catalyst of this method preparation, and intensity is relatively poor, does not relate to the production low-carbon alkene.
Summary of the invention
The technical problem to be solved in the present invention is the low problem of catalytic cracking catalyst ethylene yield that contains the production low-carbon alkene of rectorite at existing, provide a kind of heavy oil catalytic pyrolysis to produce the catalyst for cracking of low-carbon alkene, this catalyst has higher ethylene yield, and the other technical problem that the present invention will solve provides described Application of Catalyst method.
The invention provides a kind of heavy oil catalytic pyrolysis and produce the catalytic cracking catalyst of low-carbon alkene, form by the particle A of 0.5～15 weight portion and the particle B of 1 weight portion; Gross weight with particle A is a benchmark, particle A comprises 10～85 weight % al binders, the clay of 15～60 weight % molecular sieves and 0～75 weight %, described molecular sieve is the MFI structural zeolite or is MFI structural zeolite and y-type zeolite that described clay is one or more in kaolin, imvite, diatomite, galapectite, saponite, sepiolite, attapulgite, hydrotalcite and the bentonite; Gross weight with particle B is a benchmark, and described particle B forms by the rectorite of 20～80 weight % with in the silica binder of silica 20～80 weight %.
The present invention also provides the preparation method of catalytic cracking catalyst provided by the invention, comprise: prepare particle A and particle B respectively, according to particle A: the part by weight of particle B=0.5～15: 1 mixes particle A and particle B, wherein, the preparation method of particle A comprises that preparation comprises al binder, molecular sieve, contain or slurries not argillaceous spray-dired step; The preparation method of particle B comprises: waterglass and sulfuric acid mixed, and preparation Ludox slurries, keeping the Ludox slurry pH value is 1.0～3.0, then rectorite is joined in the above-mentioned slurries, stirs spray drying forming, roasting.
The invention provides a kind of catalytic cracking method, the step that the catalyst that being included under the catalytic pyrolysis condition provides heavy oil and the invention described above contacts; Wherein said catalytic pyrolysis condition comprises: 550～700 ℃ of reaction temperatures, and oil ratio (weight ratio of catalyst and raw material) is 6～30, feeds diluent gas in the course of reaction, the weight ratio of diluent gas and heavy oil feedstock is 0.1～1: 1.
Catalytic cracking catalyst provided by the invention, anti-wear performance is good, is used for heavy oil catalytic pyrolysis and produces low-carbon alkene, heavy oil cracking ability is strong, have the better conversion ability for the high raw material of blending ratio, and have higher productivity of low carbon olefin hydrocarbon, especially have higher ethylene yield; Compare with the existing production light olefins catalyst that contains rectorite, ethylene yield is higher, the constant or raising of productivity of propylene, and the productivity of low carbon olefin hydrocarbon height, coke yield is lower, the catalyst activity height.Method for preparing catalyst provided by the invention can use the preparation of natural calcium type rectorite to contain the catalyst of rectorite, and preparation technology is simple, the prepared production light olefins catalyst that contains rectorite, and anti-wear performance is good, good sphericity, fluidizing performance is good; The crystallization reservation degree height of molecular sieve in the catalyst, heat and good hydrothermal stability; Prepared catalyst has better heavy oil conversion performance and productivity of low carbon olefin hydrocarbon.
The method of producing low-carbon alkene by catalytic pyrolysis provided by the invention is applicable to heavy oil catalytic pyrolysis production low-carbon alkene.Described heavy oil is decompressed wax oil, decompression residuum, normal pressure wax oil, reduced crude for example, one or more in the deasphalted oil.
The specific embodiment
Heavy oil catalytic pyrolysis provided by the invention is produced the catalytic cracking catalyst of low-carbon alkene and is made up of two kinds of composition grains, and wherein, particle A comprises al binder, molecular sieve, contains or argillaceous not; Weight with particle A is benchmark, comprises among the described particle A in aluminium oxide 10～85 weight % al binders, in butt 15～60 weight % molecular sieves, in the described clay of butt 0～75 weight %; Preferably include 20-30 weight % al binder, 20-35 weight % molecular sieve, the described clay of 35-60 weight %.Described molecular sieve is the MFI structural zeolite or also contains y-type zeolite, in order to make described catalyst have higher productivity of low carbon olefin hydrocarbon and to have lower coke yield, described molecular sieve is preferably the MFI structural zeolite, weight with particle A is benchmark, and the content of described MFI structural zeolite is 15～60 weight %.Described MFI structural zeolite is a pentasil type 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, and the mol ratio of silica and aluminium oxide is 15-300 in the zeolite.Described clay is one or more in kaolin (for example halloysite), imvite, diatomite, galapectite, saponite, sepiolite, attapulgite, hydrotalcite, the bentonite, is preferably kaolin.The weight ratio preferred 0.3～1.1: 1 of rectorite and MFI structure molecular screen in the catalyst.
Can also contain Cracking catalyst inorganic oxide matrix commonly used among the described particle A, described inorganic oxide matrix is aluminium oxide, silica, silica-alumina for example.Weight with particle A is benchmark, is no more than 85 weight % in the content of the described inorganic oxide matrix of oxide; In the time of can also containing rare earth oxide among the particle A, be benchmark with the weight of particle A, the content of rare earth oxide is no more than 5 weight %.
Described particle B preferably is made up of the rectorite of 40～75 weight % and the silica binder of 25～60 weight %.Described rectorite can also be rare earth modified rectorite.With RE
2O
3Meter, the content of rare earth modified rectorite middle rare earth oxide is no more than 5 weight %.The basal spacing d001 value of described rectorite is 2.7-5.0nm, and specific area is 100-300m
2/ g.
Catalytic cracking catalyst preparation method provided by the invention, preparation contains the particle A of molecular sieve and al binder and contains rectorite and the particle B of silica respectively, then two kinds of particles is mixed.In order to make prepared catalyst have better abrasion resistance properties and higher productivity of low carbon olefin hydrocarbon and lower coke yield, a kind of preferred for preparation method of catalyst provided by the present invention may further comprise the steps:
(1) preparation al binder slurries;
(2) in the slurries that step (1) obtains, add molecular sieve, making beating;
(3) in the slurries that step (2) obtains, add kaolin, making beating;
(4) the slurries spray drying forming that step (3) is obtained obtains particle A;
(5) use H
2SO
4Acidified sodium silicate stirs simultaneously, to the pH value of gained mixture be 1.0～3.0;
(6) rectorite is joined in the mixture that step (5) obtains making beating;
(7) the slurries spray drying forming that step (6) is obtained obtains particle B.
(8) particle A and particle B are mixed.
The described preparation al binder of step (1) slurries comprise al binder are 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, have a diaspore structure hydrated alumina, have 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 one or more, and preferred al binder is boehmite and/or aluminium colloidal sol.When described al binder comprises boehmite, preferred earlier with the boehmite acidifying, obtain the acidification pseudo-boehmite slurries, and then mix with other al binder, molecular sieve and clay, wherein, to make the pH value of acidification pseudo-boehmite slurries be 2～4 to the consumption of acid, and described acid is one or more in hydrochloric acid, nitric acid and the phosphoric acid for example.Weight with resulting granules A is benchmark, and the alumina amount of being introduced by al binder among the described particle A is preferably 10～40 weight %.
Add molecular sieve in the preparation process (2), can add the solid molecular sieves powder, also can add molecular sieve pulp.Described molecular sieve pulp can for example mix water according to existing method preparation with molecular sieve, making beating, and beating time preferably was not less than 10 minutes, more preferably 15～60 minutes.Beating time was not less than preferred 15～60 minutes 10 minutes after introducing molecular sieve.Described molecular sieve is the MFI structural zeolite or is MFI structural zeolite and y-type zeolite, be 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, its silica alumina ratio (mol ratio of silica and aluminium oxide) is 15-300.
In the preparation process (3), described clay is one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, sepiolite, attapulgite, hydrotalcite, the bentonite for example; Be preferably kaolin.
Among the catalytic cracking catalyst preparation method provided by the invention, can also introduce matrix, described matrix can be introduced in step (2) or (3), introduces the preferred making beating in back 15～60 minutes.Described matrix is selected from one or more of inorganic oxide and precursors of inorganic oxides, and described clay is preferable over step (2) and introduces afterwards.Described inorganic oxide is rare earth oxide, silica, gama-alumina for example, and described precursors of inorganic oxides is aluminium colloidal sol, rare-earth salts, waterglass for example.When introducing rare-earth salts, described rare-earth salts is preferably introduced in the slurries before the spray-drying after introducing clay.Particle can all be introduced rare-earth salts in two, preferably join in the particle that contains rectorite and binding agent, and be benchmark with the particle weight that contains rectorite and binding agent, be no more than 5 weight % in the introducing amount of oxide rare earth.
The described sulfuric acid acidation waterglass of using of step (5) is included in to stir adds sulfuric acid solution down in water glass solution, to the pH value be 1～3, wherein, the concentration of water glass solution is that 18-40 weight % is (with SiO
2Meter), sulfuric acid solution concentration is 25-50 weight %.The mixture that sulfuric acid solution and water glass solution form, the content of silica is preferably 5-15 weight %, and the pH value is 1～3.Described rectorite is calcium type rectorite or rare earth modified rectorite, is preferably natural calcium type rectorite.Add the preferred making beating in acid back 30～60 minutes.The Ludox that step (6) is prepared and the solid content of rectorite slurries are 20～40 weight %, and the pH value is preferably 1.2～2.0.
Among the catalytic cracking catalyst preparation method provided by the invention, described spray-drying can adopt prior art, and the present invention does not have specific (special) requirements.
Among the catalytic cracking catalyst preparation method provided by the invention, also comprise the step of roasting.Particle A and particle B proportionally can be mixed it after the roasting respectively again, also can be with roasting again after particle A and the particle B mixing.Roasting condition is a roasting condition habitual in the catalytic cracking catalyst preparation process, does not have specific (special) requirements.The temperature of roasting is preferably 450～550 ℃, and the time is preferably 1～6 hour.
Catalytic cracking catalyst provided by the invention is applicable to heavy oil catalytic pyrolysis technology, is used to handle height and mixes the production of slag feedstock oil and have heavy oil conversion performance preferably, and the productivity of low carbon olefin hydrocarbon height.Catalyst provided by the invention can use separately, also can mix the back with other catalytic pyrolysis auxiliary agent and use, and for example mixes the back with the CO combustion adjuvant and uses.
Catalytic cracking method provided by the invention can be according to existing method, generally includes catalyst is contacted in riser and/or fluidized-bed reactor with heavy oil feedstock, reacts reaction time 0.2-20 second; Reaction product isolated and reclaimable catalyst; Product is sent into subsequent separation system and is carried out the product separation, obtains product liquid and the gaseous product that contains ethene, propylene, and reclaimable catalyst Returning reactor after stripping, regeneration recycles.Described catalytic pyrolysis condition is: reaction temperature 550-700 ℃, reaction time 0.5-20 second, preferred 0.5-10 second, the weight ratio of catalyst and feedstock oil is 6-30, feed for example steam of diluent gas in the course of reaction, the weight ratio of diluent gas and raw material is 0.1-1: 1.Described catalyst is the catalyst that heavy oil catalytic pyrolysis provided by the invention is produced low-carbon alkene.
The following examples will give further instruction to the present invention, but not thereby limiting the invention.
In each embodiment and Comparative Examples, Na in the zeolite
2O, Fe
2O
3, NiO, Al
2O
3, SiO
2Content measure [referring to " Science Press, nineteen ninety publishes for petrochemical industry analytical method (RIPP experimental technique), volumes such as Yang Cuiding] with x-ray fluorescence method.
Embodiment 1
(1) 20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63 weight %) are mixed, making beating, regulating its pH value with hydrochloric acid (concentration 30 weight %, down together) is 3; (the Qilu Petrochemical catalyst plant is produced, Al to add 10Kg aluminium colloidal sol
2O
3Content is 21.7 weight %), stirred 40 minutes, obtain the al binder slurries, its pH value is 2.7;
(2) in aluminium that step (1) obtains bonding slurries, add molecular sieve pulp 20Kg (wherein contain ZRP zeolite 8Kg, ZRP zeolite silica alumina ratio 40, phosphorous 2.5 weight % contain rare earth (RE
2O
3) 1 weight %, be catalyst Shandong branch company of China Petrochemical Industry product);
(3) 19Kg halloysite (Suzhou china clay company industrial products, solid content 72.3 weight %) is joined in the slurries that step (2) obtains, pulled an oar 30 minutes;
(4) the slurries spray-drying that step (3) is obtained obtains particle A;
(5) with 10Kg decationized Y sieve water and 18Kg waterglass (SiO
2Content 28.4 weight %) mix, add the H of 10Kg concentration 50 weight %
2SO
4, obtain the pH value and be 1.5 Ludox slurries;
(6) stir and down 15Kg rectorite (Zhongxiang City, Hubei rectorite, solid content 87 weight %, calcium oxide content are 2.0 weight %) to be joined in the Ludox slurries that step (5) obtains, add the back and stirred 30 minutes, the pH value of slurries is 1.8;
(7) the slurries spray-drying that obtains of step (6).Obtain particle B;
(8) particle A and particle B were mixed by weight 5: 1,500 ℃ of roastings 1.5 hours, the free Na ion of flush away then, drying obtains catalyst 1.
Embodiment 2
(1) 20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63 weight %) are mixed, making beating, regulating its pH value with hydrochloric acid is 3; (the Qilu Petrochemical catalyst plant is produced, Al to add 10Kg aluminium colloidal sol
2O
3Content is 21.7 weight %), stirred 40 minutes.Obtain the pH value and be 2.7 al binder slurries;
(2) in the al binder slurries that step (1) obtains, add molecular sieve pulp 20Kg and (wherein contain ZRP zeolite 5Kg, DASY2.0 zeolite 1Kg; ZRP zeolite silica alumina ratio 60, phosphorous 2.5 weight % contain rare earth (RE
2O
3) 1 weight %; The DASY2.0 zeolite contains rare earth (RE
2O
3) 2 weight %; Two kinds of zeolites are catalyst Shandong branch company of China Petrochemical Industry product);
(3) 15Kg halloysite (Suzhou china clay company industrial products, solid content 72.3 weight %) is joined in the slurries that step (2) obtains, pulled an oar 30 minutes;
(4) the slurries spray-drying that obtains in step (3) obtains particle A;
(5) 10Kg decationized Y sieve water is mixed with 30Kg waterglass (the same), add the H of 10Kg50 weight %
2SO
4Solution obtains the Ludox slurries, and its pH value is 1.8;
(6) 7Kg rectorite (with embodiment 1 used rectorite) is joined in the Ludox slurries that step (5) obtains, stir simultaneously, add the back and stirred 45 minutes, the pH value of final slurries is 1.8;
(7) the slurries spray-drying that step (6) is obtained obtains particle B;
(8) particle A and particle B were mixed by weight 10: 1,550 ℃ of roastings free Na ion of flush away after 1.5 hours, drying obtains catalyst 2.
Embodiment 3
(1) 20Kg decationized Y sieve water and 10Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63 weight %) are mixed, making beating, regulating its pH value with hydrochloric acid is 3; (the Qilu Petrochemical catalyst plant is produced, Al to add 10Kg aluminium colloidal sol
2O
3Content is 21.7 weight %), stirred 40 minutes;
(2) in the slurries that step (1) obtains, add molecular sieve pulp 30Kg (wherein contain ZRP zeolite 11Kg, ZRP silica alumina ratio 60, phosphorous 2.5 weight % contain rare earth (RE
2O
3) 1 weight %, be catalyst Shandong branch company of China Petrochemical Industry product);
(3) 19Kg halloysite (Suzhou china clay company industrial products, solid content 72.3 weight %) is joined in the slurries that step (2) obtains, pulled an oar 30 minutes;
(4) the slurries spray-drying that step (3) is obtained obtains particle A;
(5) with 10Kg decationized Y sieve water and 20Kg water glass solution (SiO
2Content 28.4 weight %) mix, add the H of 13Kg concentration 50 weight %
2SO
4Solution obtains the Ludox slurries, and its pH value is 1.75;
(6) 13Kg rectorite (Zhongxiang City, Hubei rectorite, solid content 87 weight %, calcium oxide content 2 weight %) is joined in the Ludox slurries that step (5) obtains, stir simultaneously, the pH value of final slurries is 1.5;
(7) the slurries spray-drying of step (6).Obtain particle B.
(8) particle A and particle B were mixed by weight 1: 1,600 ℃ of roastings 2 hours, the flush away Na ion that dissociates, drying obtains catalyst 3.
Comparative Examples 1
Method according to CN1107080A embodiment 1 prepares catalyst D1.Described catalyst comprises 24 weight %ZRP zeolites (with the ZRP zeolite of embodiment 3), 31 weight % kaolin, tired soil and the 25 weight % alumina binder of taking off of 20 weight %.
Comparative Examples 2
Method (referring to CN1048428C) preparation catalyst according to the DCC industrial catalyst.
With 92.6Kg decationized Y sieve water and 38.7Kg halloysite (Suzhou china clay company industrial products, solid content 72.3 weight %) mix making beating, add 15.9Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63 weight %) again, its pH is transferred to 3 with hydrochloric acid, 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 13.5Kg aluminium colloidal sol
2O
3Content is 21.7 weight %), stirred 40 minutes.Add molecular sieve pulp 32.1Kg and (wherein contain DASY2.0 zeolite 6.3kg, ZSP-3 zeolite 4.2Kg, be all catalyst Shandong branch company of China Petrochemical Industry product, rare earth oxide content is 2 weight % in the described DASY2.0 zeolite), making beating, spray drying forming, the flush away Na ion that dissociates is drying to obtain contrast medium D2.
Embodiment 4
According to 10: 1 physical mixed of weight, 550 ℃ of roastings are the flush away Na ion that dissociates after 1 hour with the particle B of the catalyst D2 of Comparative Examples 2 preparation and embodiment 2 preparations, and drying obtains catalyst 4, and its physico-chemical property is listed in table 1.
Table 1
| The embodiment numbering | Comparative Examples 1 | Comparative Examples 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| The catalyst numbering | D1 | D2 | 1 | 2 | 3 | 4 |
| AI，％ | 2.1 | 2.0 | 1.4 | 0.9 | 1.0 | 2.2 |
| Initial activity | 60 | 65 | 72 | 70 | 69 | 66 |
| 800 ℃/4h activity (MA) | 52 | 64 | 66 | 64 | 65 | 58 |
Embodiment 5
On the small fixed flowing bed device, the mixed material (character sees Table 2) of getting grand celebration VGO and decompression residuum is a raw material, and catalyst sample 1～4 is estimated, and reaction temperature is 565 ℃, and agent weight of oil ratio is 10, weight (hourly) space velocity (WHSV) 4h
-1, water injection rate (accounting for raw material) 26 weight %.Catalyst sample is in advance through 800 ℃, and 100% steam treatment 17 hours, catalyst loading amount are 180 grams.Evaluation result sees Table 3.
Comparative Examples 3
Method according to embodiment 5 is estimated D2, D1 catalyst.Evaluation result sees Table 3.
Table 2
Table 3
| The catalyst source | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 |
| The catalyst numbering | 1 | 2 | 3 | 4 | D1 | D2 |
| Reaction temperature, ℃ | 565℃ | 565℃ | 565℃ | 565℃ | 565℃ | 565℃ |
| Oil ratio, w/w | 10 | 10 | 10 | 10 | 10 | 10 |
| Dry gas, weight % | 8.67 | 7.66 | 8.21 | 7.23 | 6.95 | 7.61 |
| Liquefaction vapour, weight % | 38.66 | 36.49 | 37.06 | 34.67 | 36.05 | 34.98 |
| Coke, weight % | 8.72 | 9.21 | 9.06 | 10.56 | 10.34 | 10.09 |
| Gasoline, weight % | 33.95 | 32.45 | 34.24 | 33.21 | 33.85 | 32.05 |
| Diesel oil, weight % | 6.52 | 8.73 | 8.18 | 11.17 | 9.3 | 11.83 |
| Heavy oil, weight % | 3.47 | 5.46 | 3.25 | 3.16 | 3.51 | 3.44 |
| Ethylene yield, weight % | 3.68 | 2.75 | 3.54 | 2.31 | 2.17 | 1.32 |
| Productivity of propylene, weight % | 15.08 | 13.01 | 14.98 | 11.67 | 13.06 | 11.11 |
| The butylene productive rate, weight % | 10.39 | 9.45 | 11.26 | 10.85 | 11.07 | 10.06 |
By table 3 as seen, catalyst provided by the invention has higher ethene and productivity of propylene, is unexpectedly also to obtain higher liquefaction productive rate, and has lower coke yield.
Claims (10)
1. the catalyst of a heavy oil catalytic pyrolysis production low-carbon alkene is made up of the particle A of 0.5～15 weight portion and the particle B of 1 weight portion; Gross weight with particle A is a benchmark, particle A comprises the clay of 10～85 weight % al binders, 15～60 weight % molecular sieves and 0～75 weight %, described molecular sieve is MFI structural zeolite or MFI structural zeolite and y-type zeolite, and described clay is one or more in kaolin, imvite, diatomite, galapectite, saponite, sepiolite, attapulgite, hydrotalcite and the bentonite; Gross weight with particle B is a benchmark, and described particle B forms by the rectorite of 20～80 weight % with in the silica binder of silica 20～80 weight %.
2. according to the described catalyst of claim 1, it is characterized in that described particle B is made up of the rectorite of 40～75 weight % and the silica binder of 25～60 weight %.
3. according to the described catalyst of claim 2, it is characterized in that described catalyst is made up of the particle A of 1～10 weight portion and the particle B of 1 weight portion.
4. according to the described catalyst of claim 1, it is characterized in that described molecular sieve is the MFI structural zeolite, is benchmark with the weight of particle A, and the content of described MFI structural zeolite is 15～60 weight %; The mol ratio of silica and aluminium oxide is 15-300 in the zeolite of described MFI structure.
5. the preparation method of each described catalytic cracking catalyst of claim 1～4, comprise: prepare particle A and particle B respectively, according to particle A: the weight ratio of particle B=0.5～15: 1 is mixed particle A and particle B, wherein, the preparation method of particle A comprises that preparation comprises al binder, molecular sieve, contain or slurries not argillaceous spray-dired step; The preparation method of particle B comprises: waterglass and sulfuric acid mixed, and preparation Ludox slurries, the Ludox slurry pH value is 1.0～3.0, rectorite is joined in the above-mentioned Ludox slurries then, stirs spray drying forming, roasting.
6. in accordance with the method for claim 5, it is characterized in that the preparation method of described particle A:
(1) preparation al binder slurries;
(2) in the slurries that step (1) obtains, add molecular sieve, making beating;
(3) in the slurries that step (2) obtains, add kaolin, making beating;
(4) the slurries spray drying forming that step (3) is obtained obtains particle A.
7. in accordance with the method for claim 6, it is characterized in that described al binder is boehmite and/or aluminium colloidal sol, the pH value of the slurries that step (1) obtains is 2～4.
8. in accordance with the method for claim 5, it is characterized in that the concentration of prepared Ludox slurries is with SiO
2Count 5-15 weight %.
9. in accordance with the method for claim 8, it is characterized in that the solid content of prepared Ludox and rectorite slurries is 20～40 weight %, the pH value is 1.2～2.0.
10. the method for a producing low-carbon alkene by catalytic pyrolysis, be included under the catalytic pyrolysis condition step that catalyst that each described heavy oil catalytic pyrolysis of heavy oil and claim 1～4 is produced low-carbon alkene contacts, described catalytic pyrolysis condition comprises: 550～700 ℃ of reaction temperatures, the weight ratio of catalyst and feedstock oil is 6～30, feed diluent gas in the course of reaction, the weight ratio of diluent gas and heavy oil feedstock is 0.1～1: 1.
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| CN103506152B (en) * | 2012-06-25 | 2015-10-28 | 中国石油化工股份有限公司 | A kind of catalyst processing hydrotreated feed oil |
| CN105478162B (en) * | 2014-10-11 | 2019-05-17 | 中国石油化工股份有限公司 | Reduce the catalyst of green coke low-carbon olefines high-output |
| CN106140291B (en) * | 2015-04-16 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of Cracking catalyst containing modified MFI structure zeolite |
| WO2020078434A1 (en) * | 2018-10-18 | 2020-04-23 | 中国石油化工股份有限公司 | Mfi structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof |
| US11975980B2 (en) | 2018-10-18 | 2024-05-07 | China Petroleum & Chemical Corporation | MFI structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof |
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| CN1107080A (en) * | 1994-02-18 | 1995-08-23 | 中国石油化工总公司 | Laminar column molecular sieve catalyst of high yield olefines |
| US5583082A (en) * | 1994-10-07 | 1996-12-10 | Board Of Trustees Operating Michigan State University | Stable supergallery pillared clay compositions |
| CN1721505A (en) * | 2004-07-14 | 2006-01-18 | 中国石油化工股份有限公司 | Catalytic conversion method for selective preparation of micromolecular olefin |
| CN101130162A (en) * | 2006-08-24 | 2008-02-27 | 中国石油化工股份有限公司 | Cracking catalyst and its preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1107080A (en) * | 1994-02-18 | 1995-08-23 | 中国石油化工总公司 | Laminar column molecular sieve catalyst of high yield olefines |
| US5583082A (en) * | 1994-10-07 | 1996-12-10 | Board Of Trustees Operating Michigan State University | Stable supergallery pillared clay compositions |
| CN1721505A (en) * | 2004-07-14 | 2006-01-18 | 中国石油化工股份有限公司 | Catalytic conversion method for selective preparation of micromolecular olefin |
| CN101130162A (en) * | 2006-08-24 | 2008-02-27 | 中国石油化工股份有限公司 | Cracking catalyst and its preparing process |
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