CN1853773A - Alumina dry glue containing silicon and boron and production thereof - Google Patents
Alumina dry glue containing silicon and boron and production thereof Download PDFInfo
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- CN1853773A CN1853773A CN 200510046347 CN200510046347A CN1853773A CN 1853773 A CN1853773 A CN 1853773A CN 200510046347 CN200510046347 CN 200510046347 CN 200510046347 A CN200510046347 A CN 200510046347A CN 1853773 A CN1853773 A CN 1853773A
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Abstract
A dry alumina colloid containing Si and B is prepared through continuously forming colloid while adding Si and B assistants step by step for high and uniform dispersity of Si and B. It can be used as the carrier precursor of catalyst to improve the hydrogenation activity of catalyst, especially the hydrodenitrifying activity.
Description
Technical field
The present invention relates to alumina dry glue of a kind of siliceous and boron and preparation method thereof, particularly a kind of suitable alumina dry glue as the carrier of hydrogenating catalyst for heavy oil material 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 catalysis 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 active metal component generation strong interaction.The sintering of active metal component 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 to be carried out modification, normally its predecessor aluminium hydroxide is carried out modification, for example adopt 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 greatly, 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.
CN 1048037C discloses a kind of preparation method of alumina dry glue of siliceous and phosphorus, adopts to contain the aluminium ion salting liquid and add ammoniacal liquor and become glue, aging, filtration, washing and drying steps preparation, and silicon is to adopt substep to become the glue method to add with phosphorus.The dried glue of this modified aluminas is that to adopt silicon and phosphorus be auxiliary agent, is that the hydrogenation activity of the catalyst of carrier awaits further to improve with it.
CN 1082387C discloses a kind of mesoporous aluminas gel and preparation method thereof, evenly disperses one or more to be selected from the oxide of silica, boron oxide, phosphorous oxide in this alumina gel.The specific area of described alumina gel is 260-700m
2/ g, pore volume are 0.2-1.0cm
3/ g, average pore diameter only is 2-7nm, wherein the mol ratio of silica, boron oxide or phosphorous oxide and aluminium oxide is 0-4.0.This alumina gel adopts alfol compound and silicon alcohol compound and the preparation of alkaline solution Hydrolyze method, 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 alumina dry glue of a kind of siliceous and boron and preparation method thereof.The alumina dry glue of the siliceous and boron of the present invention is especially suitable for use as catalyst for hydro-processing heavy distillate, especially the carrier material of hydrodenitrogenation catalyst.
The present invention is siliceous to have following character with alumina dry glue boron after high-temperature roasting: the weight with butt is benchmark, and is siliceous with SiO
2Count 1wt%-15wt%, boracic is with B
2O
3Count 2wt%-18wt%; Specific area is 350m
2/ g-500m
2/ g, pore volume are 0.8ml/g-1.3ml/g, average pore diameter 8nm-13nm.
The siliceous employing with the alumina dry glue of boron of the present invention becomes the glue method to prepare continuously, comprises the steps:
(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 the siliceous oxygen anion of metering then, 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, promptly obtain siliceous and alumina dry glue boron.
The inventive method is after aluminium oxide becomes glue, and substep is introduced silicon additive and boron additive, and following advantage is arranged:
(1), compare with kneading method, the inventive method can make two kinds of auxiliary agents all be dispersed in the surface of aluminium oxide with coprecipitation, rather than enter alumina body mutually in, thereby can give full play to the effect of auxiliary agent;
(2), simultaneously add silicon and boron additive, help improving the pore structure of aluminium oxide, the alumina dry glue of siliceous and boron is after roasting, and its specific surface and pore volume are bigger, and bore dia is big, pore distribution concentration;
(3), to adopt silicon and boron be auxiliary agent in the present invention, improves the acid amount of alumina surface, the acid that has also improved alumina surface simultaneously distributes.
(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, increased the intensity in activated centre quantity and activated centre, making with alumina dry glue of the present invention is that the catalyst that carrier material prepares has higher activity.
The present invention is siliceous and the boron alumina dry glue can be used alone as the big bore dia of various needs, suitable acid is measured and the sour catalyst carrier that distributes, also can mix catalyst carrier in varing proportions as various suitable pore size distributions and acid distribution with the aperture aluminium oxide, such as carrier of hydrogenating catalyst, especially be fit to do the carrier of hydrodenitrogenation catalyst.
The specific embodiment
The concrete preparation process of the alumina dry glue of the siliceous and boron of the present invention is as follows:
(1) adds a certain amount of deionized water at a container, under uniform temperature and stirring condition, add and contain aluminum ions acidic salt solution, these contain the solution that aluminum ions salting liquid can be aluminium chloride, aluminum sulfate or aluminum nitrate, its concentration is 2/g100ml-8g/100ml, is preferably 3g/100ml-6g/100ml (with Al
2O
3Meter), add ammoniacal liquor when adding acidic salt solution, the concentration of ammoniacal liquor 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.
Becoming glue process control pH value is 7.0-11.0, is 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, the silicon-containing compound that adds metering then, as sodium metasilicate or solution of sodium metasilicate through, concentration is 4g/100ml-10g/100ml, is preferably 5g/100ml-8g/100ml (with SiO
2Meter), continues aging 20min-240min, be preferably 30min-60min;
(3) behind aging the end, filter and wash to anion/Al
2O
3＜2.0wt% is preferably＜0.3wt%;
(4) add the boron-containing compound that measures, the control temperature is preferably 40 ℃-70 ℃ at 30 ℃-90 ℃; Stir 15min-75min, be preferably 30min-60min.Wherein said boron-containing compound can be boric acid or borate, and it can add in the following way: a, with filter cake making beating, and boron-containing compound directly adds in the slurries; B, wet cake is added in the boron-containing compound aqueous solution;
(5) filter and with filter cake at 110 ℃ of-130 ℃ of dry 12h-24h, filter cake is crushed to＜180 orders; Or, promptly obtain alumina dry glue of the present invention directly with the slurries spray-drying.
In the above-mentioned steps, the inventory of silicon and boron element is all undertaken by the content ratio in the aluminium oxide of final siliceous and boron.
The alumina dry glue that makes siliceous and boron with determination of nitrogen adsorption specific surface, pore volume, average pore diameter and pore size distribution, has following characteristics behind 500 ℃ of-700 ℃ of roasting 0.5h-10h:
Specific surface 350m
2/ g-500m
2/ g is preferably 400m
2/ g-450m
2/ g;
Pore volume 0.8ml/g-1.3ml/g is preferably 0.9ml/g-1.1ml/g;
Average pore diameter 8nm-13nm; Be preferably 8nm-11nm;
Infrared acidity ≮ 0.700mmol/g is preferably 0.700mmol/g-0.960mmolg/, is preferably 0.700mmol/g-0.930mmol/g.
In its chemical composition, siliceous with SiO
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.
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 solution 40ml that contains the 4.8g sodium metasilicate, and system continues aging 75min under above-mentioned pH value and temperature conditions.Filter and wash to Cl
-/ Al
2O
3＜0.3wt%.
After filter cake added water purification making beating, add 43g boric acid, the control temperature is at 50 ℃, and charging 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 the dried glue L-1 of modified aluminas.
Embodiment 2
In a 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 25min under above-mentioned pH value and temperature conditions, adds the solution 100ml that contains the 15.3g sodium metasilicate.System continues aging 75min under above-mentioned pH value and temperature conditions, filter and wash to SO
4 2-/ Al
2O
3＜1.5wt%.
The boric acid of 34.6g is dissolved in the water purification, adds the wet cake making beating then, the control temperature is at 55 ℃, and the time is 40min.
Filter and with filter cake behind 130 ℃ of dry 8h, it is crushed to granularity accounts for more than the 95wt% less than 180 orders, obtain the dried glue L-2 of modified aluminas.
Embodiment 3
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 8.5, temperature is 64 ℃, the reinforced time is 120min.
After stopping to feed in raw material, system is aging 60min under above-mentioned pH value and temperature conditions, adds the solution 245ml that contains the 32g sodium metasilicate.System continues aging 45min under above-mentioned pH value and temperature conditions, filtration washing is to SO
4 2-/ Al
2O
3＜1.5w%.
After filter cake added water purification making beating, add the boric acid of 30g, the control temperature is at 45 ℃, and the time is 40min.
Filter cake is crushed to granularity with it accounts for more than the 95w% behind 130 ℃ of dry 8h, obtain the dried glue L-3 of modified aluminas less than 180 orders.
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 solution 150ml 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%.
The boric acid of 58.6g is dissolved in the water purification, adds the wet cake making beating, the control temperature is 50 ℃, and the time is 30min.
Filter and with filter cake behind 130 ℃ of dry 8h, it is crushed to granularity accounts for more than the 95wt% less than 180 orders, obtain the dried glue L-4 of modified aluminas.
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 24g sodium metasilicate.System continues aging 75min under above-mentioned pH value and temperature conditions, filter and wash to Cl
-/ Al
2O
3＜0.3wt%.
After filter cake added water purification making beating, add the boric acid of 14.5g, the control temperature is at 65 ℃, and the time is 40min.
Filter and with filter cake behind 130 ℃ of dry 8h, it is crushed to granularity accounts for more than the 95wt% less than 180 orders, the dried glue L-5 of modified aluminas.
The alumina dry glue that embodiment 1-5 is made is analyzed its character behind 520 ℃ of roasting 4h, the results are shown in Table 1.
The character of table 1 modified aluminas
| The aluminium oxide numbering | L-1 | L-2 | L-3 | L-4 | L-5 | L-A |
| SiO 2，wt％ | 1.98 | 5.2 | 7.9 | 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 6
Get the alumina dry glue 130g of embodiment 3 preparation, sneak into the SB alumina powder prepared adhesive of 122g nitric acid peptization, mix pinch 20min after, roll 10min again, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4, behind 130 ℃ of dry 8h, roasting 4h under 520 ℃ of conditions.
Get activation back 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 it behind 130 ℃ of dry 8h, in under 500 ℃ of conditions, activating 4h, get 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 the siliceous and dried glue of phosphorus oxidation aluminium: the 30g boric acid among the embodiment 3 is replaced with 13.4g phosphoric acid, and all the other steps are with embodiment 3, the dried glue L-A of modified aluminas;
(2) preparation of reference catalyst C-A: the 130g alumina dry glue among the embodiment 6 is replaced with the siliceous and dried glue L-A of phosphorus oxidation aluminium of 130g, and all the other steps get catalyst C-A with embodiment 6.
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 by 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, employing the present invention is siliceous makes the reference catalyst of the hydrodenitrogenationactivity activity of catalyst significantly better than the alumina dry glue preparation of siliceous and phosphorus with alumina dry glue boron.
Claims (14)
1, a kind of alumina dry glue of siliceous and boron, it is characterized in that described alumina dry glue has following character after roasting: the weight with butt is benchmark, and is siliceous with SiO
2Count 1wt%-15wt%, boracic is with B
2O
3Count 2wt%-18wt%, pore volume is 0.8ml/g-1.3ml/g, specific surface 350m
2/ g-500m
2/ g, average pore diameter 8nm-13nm.
2, alumina dry glue according to claim 1 is characterized in that, is benchmark with the weight of butt, and is siliceous with SiO
2Count 1wt%-13wt%, boracic is with B
2O
3Count 5wt%-15wt%.
3, alumina dry glue according to claim 1 is characterized in that, its specific surface is 400m after roasting
2/ g-450m
2/ g, average pore diameter 8nm-11nm.
According to the arbitrary described alumina dry glue of claim 1-3, it is characterized in that 4, described alumina dry glue is after roasting, its infrared acidity is 0.700mmol/g-0.960mmol/g.
According to the arbitrary described alumina dry glue of claim 1-3, it is characterized in that 5, described alumina dry glue is after roasting, its infrared acidity is 0.700mmol/g-0.930mmol/g.
6, the preparation method of the arbitrary described alumina dry glue of a kind of claim 1-5 comprises the steps:
(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 the siliceous oxygen anion of metering then, 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, promptly obtain siliceous and alumina dry glue boron.
7, preparation method according to claim 6 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 2.0g/100ml-8.0g/100ml, described alkaline solution is an ammoniacal liquor, and its concentration is with NH
3Count 6g/100ml-15g/100ml.
8, preparation method according to claim 6 is characterized in that, acidic salt solution is an aluminum sulfate solution described in the step (1), and described alkaline solution is a sodium aluminate solution, and its concentration is with Al
2O
3Count 10.0g/100ml-25.0g/100ml.
9, preparation method according to claim 6 is characterized in that, wherein the control pH value is 7.5-9.5 in the step (1), and temperature is 30 ℃-90 ℃, and charging time is controlled at 30min-240min.
10, preparation method according to claim 6 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 4.0g/100ml-10.0g/100ml.
11, preparation method according to claim 6 is characterized in that, boron-containing compound is boric acid or borate described in the step (4), and its adding mode is: a, with filter cake making beating, and boron-containing compound directly adds in the slurries; Or b, wet cake is added in the boron-containing compound aqueous solution.
12, preparation method according to claim 6 is characterized in that, wherein the control temperature is 30 ℃-90 ℃ in the step (4).
13, preparation method according to claim 6 is characterized in that, wherein the control temperature is 40 ℃-70 ℃ in the step (4).
14, preparation method according to claim 6 is characterized in that, baking temperature is 110 ℃-130 ℃ in the described step (5), and be 12h-24h drying time.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451672A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Aluminum hydroxide dry glue containing silicon and boron and preparation method thereof |
| CN102039116B (en) * | 2009-10-16 | 2013-08-28 | 中国石油化工股份有限公司 | Boron-containing aluminum hydroxide solid elastomer and preparation method thereof |
| CN105102123A (en) * | 2013-04-03 | 2015-11-25 | 日挥触媒化成株式会社 | Support for hydrotreating catalyst, method for producing same, hydrotreating catalyst and method for producing same |
| CN105709851A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | preparation method of aluminium oxide-based carrier containing silicon and boron |
| CN105709788A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
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| GB2101005B (en) * | 1981-06-02 | 1984-09-05 | Asia Oil Co Ltd | Hydrogenation catalyst |
| US5223472A (en) * | 1992-04-14 | 1993-06-29 | Union Oil Company Of California | Demetallation catalyst |
| CN1030395C (en) * | 1992-11-05 | 1995-11-29 | 中国石油化工总公司抚顺石油化工研究院 | Heavy oil hydrodenitrogenation catalyst |
| CN1048651C (en) * | 1994-06-29 | 2000-01-26 | 中国石油化工总公司抚顺石油化工研究院 | Process for preparation of hydrogenating catalyst carrier |
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| CN102451672A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Aluminum hydroxide dry glue containing silicon and boron and preparation method thereof |
| CN102451672B (en) * | 2010-10-15 | 2013-11-20 | 中国石油化工股份有限公司 | Aluminum hydroxide dry glue containing silicon and boron and preparation method thereof |
| CN105102123A (en) * | 2013-04-03 | 2015-11-25 | 日挥触媒化成株式会社 | Support for hydrotreating catalyst, method for producing same, hydrotreating catalyst and method for producing same |
| CN105102123B (en) * | 2013-04-03 | 2018-04-03 | 日挥触媒化成株式会社 | Hydrotreating catalyst carrier, its manufacture method, hydrotreating catalyst and its manufacture method |
| CN105709851A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | preparation method of aluminium oxide-based carrier containing silicon and boron |
| CN105709788A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN105709851B (en) * | 2014-12-02 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of preparation method of siliceous and boron alumina-based supports |
| CN105709788B (en) * | 2014-12-02 | 2018-11-06 | 中国石油化工股份有限公司 | The preparation method of hydrotreating catalyst |
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