CN1509808A - Porous monox-alumina and preparing method thereof - Google Patents
Porous monox-alumina and preparing method thereof Download PDFInfo
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Abstract
A porous silicon oxide-aluminium oxide used as the carrier of adsorbents and catalysts has the crystal type chosen from those of gamma-alumina, eta-alumina, theta-alumina, delta-alumina and x-alumina, BET specific surface area of 150-350 sq.m/g, pore volume of 0.15-1.5 cu.m/g, and K number of 1.0-15. It is prepared through mixing the hydrate of alumina with disordered Si-contained molecular sieve or its composition, and calcining at 350-850 deg.C for 2-8 hr.
Description
Technical field
The invention relates to a kind of poriness silicon oxide-alumina product and preparation method thereof.
Background technology
Transitional face Al
2O
3As γ-Al
2O
3, because of have high-ratio surface, good anti-agglutinatting property energy and during as catalyst carrier to the polymolecularity of reactive metal, make it be widely used in catalyst carrier.But its acidity is lower.Have the oxide of anti-burning that divergence hole distributes with respect to molecular sieve---poriness silicon oxide-aluminium oxide be another kind have high-ratio surface, good anti-agglutinatting property can catalyst carrier.Preparation as petroleum refining industry in during widely used catalyst for hydrotransforming hydrocarbon, poriness silicon oxide-aluminium oxide is compared by force acid with aluminium oxide; With contain molecular sieve carrier and compare that lytic activity relaxes, average pore size is big, pyrolysis product heavy ends selectivity height.In addition, when adopting poriness silicon oxide-alumina support to prepare the anti-sulphur noble metal of non-molecular sieve type dearomatization catalyst, its performance obviously is better than catalyst (Takashi Fujikawa etc., the Aromatic Hydrogenation ofDistillates Over SiO of alumina support preparation
2-Al
2O
3-Supported Noble Metal Catalysts, Appl.Catalysis A:General 192,2000,253-261).
The common method of preparation poriness silicon oxide-alumina support is by alkali silicate and contains altogether glue or become glue step by step of aluminium salt, but this method is difficult to obtain the purity high product.For this reason, patent USP5,045,519 has provided a kind of preparation high-purity silicon oxide-method of alumina: with deionized water hydrolyzable alkoxy oxygen base aluminium, simultaneously or introduce orthosilicic acid subsequently, the introducing amount of silicon counts 0.5～50% with silica.This high-purity silicon oxide-alumina support has porous and high thermal stability.
For poriness silicon oxide-alumina support, the content of silica mainly can influence catalyst surface acid content and type, pore structure, the active metal component distribution on carrier etc.People such as K.Saiprasad Rao study (J.Cat. to poriness silicon oxide-alumina support load Ni-W active metal catalyst, 115,277-281,1989) after point out, along with the distribution of increase reactive metal on carrier of silicone content with variation, and then hydrogenation activity is descended; Aluminium oxide attribute more in the carrier is to improving or guaranteeing that the hydrogenation activity of catalyst then is favourable.
(Appl.Catal.A:General 196 for people such as W.Daniell, 247-260,2000) adopt low temperature FTIR and XPS method to by as patent USP5,045, the acid matter of high-purity poriness silicon oxide-aluminium oxide that 519 technology are prepared, silica distribute and study, point out: when silica introducing amount was 1.5～5%, L acid or the acid matter of B of comparing carrier with aluminium oxide did not produce detectable variation; Silica introducing amount 10～20% o'clock has the detectable B acid that belongs to alumino-silicate surface bridge hydroxyl group to exist; When this B acid that belongs to alumino-silicate surface bridge hydroxyl group 30～40% time of silica introducing amount measures existing maximum.
Adopt prior art can prepare the poriness silicon oxide-alumina support of various Different Silicon/aluminum ratios, but the problem one that exists is for making the sour enough height of measuring of B in poriness silicon oxide-aluminium oxide, must improve the introducing amount of silica, and too high silica content will directly influence the serviceability of poriness silicon oxide-aluminium oxide.Problem two is that the validity of introducing silicon is on the low side.So-called validity, the unit introducing amount that is meant silicon promptly belong to the size of the B acid site number contribution of surperficial bridge hydroxyl group to improving poriness silicon oxide-aluminium oxide acidity.
Summary of the invention
Purpose of the present invention provides a kind of available silicon content high poriness silicon oxide-alumina product promptly at the deficiencies in the prior art on its basis.
Another object of the present invention provides the preparation method of this poriness silicon oxide-alumina product.
Poriness silicon oxide-aluminium oxide that available silicon content provided by the invention is high has the crystal formation that is selected from one or more aluminium oxide among γ, η, θ, δ and the x, silica content wherein is the heavy % of 1.0-40, the heavy % in alkali metal content＜1, BET specific surface 150-350m
2/ g, pore volume 0.15-1.5m
3/ g, the k value is 1.0-15; Said k=B/M
SiO2, wherein k is that corresponding silica-alumina B acid amount is measured in unit mole silica introducing, B is a silica-alumina B acid amount, M
SiO2Be silica molar fraction in the silica-alumina.
The preferred product feature of this poriness silicon oxide-aluminium oxide is: have the crystal formation of γ and/or η aluminium oxide, silica content wherein is the heavy % of 1.0-35, the heavy % in alkali metal content＜1, BET specific surface 150-320m
2/ g, pore volume 0.2-1.3m
3/ g, the k value is 1.0-13.
Said poriness silicon oxide among the present invention-aluminium oxide B acid amount system adopts Bio-Rad IFS-3000 type determination of infrared spectroscopy.Concrete grammar is as follows: be pressed into about 10mg/cm behind sample self porphyrize
2The self-supporting sheet, place the original position pond of infrared spectrometer, in 350 ℃, 10
-3Pa vacuum lower surface purified treatment 2 hours is reduced to room temperature and is introduced the pyridine saturated vapor, after the adsorption equilibrium 15 minutes, vacuumizes desorption 30 minutes under 200 ℃, reduces to room temperature measuring absorption pyridine vibrational spectrum.Sweep limits is 1400cm
-1-1700cm
-1, with 1545cm
-1The peak height of bands of a spectrum is measured with its B acid of ratio value defined of sample strip weight.
Silica molar fraction employing X fluorescence method among the present invention in said poriness silicon oxide-aluminium oxide (Yang Cuiding etc., petrochemical industry analytical method (RIPP test method), Science Press, 1990, P380) working sample calculates after forming.
The preparation method of poriness silicon oxide-aluminium oxide provided by the invention can be: containing si molecular sieves or containing the composition that disordering contains si molecular sieves and mix the hydrate of aluminium oxide and at least a disordering, in 350～850 ℃, best 500～650 ℃ of roastings 2～8 hours, best 3～6 hours.
The preparation method of poriness silicon oxide-aluminium oxide provided by the invention can also be: will be selected from containing si molecular sieves or contain the composition that disordering contains si molecular sieves and directly mixing of the aluminium oxide of one or more crystal formations among γ, η, θ, δ and the x and at least a disordering.
The hydrate of used aluminium oxide is selected from one or more the mixture among hibbsite, monohydrate alumina and the unformed aluminium hydroxide in the inventive method.The hydrate of said aluminium oxide also can be the modifier of this hydrate, as add the modifier of silicon, titanium, magnesium boron, zirconium, thorium, niobium, rare earth etc., the modifier of wherein preferred silicon, they can adopt prior art, are prepared as the method for USP5045519.
Said disordering molecular sieve comprises any one siliceous molecular sieve of disordering, for example silicon metal-the aluminate of disordering, silicon-phosphorus-aluminate, faujasite, ZSM series zeolite etc., the preferably faujasite of disordering or the ZSM series zeolite of disordering.
Be applicable to that the condition that disordering molecular sieve of the present invention should satisfy is: when adopting XRD to characterize, with original molecule sieve relative intensity is that 100% characteristic peak is a benchmark, the relative intensity that disordering contains this characteristic peak of si molecular sieves is below 15%, to be preferably below 10%.
Containing si molecular sieves or containing the ratio that composition that disordering contains si molecular sieves mixes of the hydrate of aluminium oxide and disordering should be that the heavy % of 1.0-40 is as the criterion with the silica content in the poriness silicon oxide-aluminium oxide that finally makes.
Containing si molecular sieves or containing the composition that disordering contains si molecular sieves of disordering can be in the hydrated alumina preparation process be directly introduced, also can be by itself and commercially available one or more hydrated alumina mechanical mixture are introduced.When introducing in the hydrated alumina preparation process, the control of alkali metal content can be finished in the hydrated alumina water-washing process synchronously; When directly mixing with the commercial alumina hydrate, disordering contains si molecular sieves and preferably carries out ion-exchange individually and remove alkali metal.
Disordering contains si molecular sieves and can obtain by following two kinds of approach:
Article one, approach is to prepare the partially-crystallized si molecular sieves that contains.This partially-crystallized method can adopt in the prior art incomplete crystallization to prepare the method for low-crystallinity molecular sieve, for example C.P.Nicolaides is at ANovel Familyof Solid Acid Catalysts:Substantially Amorphous or Partially Crystalline ZeoliticMaterials, Applied Catalysis A:General 185,1999, reported among the 211-217.
The second approach is that the si molecular sieves that contains with complete crystallization carries out disordering and handles.The method that disordering is handled can adopt various prior aries, for example for the molecular sieve of low-crystallinity, mainly is meant X type and Y zeolite, at the atmosphere of relatively dry such as steam partial pressure less than 1psig, preferably less than carrying out high-temperature roasting under the 0.2psig; And for example, at high temperature and a certain amount of V
2O
5Or MoO
3Make the Y zeolite disordering under existing, this disordering trend increases (J.Thoret with the rising of temperature and/or the increase of metal oxide content, etc.Solid-StateInteraction Between NaY Zeolite and Vanadium Pentoxide, Molybdenum Trioxide, orTungsten Trioxide, Zeolites, 13,1993,269-275); For another example, at the existence V of water vapour
2O
5Make Y zeolite disordering (Carlos A.Trujillo, etc.The Mechnism of Zeolite Y Destruction bySteam in the Presence of Vanadium, Journal of Catalysis 168,1-15,1997); Adopt halide to handle Y zeolite under certain condition, and can cause disordering (Kurt A.Becker, CatalyticFaraday Trans.I equally, 1987,83,535～545), (Kurt A.Becker, etc., Modification of HY-Zeolitewith Trifluoromethane, React.Kinet.Catal.Lett., Vol.29, No.1,1-7,1985).
Two pieces of Chinese patents of CN1197691A and CN1276267A disclose with aluminium salt respectively or a kind ofly except that alkali metal have become alkali metal salt to become acid metal salt to handle molecular sieve with a kind of, can realize acidic zeolite is carried out modulation.According to method provided by the invention, the molecular sieve after simple ion-exchange and disordering processing is keeping original solid acid attribute substantially, and the ion-exchange before the molecular sieve disordering can adopt any one process well known in the art to realize.It can be any water-soluble being used for the used salt of ion-exchange: ammonium salt such as ammonium chloride, ammonium nitrate, ammonium sulfate; Aluminium salt such as aluminum nitrate, aluminum sulfate and other are intended to introduce by ion-exchange the slaine of molecular sieve.
According to different application purposes, the precursor of poriness silicon oxide-aluminium oxide provided by the invention, promptly the hydrate of aluminium oxide and disordering contain si molecular sieves or contain mixture that disordering contains the composition of si molecular sieves can be before roasting first moulding also can be in reshaping after the roasting.Moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.For example when extrusion, hydrated alumina can be mixed and add an amount of extrusion aid and/or adhesive, extrusion molding then with the mixture of disordering molecular sieve with suitable quantity of water.The kind of described extrusion aid, peptizing agent and consumption all can be this area routines.
Poriness silicon oxide-aluminium oxide provided by the invention has improved the validity of introducing silicon significantly, and its k value can be up to 15.And the silica content of prior art for preparing less than the k value of poriness silicon oxide-aluminium oxide of 60 heavy % all less than 1.0.
Poriness silicon oxide-aluminium oxide provided by the invention can be directly as the carrier of various adsorbents and various catalyst, also can be used as the matrix of catalyst and/or the precursor of binding agent and mix use with any one or a few porous high-temperature inorganic oxide of other prior art for preparing, these porous high-temperature inorganic oxides can be selected from: aluminium oxide, silica, titanium oxide, magnesia, silica-alumina, silica-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, oxidation titania-zirconia and ternary oxide such as silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-magnesia and silica-alumina-zirconia and their mixture are used for as hydrotreatment, hydrocracking, catalytic cracking, isomerization, alkylation, catalyst such as disproportionation.For example as a kind of matrix precursor, it can with combination of components such as zeolite, clay, also can make the catalyst of various desired properties with zeolite and/or metal component combination.
Description of drawings
Fig. 1 is the forward and backward x-ray diffraction spectra of Y zeolite disordering.A wherein is the spectral line before the disordering; B, C, D are the spectral line after the disordering.
Fig. 2 is the raw material proportioning according to synthetic ZSM-5 molecular sieve, the x-ray diffraction spectra of the complete crystallization that obtains (spectral line E) and partially-crystallized (spectral line F) product.
Fig. 3 is poriness silicon oxide-aluminium oxide (spectral line L) and the γ-Al that poriness silicon oxide-aluminium oxide provided by the invention (spectral line G, H, I, J, K), art methods make
2O
3The x-ray diffraction spectra of (spectral line M).
The specific embodiment
Following example will be further described the present invention, but not thereby limiting the invention.
Example 1
This case description the preparation of disordering Y zeolite sample.
With 800 gram NaY type molecular sieve (SiO
2/ Al
2O
3=4.8, degree of crystallinity is defined as 100%, Chang Ling refinery product) placing 4000 milliliters, concentration is ammonium chloride (Beijing Chemical Plant's product of 1.0 moles, analyze pure) in the aqueous solution, exchange is 1 hour under 90 ℃ of stirrings, filters, and spends deionised water and does not detect to there being chlorion, 120 ℃ of oven dry, 550 ℃ of roastings 4 hours.Repeat the Y zeolite A that said process obtains the heavy % of sodium content (in sodium oxide molybdena)＜0.35 (flame atomic absorption spectrometry mensuration) for twice, recording sample degree of crystallinity with x-ray diffraction method is 76%.
It is ammonium fluoride (Beijing Chemical Plant's product of 0.2 mole that ion-exchange sample 200 gram of learning from else's experience places 1000 milliliters, concentration, analyze pure) in the aqueous solution, filter 120 ℃ of oven dry after 1 hour in stirring at normal temperature, 700 ℃ of roastings 4 hours obtain Y zeolite disordering sample B.
The x-ray diffraction spectra of sample A and B is seen Fig. 1, and the composition of sample B sees Table 1.
Example 2
This case description the preparation of disordering Y zeolite sample.
Getting Y zeolite sample 200 grams of example 1 after ion-exchange places 1000 milliliters to contain 12 gram aluminum nitrate (Beijing Chemical Plant's products, analyze pure) the aqueous solution in, filter after 1 hour in stirring at normal temperature, 120 ℃ of oven dry, sample places tube furnace, amount by 100 Grams Per Hours feeds deionized water, is warming up to 600 ℃, constant temperature 4 hours.Recording sample degree of crystallinity with x-ray diffraction method is 52%.
It is 0.1 mole ammonium fluoride aqueous solution that sample is placed 1 000 milliliters, concentration, filter after 1 hour in stirring at normal temperature, and 120 ℃ of oven dry, 550 ℃ of roastings 4 hours obtain Y zeolite disordering sample C.
The x-ray diffraction spectra of sample C sees that Fig. 1, composition see Table 1.
Example 3
This case description the preparation of disordering Y zeolite sample.
Getting Y zeolite sample 200 grams of example 1 after ion-exchange places 1000 milliliters to contain 12 gram aluminum nitrates, 7.0 gram ammonium metatungstate (Beijing Chemical Plant's products, analyze pure) the aqueous solution in, filter after 1 hour in stirring at normal temperature, 120 ℃ of oven dry, sample places tube furnace, amount by 100 Grams Per Hours feeds deionized water, is warming up to 500 ℃, constant temperature 4 hours.Recording sample degree of crystallinity with x-ray diffraction method is 32%.
It is 0.1 mole ammonium fluoride aqueous solution that sample is placed 1000 milliliters, concentration, filter after 1 hour in stirring at normal temperature, and 120 ℃ of oven dry, 550 ℃ of roastings 4 hours obtain Y zeolite disordering sample D.
The x-ray diffraction spectra of sample D sees that Fig. 1, composition see Table 1.
Example 4
This case description the preparation of partially-crystallized ZSM-5 sieve sample.
According to document Applied Catalysis A:General 185,1999, the 211-217 describing method carries out, the synthetic H-ZSM-5 product E that obtains under 150 ℃ of crystallization conditions; Under 90 ℃ of crystallization conditions, synthesize and obtain partially-crystallized product F.The x-ray diffraction spectra of sample E and F is seen Fig. 2.The composition of sample F sees Table 1.
With product E is that benchmark is 6% by the degree of crystallinity that following formula can calculate sample F.
Table 1
| Sample | Chemical composition | |||
| ??SiO 2 | ??Al 2O 3 | ????F | ??WO 3 | |
| ????B | ??75.4 | ??23.3 | ????1.3 | ??/ |
| ????C | ??74.3 | ??24.8 | ????0.9 | ??/ |
| ????D | ??73.5 | ??24.0 | ????0.1 | ??2.4 |
| ????F | ??80.4 | ??1.7 | ????/ | ??/ |
Example 5
This case description the preparation of poriness silicon oxide-aluminium oxide provided by the invention.
The diaspore of employed hydrated alumina for being prepared in this example according to Chinese patent CN1250746A example 6.
Getting 1.5 liters of concentration is 60 gram Al
2O
3/ liter sodium aluminate solution, place one 2 liters one-tenth glue jar, 60 ℃ of initial temperatures feed CO from the bottom that becomes the glue jar
2Content is carbon dioxide and the Air mixing gas of 90 body %, and the flow of gaseous mixture is 1.5 meters
3/ hour, reacting 15 minutes, pH drops to 8.8, and this moment, reaction temperature was 73 ℃, stopped into the glue reaction, added sodium carbonate rapidly, made slurry pH value rise to 11.0.Be warming up to 90 ℃ and wore out 4 hours, filter, wash 4 times with 20 times of 90 ℃ of deionized waters to solid content.Get disordering sample B 80 grams that make in the example 1 of the present invention and mix making beating, filter back 120 ℃ of oven dry with washing back filter cake.The gained dried mixture in 550 ℃ of roastings 4 hours, is promptly got poriness silicon oxide provided by the invention-alumina sample G.
The x-ray diffraction spectra of sample G is seen Fig. 3.Its silica content, B acid amount, silica molar fraction and k value see Table 2.
Example 6
This case description the preparation of poriness silicon oxide-aluminium oxide provided by the invention.
Employed hydrated alumina is the diaspore SB powder that German Condea company produces in this example.
Take by weighing disordering sample C 25 grams, nitric acid 1.5 grams, methylcellulose 2.5 grams and deionized water 85 grams that make in SB powder 1 00 grams, the example of the present invention 2 respectively, fully mix the trefoil hole orifice plate extrusion of back with φ 1.8.The strip of gained in 4 hours, 600 ℃ roastings of 120 ℃ of dryings 4 hours, is promptly obtained poriness silicon oxide provided by the invention-alumina sample H.
The x-ray diffraction spectra of sample H is seen Fig. 3.Its silica content, B acid amount, silica molar fraction and k value see Table 2.
Example 7
This case description the preparation of poriness silicon oxide-aluminium oxide provided by the invention.
Employed hydrated alumina generates a diaspore CL powder for the Chang Ling oil plant in this example.
Take by weighing disordering sample D 5 grams, nitric acid 1.5 grams, methylcellulose 2.5 grams and deionized water 90 grams that make in CL powder 100 grams, the example of the present invention 3 respectively, fully mix the circular port orifice plate extrusion of back with φ 3.6.The strip of gained in 4 hours, 700 ℃ roastings of 120 ℃ of dryings 4 hours, is promptly obtained poriness silicon oxide provided by the invention-aluminium oxide I.
The x-ray diffraction spectra of sample I is seen Fig. 3.Its silica content, B acid amount, silica molar fraction and k value see Table 2.
Example 8
This case description poriness silicon oxide-aluminium oxide provided by the invention and preparation method thereof.
The boehmite SD powder that the hydrated alumina that uses in this example is produced as Shandong Aluminum Plant.
Get SD powder 150 gram respectively, preparation sample F 4.5 grams mix in the example 4, add 300 milliliters of deionized waters in mixture, and normal temperature stirred 30 minutes down, filter, and 150 ℃ of dryings 6 hours, 550 ℃ of roastings 3 hours obtain poriness silicon oxide-aluminium oxide J.
The X-ray diffraction pattern of sample J is seen Fig. 3, and its silica content, B acid amount, silica molal quantity and k value see Table 2.
Example 9
This case description poriness silicon oxide-aluminium oxide provided by the invention and preparation method thereof.
Get in the example 6 SB powder 100 grams and place 450 ℃ of roastings of Muffle furnace 4 hours, obtain sample M, its X-ray diffraction pattern is seen Fig. 3.
Get M sample 50 gram respectively, disordering C sample 3 grams mix, and add 200 milliliters of deionized waters in mixture, and normal temperature stirred 30 minutes down, filter, and 120 ℃ of dryings 6 hours, 500 ℃ of roastings 3 hours obtain poriness silicon oxide-aluminium oxide K.
The X-ray diffraction pattern of sample K is seen Fig. 3, and its silica content, B acid amount, silica molal quantity and k value see Table 2.
Comparative Examples
Directly get Condea company poriness silicon oxide-aluminium oxide commodity Siral 40 as reference.This product is seen Fig. 3 through the x-ray diffraction spectra of 600 ℃ of roastings after 4 hours.Its silica content, B acid amount, silica molar fraction and k value see Table 2.
Provided γ-Al among Fig. 3 and the table 2 simultaneously
2O
3The corresponding information of sample M is to illustrate that poriness silicon oxide-aluminium oxide provided by the invention has the feature of the transition aluminas that is transformed into by hydrated alumina in contrast.
Table 2
| ???G | ??H | ??I | ????J | ????K | Comparative Examples | ?γ-Al 2O 3 | |
| ?SiO 2(heavy %) | ???32.5 | ??13.5 | ??3.1 | ????3.6 | ????4.2 | ????40.0 | ????0.0 |
| ?M SiO2 | ???0.45 | ??0.21 | ??0.051 | ????0.063 | ????0.07 | ????0.5 | ????0.0 |
| ?B(Acmg -1) | ???4.7 | ??1.5 | ??0.2 | ????0.1 | ????0.3 | ????0.3 | ????0.0 |
| ?K | ???10.4 | ??7.1 | ??3.9 | ????1.6 | ????4.2 | ????0.6 | ????0.0 |
| Specific surface (m 2/g) | ???189 | ??204 | ??265 | ????234 | ????237 | ????210 | ????243 |
| Pore volume (ml/g) | ???0.46 | ??0.44 | ??0.48 | ????0.38 | ????0.45 | ????0.60 | ????0.43 |
| Average pore size () | ???97 | ??86 | ??72 | ????54 | ????85 | ????75 | ????80 |
Claims (10)
1, a kind of poriness silicon oxide-aluminium oxide is characterized by and has the crystal formation that is selected from one or more aluminium oxide among γ, η, θ, δ and the x, and silica content wherein is the heavy % of 1.0-40, the heavy % in alkali metal content＜1, BET specific surface 150-350m
2/ g, pore volume 0.15-1.5m
3/ g, the k value is 1.0-1 5; Said k=B/M
SiO2, wherein k is that corresponding silica-alumina B acid amount is measured in unit mole silica introducing, B is a silica-alumina B acid amount, M
SiO2Be silica molar fraction in the silica-alumina.
2, according to the said poriness silicon oxide-aluminium oxide of claim 1, it is characterized by crystal formation with γ and/or η aluminium oxide, silica content wherein is the heavy % of 1.0-35, the heavy % in alkali metal content＜1, BET specific surface 150-320m
2/ g, pore volume 0.2-1.3m
3/ g, the k value is 1.0-12.
3, the preparation method of the said poriness silicon oxide-aluminium oxide of claim 1, it is characterized by with the containing si molecular sieves or contain the composition that disordering contains si molecular sieves and mix of the hydrate of aluminium oxide and at least a disordering, in 350～850 ℃ of roastings 2～8 hours.
4, according to the said preparation method of claim 3, the hydrate that it is characterized by said aluminium oxide is selected from one or more the mixture among hibbsite, monohydrate alumina and the unformed aluminium hydroxide; The hydrate of said aluminium oxide also can be the modifier that above-mentioned hydrate adds silicon, titanium, magnesium boron, zirconium, thorium, niobium, rare earth.
5, according to the said preparation method of claim 3, it is characterized by roasting is to carry out 3～6 hours at 500～650 ℃.
6, the preparation method of the said poriness silicon oxide-aluminium oxide of claim 1 is characterized by and will be selected from containing si molecular sieves or contain the composition that disordering contains si molecular sieves and directly mixing of the aluminium oxide of one or more crystal formations among γ, η, θ, δ and the x and at least a disordering.
7, according to the preparation method of claim 3 or 6 said poriness silicon oxide-aluminium oxide, wherein said disordering contains the faujasite that si molecular sieves is a disordering or the ZSM series zeolite of disordering.
8, according to the preparation method of claim 3 or 6 said poriness silicon oxide-aluminium oxide, it is when adopting XRD to characterize that wherein said disordering contains si molecular sieves, with original molecule sieve relative intensity is that 100% characteristic peak is a benchmark, and the relative intensity that disordering contains this characteristic peak of si molecular sieves is below 15%.
9, according to the preparation method of the said poriness silicon oxide-aluminium oxide of claim 8, it is when adopting XRD to characterize that wherein said disordering contains si molecular sieves, with original molecule sieve relative intensity is that 100% characteristic peak is a benchmark, and the relative intensity that disordering contains this characteristic peak of si molecular sieves is below 10%.
10, according to the preparation method of claim 3 or 6 said poriness silicon oxide-aluminium oxide, it is partially-crystallized contain si molecular sieves or the si molecular sieves that contains of complete crystallization is carried out disordering and handles and obtain by preparing that wherein said disordering contains si molecular sieves.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102233282A (en) * | 2010-04-30 | 2011-11-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst taking silicon oxide-aluminum oxide as carrier and application thereof |
| CN101555417B (en) * | 2008-09-04 | 2013-09-04 | 北京三聚环保新材料股份有限公司 | Denitrifier and preparation method thereof |
| CN114749170A (en) * | 2021-01-11 | 2022-07-15 | 中国石油化工股份有限公司 | Silicon-aluminum particle aggregate, and manufacturing method and application thereof |
-
2002
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| CN101555417B (en) * | 2008-09-04 | 2013-09-04 | 北京三聚环保新材料股份有限公司 | Denitrifier and preparation method thereof |
| CN102233282A (en) * | 2010-04-30 | 2011-11-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst taking silicon oxide-aluminum oxide as carrier and application thereof |
| CN102233282B (en) * | 2010-04-30 | 2013-06-26 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst taking silicon oxide-aluminum oxide as carrier and application thereof |
| CN114749170A (en) * | 2021-01-11 | 2022-07-15 | 中国石油化工股份有限公司 | Silicon-aluminum particle aggregate, and manufacturing method and application thereof |
| CN114749170B (en) * | 2021-01-11 | 2023-09-01 | 中国石油化工股份有限公司 | Silicon-aluminum particle aggregate, and manufacturing method and application thereof |
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