CN103372464A - Dual-pore composite alumina material - Google Patents
Dual-pore composite alumina material Download PDFInfo
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- CN103372464A CN103372464A CN2012101079524A CN201210107952A CN103372464A CN 103372464 A CN103372464 A CN 103372464A CN 2012101079524 A CN2012101079524 A CN 2012101079524A CN 201210107952 A CN201210107952 A CN 201210107952A CN 103372464 A CN103372464 A CN 103372464A
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Abstract
The invention relates to a dual-pore composite alumina material, consisting of the following components in percentage by weight: 0.5-60% of small-hole alumina, 10-80% of large-hole alumina and 0.5-30% of a small-grain titanium silicon molecular sieve, wherein the titanium silicon molecular sieve is ETS-10 and is subjected to hydrothermal treatment or alkali treatment modification, the grain size of the molecular sieve is less than 0.5 micron, the specific area of the material is 200m<2>/g-400m<2>/g, the pore volume is 0.30ml/g-0.60ml/g, the distribution of the pores of which the pore sizes are 3-6nm accounts for 10-40% of the total pore volume, and the distribution of the pores of which the pore sizes are 8-20nm accounts for 60-90% of the total pore volume. The dual-pore composite alumina material is used for preparing an adsorbent and a catalyst carrier.
Description
Technical field
The present invention relates to a kind of double-hole composite aluminium oxide material, particularly a kind of composite aluminium oxide material that double-hole distributes that has that is applicable to the components such as adsorbent, catalyst.
Background technology
Aluminium oxide is because of its suitable specific area and pore structure, good hydrothermal stability, and the suitable character such as acidity are widely used in catalyst carrier.Used hydrotreating catalyst (except the hydrocracking) and reforming catalyst nearly all adopts Al in the petroleum refining industry now
2O
3Carrier for main component.
In actual application, usually alumina powder jointed material had definite shape through making after the processing and forming, a particle of size.Duct in these particles is the inevitable passage that material spreads.In the catalyst application, the pore structure that different catalysts requires is not quite similar.Usually the macropore of aluminium oxide is the passage that reactive material enters catalyst inside; And has the scene that the aperture that enriches surface area or mesopore are catalytic reaction.
In addition, the aluminium oxide that is used as catalyst or adsorbent adopts auxiliary agent that it is carried out modification usually, and auxiliary agent commonly used has one or more in zirconium, silicon, phosphorus, titanium, boron, magnesium, the fluorine etc.The main purpose that adds these auxiliary agents be acidity, the pore structure of modulation aluminium oxide and improve active component and aluminium oxide between interaction etc.But because catalyst or absorbent preparation process are complicated, performance is subjected to the impact of various factors larger, and various auxiliary agents are to introduce in the aluminium oxide with unbodied state usually, if these unbodied auxiliary agents can not be good in conjunction with causing harmful effect to acidity and the pore structure of aluminium oxide with aluminium oxide.When introducing multiple auxiliary agent in the aluminium oxide, the complexity of alumina preparation will obviously improve in addition, and the performance of the degree direct influence aluminium oxide of the mutual coordination coupling between the various auxiliary agent.If these auxiliary agents are introduced in the aluminium oxide with a kind of form with functionalization ordered structure, just can carry out modulation by more effective acidity, pore structure and other physico-chemical properties to aluminium oxide, and the cooperative effect that can bring into play different auxiliary agents can be simplified the alumina preparation flow process simultaneously, reduce the influence factor of alumina preparation process, improve the repeatability of alumina preparation.
CN101114454A discloses a kind of preparation method with macroporous aluminium oxide of diplopore distribution, and this method adds the pore creating materials such as carbon black, cellulose, starch and prepares the aluminium oxide with diplopore distribution in the process of aluminium oxide moulding.The carrier mesoporous skewness that this legal system is standby, the duct connectivity is poor, and the crushing strength of carrier is subjected to the kind of pore creating material and consumption to affect larger.
CN102020298A discloses a kind of preparation method with aluminium oxide of diplopore distribution, and this method is passed through at alumina precursor---introduce long chain quaternary class surfactant and long-chain non-ionic surface active agent in the aluminium hydroxide preparation process as pore creating material.And prepare pore size distribution at the alumina material that double-hole distributes that has between 3.4～3.8nm and between 9.8～24.5nm with trimethylbenzene, benzene or atoleine as expanding agent.This method need at first prepare the aluminium hydroxide wet gel, complicated process of preparation, and affect the many factors that the aluminium hydroxide wet gel prepares, be not easy control.
CN 0012315.0 discloses the Al that a kind of large aperture contains Ti and Si composite assistant
2O
3Carrier and preparation method thereof.This invention is introduced in the process of preparation aluminium hydroxide and is contained the Si compound and contain the Ti compound.This preparation process technique is simple, and cost is low.While TiO
2And SiO
2At Al
2O
3The surface is uniformly dispersed, and this invention contains the Al of Ti, Si
2O
3Have good peptization, eliminated conventional siliceous Al
2O
3Pore size distribution disperse, the poor shortcoming of peptization, the titaniferous silica alumina supporter of this invention, has large aperture, average pore size is 10～15nm, can be used for the preparation of large aperture hydrotreating catalyst or hydrogenation conversion catalyst, but owing to have stronger surface acidity, reduced the yield of fluid product.
Summary of the invention
The objective of the invention is to develop a kind of double-hole composite aluminium oxide material, be specially adapted to the hydrofining catalyst carrier of petrol and diesel oil cut inferior in the petroleum refining field, carrier has double-hole and distributes, and through element titanium and silicon modification.
Double-hole composite aluminium oxide material of the present invention comprises following component: little porous aluminum oxide, macroporous aluminium oxide, modification small-crystallite titanium-silicon molecular sieve and adhesive.Wherein the aperture alumina content is 0.5～60wt.%; Macroporous aluminium oxide content is 10～80wt.%, preferably 40～80wt.%; The content of modification small-crystallite titanium-silicon molecular sieve is 0.5～30wt.%, preferably 5～30wt.%; The content of adhesive is 0～30wt.%, preferably 0～20wt.%.
Double-hole composite aluminium oxide material of the present invention is take little porous aluminum oxide, macroporous aluminium oxide, small-crystallite titanium-silicon molecular sieve as carrier, and wherein the aluminium oxide of two kinds of different pore sizes is main carriers components of catalyst, and Heat stability is good, pore-size distribution suit; Small-crystallite titanium-silicon molecular sieve is as the main acidic components of catalyst, the synthetic employing hydrothermal synthesis method experience sol-gel process of small-crystallite titanium-silicon molecular sieve, and carry out modification by means such as hydrothermal treatment consists, acid treatment, alkali treatments and make it have dual pore distribution.
The specific area of double-hole composite aluminium oxide material of the present invention is 200m
2/ g～400m
2/ g, pore volume are 0.30ml/g～0.60ml/g, and its mesoporous accounts for 10%～40% of total pore volume in the pore size distribution of 3nm～6nm, and the aperture accounts for 60%～90% of total pore volume in the pore size distribution of 8nm～20nm.
Described aluminium oxide aperture is 3～10nm and 10～40nm.
Described HTS is ETS-10, and the zeolite crystal size is less than 0.5 μ m, and the aperture is 3～5nm and 10～40nm; TiO
2/ SiO
2Mol ratio is 0.1～0.5, Na
2O and K
2O weight content total＜0.2wt.%.
The preparation method of double-hole composite aluminium oxide material of the present invention comprises, with macroporous aluminium oxide, little porous aluminum oxide, modification small-crystallite titanium-silicon molecular sieve dry powder, binding agent and extrusion aid, mix in proportion, extruded moulding, drying, roasting obtain composite alumina.Or with macropore boehmite, aperture boehmite, modification small-crystallite titanium-silicon molecular sieve dry powder, binding agent, extrusion aid, proportionally mix, then extruded moulding through super-dry, roasting, obtains composite alumina.
The ETS-10 zeolite crystal of the present commercial Application of bibliographical information is usually greater than 4 μ m, and the aperture is at 3～4.5nm.Compare with the ETS-10 molecular sieve of large crystal grain substance pore size distribution, the ETS-10 molecular sieve that little crystal grain double-hole distributes can better be scattered in the aluminium oxide, its pore distribution characteristics are close with aluminium oxide duct characteristic distributions, so that composite aluminium oxide material has better duct diffusion, can shorten reactant in the composite aluminium oxide material duct the time of staying and reduce diffusional resistance, the small crystal grain molecular sieve top layer can form more lattice defect and room simultaneously, can form more activated centre or play the effect that promotes to form the activated centre.
Described double-hole composite aluminium oxide material of the present invention adopts has the aluminium oxide of different pore size, the small-crystallite titanium-silicon molecular sieve that double-hole distributes, form by HTS is incorporated into titanium, element silicon in the composite aluminium oxide material, and aluminium oxide is carried out acidity and surface electrochemistry character is carried out modification.In addition, because the ETS-10 molecular sieve has similar pore distribution to aluminium oxide, more be conducive to the diffusion of material in composite alumina.
Description of drawings
The conventional ETS-10 molecular sieve of Fig. 1 and the contrast of double-hole ETS-10 molecular sieve bore diameter.
The specific embodiment
A kind of double-hole composite aluminium oxide material of the present invention, employed HTS character is as follows: TiO
2/ SiO
2Mol ratio is 0.1～0.5, preferably 0.15～0.45, and Na
2O and K
2O weight content total＜0.2wt.%, best＜0.15wt.%, the zeolite crystal size is not more than 0.5 μ m.
Aluminium oxide used in the present invention is industrial boehmite, or has the commercial alumina of pore size distribution.
Double-hole composite aluminium oxide material of the present invention can use refractory inorganic oxides as the adhesive component of composite aluminium oxide material in the preparation, such as in clay, silica, aluminium oxide, sial, zirconia, the titanium oxide one or more, the weight content of adhesive component in final catalyst is 0wt.%～40wt.%.When preparing, catalyst carrier of the present invention also can not add adhesive component, but direct kneading extruded moulding.
The present invention is in the preparation process of double-hole composite aluminium oxide material, can adopt extrusion aid during extrusion, extrusion aid commonly used can be one or more in sesbania powder, citric acid, oxalic acid, cellulose, starch, the high molecular surfactant, preferably sesbania powder, citric acid and high molecular surfactant.
The shape of double-hole composite aluminium oxide material of the present invention can be sheet, sphere, cylindrical bars or irregular strip (clover, bunge bedstraw herb), preferably cylindrical bars and irregular strip (clover, bunge bedstraw herb).The diameter of catalyst can for the slice of 0.8mm～2.0mm or＞the thick bar of 2.5mm, be preferably the slice of 1.0mm～1.8mm.
The following examples will be further described a kind of double-hole composite aluminium oxide material provided by the invention, but not thereby limiting the invention.
Get 10g aperture boehmite, 90g macropore boehmite adds 5g sesbania powder, mix, the mixed solution kneading that dropping is comprised of 7.5g nitric acid (68wt.%), 5g citric acid and 100g deionized water, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of dry 2h then at 550 ℃ of roasting 4h, make double-hole composite aluminium oxide material A.
Embodiment 2
Get 20g aperture boehmite, the 80g macropore adds 5g sesbania powder, mix, the mixed solution kneading that dropping is comprised of 7.5g nitric acid (68wt.%), 5g citric acid and 100g deionized water, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of dry 4h then at 550 ℃ of roasting 4h, make double-hole composite aluminium oxide material B.
Embodiment 3
Get 40g aperture boehmite, 60g macropore boehmite, add 5g sesbania powder, mix, the mixed solution kneading that dropping is comprised of 7.5g nitric acid (68wt.%), 5g citric acid and 100g deionized water, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of dry 4h, then at 550 ℃ of roasting 4h, make double-hole composite aluminium oxide material C.
Embodiment 4
Get 10g aperture boehmite, 90g macropore boehmite, the 10g crystallite dimension is less than ETS-10 molecular sieve and the 5g sesbania powder of 2 μ m, mix, the mixed solution kneading that dropping is comprised of 7.5g nitric acid (68wt.%), 5g citric acid and 100g deionized water, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of dry 4h, then at 550 ℃ of roasting 4h, make double-hole composite aluminium oxide material D.
Embodiment 5
Get 10g aperture boehmite, 90g macropore boehmite, the 10g crystallite dimension is processed less than 2 μ m and through alkali lye has ETS-10 molecular sieve and the 5g sesbania powder that double-hole distributes, mix, the mixed solution kneading that dropping is comprised of 7.5g nitric acid (68wt.%), 5g citric acid and 100g deionized water, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of dry 4h, then at 550 ℃ of roasting 4h, make double-hole composite aluminium oxide material E.
Embodiment 6
Get 10g aperture boehmite, 90g macropore boehmite, the 20g crystallite dimension is processed less than 2 μ m and through alkali lye has ETS-10 molecular sieve and the 5g sesbania powder that double-hole distributes, mix, the mixed solution kneading that dropping is comprised of 7.5g nitric acid (68wt%), 5g citric acid and 100g deionized water, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of dry 4h, then at 550 ℃ of roasting 4h, make double-hole composite aluminium oxide material F.
Embodiment 7
Get 20g aperture boehmite, 80g macropore boehmite, the 20g crystallite dimension has ETS-10 molecular sieve and the 5g sesbania powder that double-hole distributes less than 2 μ m and through processing, mix, the mixed solution kneading that dropping is comprised of 7.5g nitric acid (68wt.%), 5g citric acid and 100g deionized water, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of dry 4h, then at 550 ℃ of roasting 4h, make double-hole composite aluminium oxide material G.
Embodiment 8
Get 10g aperture boehmite, 90g macropore boehmite, 20g HTS (the large crystal grain single hole distribution HTS of tradition, crystallite dimension is greater than 4 μ m) and 5g sesbania powder, mix, drip the mixed solution kneading that is formed by 7.5g nitric acid (68wt.%), 5g citric acid and 100g deionized water, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of dry 4h then at 550 ℃ of roasting 4h, make double-hole composite aluminium oxide material H.
Table 1 composite aluminium oxide material physico-chemical property.
| Material | Specific surface, m 2/g | Small aperture, nm | The aperture pore volume, ml/g | Macropore diameter, nm | The macropore pore volume, ml/g |
| A | 431 | 3～5 | 0.16 | 8～20 | 0.47 |
| B | 412 | 3～5 | 0.22 | 8～20 | 0.40 |
| C | 374 | 3～5 | 0.30 | 8～20 | 0.32 |
| D | 418 | 3～5 | 0.21 | 8～20 | 0.46 |
| E | 423 | 3～5 | 0.21 | 8～20 | 0.49 |
| F | 411 | 3～5 | 0.24 | 8～20 | 0.47 |
| G | 394 | 3～5 | 0.25 | 8～20 | 0.48 |
| H | 401 | 3～5 | 0.24 | 8～20 | 0.38 |
Claims (1)
1. double-hole composite aluminium oxide material, it is characterized in that: this double-hole composite aluminium oxide material is comprised of little porous aluminum oxide, macroporous aluminium oxide, small-crystallite titanium-silicon molecular sieve and adhesive; Wherein the aperture alumina content is 0.5～60wt.%; Macroporous aluminium oxide content is 10～80wt.%; The content of small-crystallite titanium-silicon molecular sieve is 0.5～30wt.%; The content of adhesive is 0～30wt.%;
Described aluminium oxide aperture is 3～10nm and 10～40nm,
Described HTS is ETS-10, and by hydrothermal treatment consists or alkali treatment modifying, the zeolite crystal size is less than 0.5 μ m, and the aperture is 3～5nm and 10～40nm; TiO
2/ SiO
2Mol ratio is 0.1～0.5, Na
2O and K
2O weight content total＜0.2wt.%;
The specific area of double-hole composite aluminium oxide material is 200m
2/ g～400m
2/ g, pore volume are 0.30ml/g～0.60ml/g, and its mesoporous accounts for 10%～40% of total pore volume in the pore size distribution of 3nm～6nm, and the aperture accounts for 60%～90% of total pore volume in the pore size distribution of 8nm～20nm.
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|---|---|---|---|
| CN2012101079524A CN103372464A (en) | 2012-04-13 | 2012-04-13 | Dual-pore composite alumina material |
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|---|---|---|---|
| CN2012101079524A CN103372464A (en) | 2012-04-13 | 2012-04-13 | Dual-pore composite alumina material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105728059A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | Catalyst carrier, preparation method therefor and application of catalyst carrier |
| CN107583598A (en) * | 2016-07-08 | 2018-01-16 | 张翠华 | A kind of Dual-pore composite alumina material |
| CN108283942A (en) * | 2017-01-10 | 2018-07-17 | 中国石油化工股份有限公司 | Modified alpha-alumina supports and preparation method thereof and silver catalyst and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103009A (en) * | 1993-11-23 | 1995-05-31 | 中国石油化工总公司 | Preparing method for aluminium oxide carrier with double-hole |
| US20040266607A1 (en) * | 2003-03-28 | 2004-12-30 | China Petroleum & Chemical Corporation Of Beijing, China | Y-zeolite-containing composite material and a process for preparing the same |
| CN1883802A (en) * | 2005-06-20 | 2006-12-27 | 中国石油天然气集团公司 | Microporous and mesoporous composite hydrogenation catalyst carrier materials and process for preparing same |
-
2012
- 2012-04-13 CN CN2012101079524A patent/CN103372464A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103009A (en) * | 1993-11-23 | 1995-05-31 | 中国石油化工总公司 | Preparing method for aluminium oxide carrier with double-hole |
| US20040266607A1 (en) * | 2003-03-28 | 2004-12-30 | China Petroleum & Chemical Corporation Of Beijing, China | Y-zeolite-containing composite material and a process for preparing the same |
| CN1883802A (en) * | 2005-06-20 | 2006-12-27 | 中国石油天然气集团公司 | Microporous and mesoporous composite hydrogenation catalyst carrier materials and process for preparing same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105728059A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | Catalyst carrier, preparation method therefor and application of catalyst carrier |
| CN107583598A (en) * | 2016-07-08 | 2018-01-16 | 张翠华 | A kind of Dual-pore composite alumina material |
| CN108283942A (en) * | 2017-01-10 | 2018-07-17 | 中国石油化工股份有限公司 | Modified alpha-alumina supports and preparation method thereof and silver catalyst and application |
| CN108283942B (en) * | 2017-01-10 | 2021-07-30 | 中国石油化工股份有限公司 | Modified alpha-alumina carrier and preparation method thereof, silver catalyst and application |
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Application publication date: 20131030 |