CN1488434A - Silicon-containing alumina supporter and preparing method thereof - Google Patents
Silicon-containing alumina supporter and preparing method thereof Download PDFInfo
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- CN1488434A CN1488434A CNA021331448A CN02133144A CN1488434A CN 1488434 A CN1488434 A CN 1488434A CN A021331448 A CNA021331448 A CN A021331448A CN 02133144 A CN02133144 A CN 02133144A CN 1488434 A CN1488434 A CN 1488434A
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Abstract
The invention refers to a kind of multi-hole silicon aluminium oxide carrier and the manufacturing method. The carrier hole capacity is 0.55~0.68ml/g, the average diameter is 6.5~9.5nm, the ratio surface area is 270~320m2/g, the accumulation density is 0.58~0.68g/ml, the silicon content is 0.5~10% accounted by silicon dioxide. The manufacturing method is: adds in high dispersity silicon compound such as nano silicon dioxide in the mixing process of Riopone or aluminum oxide and deioned water or liquid, and forms into plastic, then it is formed, dried and baked into catalyst carrier. The catalyst in the invention has a good physical and chemical performance and usage performance.
Description
1, technical field
The present invention relates to a kind of siliceous alumina support and preparation method thereof, particularly after adding silicon additive, can keep the preparation method of the siliceous alumina support of porous of aluminium oxide microstructure characteristics.
2, background technology
Usually, the hydrogenation pretreatment catalyst of hydrocarbon feed, great majority are carrier with aluminium oxide and the aluminium oxide that contains minor amount of silicon.The surface nature of carrier such as carrier surface acid amount, acid strength etc. and porous such as average pore diameter or specific area etc. all can produce considerable influence to catalyst property.People prove during to the promotor action of aluminium oxide at research silica, the intervention of silica at aspects such as acid matter and metal dispersion matter to catalyst generation effect.Discover, in aluminium oxide, add an amount of silica after, can improve the acid amount and the acid strength of aluminium oxide; Simultaneously, when taking place to interact between the two, according to the minimum principle of maximum system energy, silica at first will act on the strong activated centre of alumina surface, the result has weakened the effect in alumina surface activated centre, aluminium oxide and intermetallic interaction are relaxed, help metal dispersion and active performance.Traditional hydrogenation pretreatment catalyst used carrier, great majority adopt the siliceous alumina support of the precipitation method or coprecipitation preparation, and in preparation process, the silicon source of introducing system is that mensuration dissolubility silicic salt or silica sol liquid belong to the colloidal type material.This silicon source and adding method thereof exist the influence of process to the character and/or the microstructure of aluminium oxide.The colloidal substance that exists with the micelle form contacts the inhomogeneous state that is in the system aluminium oxide, especially when alumina concentration in the reaction system increases, the inhomogeneities of system is more obvious, cause the inhomogeneity of product aluminium oxide physico-chemical property easily, thereby influence the surface nature and the serviceability of siliceous alumina support.
US4,758,544 have described and have a kind ofly prepared aluminium oxide-aluminum phosphate-silica support with coprecipitation, and the method for the catalyst of load tungsten-nickel-fluorine.Owing to be to adopt coprecipitation that silicon and P elements are joined in the carrier, certainly will have most of silicon and P elements be dispersed in alumina body mutually in, influenced the structure of aluminium oxide itself, and can not give full play to the effect of auxiliary agent.
It is raw material that Chinese invention patent CN1048651C has described with aluminum sulfate and sodium metaaluminate, adopt the precipitation method to prepare siliceous and the production process phosphorus oxidation alumina supporter, the silicon source of introducing in this preparation process is a soluble glass, and element silicon mainly plays the modulation support acidity, secondly is the reaming effect.Because the silicon source is the colloidal substance that exists with the micelle form, is in inhomogeneous state when contacting with the system aluminium oxide, making has influenced the raising of catalyst use character by the skewness of silicon additive on alumina support.Chinese patent CN1030395 proposes to add silica sol liquid in the mixing, forming process at boehmite and prepares siliceous alumina support, and element silicon can play the reaming effect.As mentioned above, also there is the silicon problem of uneven distribution in this method.
3, summary of the invention
At the deficiencies in the prior art, the present invention proposes a kind of auxiliary agents of silicon and is evenly distributed on alumina support, and does not influence the alumina pore structure, can effectively regulate siliceous aluminium oxide of catalyst surface character and preparation method thereof.
The present invention is a kind of alumina support that contains auxiliary agents of silicon, contains silica 0.5～10% by weight, is preferably 2～8%, and auxiliary agents of silicon is evenly distributed on alumina surface, and epiphase sial atomic ratio is greater than 0.15, and the acidity of carrier is 0.6～0.8Mmol/g.The carrier pore volume is 0.55～0.68ml/g, and specific area is 270～320m
2/ g, bulk density is 0.58～0.68g/ml, average pore diameter is 6.5～9.5nm.
The preparation method of the siliceous alumina support of the present invention is: aluminium hydroxide or ratio on demand such as aluminium oxide and extrusion aid are mixed, add the fully mixed plastics of pinching into such as peptization acid, and in aforementioned process, add the nanometer silicon-containing compound, mix and pinch into plastic aftershaping, drying, roasting, promptly make the siliceous alumina support of porous of the present invention.The preferred nano silicon of above-mentioned nanometer silicon-containing compound, particle diameter is 6～100nm.The adding method of above-mentioned nanometer silicon-containing compound can for (a) nanometer silicon-containing compound with contain aluminium source material (aluminium hydroxide or aluminium oxide) and mix, (b) the nanometer silicon-containing compound contains in the material of aluminium source with deionized water wetting back adding, (c) add after the nanometer silicon-containing compound mixes with the peptization acid solution and contain in the material of aluminium source, (d) add the nanometer silicon-containing compound again behind the adding peptization acid solution, (e) mix (making peptizing agent) with all or part of aperture aluminium hydroxide with peptization acid solution and nanometer silicon-containing compound, mix with macropore aluminium hydroxide then, (f) substep adds, at above-mentioned (a), (b), (c), (d) wantonly two steps or two steps add respectively in above and (e).
The inventive method has changed the preparation method of traditional siliceous alumina support, by taking the technology of new silicon source and unique interpolation auxiliary agents of silicon, can keep aluminium oxide microstructure characteristics, can make element silicon be enriched in carrier surface and evenly dispersion again, played the surface nature of modulation carrier, surface acid property particularly, and then regulating catalyst acid and/or improve interaction between active component and carrier more effectively.Specifically have following advantage:
(1) owing to not increasing additional step, simple and easy to do, grasp easily.
(2) granularity is little because the nano silicon that uses has, high dispersion and excellent characteristics such as stability, eliminated the influence of process to the aluminium oxide microstructure, can effectively control product property, can relax restriction simultaneously, reduce production costs aluminium oxide precursor-boehmite.
(3) generate the back at aluminium oxide (or aluminium hydroxide) and add auxiliary agents of silicon, the preparation process of aluminium oxide is not had influence, help enrichment of carrier surface silicon and evenly dispersion, played the effect of the surface nature of modulation carrier.
The technology of new silicon source of (4) being taked and unique interpolation auxiliary agents of silicon has played the acid of regulating catalyst and/or has improved interaction between active component and carrier, and more surface-active center is provided.
4, the specific embodiment
The present invention is by the source and the adding method of auxiliary agents of silicon in the siliceous alumina support of change, and then the performance of improvement carrier.The present invention about the concrete way of the siliceous alumina support preparation of porous is: take by weighing a certain amount of macropore aluminium hydrate powder and/or aperture aluminium hydrate powder and extrusion aid and mix, the peptizing agent that contains nano silicon or the adding that add amount of calculation contain inorganic aqueous acid and nano silicon (the silica addition is 0.5～10%), mix and pinch evenly, become plastic, on banded extruder, be extruded into bar.Bar after the shaping descended dry 8～16 hours at 90 ℃～150 ℃, placed roaster then, was warming up to 450～650 ℃, and constant temperature calcining 1～6 hour obtains the siliceous alumina support of porous of the present invention at last.The pore volume of above-mentioned macroporous aluminium oxide is 0.7～1.1ml/g, and average pore diameter is 6.0～11.0nm, and specific area is 300～380m
2/ g, the pore volume of little porous aluminum oxide wherein are 0.2～0.6ml/g, and average pore diameter is 2.0～10.0nm, and specific area is 200～300m
2/ g.The weight mixing ratio of macroporous aluminium oxide and little porous aluminum oxide is 1: 1～1: 5.The mixing portion of little porous aluminum oxide and macroporous aluminium oxide is 5: 1～25: 1 with the ratio of doing the peptizing agent part.
The present invention goes for auxiliary agents such as auxiliary agent titanium, boron, zirconium about the adding method of auxiliary agents of silicon, as adopt nanometer titaniferous materials, nanometer to contain boron substance, nano zirconium-containing material as carrier auxiliary agent source, preparation contains the catalyst or the catalyst carrier of above-mentioned one or more auxiliary agents.
The siliceous alumina support of porous of the present invention can be used for preparing the mink cell focus hydrogenation pretreatment catalyst, in particular for preparation heavy distillate hydrogenation pretreatment catalyst.
Further specify technical solution of the present invention below in conjunction with embodiment.
Embodiment 1
Take by weighing Chinese Chang Ling oil-refining chemical limited company catalyst plant respectively with in the aluminum sulfate and the prepared macropore aluminium hydrate powder 188.0g of sodium metaaluminate, aperture aluminium hydrate powder 226.0g (pore volume 0.498ml/g, average pore diameter is 8.1nm, and specific area is 228m
2/ g), the nano silicon of Tianjin chemical inc production accounts for 4.0%, 75.0g deionized water, extrusion aid sesbania powder 12.0g and 8g citric acid mix, and add the solution that is mixed with by 26.0g40% salpeter solution and 325.0g deionized water, mix and pinch into plastic, be extruded into the clover bar of designed size on banded extruder, drying is 8 hours under 110 ℃ of conditions of baking temperature, then 500 ℃ of following roastings 4 hours, be sample (1), character sees Table 1.
Embodiment 2
In embodiment 1,4.0%g changes 6.1% into nano silicon, i.e. cost example, and character sees Table 1 (2).
Embodiment 3
In embodiment 1,4.0%g changes 2.3% into nano silicon, i.e. cost example, and character sees Table 1 (3).
Embodiment 4
In embodiment 1, sintering temperature changes 550 ℃ into, i.e. cost example, and character sees Table 1 (4).
Embodiment 5
In embodiment 1, sintering temperature changes 580 ℃ into, i.e. cost example, and character sees Table 1 (5).
Embodiment 6
In embodiment 1, the adding method of nano silicon is: nano silicon mixes with salpeter solution, adds then in macropore aluminium hydroxide and the aperture aluminium hydroxide, and other step is with embodiment 1, i.e. cost example, and character sees Table 1 (6).
Embodiment 7
In embodiment 1, change nano silicon into 5.5%, make peptizing agent by 10% and salpeter solution of nano silicon and aperture aluminium hydroxide, mix with macropore aluminium hydroxide and residue aperture aluminium hydroxide then, other is with embodiment 1, i.e. cost example, and character sees Table 1 (7).
Embodiment 8
In embodiment 1, change nano silicon into 3.0%, wherein nano silicon is divided into two equal portions, a with add the wetting back of deionized water and add in the aluminium hydroxide material, another part adds in the aluminium hydroxide material after making peptizing agent with 5% and salpeter solution of aperture aluminium hydroxide, other step is with embodiment 1, i.e. cost example, and character sees Table 1 (8).
Comparative example 1
In embodiment 1, without nano silicon, with the silica sol liquid of 85.0g20%, water 325g changes 340g into, i.e. cost example, and character sees Table 1 (9).
Comparative example 2
In embodiment 1, it is raw material that the macropore aluminium hydrate powder changes into alchlor, ammoniacal liquor and liquid sodium silicate, the siliceous aluminium hydrate powder of macropore that adopts the precipitation method to produce, silicone content is 5.5%, does not add nanometer silica, and water 325g changes 400g into, be the cost example, character sees Table 1 (10).
Embodiment 9
The siliceous alumina support of porous with the embodiment of the invention 1 described process preparation, flooded 120 minutes by general infusion process with molybdenum-nickel-phosphorus solution, the superfluous liquid of elimination is after 110 ℃ of following dryings, 480 ℃ of roastings 3 hours, obtain a kind of heavy distillate hydrogenation pretreatment catalyst.At hydrogen dividing potential drop 14.7MPa, volume space velocity 1.0h
-1, hydrogen to oil volume ratio 1000: 1 is handled Iranian VGO oil (sulphur 1.1%, nitrogen 0.12%, aromatic hydrocarbons 42.8%) under the process conditions that reaction temperature is 372 ℃, and its desulfurization degree is 99.8%, and denitrification percent is 99.5%.Illustrate that the catalyst made from siliceous alumina support of the present invention has good serviceability.
The physicochemical property of each embodiment carrier of table 1
XPS
The physics and chemistry pore volume is piled up TPD-NH3 than table 3～15nm hole, aperture
Character ml/g area nm directly accounts for the total Si/Al of total hole density (total acid content) total content (former epiphase Si/Al
m
2/ g directly divides rate, % g/ml Mmol/g SiO
2% ratio) (atomic ratio)
(1) 0.61 302 7.9 90.7 0.63 0.67 4.00 0.0354 0.164
(2) 0.63 312 8.1 90.0 0.62 0.77 6.20 0.0562 0.190
(3) 0.61 300 7.8 91.5 0.63 0.65 2.20 0.0191 0.158
(4) 0.63 290 8.3 88.6 0.60 0.68 4.05 0.0359 0.161
(5) 0.65 280 8.5 89.0 0.58 0.70 4.07 0.0361 0.160
(6) 0.61 308 7.8 91.2 0.63 0.69 4.10 0.0363 0.169
(7) 0.63 310 7.9 92.0 0.62 0.75 5.40 0.0485 0.186
(8) 0.62 303 8.0 91.7 0.63 0.65 3.07 0.0269 0.160
(9) 0.64 280 8.4 85.9 0.56 0.55 5.50 0.0495 0.138
(10)) 0.65 285 8.5 86.1 0.58 0.53 2.51 0.0217 0.127
As can be seen from Table 1, adopt under silicon of the present invention source and the addition sequence condition, the physicochemical property of each embodiment is basic identical, the difference of dioxide-containing silica in the carrier, it is very nearly the same that 3～15nm aperture accounts for total aperture branch rate, along with the increase of dioxide-containing silica in the carrier, specific area, pore volume change little.Add nano silicon of the present invention and can make element silicon enrichment surface and evenly dispersion, x-ray photoelectron spectroscopy XPS measures carrier epiphase silicon and disperses all than adding the good of silica sol liquid and liquid sodium silicate; Therefore, increased the acidity of carrier surface solid acid, ammonia absorption acidity is than the height that adds silica sol liquid and liquid sodium silicate.The physicochemical property of carrier is subjected to the temperature effect maximum of roasting, and along with the rising of sintering temperature, the pore volume of carrier, aperture also increase thereupon, and specific area descends, and bulk density obviously reduces.
Claims (9)
1, a kind of siliceous alumina support contains silica 0.5～10% by weight, it is characterized in that silicon is evenly distributed on alumina surface, and the acidity of carrier is 0.6～0.8Mmol/g.
2, according to the described siliceous alumina support of claim 1, it is characterized in that described carrier dioxide-containing silica is 2～8%, pore volume is 0.55～0.68ml/g, specific area is 270～320m
2/ g, average pore diameter is 6.5～9.5nm, carrier epiphase sial atomic ratio is greater than 0.15.
3, the preparation method of the described siliceous alumina support of a kind of claim 1, process is:
(1) aluminium hydroxide or aluminium oxide and extrusion aid are mixed, add peptizing agent etc. and fully mix and pinches into plastic;
(2) mix and to pinch into plastic aftershaping, drying, roasting, make the siliceous alumina support of porous;
It is characterized in that adding the nanometer silicon-containing compound in the process in described step (1), addition contains silica 0.5～10% in final vehicle weight.
4, according to the preparation method of the described siliceous alumina support of claim 3, it is characterized in that described nanometer silicon-containing compound is a nano silicon, particle diameter is 6～100nm.
5,, it is characterized in that the adding method of described nanometer silicon-containing compound is selected one of following mode according to the preparation method of the described siliceous alumina support of claim 3:
(a) the nanometer silicon-containing compound with contain aluminium source mixing of materials;
(b) the nanometer silicon-containing compound contains in the material of aluminium source with deionized water wetting back adding;
(c) add after the nanometer silicon-containing compound mixes with the peptization acid solution and contain in the material of aluminium source;
(d) add the nanometer silicon-containing compound again behind the adding peptization acid solution;
(e) mix as peptizing agent with peptization acid solution and nanometer silicon-containing compound with all or part of aperture aluminium hydroxide, mix with macropore aluminium hydroxide then;
(f) substep adds, at above-mentioned (a) and (b), (c), (d) and (e) wantonly two steps or two go on foot more than in adding respectively.
6,, it is characterized in that the drying of described siliceous alumina support, roasting condition are according to the preparation method of the described siliceous alumina support of claim 3: after under 90～150 ℃ dry 8～16 hours, at 450～650 ℃, constant temperature calcining 1～6 hour.
7, according to the preparation method of the described siliceous alumina support of claim 3, it is characterized in that described aluminium oxide comprises macroporous aluminium oxide and little porous aluminum oxide, both weight mixing ratios are 1: 1～1: 5.
8, according to the preparation method of the described siliceous alumina support of claim 7, the pore volume that it is characterized in that described macroporous aluminium oxide is 0.7～1.1ml/g, and average pore diameter is 6.0～11.0nm, and specific area is 300～380m
2/ g; The pore volume of little porous aluminum oxide is 0.2～0.6ml/g, and average pore diameter is 2.0～10.0nm, and specific area is 200～300m
2/ g.
9,, it is characterized in that in described (5) the kind mode that the mixing portion of little porous aluminum oxide and macroporous aluminium oxide is 5: 1～25: 1 with the part by weight of doing the peptizing agent part according to the preparation method of the described siliceous alumina support of claim 5.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133144 CN1197650C (en) | 2002-10-10 | 2002-10-10 | Silicon-containing alumina supporter and preparing method thereof |
| CA2501973A CA2501973C (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| EP03753239.7A EP1552880B1 (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| AU2003272858A AU2003272858A1 (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| JP2004545680A JP5006516B2 (en) | 2002-10-10 | 2003-09-29 | Silicon-containing alumina support, method for preparing the same, and catalyst containing the alumina support |
| PCT/CN2003/000839 WO2004037408A1 (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| KR1020057006163A KR100884595B1 (en) | 2002-10-10 | 2003-09-29 | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| US10/682,221 US6875722B2 (en) | 2002-10-10 | 2003-10-09 | Silicon-containing alumina support, a process for preparing the support and a catalyst containing the support |
| US11/069,034 US7253135B2 (en) | 2002-10-10 | 2005-02-28 | Silicon-containing alumina support, a process for preparing the support and a catalyst containing the support |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133144 CN1197650C (en) | 2002-10-10 | 2002-10-10 | Silicon-containing alumina supporter and preparing method thereof |
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| Publication Number | Publication Date |
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| CN1488434A true CN1488434A (en) | 2004-04-14 |
| CN1197650C CN1197650C (en) | 2005-04-20 |
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| CN 02133144 Expired - Lifetime CN1197650C (en) | 2002-10-10 | 2002-10-10 | Silicon-containing alumina supporter and preparing method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145296A (en) * | 2010-02-10 | 2011-08-10 | 中国石油化工股份有限公司 | Hydroprocessing catalyst and preparation method of hydroprocessing catalyst and preparation method of lubricant base oil |
| CN102029192B (en) * | 2009-09-28 | 2013-01-09 | 中国石油化工股份有限公司 | Silicon-containing alumina and preparation method thereof |
| CN104010725A (en) * | 2012-09-20 | 2014-08-27 | 巴斯夫欧洲公司 | Chroma alumina catalysts for alkane dehydrogenation |
| CN104588056A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Catalyst used for preparation of dimethyl ether through dehydration of methanol and preparation method thereof |
| CN105709829A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Heteropoly acid catalyst and preparation method thereof |
| CN105983447A (en) * | 2015-03-03 | 2016-10-05 | 中国石油天然气股份有限公司 | Catalyst carrier granularity control method |
-
2002
- 2002-10-10 CN CN 02133144 patent/CN1197650C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029192B (en) * | 2009-09-28 | 2013-01-09 | 中国石油化工股份有限公司 | Silicon-containing alumina and preparation method thereof |
| CN102145296A (en) * | 2010-02-10 | 2011-08-10 | 中国石油化工股份有限公司 | Hydroprocessing catalyst and preparation method of hydroprocessing catalyst and preparation method of lubricant base oil |
| CN102145296B (en) * | 2010-02-10 | 2013-07-31 | 中国石油化工股份有限公司 | Hydroprocessing catalyst and preparation method of hydroprocessing catalyst and preparation method of lubricant base oil |
| CN104010725A (en) * | 2012-09-20 | 2014-08-27 | 巴斯夫欧洲公司 | Chroma alumina catalysts for alkane dehydrogenation |
| CN104588056A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Catalyst used for preparation of dimethyl ether through dehydration of methanol and preparation method thereof |
| CN105709829A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Heteropoly acid catalyst and preparation method thereof |
| CN105709829B (en) * | 2014-12-02 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of heteropoly acid catalyst and preparation method thereof |
| CN105983447A (en) * | 2015-03-03 | 2016-10-05 | 中国石油天然气股份有限公司 | Catalyst carrier granularity control method |
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