CN1853785A - Silicon and boron contained alumina carrier and production thereof - Google Patents
Silicon and boron contained alumina carrier and production thereof Download PDFInfo
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- CN1853785A CN1853785A CN 200510046345 CN200510046345A CN1853785A CN 1853785 A CN1853785 A CN 1853785A CN 200510046345 CN200510046345 CN 200510046345 CN 200510046345 A CN200510046345 A CN 200510046345A CN 1853785 A CN1853785 A CN 1853785A
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Abstract
A Si and B contained alumina carrier for the hydrogenating catalyst, especially the hydrodenitrifying catalyst, is prepared from macroreticular alumina and millipore alumina through continuously forming colloid while introducing Si and B step by step to disperse the most of Si and B on the surface of alumina.
Description
Technical field
The present invention relates to a kind of alumina support of siliceous and boron, catalyst for hydro-processing heavy distillate carrier of particularly a kind of siliceous and boron and preparation method thereof.
Background technology
As everyone knows, aluminium oxide particularly has a very wide range of applications in the catalytic hydrogenation field at catalytic field as carrier material.But aluminium oxide is as a little less than the catalyst carrier acidity, and mainly is L acid, and B acid is then extremely weak or think and do not contain B acid; Easily form the species (for example easily and nickel formation nickel aluminate) of non-activity with metal active constituent generation strong interaction.The sintering of metal active constituent or carrier easily takes place and influence activity of such catalysts, stability etc. as catalyst carrier with aluminium oxide merely, therefore as catalyst carrier the time, add one or more other elements usually, with the acid of regulating catalyst and/or improve interaction between active component and carrier.
The comparatively common practice is in catalyst preparation process alumina catalyst support or its predecessor aluminium hydroxide to be carried out modification, for example adopts infusion process, kneading method, coprecipitation or solution melt method that auxiliary agents such as F, Si, B, P are joined in the carrier.SiO
2Be carrier component or the modified additive of using always, itself acidity is very weak or do not have acidity, but and aluminium oxide in conjunction with after can improve the acidity of aluminium oxide, thereby can promote the reaction of those acidic site catalysis.Simultaneously, SiO
2Can also improve the interaction of carrier and active metal component, distribute mutually, increase active sites quantity thereby change activity.
Chinese patent CN1048037C discloses alumina support of a kind of siliceous and phosphorus and preparation method thereof.This alumina support is mixed by a kind of siliceous and macroporous aluminium oxide and a kind of little porous aluminum oxide phosphorus, and macroporous aluminium oxide wherein siliceous and phosphorus becomes the glue method to prepare by substep.This modified aluminas is that to adopt silicon and phosphorus be auxiliary agent, and total acidity is low, awaits further to improve with the hydrogenation activity of the catalyst of its carrier.
Chinese patent CN1082387C discloses a kind of mesoporous aluminas gel and preparation method thereof, can evenly disperse one or more to be selected from the oxide of silica, boron oxide, phosphorous oxide in this alumina substrate.The specific area of described mesoporous aluminas gel is 260-700m
2/ g, pore volume are 0.2-1.0cm
3/ g, average pore diameter is 2-7nm, wherein the mol ratio of boron oxide and aluminium oxide is 0-4.0.This aluminium oxide preparation process adopts the organic aluminium salt Hydrolyze method to make, and the oxide of described silicon, boron and phosphorus joins in the carrier by coprecipitation, preparation method's complexity.Owing to be to adopt coprecipitation that silicon, boron and P elements are added aluminium oxide, certainly will have most silicon, boron and P elements be dispersed in alumina body mutually in, thereby can not give full play to its effect.Coprecipitation is that multiple material precipitates simultaneously in addition, and identical deposition condition can not be the best deposition condition of multiple material simultaneously, thereby influences the physical and chemical performance of final carrier.And the alumina gel bore dia that this method makes is less, is only applicable to the carrier of catalyst for hydrorefining distillate oil.
Summary of the invention
The purpose of this invention is to provide macropore alumina supporter of a kind of siliceous and boron and preparation method thereof.Institute is siliceous in the alumina support of the present invention is enriched in alumina surface with boron, and has bigger specific surface and pore volume, thereby is especially suitable for use as the carrier of catalyst for hydro-processing heavy distillate.
Alumina support of the present invention is made up of the macroporous aluminium oxide of siliceous and boron and aperture aluminium oxide.Macroporous aluminium oxide wherein is siliceous with SiO
2Count 1wt%-15wt%, boracic is with B
2O
3Count 2wt%-18wt%, specific area 350m
2/ g-500m
2/ g, pore volume 0.8ml/g-1.3ml/g, average pore diameter 8nm-13nm; The specific area 200m of described alumina support
2/ g-450m
2/ g, pore volume 0.3ml/g-0.8ml/g, average pore diameter 6nm-10nm.
The siliceous preparation method with the boron alumina support of the present invention is as follows: adopt into gluing method and prepare siliceous and macroporous aluminium oxide boron, mix with one or more little porous aluminum oxides and adhesive, extrusion aid, roll, extrusion, drying, roasting make alumina support of the present invention.
Above-mentioned siliceous and macroporous aluminium oxide boron prepares as follows:
(1) fills in the container of water one, under agitation constantly add and contain aluminum ions acidic salt solution, add alkaline solution simultaneously and be carried out to glue;
(2) behind reinforced the end, above-mentioned system wears out a period of time, adds the alkali metal soln of siliceous oxygen anion, continues aging;
(3) filter and wash to anion/Al
2O
3＜2wt%;
(4) add the boron-containing compound that measures;
(5) filter also drying, obtain siliceous and macroporous aluminium oxide boron.
In the above-mentioned steps, the inventory of silicon and boron element is all undertaken by the content ratio in the aluminium oxide butt of final siliceous and boron.
Used little porous aluminum oxide is aluminium chloride-ammoniacal liquor method, carbonizatin method or the boehmite of aluminum sulfate method production and the SB alumina powder of Zlegler synthetic reaction accessory substance etc. in the alumina support preparation process of the present invention.
Above-mentioned macroporous aluminium oxide, aperture aluminium oxide are mixed, add adhesive mix with extrusion aid (citric acid, sesbania powder) pinch, roll, moulding, drying, roasting, make the siliceous alumina support with boron of the present invention; Wherein said baking temperature is 40 ℃-180 ℃, is preferably 100 ℃-150 ℃, and be 0.5h-24h drying time, is preferably 1h-8h; Described sintering temperature is 400 ℃-700 ℃, is preferably 500 ℃-600 ℃, and roasting time is 0.5h-24h, is preferably 1h-8h.
Described adhesive comprises little porous aluminum oxide and peptizing agent, as the little porous aluminum oxide of adhesive with roasting after the weight of carrier be benchmark, be 5wt%-30wt% in aluminium oxide content.Described peptizing agent is one or more in aluminum nitrate, citric acid, nitric acid, acetic acid and the oxalic acid.Also can add zirconia, titanium oxide-magnesia and their mixture in the described adhesive.
Support shapes after the described moulding can be sheet, spherical, cylinder bar and special-shaped bar (clover, bunge bedstraw herb), preferably cylinder bar and special-shaped bar (clover, bunge bedstraw herb).Support shapes can be diameter 0.8mm-2.5mm slice and＞the thick bar of 2.5mm.
Carrier of the present invention is to adopt macropore siliceous and aluminium oxide and little porous aluminum oxide boron additive to mix, and its effect is as follows:
(1), used macropore is siliceous is to adopt substep to become the preparation of glue method with the aluminium oxide of boron additive, compare with kneading method with coprecipitation, the inventive method can make two kinds of auxiliary agents all be dispersed in the surface of aluminium oxide, the body of avoiding entering aluminium oxide mutually in, and can give full play to the effect of auxiliary agent;
(2), employing is siliceous and the macroporous aluminium oxide of boron additive, makes alumina support have bigger specific surface and pore volume, large aperture, the characteristics of pore distribution concentration;
(3), the macroporous aluminium oxide that adopts of the present invention is to be auxiliary agent with silicon and boron, improved the total acid content on macroporous aluminium oxide surface, the acid that has improved its surface distributes, simultaneously with its preparation alumina support, the acid matter of also having regulated alumina carrier surface.
(4) because the electronegativity of boron than the height of aluminium, makes Al
2O
3-B
2O
3The B-OH acidity on surface is stronger than Al-OH, so introduce the dispersion that boron additive more helps to improve active phase with the inventive method, and make active easier reduction and sulfuration mutually, and increased the intensity in activated centre quantity and activated centre, make catalyst have higher activity with this preparing carriers.
The catalyst for preparing after the supported carrier hydrogenation active metals of the present invention has higher H DN reactivity worth, can be used for the carrier of catalyst such as hydrocracking preliminary treatment, fraction oil hydrogenation refining, FCC pretreatment of raw material and MHUG.Be particularly suitable for doing the carrier of catalyst for hydro-processing heavy distillate.
The specific embodiment
According to the preparation method of alumina support provided by the invention, its concrete steps are as follows respectively:
(a) preparation of siliceous and boron macroporous aluminium oxide
The macroporous aluminium oxide of used siliceous and boron in the alumina support preparation process of the present invention, by becoming the preparation of glue method, it can make less silicon of content and boron element major part be scattered in alumina surface, and concrete preparation process is as follows:
(1) add a certain amount of deionized water in a container, under uniform temperature and stirring condition, add and contain aluminum ions acidic salt solution, these contain the solution that aluminum ions acidic salt solution can be aluminium chloride, aluminum sulfate or aluminum nitrate, and its concentration is with Al
2O
3Count 2g/100ml-8g/100ml, be preferably 3g/100ml-6g/100ml, add ammoniacal liquor simultaneously and be carried out to glue, ammonia concn is with NH
3Count 6g/100ml-15g/100ml; When described acidic salt solution is aluminum sulfate solution, can add sodium aluminate solution and be carried out to glue, sodium aluminate solution concentration is with Al
2O
3Count 10g/100ml-25g/100ml, be preferably 12g/100ml-20g/100ml; And control pH value 7.0-11.0, being preferably 7.5-9.5, temperature is controlled at 30 ℃-90 ℃, is preferably 40 ℃-70 ℃; Charging time is controlled at 30min-240min, is preferably 30min-120min.
(2) stop reinforced after, above-mentioned system is aging 10min-120min under pH value identical with becoming the adhesive tape part and temperature, preferably aging 20min-100min adds the sodium metasilicate or the solution of sodium metasilicate through of metering then, its concentration is with SiO
2Count 4g/100ml-10g/100ml, be preferably 5g/100ml-8g/100ml, continue aging 20min-240min, be preferably 30min-60min.
(3) behind aging the end, filter and wash extremely to anion/Al
2O
3＜2.0wt% is preferably＜0.3wt%
(4) add the boron-containing compound that measures, as boric acid or borate, the control temperature is preferably 40 ℃-70 ℃ at 30 ℃-90 ℃, and mixing time is 15min-75min, is preferably 30min-60min.Boron-containing compound can add in the following way: a, with after the filter cake making beating adds boron-containing compound in the slurries or b, wet cake is joined in the boron-containing compound aqueous solution.
(5) filter, and with filter cake at 110 ℃ of-130 ℃ of dry 12h-24h.
In the above-mentioned steps, the inventory of silicon and boron element is all undertaken by the content ratio in the macroporous aluminium oxide butt of final siliceous and boron.
The macroporous aluminium oxide that makes siliceous and boron with determination of nitrogen adsorption specific surface, pore volume, average pore size and pore size distribution, has following character behind 500 ℃ of-700 ℃ of roasting 0.5h-10h:
Specific surface 350m
2/ g-500m
2/ g, preferably 400m
2/ g-450m
2/ g,
Pore volume 0.8ml/g-1.3ml/g, best 0.9ml/g-1.1ml/g,
Average pore diameter 8nm-13nm, preferably 8nm-11nm;
Infrared acidity ≮ 0.700mmol/g is preferably 0.700mmol/g-0.960mmol/g, is preferably 0.700mmol/g-0.930mmol/g.
Weight with the aluminium oxide butt is benchmark, and is siliceous with SiO in its chemical composition
2Meter 1wt%-15wt% is preferably 1wt%-13wt%; Boracic is with B
2O
3Meter 2wt%-18wt% is preferably 5wt%-15wt%.
Infrared acidity among the present invention is to adopt U.S. Buddhist nun high-tensile strength company's Fourier infrared spectrograph (FIR-560 type) to measure.
(b) preparation of siliceous and boron alumina support
After (a) being gone on foot the macroporous aluminium oxide and the mixing of part aperture aluminium oxide of the siliceous and boron for preparing, the little porous aluminum oxide of another part and peptizing agent, water are made adhesive, add to mix with extrusion aid and pinch, to roll the back extruded moulding, the wherein siliceous and macroporous aluminium oxide of boron and the weight ratio of little porous aluminum oxide are 10: 1-1: 10.Support shapes can be cylindric, clover or bunge bedstraw herb, is preferably three leaf list or bunge bedstraw herbs.The bar of extruding is through 100 ℃ of-180 ℃ of dry pelletizings, and behind 400 ℃ of-700 ℃ of following roasting 0.5h-8h, and measuring with n2 absorption apparatus has following characteristics:
Specific surface 200m
2/ g-450m
2/ g, preferred 260m
2/ g-350m
2/ g,
Pore volume 0.3ml/g-0.8ml/g, preferred 0.5ml/g-0.7ml/g,
Average pore diameter 6nm-10nm is preferably 7nm-9nm,
Described peptizing agent is one or more in aluminum nitrate, nitric acid, the acetic acid.
The used little porous aluminum oxide of the present invention, the little porous aluminum oxide as SB aluminium oxide, carbonizatin method aluminium oxide and Fushun catalyst plant are produced with aluminium chloride and ammoniacal liquor method requires it to contain the gibbsite amount and is no more than 5.0wt%, changes into γ-Al
2O
3After have following characteristics:
General range preferred range pore volume (Ethanol Method) 0.3ml/g-0.6ml/g 0.35ml/g-0.55ml/g
Specific surface (BET method) 200m
2/ g-300m
2/ g 220m
2/ g-270m
2/ g
Further specify technical solution of the present invention by the following examples.
Embodiment 1
Add the 1000ml water purification in a container, be warming up to 65 ℃, add the solution 3700ml that contains 310g aluminium chloride, adding concentration simultaneously is 10gNH
3The ammonia spirit of/100ml, control pH value 8.2, temperature is 62 ℃, the reinforced time is 60min.After stopping to feed in raw material, system is aging 50min under above-mentioned pH value and temperature conditions, adds the 40ml solution that contains the 4.8g sodium metasilicate.System continues aging 75min under above-mentioned pH value and temperature conditions, filtration washing is to Cl
-/ Al
2O
3＜0.3wt%.After filter cake added water purification making beating, add the boric acid of 43g, the control temperature is in 50 ℃, and the time is 40min.Filter and with filter cake at 130 ℃ of dry 8h, it is crushed to granularity accounts for more than the 95wt% less than 180 orders, obtain siliceous and the boron macroporous aluminium oxide.
Get above-mentioned macroporous aluminium oxide 121g, sneak into the SB alumina powder prepared adhesive of 130g nitric acid peptization, mix pinch 20min after, roll 10min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4.Behind 130 ℃ of dry 8h under 520 ℃ of conditions roasting 4h, obtain carrier S-1.
Embodiment 2
In-container, add the 1000ml water purification, be warming up to 65 ℃, add and contain 560g aluminum sulfate (Al
2(SO
4)
318H
2O) solution 3700ml, adding concentration simultaneously is 10gNH
3The ammonia spirit of/100ml, control pH value 7.6, temperature is 60 ℃, the reinforced time is 80min.After stopping to feed in raw material, system is aging 15min under above-mentioned pH value and temperature conditions, adds the 100ml solution that contains the 15.3g sodium metasilicate.System continues aging 75min under above-mentioned pH value and temperature conditions.Filtration washing is to SO
4 2-/ Al
2O
3＜1.5wt%.The boric acid of 34.6g is added in the water purification, wait to dissolve the back and add the filter cake making beating, 55 ℃ of control temperature, the time is 40min.Filter, filter cake is crushed to granularity with it accounts for more than the 95wt% behind 130 ℃ of dry 8h, obtain modified macroporous aluminium oxide less than 180 orders.
Get above-mentioned macroporous aluminium oxide 60g, sneak into the SB alumina powder prepared adhesive of 96g nitric acid peptization, mix pinch 20min after, roll 10min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4.Behind 130 ℃ of dry 8h under 520 ℃ of conditions roasting 4h, obtain carrier S-2.
Embodiment 3
In a container, add the 1000ml water purification, be warming up to 65 ℃, add aluminum sulfate 300g (Al
2(SO
4)
318H
2O) solution 2000ml, adding 1011g concentration simultaneously is 15gAl
2O
3The sodium aluminate solution of/100ml, control pH value 8.5, temperature is 64 ℃, the reinforced time is 120min.After stopping to feed in raw material, system is aging 15min under above-mentioned pH value and temperature conditions, adds the 245ml solution that contains the 32.0g sodium metasilicate.System continues aging 45min under above-mentioned pH value and temperature conditions, filtration washing is to SO
4 2-/ Al
2O
3＜1.5wt%.After filter cake added water purification making beating, add the boric acid of 30g, 45 ℃ of control temperature, the time is 40min.Filter cake is crushed to granularity with it accounts for more than the 95w% behind 130 ℃ of dry 8h, obtain modified macroporous aluminium oxide less than 180 orders.
Get above-mentioned macroporous aluminium oxide 100g, sneak into the SB alumina powder prepared adhesive of 105g nitric acid peptization, mix pinch 20min after, roll 10min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4.Behind 130 ℃ of dry 8h under 520 ℃ of conditions roasting 4h, obtain carrier S-3.
Embodiment 4
In a container, add the 1000ml water purification, be warming up to 65 ℃, add and contain 300g aluminum sulfate (Al
2(SO
4)
318H
2O) solution 2000ml, adding 1011g concentration simultaneously is 15.0gAl
2O
3The sodium aluminate solution of/100ml, control pH value 8.0, temperature is 65 ℃, the reinforced time is 120min.After stopping to feed in raw material, system is aging 30min under above-mentioned pH value and temperature conditions, adds the 150ml solution that contains the 11.4g sodium metasilicate.System continues aging 75min under above-mentioned pH value and temperature conditions, filtration washing is to SO
4 2-/ Al
2O
3＜1.5wt%.58.6g boric acid is added in the water purification, wait to dissolve the back and add the filter cake making beating, 50 ℃ of temperature controls, the time is 40min.Filter cake is crushed to granularity with it accounts for more than the 95wt% behind 130 ℃ of dry 8h, obtain modified macroporous aluminium oxide less than 180 orders.
Get above-mentioned macroporous aluminium oxide 114g, sneak into the SB alumina powder prepared adhesive of 125g nitric acid peptization, mix pinch 20min after, roll 10min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4.Behind 130 ℃ of dry 8h under 520 ℃ of conditions roasting 4h, obtain carrier S-4.
Embodiment 5
Add the 1000ml water purification in a container, be warming up to 65 ℃, add the solution 3700ml that contains 310g aluminium chloride, adding concentration simultaneously is 10gNH
3The ammonia spirit of/100ml, control pH value 7.8, temperature is 62 ℃, the reinforced time is 70min.After stopping to feed in raw material, system is aging 15min under above-mentioned pH value and temperature conditions, adds the 140ml solution that contains the 24.0g sodium metasilicate.System continues aging 75min under above-mentioned pH value and temperature conditions, filtration washing is to Cl
-/ Al
2O
3＜0.3wt%.After filter cake added water purification making beating, add the boric acid of 14.5g, 55 ℃ of control temperature, the time is 40min.Filter, cake is crushed to granularity accounts for more than the 95wt% behind 130 ℃ of dry 8h, get modified macroporous aluminium oxide less than 180 orders.
Get above-mentioned macroporous aluminium oxide 100g, sneak into the SB alumina powder prepared adhesive of 107g nitric acid peptization, mix pinch 20min after, roll 10min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4.Behind 130 ℃ of dry 8h under 520 ℃ of conditions roasting 4h, obtain carrier S-5.
Embodiment 6
Get S-3 carrier strip 100g, with containing the 96g molybdenum oxide, after filtering behind the molybdenum of 25.6g basic nickel carbonate, 7.0ml85% phosphoric acid, nickel, the phosphorus solution 200ml dipping 120min, with its behind 130 ℃ of dry 8h under 500 ℃ of conditions roasting 4h, catalyst C-3.
Comparative example 1
C-A is that concrete steps are as follows with reference to the reference catalyst of CN 1048037C method preparation:
(1) preparation of siliceous and phosphorus carrier: the 30g boric acid among the embodiment 3 is replaced with 13.4g phosphoric acid, and all the other steps are with embodiment 3, modified support S-A;
(2) preparation of reference catalyst C-A: the S-3 carrier among the embodiment 6 is replaced with the S-A carrier, and all the other steps get catalyst C-A with embodiment 6.
The macroporous aluminium oxide that embodiment 1-5 and comparative example 1 are obtained is analyzed its character at 520 ℃ of roasting 4h, the results are shown in table 1 and table 2.
The physico-chemical property of table 1 alumina support of the present invention
| Bearer number | S-1 | S-2 | S-3 | S-4 | S-5 | S-A |
| Specific surface, m 2/g | 340 | 321 | 305 | 328 | 324 | 320 |
| Pore volume, ml/g | 0.64 | 0.62 | 0.6l | 0.56 | 0.59 | 0.66 |
| Macroporous aluminium oxide character | ||||||
| SiO 2，wt％ | 1.98 | 5.2 | 8.3 | 3.0 | 10.6 | 3.5 |
| B 2O 3，wt％ | 16.2 | 8.9 | 6.1 | 11.2 | 3.9 | 3.0 (P 2O 5) |
| Specific area, m 2/g | 401 | 440 | 436 | 445 | 448 | 400 |
| Pore volume, ml/g | 1.03 | 1.12 | 0.98 | 1.09 | 1.06 | 1.02 |
| Average pore diameter, nm | 10.1 | 11.3 | 10.2 | 9.2 | 10.5 | 10.0 |
| Infrared acidity, mMol/g | 0.930 | 0.793 | 0.746 | 0.823 | 0.720 | 0.461 |
In order to compare the present invention siliceous and boron aluminium oxide and siliceous and acid matter phosphorus oxidation aluminium, adopt temperature programmed desorption (TPD-NH
3) method records the total acid content and the sour distributed data of L-1, L-3 and L-A modified aluminas, specifically sees Table 2.
The acid of table 2 modified aluminas distributes
| Modified aluminas | L-1 | L-3 | L-A | |
| Total acid content, mMol/g | 1.39 | 1.26 | 0.96 | |
| Acid distributes, % | 150-250℃ | 39.1 | 40.3 | 42.1 |
| 250-400℃ | 49.0 | 45.6 | 38.9 | |
| ＞400℃ | 11.9 | 14.2 | 19.0 | |
As shown in Table 2, acidity, the particularly quantity of weak acid center and middle strong acid center (in the table 2, the acid amount of sour distribution 250-400 ℃ correspondence) that the present invention adopts silicon and boron additive to significantly improve alumina surface increase considerably, promoted the catalytic reaction of this acidic site, especially hydrodenitrogeneration reaction.
Embodiment 7
Adopt identical feedstock oil, under identical process conditions, C-3 catalyst and C-A catalyst are carried out active comparative evaluation's test, the results are shown in Table 3.
Table 3 catalyst of the present invention and the contrast of reference catalyst denitrification activity evaluation result
| Catalyst | C-A | C-3 |
| Type | The reference example | The present invention |
| The reactive hydrogen dividing potential drop, MPa | 14.7 | 14.7 |
| Reaction temperature, ℃ | 372 | 372 |
| Volume space velocity, h -1 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio, v/v | 1000∶1 | 1000∶1 |
| The feedstock oil nitrogen content, μ g/g | 1205 | 1205 |
| Generate oily nitrogen content, μ g/g | 14.0 | 2.8 |
| Relative denitrification activity | 100 | 136 |
Annotate: denitrification activity regulation reference agent C-A is 100 relatively, and all the other are pressed
Relative denitrification activity=[ln (Nf/Np)/ln (Nf/Npr)] * 100
Wherein: Nf is the feedstock oil nitrogen content, and Npr and Np are respectively the generation oil nitrogen content of reference agent C-A and catalyst C-3 hydrotreatment.
By table 3 as seen, adopt the hydrodenitrogenationactivity activity of catalyst of alumina support of the siliceous and boron of the present invention apparently higher than the reference catalyst of the alumina support preparation of siliceous and phosphorus.
Claims (17)
1, a kind of alumina support of siliceous and boron is characterized in that, this alumina support is made up of siliceous and macroporous aluminium oxide and aperture aluminium oxide boron, and macroporous aluminium oxide wherein is siliceous with SiO
2Count 1wt%-15wt%, boracic is with B
2O
3Count 2wt%-18wt%, its specific area 350m
2/ g-500m
2/ g, pore volume 0.8ml/g-1.3ml/g, average pore diameter 8nm-13nm.
2, alumina support according to claim 1 is characterized in that, described macroporous aluminium oxide is siliceous with SiO
2Count 1wt%-13wt%, boracic is with B
2O
3Count 5wt%-15wt%, its specific area 400m
2/ g-450m
2/ g, pore volume 0.9ml/g-1.1ml/g, average pore diameter 8nm-11nm.
3, alumina support according to claim 1 and 2 is characterized in that, the infrared acidity of described macroporous aluminium oxide is 0.700mmol/g-0.960mmol/g.
4, alumina support according to claim 1 and 2 is characterized in that, the infrared acidity of described macroporous aluminium oxide is 0.700mmol/g-0.930mmol/g.
5, alumina support according to claim 1 is characterized in that, the specific surface of described little porous aluminum oxide is 200m
2/ g-300m
2/ g, pore volume are 0.3ml/g-0.6ml/g.
6, alumina support according to claim 1 is characterized in that, the specific area of described alumina support is 200m
2/ g-450m
2/ g, pore volume are 0.3ml/g-0.8ml/g, average pore diameter 6nm-10nm.
7, the preparation method of the arbitrary described alumina support of claim 1-6, the macroporous aluminium oxide that comprises the steps: siliceous and boron and little porous aluminum oxide and adhesive, extrusion aid be mixed to be pinched, roll, moulding, drying, roasting make alumina support.
8, preparation method according to claim 7 is characterized in that described drying condition is: 40 ℃-180 ℃ of temperature, time 0.5h-24h; Described roasting condition is: 400 ℃-700 ℃ of temperature, time 0.5h-24h.
9, preparation method according to claim 7 is characterized in that, described macroporous aluminium oxide prepares as follows:
(1) fill in the container of water one, under agitation also stream adds continuously and contains aluminum ions acidic salt solution, adds alkaline solution simultaneously and is carried out to glue;
(2) behind reinforced the end, above-mentioned system is aging, adds the alkali metal soln of siliceous oxygen anion, continues aging;
(3) filter and wash to anion/Al
2O
3＜2.0wt%;
(4) add the boron-containing compound that measures;
(5) filter also drying, obtain siliceous and macroporous aluminium oxide boron.
10, preparation method according to claim 9 is characterized in that, described to contain aluminum ions acidic salt solution be aluminium chloride, aluminum sulfate or aluminum nitrate solution, and its concentration is with Al
2O
3Count 2g/100ml-8g/100ml, described alkaline solution is an ammoniacal liquor, and its concentration is with NH
3Count 6g/100ml-15g/100ml.
11, preparation method according to claim 9 is characterized in that, described acidic salt solution is an aluminum sulfate solution, and described alkaline solution is a sodium aluminate solution, and its concentration is with Al
2O
3Count 10g/100ml-25g/100ml.
12, preparation method according to claim 9 is characterized in that, step (1) control pH value 7.0-11.0, and temperature is controlled at 30 ℃-90 ℃, and charging time is controlled at 30min-240min.
13, preparation method according to claim 9 is characterized in that, the alkali metal soln of siliceous oxygen anion is sodium metasilicate or sodium metasilicate solution described in the step (2), with SiO
2Meter concentration is 4g/100ml-10g/100ml.
14, preparation method according to claim 9 is characterized in that, boron-containing compound is boric acid or borate described in the step (4), and its adding mode is: a, with after the filter cake making beating adds boron-containing compound in the slurries; Or b, wet cake is joined in the boron-containing compound aqueous solution.
15, preparation method according to claim 9 is characterized in that, wherein the control temperature is 30 ℃-90 ℃ in the step (4).
16, preparation method according to claim 9 is characterized in that, wherein the control temperature is 40 ℃-70 ℃ in the step (4).
17, preparation method according to claim 9 is characterized in that, baking temperature is 110 ℃-130 ℃ in the described step (5), and be 12h-24h drying time.
Priority Applications (1)
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