CN100497531C - Cracking catalyst - Google Patents
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- CN100497531C CN100497531C CNB2005100681757A CN200510068175A CN100497531C CN 100497531 C CN100497531 C CN 100497531C CN B2005100681757 A CNB2005100681757 A CN B2005100681757A CN 200510068175 A CN200510068175 A CN 200510068175A CN 100497531 C CN100497531 C CN 100497531C
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Abstract
This invention published a fluidization cracking catalyst. The main components of the catalyst are 5~70% (w/w) cracked active component, 5~80%clay and 10~60%agglomerant. Y-type of molecular sieve and 3~20% sialic material which based on catalyst and had been acidized within the cracked active component is the characteristic of the catalyst. The sialic material has a phase structure as thin diaspore. Its formula (calculated by weight of oxidants) is (0-0.3) Na2O . (40-90) Al2O3 . (10-60) SiO2. It has specific area 200~400m2/g, average aperture 8~20nm, most probable aperture 5~15nm.The acidification treatment mentioned was inorganic acid and sialic material (ratio of the tow: 0.1~0.3) kept contacting for 0.5~3h under room-temperature ~80DEG C.This catalyst has well intensity, high stability of activity, low yield of heavy oil and strong capability of conversion for crude oil.
Description
Technical field
The invention relates to a kind of cracking catalyst, specifically about a kind of fluidized catalytic cracking catalyst that contains the mesoporous Si-Al material.
Background technology
Catalytic cracking is a kind of oil refining process, be widely used in the refining of petroleum industry, as the most important course of processing in the crude oil secondary processing, this technology is the main means of production of liquefied petroleum gas (LPG), gasoline, kerosene and diesel oil, occupies critical role in refinery.In catalytic cracking and hydrocracking process, the residual oil of heavy ends such as vacuum distillate or more heavy constituent reacts in the presence of catalyzer, be converted into gasoline, distillate and other liquid cracked product and the lighter following gaseous state cracked product of four carbon, in these reaction process, need to use catalytic material usually with high cracking activity.
The micro-pore zeolite catalytic material has good shape selective catalysis performance and very high cracking reaction activity owing to it, and is widely used in refining of petroleum and the processing industry.But along with exhausting day by day and the requirement of aspect such as environment protection of petroleum resources; particularly the crude oil high boiling component that becomes 500 ℃ of heavy rising tendencys (〉 day by day increases) and market to the heavy demand of light-end products; in refining of petroleum industry, more and more pay attention to deep processing to heavy oil and residual oil; the part refinery begins to mix refining vacuum residuum, even directly with the long residuum is cracking stock.Traditional micro porous molecular sieve catalytic material is because its duct is less, bigger raw molecule is demonstrated tangible restriction diffusion, cause apparent reactive behavior to reduce, limit macromolecular catalyzed reaction to a great extent, therefore be not suitable for being applied to the catalytic cracking reaction of heavy endss such as heavy oil and residual oil.
For improving the heavy oil selectivity of catalytic cracking, the macromole of heavy oil fraction is transformed, also will reduce the further conversion of intermediate oil and petroleum naphtha simultaneously, this just needs to use the aperture bigger, reactant molecule is not had diffusional limitation, and have the material of higher cracking activity.And traditional micro porous molecular sieve only is beneficial to micromolecular cracking, and therefore mesoporous the and research and development macropore catalytic material more and more are subject to people's attention.
The appearance of mesopore molecular sieve is in 1992, at first succeeds in developing (BeckJS, Vartuli J Z by U.S. Mobil company, Roth W J et al., J.Am.Chem.Comm.Soc., 1992,114,10834-10843), called after M41S series mesopore molecular sieve, comprise MCM-41 (MobilCorporation Material-41) and MCM-48 etc., the aperture of molecular sieve can reach 1.6～10nm, and is evenly adjustable, and pore size distribution is concentrated, specific surface area and pore volume are big, high adsorption capacity; But because the hole wall structure of this molecular sieve analog is a undefined structure, thus hydrothermal stability difference and acidity a little less than, can't satisfy the operational condition of catalytic cracking, industrial application is very restricted.
For solving the problem of mesopore molecular sieve hydrothermal stability difference, number of research projects just concentrates on and improves on the molecular sieve pore wall thickness, adopt neutral template can obtain the thicker molecular sieve of hole wall, but the more weak shortcoming of its acidity still exists.A kind of novel mesopore molecular sieve is disclosed in CN 1349929A, on the hole wall of this molecular sieve, introduced the primary and secondary structural unit of zeolite, make its basic structure with traditional zeolite molecular sieve, this mesopore molecular sieve has strongly-acid and superelevation hydrothermal stability.But, the deficiency of this molecular sieve is to need to use expensive template, and the aperture only has about 2.7nm, still have bigger space steric effect for the macromole cracking reaction in the heavy oil, structure is easily subsided under the high-temperature water heat condition, cracking activity is relatively poor, does not therefore see its large-scale industrial application so far as yet.
In the catalytic cracking field, silica-alumina material has stronger acid sites owing to it and good cracking performance is used widely.The proposition of mesoporous notion, again for the preparation of new catalyst provide may, but present result of study focuses mostly on and using expensive organic template and organosilicon source, and majority will pass through high temperature hydro-thermal last handling process.Disclose a kind of monodisperse mesoporous aluminium silicon composite material among the US5051385, earlier acid inorganic aluminate and silicon sol have been mixed back adding alkali, the aluminium content of the silica-alumina material that obtains is at 5～40 heavy %, and the aperture is between 20～50nm, and specific surface area reaches 50～100m
2/ g.Disclosed method is load silicon oxide particle or a hydrated silica on the porous boehmite among the US4708945, again with the gained mixture in hydrothermal treatment consists more than 600 ℃, make silica supportedly at the lip-deep catalyzer of class boehmite, the surface-area of this material is 100～200m
2/ g, mean pore size 7～7.5nm.Disclose serial sour cracking catalyst in US4440872, the carrier of some of them catalyzer is by at γ-Al
2O
3Last dipping silane makes after 500 ℃ of roastings or steam-treated then.US2394796 discloses dipping silicon tetrachloride or tetraethyl silicane on the porous hydrated aluminum oxide, obtains aluminium silicon composite material through hydrolysis then.Adopting inorganic aluminate and water glass among the CN 1353008 is raw material, forms stable silicon-aluminum sol clearly through processes such as precipitation, dispergation, and back drying obtains white gels, and roasting obtained Si-Al catalysis material after 1～20 hour under 350 ℃～650 ℃ conditions.
Disclose a kind of mesoporous Si-Al material in CN1565733A, this silica-alumina material has the phase structure of pseudo-boehmite, and its pore size distribution is concentrated, and specific surface area is greater than 200～400m
2/ g, pore volume are 0.5～2.0ml/g, and mean pore size is between 8～20nm, and the most probable aperture is 5～15nm.The preparation of this mesoporous Si-Al material need not used organic formwork agent, and synthetic cost is low, and the silica-alumina material that obtains has high cracking activity and hydrothermal stability, shows good macromole cracking performance in catalytic cracking reaction.
Summary of the invention
The inventor is surprised to find that, said mesoporous Si-Al material is after adding cracking catalyst as the part of active component after the acidification in above-mentioned CN1565733A, prepared catalyzer shows that not only intensity is significantly improved, be beneficial to the industrial application of catalyzer, and show that the hydro-thermal activity stability also increases.
Therefore, the objective of the invention is on the basis of existing technology, a kind of catalyst strength height, cracking catalyst that the hydro-thermal activity stability is good are provided.
Cracking catalyst provided by the invention mainly is made up of cracking activity constituent element, clay and binding agent, contains Y zeolite and a kind of mesoporous Si-Al material through acidification in the wherein said cracking activity constituent element.
More particularly, cracking catalyst provided by the invention is mainly by the cracking activity constituent element of 5～70 heavy %, the binding agent of the clay of 5～80 heavy % and 10～60 heavy % is formed, it is characterized in that containing Y zeolite in the said cracking activity constituent element and be that benchmark, content are a kind of mesoporous Si-Al materials through acidification of 3～20 heavy %, preferred 5～15 heavy % with the catalyzer, said mesoporous Si-Al material, phase structure with pseudo-boehmite in the anhydrous chemical expression of oxide weight is: (0-0.3) Na
2O (40-90) Al
2O
3(10-60) SiO
2, its specific surface area is 200～400m
2/ g, pore volume are 0.5～2.0ml/g, and mean pore size is 8～20nm, and the most probable aperture is 5～15nm, and said acidification is in room temperature to 80 ℃, under 0.1～0.3 sour aluminum ratio condition mesoporous Si-Al material is contacted 0.5～3 hour with mineral acid.
The content of said cracking activity constituent element in catalyzer is 5～70 heavy %, and preferred 15～60 heavy % contain Y zeolite and a kind of mesoporous Si-Al material through acidification, can also contain MFI structure Si-Al molecular sieve and/or beta zeolite.
Said Y zeolite is selected from one or more the mixture among HY, USY, REUSY, REY, REHY, the REDASY, or the Y zeolite that obtains through various metal oxide treated.Content of rare earth in the said Y zeolite (REUSY, REY, REHY, REDASY) that contains rare earth is with RE
2O
3Count 0.5～20 heavy %.
Said mesoporous Si-Al material has the phase structure of pseudo-boehmite, in the anhydrous chemical expression of oxide weight is: (0-0.3) Na
2O (40-90) Al
2O
3(10-60) SiO
2, its specific surface area is 200～400m
2/ g, pore volume is 0.5～2.0ml/g, preferred 1.O～2.0ml/g, mean pore size is 8～20nm, preferred 10～20nm, the most probable aperture is 5～15nm, preferred 10～15nm, this mesoporous Si-Al material has detailed explanation in CN1565733A, this no longer numerous stating, the inventor is applied to its acidification in the cracking catalyst.Said acidification is meant the process that the mesoporous Si-Al material is contacted with mineral acid, and the condition of this process is a room temperature to 80 ℃, and sour aluminium weight ratio is 0.1～0.3, and is preferred 0.15～0.25, and acidificatoin time is 0.5～3 hour, preferred 1～2 hour.Said mineral acid is selected from mineral acid commonly used such as hydrochloric acid, nitric acid, and in an embodiment, the contriver is that the acidification process is carried out in representative with 36% hydrochloric acid, but does not therefore limit the scope of used mineral acid.
In the cracking catalyst provided by the invention, active component can also contain MFI structure molecular screen and/or beta zeolite.Wherein, the MFI structure molecular screen can be selected from ZSM-5 zeolite or belong to the Si-Al molecular sieve of MFI structure with it together, can be for rare earth modified or through the ZSM-5 zeolite of rare earth and phosphorus modification (brief note is ZRP, as putting down in writing among the CN1093101A).When containing MFI structure molecular screen and/or beta zeolite in the said cracking activity constituent element, having the Si-Al molecular sieve of MFI structure and the weight ratio of Y zeolite is 0.025～1, preferred 0.1～0.5; The weight ratio of beta zeolite and Y zeolite is 0.025～0.8.
Said clay is selected from the various clays that can be used as catalyst component, and as kaolin, polynite, wilkinite etc., its content in catalyzer is 5～80 heavy %, preferred 15～60 heavy %.
Said binding agent can be selected from the mixture of one or both or three in silicon sol, aluminium colloidal sol and the pseudo-boehmite, and wherein preferred binding agent is the double aluminium binder of aluminium colloidal sol and pseudo-boehmite.The content of said binding agent in catalyzer is with SiO
2And/or Al
2O
3Meter is 10～60 heavy %, preferred 20～50 heavy %.
Catalyzer provided by the invention is with Y zeolite or Y zeolite and MFI structure molecular screen and/or beta zeolite and after mesoporous Si-Al material, clay and binding agent that acidification is crossed mixed, process spraying, roasting, washing, drying made.
Catalyzer provided by the invention has following advantage: 1) catalyzer has higher intensity, promptly lower abrasion index, and for example, its abrasion index is all at 2.5%h
-1Below, generally at 2.0%h
-1Below, and comparative catalyst's abrasion index is all greater than 2.6%h
-1, generally at 3.0%h
-1More than, therefore be more conducive to the industrial application of catalyzer; 2) the hydro-thermal activity stability of catalyzer also increases, and from the little anti-data of heavy oil as can be seen, the mesoporous Si-Al material that adds acidification helps reducing the heavy oil yield and improves the crude oil transformation efficiency as the partial cracking active component.
Embodiment
The following examples will the invention will be further described, but content not thereby limiting the invention.
In each embodiment, the Na of used mesoporous material
2O, Al
2O
3, SiO
2Content and the content of rare earth in the catalyzer measure with x-ray fluorescence method, abrasion index is measured (referring to " petrochemical complex analytical procedure (RIPP experimental technique) ", volumes such as Yang Cuiding, Science Press, nineteen ninety publishes) with the swan neck intensity meter.
Parameter such as specific surface area and pore volume is measured with the low temperature n2 absorption apparatus.
Being used for the little catalyzer anti-and the heavy oil micro anti-evaluation of light oil needs to carry out 800 ℃ respectively in advance on the fixed bed aging equipment, and 100% steam was handled in aging 4 hours and 17 hours.
The little anti-appreciation condition of light oil is: agent-oil ratio 1.28, mass space velocity 40.11h
-1, 460 ℃ of temperature of reaction, stock oil is boiling range 221-335 ℃ huge port straight distillation light diesel oil.
The little anti-appreciation condition of heavy oil is: agent-oil ratio 2.94, and catalyst inventory 5g, 500 ℃ of temperature of reaction, 600 ℃ of regeneration temperatures, stock oil is vacuum gas oil.
Embodiment 1
The mesoporous Si-Al material adopts the mesoporous Si-Al material SA-1 of embodiment 1 among the CN1565733A, and the preparation process of SA-1 is as follows: getting 100ml concentration is 90gAl
2O
3The Al of/L
2(SO
4)
3Solution places beaker, under agitation condition ammoniacal liquor is dropwise added, and until system pH=8, being neutralized into the glue temperature is 55 ℃; Adding 50ml content under agitation condition is 60gSiO
2The water glass of/L is warming up to 80 ℃ and wore out 4 hours; Use NH
4Cl solution is pressed throw out (butt): the weight ratio of ammonium salt: H2O=1:0.8:15, under 60 ℃, the sial throw out is carried out ion-exchange to remove sodium ion wherein, exchange repeats twice, carried out 0.5 hour at every turn, carry out washing filtering after each exchange, then 120 ℃ dry 15 hours down, 600 ℃ of following roastings 3 hours.The chemical constitution of SA-1 is 0.12Na
2O73.7Al
2O
326.2SiO
2, its specific surface area is 362m
2/ g, pore volume are 1.19ml/g, and mean pore size is 12.8nm, and the most probable aperture is 10nm.SA-1 is prepared into slurries, and adding down concentration at 60 ℃ is that 36% hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) carries out acidification, and sour aluminum ratio is 0.20, and acidificatoin time is 1.5 hours, obtains acidifying mesoporous Si-Al material after the filtration, is numbered SH-SA-1.
With pseudo-boehmite (solid content 65.8 heavy %, Shandong Aluminum Plant produces) add in the quantitative deionized water, after stirring, add concentration and be 36% hydrochloric acid and carry out acidification, the acid aluminum ratio is controlled at 0.15～0.2, and this moment, slurry pH value was about 1.0～1.2, stirred after 40 minutes, be warming up to 65 ℃ of static acidifyings 1 hour, this moment, slurry pH value was about 3.0.After stopping heating, add kaolin slurry (content is 40 heavy %, and China Kaolin Co., Ltd produces), aluminium colloidal sol (Al more respectively
2O
3The heavy % of content 21.5, the Shandong catalyst plant is produced) and acidifying after mesoporous Si-Al material SH-SA-1, stirs after 20 minutes, again adding REHY molecular sieve (RE in mixed serum
2O
312.3 heavy %, Na
2The heavy % of O 5.1, silica alumina ratio 4.7, the Shandong catalyst plant is produced), continue to stir after 20 minutes spraying drying and make microspherical catalyst.With this microspherical catalyst 500 ℃ of following roastings 1 hour, again in 60 ℃ with (NH
4)
2SO
4Washing ((NH
4)
2SO
4: catalyzer: H
2O=0.5:1:10) to Na
2The heavy % in O＜0.25 uses a large amount of deionized water drip washing at last, filters the back in 110 ℃ of oven dry, obtains catalyzer C-1.
Catalyzer C-1 consists of: REHY molecular sieve 35.0%, kaolin 28.0%, pseudo-boehmite 25.0%, aluminium colloidal sol 7.0%, acidifying mesoporous Si-Al material SH-SA-1 5.0%.
Test and evaluation result are listed in the table 1.
Comparative Examples 1
Prepare the comparative catalyst by the method described in the embodiment 1, the mesoporous Si-Al material that is wherein added obtains comparative catalyst DB-1 for the mesoporous Si-Al material SA-1 without acidification.
Comparative catalyst DB-1 consists of: REHY molecular sieve 35.0%, kaolin 28.0%, pseudo-boehmite 25.0%, aluminium colloidal sol 7.0%, mesoporous Si-Al material SA-1 5.0%.
Test and evaluation result are listed in the table 1.
Comparative Examples 2
Take by weighing quantitative pseudo-boehmite and mesoporous Si-Al material SA-1, add water and make slurries, after stirring, adding down concentration at 60 ℃ is that 36% hydrochloric acid carries out acidification together, and sour aluminum ratio is 0.20, acidification 1.5 hours, add kaolin slurry and aluminium colloidal sol after the acidifying, continue to stir after 20 minutes, add the REHY molecular sieve again, stir and be sprayed into microspherical catalyst after 20 minutes, obtain comparative catalyst DB-1 ' after roasting, washing, the oven dry.
Comparative catalyst DB-1 ' consists of: REHY 35.0%, kaolin 28.0%, pseudo-boehmite 25.0%, aluminium colloidal sol 7.0%, with pseudo-boehmite acidifying mesoporous Si-Al material SA-1 5.0% simultaneously.
Test and evaluation result are listed in the table 1.
Table 1
By table 1 as seen, DB-1 compares with contrast medium, and behind the adding acidifying mesoporous Si-Al material, the intensity of catalyzer C-1 obviously improves, and is more conducive to the industrial application of catalyzer; The hydro-thermal activity stability of catalyzer also increases, and from the little anti-data of heavy oil as can be seen, the mesoporous Si-Al material helps the raising of heavy oil conversion rate and crude oil transformation efficiency after acidifying.C-1 compares with contrast medium DB-1 ', and mesoporous material is carried out the raising that independent acidifying is more conducive to intensity and cracking activity.
Embodiment 2～4
Embodiment 2～4 in order to the difference replacement amount of the mesoporous Si-Al material of explanation after acidifying to the influence of catalyzer physical and chemical performance and cracking performance.
After pseudo-boehmite carried out acidification, add kaolin slurry, aluminium colloidal sol and acidifying mesoporous Si-Al material SH-SA-1, stir after 20 minutes, in mixed serum, add the REHY molecular sieve again, stir and be sprayed into microspherical catalyst after 20 minutes, obtain catalyzer C-2～4 after roasting, washing, the oven dry, wherein the consumption of acidifying mesoporous Si-Al material SH-SA-1 is respectively 8%, 12% and 16%.
Catalyzer C-2 consists of: REHY 35.0%, kaolin 28.0%, pseudo-boehmite 22.0%, aluminium colloidal sol 7.0%, SH-SA-1 8.0%.
Catalyzer C-3 consists of: REHY 35.0%, kaolin 28.0%, pseudo-boehmite 18.0%, aluminium colloidal sol 7.0%, SH-SA-1 12.0%.
Catalyzer C-4 consists of: REHY 35.0%, kaolin 25.0%, pseudo-boehmite 17.0%, aluminium colloidal sol 7.0%, SH-SA-1 16.0%.
Test and evaluation result are listed in the table 2.
Comparative Examples 3～5
Prepare the comparative catalyst by the method described in the embodiment 2～4, the mesoporous Si-Al material that is wherein added is SA-1, obtains comparative catalyst DB-2～4.
Comparative catalyst DB-2 consists of: REHY 35.0%, kaolin 28.0%, pseudo-boehmite 22.0%, aluminium colloidal sol 7.0%, mesoporous Si-Al material SA-1 8.0%.
Comparative catalyst DB-3 consists of: REHY 35.0%, kaolin 28.0%, pseudo-boehmite 18.0%, aluminium colloidal sol 7.0%, mesoporous Si-Al material SA-1 12.0%.
Comparative catalyst DB-4 consists of: REHY 35.0%, kaolin 25.0%, pseudo-boehmite 17.0%, aluminium colloidal sol 7.0%, mesoporous Si-Al material SA-1 16.0%.
Test and evaluation result are listed in the table 2.
Table 2
By table 2 as seen, compare, use acidifying mesoporous Si-Al material all can improve the intensity and the crude oil transformation efficiency of catalyzer, and effectively reduce the heavy oil yield with corresponding Comparative Examples; With the increase of replacement amount, catalyst strength reduces, but crude oil transformation efficiency and heavy oil conversion rate increase, and itself to have certain cracking activity relevant with the mesoporous Si-Al material for this.
Embodiment 5～7
Embodiment 5～7th, illustrate with the influence of the different components in the acidifying mesoporous Si-Al material SH-SA-1 replacement catalyzer to catalyzer physical and chemical performance and cracking performance.
The detailed process of spray catalyzer is with embodiment 1, but replaces the mixture of one or both or three in active component molecular sieve, kaolin and the binding agent in preparation process respectively with acidifying mesoporous Si-Al material SH-SA-1, makes catalyzer C-5～7.
Catalyzer C-5 consists of: REHY 30.0%, kaolin 28.0%, pseudo-boehmite 25.0%, aluminium colloidal sol 7.0%, acidifying mesoporous Si-Al material SH-SA-1 10.0%.
Catalyzer C-6 consists of: REHY 35.0%, kaolin 23.0%, pseudo-boehmite 25.0%, aluminium colloidal sol 7.0%, acidifying mesoporous Si-Al material SH-SA-1 10.0%.
Catalyzer C-7 consists of: REHY 30.0%, kaolin 26.0%, pseudo-boehmite 22.0%, aluminium colloidal sol 7.0%, acidifying mesoporous Si-Al material SH-SA-1 15.0%.
Test and evaluation result are listed in the table 3.
Comparative Examples 6～8
Prepare the comparative catalyst by the method described in the embodiment 5～7, the mesoporous Si-Al material that is wherein added obtains comparative catalyst DB-5～7 for the mesoporous Si-Al material SA-1 without acidification.
Comparative catalyst DB-5 consists of: REHY 30.0%, kaolin 28.0%, pseudo-boehmite 25.0%, aluminium colloidal sol 7.0%, mesoporous Si-Al material SA-1 10.0%.
Comparative catalyst DB-6 consists of: REHY 35.0%, kaolin 23.0%, pseudo-boehmite 25.0%, aluminium colloidal sol 7.0%, mesoporous Si-Al material SA-1 10.0%.
Comparative catalyst DB-7 consists of: REHY 30.0%, kaolin 26.0%, pseudo-boehmite 22.0%, aluminium colloidal sol 7.0%, mesoporous Si-Al material SA-1 15.0%.
Test and evaluation result are listed in the table 3.
Table 3
By table 3 as seen, compare, use acidifying mesoporous Si-Al material all can improve the intensity and the crude oil transformation efficiency of catalyzer, and effectively reduce the heavy oil yield with corresponding Comparative Examples.When the carrier in the replacement catalyzer, cracking activity is the strongest, because of used mesoporous material has certain cracking activity; When the cracking activity molecular sieve in the replacement catalyzer, because the cracking activity of mesoporous material is lower than molecular sieve, so the heavy oil conversion rate has decline slightly.
Embodiment 8～10
Preparation of catalysts process among the embodiment 8～10 is with embodiment 1, but in preparation process cracking activity constituent element molecular screening with Y zeolite, ZSM-5 molecular sieve (Na
2O 2.8%, and silica alumina ratio 60, the Shandong catalyst plant is produced) and beta zeolite (silica alumina ratio 30, the production of Shandong catalyst plant) in one or both or three's mixture, make catalyzer C-8, C-9, C-10.
Catalyzer C-8 consists of: REHY 32.0%, ZSM-5 molecular sieve 3.0%, kaolin 27.0%, pseudo-boehmite 23.0%, aluminium colloidal sol 7.0%, acidifying mesoporous Si-Al material SH-SA-1 8.0%.
Catalyzer C-9 consists of: REY (Na
2O 3.2%, and silica alumina ratio 5.4, the Chang Ling catalyst plant is produced) 30.0%, beta zeolite 5.0%, kaolin 25.0%, pseudo-boehmite 21.0%, aluminium colloidal sol 7.0%, acidifying mesoporous Si-Al material SH-SA-1 12.0%.
Catalyzer C-10 consists of: USY (Na
2O 0.7%, and silica alumina ratio 6.8, the Shandong catalyst plant is produced) 30.0%, ZSM-5 molecular sieve 2.0%, beta zeolite 3.0%, kaolin 27.0%, pseudo-boehmite 23.0%, aluminium colloidal sol 7.0%, acidifying mesoporous Si-Al material SH-SA-1 8.0%.
Test and evaluation result are listed in the table 4.
Comparative Examples 9～11
Prepare the comparative catalyst by the method described in the embodiment 8～10, the mesoporous Si-Al material that is wherein added obtains comparative catalyst DB-8, DB-9, DB-10 for the mesoporous Si-Al material SA-1 without acidification.
Comparative catalyst DB-8 consists of: REHY 32.0%, ZSM-5 molecular sieve 3.0%, kaolin 27.0%, pseudo-boehmite 23.0%, aluminium colloidal sol 7.0%, mesoporous Si-Al material SA-1 8.0%.
Comparative catalyst DB-9 consists of: REY 30.0%, beta zeolite 5.0%, kaolin 25.0%, pseudo-boehmite 21.0%, aluminium colloidal sol 7.0%, mesoporous Si-Al material SA-1 12.0%.
Comparative catalyst DB-10 consists of: USY 30.0%, ZSM-5 molecular sieve 2.0%, beta zeolite 3.0%, kaolin 27.0%, pseudo-boehmite 23.0%, aluminium colloidal sol 7.0%, mesoporous Si-Al material SA-1 8.0%.
Test and evaluation result are listed in the table 4.
Table 4
By table 4 as seen, compare, use acidifying mesoporous Si-Al material all can improve the intensity and the crude oil transformation efficiency of catalyzer, and effectively reduce the heavy oil yield with corresponding Comparative Examples.Under identical molecular sieve content and mesoporous material content, the type of molecular sieve does not influence crude oil and transforms, and it is higher that the heavy oil conversion rate still can keep, and it only is distributed with certain influence to product.
Embodiment 11
The mesoporous Si-Al material adopts the mesoporous Si-Al material SA-2 of embodiment 2 among the CN1565733A.The preparation process of SA-2 is as follows: getting 100ml concentration is 90gAl
2O
3The Al of/L
2(SO
4)
3Solution places beaker, under agitation condition ammoniacal liquor is dropwise added, and until system pH=8, being neutralized into the glue temperature is 55 ℃; Adding 100ml content under agitation condition is 60gSiO
2The water glass of/L is warming up to 80 ℃ and wore out 4 hours; Use NH
4Cl solution is pressed throw out (butt): the weight ratio of ammonium salt: H2O=1:0.8:15, under 60 ℃, the sial throw out is carried out ion-exchange to remove sodium ion wherein, exchange repeats twice, carried out 0.5 hour at every turn, carry out washing filtering after each exchange, then 120 ℃ dry 15 hours down, 600 ℃ of following roastings 3 hours.The chemical constitution of SA-2 is 0.09Na
2O59.1Al
2O
340.8SiO
2, its specific surface area is 315m
2/ g, pore volume are 1.26ml/g, and mean pore size is 14.5nm, and the most probable aperture is 12nm.This mesoporous material is prepared into slurries, and adding down concentration at 50 ℃ is that 36% hydrochloric acid carries out acidification, and sour aluminum ratio is 0.15, and acidificatoin time is 1.5 hours, obtains acidifying mesoporous Si-Al material after the filtration, is numbered SH-SA-2.
Preparation process obtains catalyzer C-11 with embodiment 1.
Catalyzer C-11 consists of: REHY 35.0%, kaolin 28.0%, pseudo-boehmite 21.0%, aluminium colloidal sol 8.0%, acidifying mesoporous Si-Al material SH-SA-2 8.0%.
Test and evaluation result are listed in the table 5.
Comparative Examples 12
Prepare the comparative catalyst by the method described in the embodiment 11, the mesoporous Si-Al material that is wherein added is mesoporous Si-Al material SA-2, obtains comparative catalyst DB-11.
Comparative catalyst DB-11 consists of: REHY 35.0%, kaolin 28.0%, pseudo-boehmite 21.0%, aluminium colloidal sol 8.0%, mesoporous Si-Al material SA-2 8.0%.
Test and evaluation result are listed in the table 5.
Comparative Examples 13
Form the preparation comparative catalyst according to the method for Comparative Examples 2, the catalyzer of embodiment 11, obtain comparative catalyst DB-11 '.
Comparative catalyst DB-11 ' consists of: REHY 35.0%, kaolin 28.0%, pseudo-boehmite 21.0%, aluminium colloidal sol 8.0%, with pseudo-boehmite acidifying mesoporous Si-Al material SA-2 8.0% simultaneously.
Test and evaluation result are listed in the table 5.
Table 5
By table 5 as seen, compare, use acidifying mesoporous Si-Al material can obviously improve the intensity and the crude oil transformation efficiency of catalyzer, and effectively reduce the heavy oil yield with Comparative Examples; But it is poor slightly with the result that the pseudo-boehmite acidifying obtains with the mesoporous Si-Al material.Compare with embodiment 2, when using the higher mesoporous Si-Al material SA-2 of silicone content, though to the not obviously influence of parameters such as intensity, its corresponding crude oil transformation efficiency and heavy oil conversion rate all reduce, and this acidity with the mesoporous Si-Al material of different compositions is relevant.
Embodiment 12
The Preparation of catalysts process is with embodiment 1 in the present embodiment, but is binding agent with the pseudo-boehmite only in preparation process, makes catalyzer C-12.
Catalyzer C-12 consists of: REHY molecular sieve 35.0%, kaolin 28.0%, pseudo-boehmite 27.0%, acidifying mesoporous Si-Al material SH-SA-1 10.0%.Test and evaluation result are listed in the table 6.
Embodiment 13
The Preparation of catalysts process is with embodiment 1 in the present embodiment, but is binding agent with aluminium colloidal sol only in preparation process, makes catalyzer C-13.
Catalyzer C-13 consists of: REHY molecular sieve 35.0%, kaolin 37.0%, aluminium colloidal sol 18.0%, acidifying mesoporous Si-Al material SH-SA-1 10.0%.Test and evaluation result are listed in the table 6.
Table 6
| Catalyzer | C-12 | C-13 |
| Abrasion index, %h -1 | 2.4 | 1.7 |
| Pore volume, mL/g | 0.47 | 0.43 |
| Bulk density, g/L | 0.60 | 0.62 |
| Micro-activity, 800 ℃/17hr of 800 ℃/4hr of wt% | 72 51 | 70 51 |
| Material balance, wt% | ||
| Dry gas | 1.64 | 1.55 |
| Liquefied gas | 14.72 | 14.65 |
| Gasoline | 50.64 | 50.81 |
| Diesel oil | 18.37 | 18.35 |
| Heavy oil | 8.47 | 8.66 |
| Coke | 6.16 | 5.98 |
| Transformation efficiency, wt% | 73.16 | 72.99 |
Claims (9)
1. fluid cracking catalyst, main cracking activity constituent element by 5～70 heavy %, the binding agent of the clay of 5～80 heavy % and 10～60 heavy % is formed, it is characterized in that containing Y zeolite in the said cracking activity constituent element and be that benchmark, content are a kind of mesoporous Si-Al material through acidification of 3～20 heavy % with the catalyzer, said mesoporous Si-Al material, phase structure with pseudo-boehmite in the anhydrous chemical expression of oxide weight is: (0-0.3) Na
2O (40-90) Al
2O
3(10-60) SiO
2, its specific surface area is 200～400m
2/ g, pore volume are 0.5～2.0ml/g, and mean pore size is 8～20nm, and the most probable aperture is 5～15nm, and said acidification is in room temperature to 80 ℃, under the condition of sour aluminum ratio 0.1～0.3 the mesoporous Si-Al material is contacted 0.5～3 hour with mineral acid.
2. according to the catalyzer of claim 1, wherein said cracking activity constituent element is a Y zeolite and through the mesoporous Si-Al material of acidification, and MFI structure Si-Al molecular sieve and/or beta zeolite.
3. according to the catalyzer of claim 1 or 2, wherein Y zeolite be selected among HY, USY, REUSY, REY, REHY, the REDASY one or more mixture or the Y zeolite that obtains through various metal oxide treated.
4. according to the catalyzer of claim 2, wherein MFI structure Si-Al molecular sieve is ZSM-5 zeolite or through rare earth modified or through the ZSM-5 zeolite of rare earth and phosphorus modification simultaneously.
5. according to the catalyzer of claim 1, it is characterized in that the content of said mesoporous Si-Al material through acidification is 5～15 heavy %.
6. according to the catalyzer of claim 1, wherein said mesoporous Si-Al material through acidification, pore volume is 1.0～2.0ml/g, and mean pore size is 10～20nm, and the most probable aperture is 10～15nm.
7. according to the catalyzer of claim 1, said acidification is under 0.15～0.25 sour aluminum ratio condition the mesoporous Si-Al material to be contacted 1～2 hour with mineral acid.
8. according to the catalyzer of claim 1, said binding agent is selected from the mixture of one or both or three in silicon sol, aluminium colloidal sol and the pseudo-boehmite.
9. according to the catalyzer of claim 1, said binding agent is the mixture of aluminium colloidal sol and pseudo-boehmite.
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