CN101376830B - Hydrotreating catalyst carrier and preparation thereof - Google Patents
Hydrotreating catalyst carrier and preparation thereof Download PDFInfo
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Abstract
The invention discloses a hydrotreatment catalyst carrier and a preparation method thereof. The carrier contains alumina fibers and an accessory ingredient of phosphorus; wherein, the accessory ingredient of phosphorus is partially or completely led in the form of aluminum dihydrogen phosphate. During the preparation process, the alumina fibers and the aluminum dihydrogen phosphate are added in the catalyst, thus being capable of improving the mechanical intensity and the wear resistance of the carrier, improving the stability of the catalyst, prolonging the service life of the catalyst and reducing the product cost. When the catalyst is used as the carrier of a boiling bed hydrotreatment catalyst for treating heavy fractions, the impure atoms like nitrogen, sulfur in the oil products can be removed to the largest extent; the contents of olefin and aromatic hydrocarbon can be reduced.
Description
Technical field
The present invention relates to a kind of carrier of hydrogenating catalyst and preparation method thereof, be specially adapted to boiling bed hydrogenation treatment catalyst carrier of heavy distillate hydrogenation and preparation method thereof.
Background technology
Because sulphur, nitrogen content are generally more than 0.5wt% in the heavy distillate; Also contain a certain amount of oxygen and more mechanical impurity; If untimelyly carry out pre-treatment, very easily generate and be unfavorable for subsequent transportation and substances processed, therefore to adopt the method for hydrogenation that heavy distillate is carried out pre-treatment; Remove nitrogen and heteroatomss such as sulphur, oxygen to greatest extent, improve the stability of heavy distillate.
The technology that is generally used for the heavy distillate shortening mainly is fixed bed hydrogenation technology.Fixed-bed reactor are particularly suitable for handling lighter and cleaner charging, like petroleum naphtha, intermediate oil, gas oil and common residual oil etc.The characteristics of fixed-bed reactor be operate more steady, control also be easier to.But be to use fixed-bed process hydrotreatment heavy distillate to have following several respects problem: because heavy distillate is heavier and contain more mechanical impurity, catalytic reaction condition can compare harshness; High-nitrogen stock meeting accelerator activator inactivation, the catalyzer life cycle is very short, and product property can't guarantee; The beds pressure drop is high; For satisfying product index, complicated design increases cost of investment thereby fixed bed reactor system just needs employing.And boiling bed hydrogenation technique is to make catalyzer be swelling state, and adds and eject the every day through live catalyst and keep catalyst activity.These characteristics make it can handle heavier and contain the raw material of more mechanical impurity and do not stop up bed, but at entire operation quality of production isostatic product all in the cycle, and the device production cycle is long.Simultaneously, it is more easy to control that boiling bed hydrogenation technique also has temperature of reaction, and raw material can be adjusted, and system is than advantage such as the investment of fixed bed system is low.Therefore, be a kind of good heavy distillate hydroprocessing technique with boiling bed hydrogenation technique.
Because boiling bed hydrogenation reaction self, boiling bed hydrogenation catalyst remains boiling state in reactor drum, and therefore intensity and the wear resisting property to hydrogenation catalyst has higher requirement than fixed bed hydrogenation catalyzer.At present; Boiling bed hydrogenation catalyst generally is to adopt the fixed bed hydrogenation catalyzer, and like CN1362477A and CN1458234A, this catalyzer is carrier with the refractory inorganic oxides; With group vib and/or group VIII metal is active ingredient, and each component all is to exist with fine powder sintering shape form.The intensity of this catalyzer and wear resisting property await further to improve.
Because boiling-bed catalyst is in boiling state all the time in reactor drum, the physical strength and the wear resisting property of catalyzer there is higher requirement.And boiling bed hydrogenation treatment catalyst mainly is made up of reactive metal and carrier, and its intensity and wear resisting property depend primarily on carrier.
USP5; 308; 472 disclose a kind of liquid bed mild hydrocracking catalyst for reaction carrier that is used for, and mainly are made up of porous alumina or siliceous aluminum oxide, acidifying dealuminzation Y molecular sieve, and the catalyzer of being processed by pickling process has following pore size distribution: promptly wherein be lower than 40% total pore volume and be present in the hole that diameter is lower than 10nm; At least 25%～50% total pore volume is present in the hole of diameter 10～16nm; Be present in the hole of diameter greater than 16nm with 25%～50% total pore volume, 15%～40% total pore volume is present in the hole of diameter greater than 25nm, and the total pore volume less than 10% is present in the hole of big bore dia greater than 150nm.In this carrier owing to contain the dealuminzation Y molecular sieve; Lytic activity is high on the one hand; Be difficult to guarantee hydrogenation oil property and product yield, on the other hand, the ratio that accounts for total pore volume owing to macropore in the carrier is very high; But do not propose to increase the method for support strength, so support strength and wear resistance still await further raising.
The disclosed carrier of hydrogenating catalyst that can be used for boiling bed hydrogenation of Chinese patent CN1341144A comprises at least 3.5wt% silicon-dioxide (by calculated), with catalyst prepared following pore size distribution is arranged: promptly 30%～80% the pore volume pore volume that is present in the hole neutralization at least 5% of diameter 10-20nm is present in the hole that diameter is higher than 100nm.This catalyzer is used to handle at least that the boiling point of 50wt% is higher than 538 ℃ (1000 ℉) and comprises the 2wt% sulphur and the heavy hydrocarbon feeds of 5wt% Kang Laxun carbon residue at least at least, particularly in liquid bed, carries out.This carrier is owing to have bigger pore structure, and do not propose to increase the method for support strength, so support strength and wear resistance still await further raising.
Summary of the invention
The object of the present invention is to provide good carrier of hydrogenating catalyst of a kind of physical strength and wear resisting property and preparation method thereof, particularly boiling bed hydrogenation treatment catalyst carrier and preparation method thereof.
Carrier of hydrogenating catalyst of the present invention contains aluminum oxide, and all is present in the carrier with fine powder sintering shape; Contain sapphire whisker in the said carrier; Content in carrier is 3wt%～10wt%, contains auxiliary agent phosphorus in the described carrier, and the content in carrier is 1wt%～5wt%.
Auxiliary agent phosphorus in the described support of the catalyst is partly or entirely introduced in the carrier with the form of aluminium dihydrogen phosphate.
Described sapphire whisker: length is 4～500 microns, preferred 4～200 microns, be preferably 10～80 microns, and diameter is 3～100 microns, preferred 3～50 microns, the content in support of the catalyst is preferably 3wt%～8wt%.
Described sapphire whisker is preferably selected the active oxidation aluminum fiber for use, its specific surface 120～280m
2/ g, pore volume are 0.01～0.20ml/g.
Except sapphire whisker, other components all are present in the catalyzer with fine powder sintering shape among the present invention.The aluminum oxide that exists with fine powder sintering shape is referred to as aluminum oxide, is referred to as sapphire whisker with the fibrous aluminum oxide that exists.
In the support of the catalyst according to the invention, described aluminum oxide preferably adopts magnesium-modified aluminum oxide, and auxiliary agent magnesium is 2wt%～7wt% in the content of oxide compound in modified aluminas, is preferably 2wt%～6wt.The content of magnesium-modified aluminum oxide in carrier is 10wt%-96wt%, is preferably 30wt%-90wt%.
Also can contain nano silicon in the carrier of the present invention, the content in carrier is 0～15t%, is preferably 2.5wt%～10wt%, is preferably 5wt%-10wt%.The median size of said nano silicon is 10～100nm.
The specific surface area of the preferred catalyst carrier for hydrgenating of the present invention is 260～360m
2/ g, pore volume are 0.45～0.70ml/g, and average pore diameter is 8nm～10nm and following pore size distribution: promptly diameter accounts for 70%～80% of total pore volume at the pore volume of 4-10nm, and infrared acidity is 0.35～0.55mmol/g.
Also can contain other refractory inorganic oxides in the support of the catalyst of the present invention, such as being selected from titanium oxide, zirconium white and the clay one or more.
Also can contain the conventional auxiliary agent that ordinary method adds in the support of the catalyst of the present invention, such as phosphorus, boron, zirconium, lanthanum etc.Wherein, phosphorus can also conventional phosphoric acid be introduced phosphorus except adding with the aluminium dihydrogen phosphate form described in the present invention, but the total amount of wanting phosphorus in the control catalyst carrier is below 5wt%.
The specific surface area of product of the present invention and pore volume are to adopt ASAP2400 type low temperature n2 absorption apparatus, calculate according to BET formula.Acid amount and acid matter adopt IR to record, and the sorbent material that uses is pyridine.The median size of nanoparticle is that ESEM records.
The preparation method of carrier of hydrogenating catalyst of the present invention comprises following process:
(1). aluminum oxide, selectivity add nano-silica powder end, sapphire whisker, tackiness agent and peptizing agent solution and mix, and mix and pinch into paste, extruded moulding;
(2). with above-mentioned forming composition,,, obtain support of the catalyst at 350～700 ℃ of roasting 1-12 hours 100～150 ℃ of dryings 0.5～24 hour.
In the inventive method, aluminium dihydrogen phosphate can adopt following at least a kind of method to add: (1) prepares in the process at aluminum oxide and adds; (2) after aluminium dihydrogen phosphate and aluminum oxide or nano-silica powder end mix, mix with rest materials again; (3) aluminium dihydrogen phosphate add mix in the tackiness agent after, mix with rest materials again.
Aluminum oxide used among the present invention preferably adopts magnesium-modified aluminum oxide, and its preparation process is following:
A, with alum liquor and the sodium aluminate solution of preparation under agitation condition and flow and add in the glue jar, controlled temperature is at 50～65 ℃, pH value is controlled at 7.0～8.5;
Behind B, the glued bundle of one-tenth, under agitation condition, wore out 0.5～1 hour;
C, aging back feed liquid are filtered making beating and are washed to negatively charged ion/Al
2O
3<2.0wt%.
D, the filter cake that step C is obtained are pulled an oar, and water-soluble magnesium-containing compound is made into the aqueous solution, add then in the above-mentioned slurries, stir 0.5～1 hour, filter, after the drying magnesium-modified aluminum oxide of the present invention.
In the inventive method, aluminium dihydrogen phosphate can add in step D.
Wherein sapphire whisker can adopt following adding method: (1) prepares introducing sapphire whisker powder in the process at aluminum oxide or modified aluminas, prepares such as magnesium-modified aluminum oxide and when pulling an oar or add the magnesium auxiliary agent, adds the sapphire whisker powder in the process; (2) after sapphire whisker and aluminum oxide or nano-silica powder end mix, mix with rest materials again; (3) the sapphire whisker powder add mix in the tackiness agent after, mix with rest materials again.
Described water-soluble magnesium-containing compound is one or more in magnesium nitrate, magnesium chloride, the sal epsom.
Catalyst carrier for hydrgenating of the present invention prepares that adoptable binder ingredients is the aperture refractory inorganic oxides in the process; Like in clay, silicon oxide, aluminum oxide, sial, zirconium white and the titanium oxide-Natural manganese dioxide one or more; Be preferably little porous aluminum oxide, its character is following: specific surface area 220-300m
2/ g, pore volume are 0.45-0.52ml/g.The present invention can adopt extrusion aid during extrusion in the process of preparing carriers, extrusion aid commonly used can be: one or more in sesbania powder, Hydrocerol A, oxalic acid, Mierocrystalline cellulose, starch, the polymeric surface active agent etc.Involved in the present invention to peptizing agent can be: one or more in Tai-Ace S 150, Hydrocerol A, nitric acid, acetic acid, the oxalic acid etc.
Support shapes after the described moulding can be sheet, spherical, cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei), preferably cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei).The particle diameter of carrier can be slice or the sphere of 0.8～1.2mm.
Catalyst carrier for hydrgenating of the present invention can be used for the carrier to physical strength and the demanding hydrogenation catalyst of wear resisting property; Such as boiling bed hydrogenation treatment catalyst; Can be used for handling boiling range and be 80～500 ℃ heavy distillate, be specially adapted to the hydrogenation that boiling range is 90～460 ℃ a heavy distillate.
Catalyst carrier for hydrgenating of the present invention has following advantage:
1, contains sapphire whisker in the carrier, can increase substantially carrier physical strength and wear resisting property, thereby improve the physical strength and the wear resisting property of catalyzer, prolong the work-ing life of catalyzer, reduced production cost.Especially adopt the active oxidation aluminum fiber, when improving carrier and catalyzer physical strength and wear resisting property, improved the hydrogenation activity and the stability of catalyzer.
2, become in the glue process to add water-soluble magnesium salt at aluminum oxide among this preparation method and modify, can effectively carry out modulation the acid matter and the pore structure of support of the catalyst.
3. adopt the nanometer grade silica powder, can make the hole wall of support of the catalyst thin and closely knit, under the prerequisite that has improved support of the catalyst pore volume, specific surface area, also can improve the physical strength and the wear resisting property of support of the catalyst.
4. add aluminium dihydrogen phosphate in this method,, therefore stronger adhesive effect is arranged, can effectively improve the physical strength of carrier and catalyzer because aluminium dihydrogen phosphate has more oh group.
Simultaneously; Because aluminium dihydrogen phosphate contains 6 hydroxyls, be easy to form complex compound with hydrogenation active metals, not only help the loading of reactive metal on carrier; But also through improving the interaction of carrier and reactive metal, thereby improve activity of such catalysts with the complexing action of metal.
Embodiment
The characteristics of support of the catalyst of the present invention are described through specific embodiment below.
Embodiment 1
The preparation of modified aluminas M-1
A, with concentration for containing 160gAl
2O
3The NaAlO of/L
2Solution (causticity is than 1.25-1.5) and concentration 40gAl
2O
3The Al of/L
2(SO
4)
3Solution under agitation condition and stream join 1L is housed at the bottom of in the one-tenth adhesive dispenser of water, controlled temperature is at 60 ℃, pH value 8.5.
Behind B, the glued bundle of one-tenth, under agitation condition, wore out 0.5-1 hour.
C, aging back feed liquid are filtered making beating washing four times, and the ratio of water and filter cake is 30:1.
D, get 30g magnesium nitrate (Mg (NO
3)
26H
2O) adding distil water dissolving is diluted to 250ml with volumetric flask, is made into Mg-bearing water solution; Pull an oar in the slurries with the magnesium nitrate aqueous solution adding step C gained for preparing, stirred 0.8 hour, get the magnesium aluminum oxide M-1 that contains of the present invention after filtration, the drying, its physico-chemical property is seen table 1.
Embodiment 2
The preparation of modified aluminas M-2
A, with concentration for containing 160g Al
2O
3The NaAlO of/L
2Solution (causticity mol ratio 1.25-1.5) and concentration 40g Al
2O
3The Al of/L
2(SO
4)
3Solution under agitation condition and stream join 1L is housed at the bottom of in the one-tenth adhesive dispenser of water, controlled temperature is at 60 ℃, pH value 8.5.
Behind B, the glued bundle of one-tenth, under agitation condition, wore out 0.5-1 hour.
C, aging back feed liquid are filtered making beating washing four times, and the ratio of water and filter cake is 30:1.
D, get 84g magnesium chloride Mg Cl
2The adding distil water dissolving is diluted to 250ml with volumetric flask, is made into Mg-bearing water solution; Pull an oar in the slurries with the magnesium nitrate aqueous solution adding step C gained for preparing, stirred 0.5 hour, get the magnesium aluminum oxide M-2 that contains of the present invention after filtration, the drying, its physico-chemical property is seen table 1.
Table 1 sample physico-chemical property
| The embodiment numbering | 1 | 2 |
| Sample number into spectrum | M-1 | M-2 |
| MgO，wt％ | 3.1 | 1.7 |
| Specific surface area, m 2/g | 402 | 411 |
| Pore volume, ml/g | 1.02 | 1.07 |
| Infrared acidity, mmol/g | 0.39 | 0.44 |
Embodiment 3
The preparation of carrier of hydrogenating catalyst D-1 of the present invention.
With 203.6 gram M-1,21 gram sapphire whisker powder (30 microns of length, 6 microns of diameters, specific surface 183m
2/ g, pore volume 0.08ml/g), 22.6 gram nano silicons (chemical industry ltd in Tianjin produce the pure nano silicon of branch) put into rolling machine with tackiness agent (butt 30wt%, sour al mole ratio are 0.3) and 48g aluminium dihydrogen phosphate (colourless transparent liquid) that 217 gram SB powder (pore volume 0.454ml/g, specific surface area 258m2/g) add peptizations acid preparation; Grind to squeezing paste; Extrusion, 110 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours; Make support of the catalyst D-1, its physico-chemical property is seen table 2.
Embodiment 4
The preparation of catalyst carrier for hydrgenating D-2 of the present invention.
With 145 gram M-2 and 21 gram sapphire whisker (50 microns of length, 10 microns of diameters, specific surface 150m
2/ g, pore volume 0.18ml/g), 17.4 gram nano silicon (the pure nano silicon of branch that chemical industry ltd in Tianjin produces, median sizes<100nm) restrain by SB powder (pore volume 0.454mlg, specific surface area 258m with 161
2/ g) prepare tackiness agent (butt 30wt%, sour al mole ratio are 0.3) and 30g aluminium dihydrogen phosphate (with embodiment 3) with peptization acid, said mixture is put into rolling machine; Grind to squeezing paste; Extrusion, 110 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours; Make support of the catalyst D-2, its physico-chemical property is seen table 2.
Embodiment 5
The preparation of catalyst carrier for hydrgenating D-3 of the present invention.
Comparing with embodiment 3, is to change the add-on of nano silicon into 33.5 grams by 22.6 grams, and the charging capacity of other each material and operational condition are all identical with embodiment 3, and promptly cost is routine.
Embodiment 6
The preparation of catalyst carrier for hydrgenating D-4 of the present invention.
Compare with embodiment 4, change the add-on of sapphire whisker into 15.3 grams by 21 grams, the charging capacity of other each material and operational condition are all identical with embodiment 4, and promptly cost is routine.
Embodiment 7
The preparation of catalyst carrier for hydrgenating D-5 of the present invention.
Compare with embodiment 3, change the add-on of aluminium dihydrogen phosphate into 72 grams by 48 grams, the charging capacity of other each material and operational condition are all identical with embodiment 3, and promptly cost is routine.
Comparative example-1
This example is the preparation of reference catalyst carrier J-1.Method is basic identical with embodiment 3 with composition, only removes sapphire whisker.The support of the catalyst physico-chemical property is seen table 2.
Comparative example-2
This example is the preparation of reference catalyst carrier J-2.Method is basic identical with embodiment 3 with composition, only removes aluminium dihydrogen phosphate.The support of the catalyst physico-chemical property is seen table 2.
Comparative example-3
Table 2 support of the catalyst physico-chemical property
In order to further specify the effect of carrier of the present invention, with the supported carrier hydrogenation active metals, be prepared into catalyst A and catalyst B, be used for the boiling bed hydrogenation treating processes of heavy distillate.
The preparation of Mo, Ni, P dipping solution S-1
Get the technical grade molybdenum oxide respectively and (contain MoO
399wt%) 280g, basic nickel carbonate 110g, phosphoric acid (contain H
3PO
485wt%) 30ml and deionized water are configured to 960mlMo-Ni-P dipping solution, MoO
3Content is 24.6g/100ml, and NiO content is 4.53g/100ml, and P content is the solution of 1.19g/100ml.
Embodiment 8
This example is the preparation of catalyst A.
With the above-mentioned preparation Mo of carrier D-1 usefulness, Ni, P dipping solution S-1 dipping 2 hours, 110 ℃ of dryings 4 hours, 500 ℃ of roastings 3 hours make catalyst A.In the catalyzer of gained, the content of NiO is 3.21wt%, MO
3Content be 17.4wt%, its character is following: specific surface is 232m
2/ g, pore volume are 0.365ml/g.
Embodiment 9
This example is the preparation of reference catalyst B.
Method is basic identical with embodiment 8 with composition, just removes the sapphire whisker powder, and in the catalyst B of gained, the content of NiO is 3.01wt%, MO
3Content be 17.5wt%, its character is following: specific surface is 184m
2/ g, pore volume are 0.347ml/g.
Embodiment 10
This example is the preparation of reference catalyst D.
Method is basic identical with embodiment 8 with composition, only removes aluminium dihydrogen phosphate, and among the catalyzer D of gained, the content of NiO is 3.11wt%, MO
3Content be 16.9wt%, its character is following: specific surface is 192m
2/ g, pore volume are 0.352ml/g.
Adopt the hydrogenation activity of Iranian VGO oil for raw oil evaluate catalysts A, B, D.Raw oil character is seen table 3.Be reflected on the boiling bed hydrogenation device of 3L and carry out.Reaction conditions is: 370 ℃ of temperature of reaction, hydrogen dividing potential drop 13.5MPa, liquid hourly space velocity 1.5 hours
-1, hydrogen to oil volume ratio 1350:1, the beds rate of expansion is 30%.Catalyzer is not replaced in the operation process, and 24 hours experimental result of device steady running is listed in table 4.
Table 3 raw oil character
| Project | Raw oil |
| Density, g/Dm 3 | 0.9375 |
| Boiling range, ℃ | |
| IBP/10％ | 309/438 |
| 50％/90％ | 479/514 |
| 95％/EBP | —/541 |
| Sulphur, wt% | 1.52 |
| Nitrogen, μ gg -1 | 2547 |
Table 4 evaluating catalyst result
| Numbering | Catalyst A | Catalyst B | Catalyzer D |
| Relative desulfurization degree, wt% | 100 | 96 | 92 |
| Relative denitrification percent, wt% | 98 | 94 | 93 |
Table 5 live catalyst and 24 hours rear catalyst intensity of reaction and abrasion contrast
Claims (12)
1. carrier of hydrogenating catalyst; Contain aluminum oxide, and be present in the carrier, it is characterized in that containing in the said carrier sapphire whisker and auxiliary agent phosphorus with fine powder sintering shape; Wherein sapphire whisker content is 3wt%～10wt%, and the content of auxiliary agent phosphorus is 1wt%～5wt%; Auxiliary agent phosphorus in the said carrier is partly or entirely introduced in the support of the catalyst with the form of aluminium dihydrogen phosphate; Described sapphire whisker: length is 4～500 microns, and diameter is 3～100 microns.
2. according to the described carrier of claim 1, it is characterized in that described sapphire whisker: length is 10～80 microns, and diameter is 3～50 microns.
3. according to the described carrier of claim 1, it is characterized in that the content of described sapphire whisker in support of the catalyst is 3wt%～8wt%.
4. according to the arbitrary described carrier of claim 1～3, it is characterized in that described sapphire whisker selects the active oxidation aluminum fiber for use, its specific surface 120～280m
2/ g, pore volume are 0.01～0.20ml/g.
5. according to the described carrier of claim 1, it is characterized in that described aluminum oxide adopts magnesium-modified aluminum oxide, wherein auxiliary agent magnesium is 2wt%～7wt% in the content of oxide compound in modified aluminas.
6. according to the described carrier of claim 1, it is characterized in that containing nano silicon in the described hydrotreating catalyst, the content in catalyzer is 2.5wt%～10wt%; The median size of said nano silicon is 10～100nm.
7. according to the described carrier of claim 1, it is characterized in that described catalyst carrier for hydrgenating character is following: specific surface area is 260～360m
2/ g, pore volume are 0.45～0.70ml/g, and average pore diameter is 8nm～10nm and following pore size distribution: promptly diameter accounts for 70%～80% of total pore volume at the pore volume of 4-10nm, and infrared acidity is 0.35～0.55mmol/g.
8. the preparation method of the arbitrary said carrier of hydrogenating catalyst of claim 1～7 comprises following process:
(1). aluminum oxide, selectivity add nano-silica powder end, sapphire whisker, tackiness agent and peptizing agent solution and mix, and mix and pinch into paste, extruded moulding;
(2). with above-mentioned forming composition,,, obtain support of the catalyst at 350～700 ℃ of roasting 1-12 hours 100～150 ℃ of dryings 0.5～24 hour;
Described aluminium dihydrogen phosphate adopts at least a following method: (1) prepares in the process at aluminum oxide and adds; (2) after aluminium dihydrogen phosphate and aluminum oxide or nano-silica powder end mix, mix with rest materials again; (3) aluminium dihydrogen phosphate add mix in the tackiness agent after, mix with rest materials again.
9. according to the described method of claim 8, it is characterized in that described aluminum oxide adopts magnesium-modified aluminum oxide, its preparation process is following:
A, with alum liquor and the sodium aluminate solution of preparation under agitation condition and flow and add in the glue jar, controlled temperature is at 50～65 ℃, the pH value is controlled at 7.0～8.5;
Behind B, the glued bundle of one-tenth, under agitation condition, wore out 0.5～1 hour;
C, aging back feed liquid are filtered making beating and are washed to negatively charged ion/Al
2O
3＜2.0wt%;
D, the filter cake that step C is obtained are pulled an oar, and water-soluble magnesium-containing compound is made into the aqueous solution, add then in the above-mentioned slurries, stir 0.5～1 hour, filter, after the drying magnesium-modified aluminum oxide.
10. according to the described method of claim 9, it is characterized in that described aluminium dihydrogen phosphate adds in step D.
11., it is characterized in that described aluminium dihydrogen phosphate employing method (3) adds according to the described method of claim 8.
12. according to the described method of claim 8, it is characterized in that described sapphire whisker adopts following at least a kind of method: (1) prepares introducing sapphire whisker powder in the process at aluminum oxide; (2) after sapphire whisker and aluminum oxide or nano-silica powder end mix, mix with rest materials again; (3) the sapphire whisker powder add mix in the tackiness agent after, mix with rest materials again.
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| CN102350374B (en) * | 2011-05-31 | 2013-06-12 | 常州均益新材料科技有限公司 | Catalyst carrier with run-through macropores and mesopores, catalyst and preparation method thereof |
| CN103055908A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN103055944A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of phosphorus-containing alumina carrier |
| CN103721756B (en) * | 2012-10-12 | 2015-10-28 | 上海华谊丙烯酸有限公司 | Catalyst carrier and preparation method thereof, composite oxide catalysts |
| CN107847913A (en) | 2015-07-22 | 2018-03-27 | 巴斯夫公司 | The high geometrical surface catalyst prepared is produced for vinyl acetate monomer |
| CN108187710A (en) * | 2017-12-15 | 2018-06-22 | 中国第汽车股份有限公司 | Improve the method for integral extruding type honeycomb catalyst mechanical strength |
| CN108371949A (en) * | 2018-02-07 | 2018-08-07 | 武汉凯迪工程技术研究总院有限公司 | High wear resistance alumina support and preparation method thereof |
| CN113117759B (en) * | 2019-12-31 | 2023-09-01 | 中国石油化工股份有限公司 | Protective agent and preparation method and application thereof |
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