CN102949989B - A kind of Si-Al catalysis material with boehmite crystal phase structure - Google Patents
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Abstract
A kind of Si-Al catalysis material with boehmite crystal phase structure, in terms of oxide weight, its anhydrous chemical expression is: (0～0.2) Na2O (30～33) SiO2(67～70) Al2O3, its specific surface area is 300～500m2/ g, pore volume is 0.5～1.5ml/g, and average pore size is 8～15nm, it is characterised in that 200 DEG C of infrared B-acid of the pyridine recorded of this catalysis material are 0.085～0.100 with the ratio of L acid.In this acidic silicon-aluminium catalytic material, pore property is obvious, and pore distribution concentration contains BSuan HeLSuan center simultaneously, and B-acid significantly improves with L acid ratio, and material has more preferable light oil microactivity.It addition, acidic silicon-aluminium catalytic material provided by the present invention has higher degree of crystallinity.
Description
Technical field
The present invention relates to a kind of Si-Al catalysis material with boehmite crystal phase structure, be that one has high B-acid ratio, high activity, the obvious acid material of middle hole characteristic furtherly.
Background technology
Catalytic cracking and to be hydrocracked be two very important technical processs in petroleum refining process, is widely used in PETROLEUM PROCESSING industry, occupies very important status in oil plant.In catalytic cracking and hydrocracking process, the residual oil of heavy end such as vacuum distillate or more heavy constituent reacts in the presence of a catalyst, it is converted into the gaseous cracked product of below gasoline, distillate and other liquid cracking products and four lighter carbon, these courses of reaction typically requires use there is peracidity and the catalysis material of high cracking activity.
Micro porous molecular sieve material is widely used in petroleum refining and processing industry owing to having acid and the highest stronger catalytic reaction activity.But the variation tendency that exhaustion and crude oil heaviness, in poor quality and intermingled dregs ratio example improve constantly day by day along with petroleum resources, the particularly market wilderness demand to light-end products, increasingly pay attention in PETROLEUM PROCESSING in recent years heavy oil, the deep processing of residual oil, part refinery has started to mix refining decompression residuum, even directly with reduced crude as cracked stock.Traditional micro porous molecular sieve duct is less, and channel diameter is generally less than 2nm, and the restriction in duct plays a role clearly, and is not suitable for the catalytic reaction of the macromole such as heavy oil or residual oil.
Amorphous silicon aluminum is a kind of acid material equally, not only there is B-acid center but also there is L acid center, it is the main active component in early stage catalytic cracking catalyst, but owing to the higher molecular sieve that is gradually crystallized of reaction temperature that its cracking activity is relatively low and required is substituted.But during hydrocracking reaction, owing to the aperture of amorphous silicon aluminum is relatively big, pore-size distribution is wider, and has the acid catalytic property comparing mitigation, is therefore widely used as the carrier material in being hydrocracked.
Define according to IUPAC, aperture between 2～50nm material be in (Jie) Porous materials, and the size range of the macromole such as heavy oil is in this aperture category, therefore the research of mesopore material particularly mesoporous silicon aluminum causes the great interest of catalytic field research worker.US5,051,385 discloses a kind of single dispersing mesoporous silicon aluminium composite material, adds alkali reaction and make after acid mineral aluminium salt and Ludox being mixed, and wherein aluminum content is 5～40 weight %, aperture 20～50nm, specific surface area 50～100m2/g.US4,708, disclosed in 945 is first to load silicon oxide particle or hydrated silica on porous boehmite, again by gained complex hydrothermal treatment consists certain time more than 600 DEG C, prepare silica supported catalyst on class boehmite surface, wherein silicon oxide combines with the hydroxyl of transition state boehmite, and surface area reaches 100～200m2/ g, average pore size 7～7.5nm.US4, discloses a series of acidic cracking catalyst in 440,872, the carrier of some of them catalyst is by γ-Al2O3Upper dipping silane, then prepares after 500 DEG C of roastings or steam treatment.US2,394,796 disclose dipping Silicon chloride. or silicon tetraethyl on porous hydrated alumina, then obtain aluminium silicon composite material through hydrolysis.Using inorganic aluminate and waterglass in CN1353008A is raw material, forms silicon-aluminum sol the most clearly through processes such as precipitation, washing, dispergation, by being dried to obtain white gels, then roasting 1～obtain Si-Al catalysis material in 20 hours at 350 DEG C～650 DEG C.Disclosing a kind of mesoporous silicon aluminum in CN1565733A, this silica-alumina material has structure of similar to thin diaspore, and pore-size distribution is concentrated, specific surface area about 200～400m2/ g, pore volume 0.5～2.0ml/g, average pore size is between 8～20nm, and most probable pore size is 5～15nm.The preparation of this mesoporous silicon aluminum is not required to use organic formwork agent, synthesizes low cost, and the silica-alumina material obtained has high cracking activity and hydrothermal stability, shows good macromole cracking performance in catalytic cracking reaction.
For amorphous silicon aluminum, the formation in its acid site is mainly due to defining effective Si-O-Al key, and this bonding structure is the basis constituting acid site.But the Si-O-Al key formed in conventional amorphous silica-alumina material is fewer, the aggregation tendency being derived from body mainly due to silicon source and aluminum is bigger, the degree of polymerization of primary ion is bigger in aqueous, therefore silicon, aluminum primary ion further be bonded formed Si-O-Al key ratio the lowest, the acidity ratio of the silica-alumina material obtained is relatively low.US4, disclosing a kind of in 226,743 is the method that raw material prepares silica-alumina material by common glue method by silicate, acidity or basic aluminium salt such as aluminum sulfate or sodium metaaluminate, is reached improve the purpose of sial bonding state by alkalescence to acid modulation by pH value.US4,003,825 discloses a kind of method that silica-alumina material is prepared in hydrolysis in the aqueous solution of aluminum nitrate by organo-silicon compound, but organosilicon is expensive and stability has some problems.US5,045,519 discloses a kind of method in aqueous medium, being prepared by aluminum alkoxide and positive silicic acid mixed hydrolysis silica-alumina material, the material that this method obtains has structure of similar to thin diaspore, and impurity content is low, Heat stability is good, acidity is relatively strong, but the distribution between sial is the most uniform.In order to improve the uniformity of silica-alumina material, US6,872, in 685, silicate solutions is mixed homogeneously under intense agitation with acid aluminium salt solution, form the Ludox in the presence of aluminium salt, be mixed to form common colloidal sol the most again with alkaline precipitating agent, thus prepare the amorphous silicon aluminum of high uniformity.It uses the ratio-i.e. SB value of surface and body phase sial atomic ratio, characterize the uniformity of amorphous silicon aluminum, and compare with MS-25 (Grace company) with two kinds of business silica-alumina material Siral40 (Sasol company), SB value is intended to closer to 1, illustrating that the uniformity of amorphous silica-alumina prepared by this method is higher, acidity is also higher.
Summary of the invention
It is an object of the invention to provide a kind of high B-acid ratio, high activity, middle pore property significantly have the Si-Al catalysis material of boehmite crystal phase structure.
The Si-Al catalysis material with boehmite crystal phase structure provided by the present invention, in terms of oxide weight, its anhydrous chemical expression is: (0～0.2) Na2O (30～33) SiO2(67～70) Al2O3, its specific surface area is 300～500m2/ g, preferably 350～450m2/ g, pore volume is 0.5～1.5ml/g, preferably 0.8～1.2ml/g, and average pore size is 8～15nm, preferably 9～12nm, it is characterised in that 200 DEG C of infrared B-acid of the pyridine recorded of this catalysis material are 0.085～0.100 with the ratio of L acid.
Wherein the infrared B-acid recorded of pyridine and L acid are to use pyridine temperature programming infrared spectrometry to obtain.By sample self-supporting tabletting, it is placed in the original position pond of infrared spectrometer sealing, is warming up to 350 DEG C and is evacuated to 10-3Pa, constant temperature removes the gas molecule of sample adsorption after 1 hour；Import pyridine steam after being cooled to room temperature and keep adsorption equilibrium 30 minutes, then heat to 200 DEG C, be again evacuated to 10-3Pa is also desorbed 30 minutes under this vacuum, is down to room temperature and takes the photograph spectrum, sweep limits 1400～1700cm-1, the sample Pyridine adsorption IR spectra figure through 200 DEG C of desorptions can be obtained.According to 1540cm in Pyridine adsorption IR spectra figure-1And 1450cm-1The intensity of characteristic absorption peak, calculates the relative quantity at B-acid center and L acid center.
Acidic silicon-aluminium catalytic material provided by the present invention obtains through following steps: aluminum source and aqueous slkali are neutralized plastic at room temperature to 85 DEG C by (1), and plastic terminal pH is 7～11；(2) according to SiO2∶Al2O3=1: the weight ratio of (2～3) adds silicon source, it is aged 1～10 hour at room temperature to 90 DEG C；(3) gained solid sediment is carried out ammonium exchange or acid exchange removes foreign ion；(4) by after filter cake reslurry according to hexafluosilicic acid: material butt=(0.01～0.12): the weight ratio of 1 mixes with hexafluosilicic acid, at room temperature to 80 DEG C react 0.5～2 hour；(5), after filtering washing, it is dried 10～20 hours at 100 DEG C～150 DEG C.
Any one in aluminum nitrate, aluminum sulfate or aluminum chloride of aluminum source used in the preparation process of acidic silicon-aluminium catalytic material provided by the present invention；Any one in ammonia, potassium hydroxide, sodium hydroxide or sodium metaaluminate of the alkali used；Any one in waterglass, sodium silicate, silicon tetraethyl or silicon oxide of the silicon source used.
The present invention provide acidic silicon-aluminium catalytic material preparation process employed in ammonium exchange, be by aged process after solid sediment by precipitate (butt): ammonium salt: H2O=1: (0.1～1): the weight ratio of (10～30) exchanges 1～3 time at room temperature to 100 DEG C, every time exchange 0.5～1 hour, until sodium content is less than 0.2% in solid sediment；Any one in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate of the ammonium salt of clearing house.The present invention provide acidic silicon-aluminium catalytic material preparation process employed in acid exchange, be by aged process after solid sediment by precipitate (butt): acid: H2O=1: (0.03～0.30): the weight ratio of (5～30) at least exchanges 0.2 hour at room temperature to 100 DEG C；The acid of clearing house is mineral acid, generally can be selected from any one in sulphuric acid, hydrochloric acid or nitric acid.
In the preparation process of the acidic silicon-aluminium catalytic material that the present invention provides, hexafluosilicic acid can be to be added drop-wise in material slurry by hexafluosilicic acid with the hybrid mode of material slurry, material slurry can also be joined in the fluorine silicic acid aqueous solution of dilution, preferably hexafluosilicic acid is added drop-wise in material slurry.
In acidic silicon-aluminium catalytic material provided by the present invention, pore property is obvious, and pore distribution concentration contains BSuan HeLSuan center simultaneously, and B-acid significantly improves with L acid ratio, and material has more preferable light oil microactivity.It addition, acidic silicon-aluminium catalytic material provided by the present invention has higher degree of crystallinity.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of Si-Al catalysis material.
Detailed description of the invention
The present invention is further illustrated for the following examples, but not thereby limiting the invention.
In embodiments, the Na of product2O、Al2O3、SiO2Content x-ray fluorescence method measures (seeing " Petrochemical Engineering Analysis method (RIPP experimental technique) ", Yang Cui surely waits and compiles, Science Press, and nineteen ninety publishes).Thing phase and crystallinity data use X-ray diffraction method to measure.The physicochemical data such as specific surface, pore structure uses nitrogen absorption under low temperature-desorption method to measure.Acid data acquisition measures by infrared pyridine adsorption in site measurement method.
Embodiment 1
The preparation of the acidic silicon-aluminium catalytic material that this example explanation present invention provides.
The preparation process of the present embodiment is with the process described in CN1565733A.Taking appropriate concentration is 90gAl2O3The Al of/L2(SO4)3Solution is placed in beaker, is added dropwise over by ammonia under agitation, until system pH=8, neutralizing gelling temperature is 55 DEG C；Adding quantitative concentrations under agitation is 60gSiO2The waterglass of/L, is warming up to 80 DEG C and is aged 2 hours；Use NH4Cl solution presses precipitate (butt): ammonium salt: H2The weight ratio of O=1: 0.8: 10, carries out ion exchange at 60 DEG C and removes sodium ion sial precipitate, and exchange repeats twice, carries out 0.5 hour every time, then by gained filter cake reslurry and press hexafluosilicic acid: material butt: H2Required hexafluosilicic acid is added drop-wise in the serosity of material by the weight ratio of O=0.02: 1: 10, stirring reaction 1 hour at 60 DEG C, is dried and within 15 hours, i.e. obtains the acidic silicon-aluminium catalytic material that the present invention provides after filtering washing at 120 DEG C.It is designated as BSA-1.
The X-ray diffraction spectral line of BSA-1 is shown in Figure 1；Degree of crystallinity and elementary analytical chemistry composition are shown in Table 1；The hole parameters such as specific surface area and infrared acid data are listed in table 2.
Comparative example 1
Taking appropriate concentration is 90gAl2O3The Al of/L2(SO4)3Solution is placed in beaker, is added dropwise over by ammonia under agitation, until system pH=8, neutralizing gelling temperature is 55 DEG C；Adding quantitative concentrations under agitation is 60gSiO2The waterglass of/L, is warming up to 80 DEG C and is aged 2 hours；Use NH4Cl solution presses precipitate (butt): ammonium salt: H2The weight ratio of O=1: 0.8: 10, carries out ion exchange at 60 DEG C and removes sodium ion sial precipitate, and exchange repeats twice, carries out 0.5 hour every time, is dried the Si-Al catalysis material i.e. obtaining contrast for 15 hours after filtration at 120 DEG C.It is designated as DB-1.
The X-ray diffraction spectral line of comparative sample DB-1 is shown in Figure 1；Degree of crystallinity and elementary analytical chemistry composition are shown in Table 1；The hole parameters such as specific surface area and infrared acid data are listed in table 2.
Embodiment 2
The preparation of the acidic silicon-aluminium catalytic material that this example explanation present invention provides.
Preparation process is with embodiment 1, and wherein the additional proportion of hexafluosilicic acid is hexafluosilicic acid: material butt: H2O=0.05: 1: 10, washing i.e. obtains acidic silicon-aluminium catalytic material after drying.It is designated as BSA-2.
The X-ray diffraction spectral line of BSA-2 is shown in Figure 1；Degree of crystallinity and elementary analytical chemistry composition are shown in Table 1；The hole parameters such as specific surface area and infrared acid data are listed in table 2.
Embodiment 3
The preparation of the acidic silicon-aluminium catalytic material that this example explanation present invention provides.
Preparation process is with embodiment 1, and wherein the additional proportion of hexafluosilicic acid is hexafluosilicic acid: material butt: H2O=0.08: 1: 10, washing i.e. obtains acidic silicon-aluminium catalytic material after drying.It is designated as BSA-3.
The X-ray diffraction spectral line of BSA-3 is shown in Figure 1；Degree of crystallinity and elementary analytical chemistry composition are shown in Table 1；The hole parameters such as specific surface area and infrared acid data are listed in table 2.
Embodiment 4
The preparation of the acidic silicon-aluminium catalytic material that this example explanation present invention provides.
Preparation process is with embodiment 1, and wherein the additional proportion of hexafluosilicic acid is hexafluosilicic acid: material butt: H2O=0.11: 1: 10, washing i.e. obtains acidic silicon-aluminium catalytic material after drying.It is designated as BSA-4.
The X-ray diffraction spectrogram of BSA-4 and Fig. 1 have identical feature；Degree of crystallinity and elementary analytical chemistry composition are shown in Table 1；The hole parameters such as specific surface area and infrared acid data are listed in table 2.
From table, acidic silicon-aluminium catalytic material degree of crystallinity compared with contrast material that the present invention provides increases, and B-acid significantly improves with the ratio of L acid, doubles than contrast material DB-1.
Table 1
| Sample ID | Degree of crystallinity/% | Na2O/% | Al2O3/ % | SiO2/ % |
| BSA-1 | 44.0 | 0.12 | 68.1 | 31.2 |
| BSA-2 | 46.8 | 0.09 | 68.0 | 31.4 |
| BSA-3 | 47.3 | 0.11 | 67.5 | 32.1 |
| BSA-4 | 49.1 | 0.10 | 68.4 | 31.3 |
| DB-1 | 40.3 | 0.14 | 67.5 | 31.9 |
Table 2
Embodiment 5
The preparation of the acidic silicon-aluminium catalytic material that this example explanation present invention provides.
The preparation process of the present embodiment is with the process described in CN1565733A.It is 90gAl by concentration2O3The Al of/L2(SO4)3Solution and concentration are 102gAl2O3/ L, the NaAlO of Crater corrosion 1.72Solution also flows continuous gel formation and keeps plastic pH=9.5, collects quantitative plastic serosity, and the concentration adding metering under agitation is 60gSiO2The waterglass of/L, is warming up to 70 DEG C and is aged 4 hours；Use NH4Cl solution presses precipitate (butt): ammonium salt: H2The weight ratio of O=1: 1: 15, carries out ion exchange at 60 DEG C and removes sodium ion sial precipitate, and exchange repeats twice, carries out 0.5 hour every time, then by gained filter cake reslurry and press hexafluosilicic acid: material butt: H2Required hexafluosilicic acid is added drop-wise in the serosity of material by the weight ratio of O=0.04: 1: 12, reacts 2 hours at 40 DEG C, is dried and within 15 hours, i.e. obtains the acidic silicon-aluminium catalytic material that the present invention provides after filtering washing at 120 DEG C.It is designated as BSA-5.
The X-ray diffraction spectrogram of BSA-5 and Fig. 1 have identical feature；Degree of crystallinity and elementary analytical chemistry composition are shown in Table 3；The hole parameters such as specific surface area and infrared acid data are listed in table 4.
Embodiment 6
The preparation of the acidic silicon-aluminium catalytic material that this example explanation present invention provides.
Preparation process is with embodiment 5, and wherein the additional proportion of hexafluosilicic acid is hexafluosilicic acid: material butt: H2O=0.09: 1: 12, to react 1 hour at 80 DEG C after required hexafluosilicic acid is added drop-wise in the serosity of material, washing i.e. obtains acidic silicon-aluminium catalytic material after drying.It is designated as BSA-6.
The X-ray diffraction spectrogram of BSA-6 and Fig. 1 have identical feature；Degree of crystallinity and elementary analytical chemistry composition are shown in Table 3；The hole parameters such as specific surface area and infrared acid data are listed in table 4.
Embodiment 7
The preparation of the acidic silicon-aluminium catalytic material that this example explanation present invention provides.
Preparation process, with embodiment 5, wherein presses hexafluosilicic acid: material butt: H2Filter cake serosity is joined in hexafluosilicic acid weak solution by the ratio of O=0.07: 1: 8 with vigorous stirring, and reacts 1.5 hours at 50 DEG C, and washing i.e. obtains acidic silicon-aluminium catalytic material after drying.It is designated as BSA-7.
The X-ray diffraction spectrogram of BSA-7 and Fig. 1 have identical feature；Degree of crystallinity and elementary analytical chemistry composition are shown in Table 3；The hole parameters such as specific surface area and infrared acid data are listed in table 4.
Embodiment 8
The preparation of the acidic silicon-aluminium catalytic material that this example explanation present invention provides.
Preparation process, with embodiment 5, wherein carries out the exchange of solid sediment with hydrochloric acid, by precipitate (butt): hydrochloric acid: H2The weight ratio of O=1: 0.15: 12 exchanges 0.5 hour at 70 DEG C, then presses hexafluosilicic acid: material butt: H2Filter cake serosity is joined in hexafluosilicic acid weak solution by the ratio of O=0.10: 1: 8 with vigorous stirring, and reacts 1.5 hours at 50 DEG C, and washing i.e. obtains acidic silicon-aluminium catalytic material after drying.It is designated as BSA-8.
The X-ray diffraction spectrogram of BSA-8 and Fig. 1 have identical feature；Degree of crystallinity and elementary analytical chemistry composition are shown in Table 3；The hole parameters such as specific surface area and infrared acid data are listed in table 4.
Table 3
| Sample ID | Degree of crystallinity/% | Na2O/% | Al2O3/ % | SiO2/ % |
| BSA-5 | 43.5 | 0.13 | 67.1 | 32.3 |
| BSA-6 | 47.0 | 0.10 | 67.4 | 32.0 |
| BSA-7 | 46.3 | 0.12 | 69.0 | 30.2 |
| BSA-8 | 48.9 | 0.11 | 69.3 | 30.3 |
Table 4
Embodiment 9
The original cracking activity of the acidic silicon-aluminium catalytic material that this example explanation present invention provides.
The sample that sample examples detailed above 1～8 obtained and comparative example 1 obtain roasting 1 hour at 500 DEG C, is then evaluated on fixed-bed micro-devices, is initial activity by micro-for the light oil obtained index definition alive.Raw materials used oil is the huge port straight distillation light diesel oil of boiling range 221 DEG C～335 DEG C, and appreciation condition is oil ratio 1.28, mass space velocity 40.11h-1, reaction temperature 460 DEG C.Evaluation result is listed in table 5.
As can be seen from Table 5, the acidic silicon-aluminium catalytic material that the present invention provides has higher initial activity in the case of silica alumina ratio is suitable.
Table 5
| Sample ID | Initial activity (weight %) | Sample ID | Initial activity (weight %) | |
| DB-1 | 34 | |||
| BSA-1 | 37 | BSA-5 | 38 | |
| BSA-2 | 39 | BSA-6 | 42 | |
| BSA-3 | 42 | BSA-7 | 40 | |
| BSA-4 | 44 | BSA-8 | 43 |
Claims (7)
1. having a Si-Al catalysis material for boehmite crystal phase structure, in terms of oxide weight, its anhydrous chemical expression is: (0～0.2) Na2O (30～33) SiO2(67～70) Al2O3, its specific surface area is 300～500m2/ g, pore volume is 0.5～1.5ml/g, and average pore size is 8～15nm, it is characterised in that 200 DEG C of infrared B-acid of the pyridine recorded of this catalysis material are 0.085～0.100 with the ratio of L acid.
2. according to the Si-Al catalysis material of claim 1, wherein, described specific surface area is 350～450m2/ g, pore volume is 0.8～1.2ml/g, and average pore size is 9～12nm.
3. according to the Si-Al catalysis material of claim 1, it is characterised in that obtain through following steps:
(1) aluminum source and aqueous slkali being neutralized at room temperature to 85 DEG C plastic, plastic terminal pH is 7～11；
(2) according to SiO2∶Al2O3=1: the weight ratio of (2～3) adds silicon source, it is aged 1～10 hour at room temperature to 90 DEG C；
(3) gained solid sediment is carried out ammonium exchange or acid exchange removes foreign ion；
(4) by after filter cake reslurry according to hexafluosilicic acid: material butt=(0.01～0.12): the weight ratio of 1 mixes with hexafluosilicic acid, at room temperature to 80 DEG C react 0.5～2 hour；
(5), after filtering washing, it is dried 10～20 hours at 100 DEG C～150 DEG C.
4. any one in aluminum nitrate, aluminum sulfate or aluminum chloride of according to the Si-Al catalysis material of claim 3, wherein, described aluminum source；Any one in ammonia, potassium hydroxide, sodium hydroxide or sodium metaaluminate of described alkali；Any one in waterglass, sodium silicate, silicon tetraethyl or silicon oxide of described silicon source.
5. according to the Si-Al catalysis material of claim 3, wherein, described ammonium exchange, be by aged process after solid sediment by precipitate butt: ammonium salt: H2O=1: (0.1～1): the weight ratio of (10～30) exchanges 1～3 time at room temperature to 100 DEG C, every time exchange 0.5～1 hour, until sodium content is less than 0.2% in solid sediment；Any one in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate of the ammonium salt of clearing house.
6. according to the Si-Al catalysis material of claim 3, wherein, described acid exchange, be by aged process after solid sediment by precipitate butt: acid: H2O=1: (0.03～0.30): the weight ratio of (5～30) at least exchanges 0.2 hour at room temperature to 100 DEG C；The acid of clearing house is mineral acid, any one in sulphuric acid, hydrochloric acid or nitric acid.
7. according to the Si-Al catalysis material of claim 3, wherein, described hexafluosilicic acid is to be added drop-wise in material slurry by hexafluosilicic acid with the hybrid mode of material slurry.
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| CN1048835A (en) * | 1989-07-15 | 1991-01-30 | 中国石油化工总公司石油化工科学研究院 | The preparation method of rich silicon molecular sieve by crystal skeleton |
| CN1353008A (en) * | 2001-12-06 | 2002-06-12 | 中国科学院大连化学物理研究所 | Process for preparing mesoporous Si-Al catalysis material |
| CN1854258A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Cracking catalyst |
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2011
- 2011-08-30 CN CN201110251801.1A patent/CN102949989B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048835A (en) * | 1989-07-15 | 1991-01-30 | 中国石油化工总公司石油化工科学研究院 | The preparation method of rich silicon molecular sieve by crystal skeleton |
| CN1353008A (en) * | 2001-12-06 | 2002-06-12 | 中国科学院大连化学物理研究所 | Process for preparing mesoporous Si-Al catalysis material |
| CN1854258A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Cracking catalyst |
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