CN101085935A - Coal liquefied oil boiling bed hydrogenation catalyst carrier and preparation method thereof - Google Patents
Coal liquefied oil boiling bed hydrogenation catalyst carrier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst carrier for coal liquification oil hydrogenation on boiling bed and the preparation method. Besides normal hydrogenation catalyst carrier component, the catalyst aslo contains aluminium oxide fiber, the content of which in carrier is 3- 10wt%. The mechanical strength and wearing resistance of catalyst are strong, which increases carrier stability and life length and reduces production cost. The active aluminium oxide utilization can increase the hydrogeneration activity and stability.
Description
Technical field
The present invention relates to a kind of boiling bed hydrogenation catalyst carrier and preparation method thereof, particularly ebullated bed liquefied coal coil catalyst carrier for hydrgenating and preparation method thereof.
Background technology
The technology that is generally used for the liquefied coal coil shortening mainly is fixed bed hydrogenation technology.Fixed-bed reactor are particularly suitable for handling lighter and cleaner charging, as 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 liquefied coal coil to have following several respects problem: because liquefied coal coil 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; Beds pressure drop height; 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 by 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.Boiling bed hydrogenation technique is a kind of good liquefied coal coil hydroprocessing technique.
Because ebullating bed reactor self, boiling-bed catalyst remains boiling state in reactor, and therefore intensity and the wear resisting property to catalyzer had higher requirement.At present, the hydrogenation catalyst that boiling bed hydrogenation technique adopted generally is to be carrier with the refractory inorganic oxides, is active ingredient with group vib and/or group VIII metal, 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.
CN 1362477A discloses a kind of boiling bed hydrogenation method for modifying of heavy, inferior feedstock oil.This method is in an ebullated bed reactor a plurality of conversion zones to be set, each reacting section catalyst grading loading, promptly from the reactor bottom to the top, the catalyzer aperture of each conversion zone filling is descending, specific surface area is ascending, active ascending, the ratio of expansion of each reacting section catalyst is also ascending.CN 1458234A discloses a kind of residual oil boiling bed hydrogenation reaction method, the boiling bed hydrogenation reaction is the reaction of tandem formula boiling bed hydrogenation, in a reactor, be divided into plural ebullating bed reactor section, residual oil raw material and hydrogen are from bottom to up continuously by each section ebullating bed reactor section, the catalyst function that each ebullating bed reactor section is used is arranged by hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification and transforming sequence from bottom to up, and each conversion zone uses wherein one to two kind of catalyzer.Above-mentioned two pieces of Chinese patents are about the boiling bed hydrogenation catalyst grading loading, and used hydrogenation catalyst is conventional hydrogenation catalyst, catalyst strength and wear resistance aspect is not made improvements.
Owing to contain a large amount of alkene in the liquefied coal coil, nitrogen content is generally more than 0.5wt%, also contain a large amount of oxygen,, very easily generate and be unfavorable for subsequent transportation and substances processed if untimelyly carry out pre-treatment, therefore to adopt the method for hydrogenation that liquefied coal coil is carried out pre-treatment, alkene in the saturated liquefied coal coil removes oxygen, removes heteroatomss such as nitrogen and sulphur to greatest extent, improve the stability of liquefied coal coil, so claim that also this hydrogenation process is stable hydrogenation.Because liquefied coal coil was as hydrogen supply agent after most of coal liquefaction crafts needed a certain amount of hydrogenation, the technology that has will be as the independent hydrogenation of the liquefied coal coil of hydrogen supply agent, all the other liquefied coal coils go out coal liquification device as product, the technology that has is with the whole hydrofinings of liquefied coal coil, improve stability, produce hydrogen supply agent simultaneously.
USP 5,308, and 472 disclose a kind of employed dealuminzation Y molecular sieve catalyzer that contains of ebullated bed mild hydrocracking reaction that can be used for.This catalyzer can be used for hydrodemetallation (HDM) (HDM), hydrogenating desulfurization (HDS) and the hydrocracking (HC) of heavy feed stock (as residual oil), improves the transformation efficiency of boiling point at 1000 heavy hydrocarbons, increases the intermediate oil yield simultaneously.Described catalyzer contains the VIII family metal oxide of 1.0～6.0wt%, the molybdenum oxide of 12.0～25.0wt% and the phosphorous oxides of 0.1～5.0wt%, is supported on porous alumina or siliceous aluminum oxide and the hydrogen shape acidifying dealuminzation Y molecular sieve.The specific surface area of described catalyzer is at 200～300m
2/ g, total pore volume 0.55～0.75ml/g, with 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 bore dia greater than 150nm.This catalyzer is owing to contain the dealuminzation Y molecular sieve, one side lytic activity height, be difficult to guarantee hydrogenation solvent oil character and product yield, on the other hand, a large amount of oxygen and hydrogen reaction are produced water in the liquefied coal coil, and the steam partial pressure of reactive system is raise, and molecular sieve reaches ruined phenomenons such as caving in can appear in bigger hole, thereby the loss pore structure influences activity of such catalysts and stability and catalyzer work-ing life.And in the catalyzer macropore to account for the ratio of total pore volume very high, be not suitable for handling liquefied coal coil, catalyst strength and wear resistance still await further raising.
Chinese patent CN 1341144A discloses a kind of hydrotreating catalyst that can be used for boiling bed hydrogenation.Described catalyzer relates to a kind of hydrotreating catalyst that is loaded in the alkaline components (pressing oxide compound calculating) of the group VIII non-noble metal hydrogenation metal component that comprises 7～20wt% group vib hydrogenation metal component (press trioxide calculate), 0.5～6wt% (press oxide compound calculates) on the carrier and 0.1～2wt%.Wherein said carrier comprises 3.5wt% silicon-dioxide (by calculated) at least, and this catalyzer has surface-area 150m at least
2/ g, total pore volume be 0.55ml/g and following pore size distribution at least: 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 preferably has in diameter is lower than the hole of 10nm and is lower than 25% total pore volume.This catalyzer is used to handle at least, and 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 carry out in ebullated bed, this catalyzer has good contaminant removal and low mud forms ability.This catalyzer is owing to have bigger pore structure, and do not propose to increase the method for catalyst strength, so catalyst strength and wear resistance still await further raising.Contain Alkali-Metal Na in the catalyzer, can the hydrogenation activity and the stability of catalyzer be exerted an influence.
Summary of the invention
The object of the present invention is to provide that a kind of physical strength and wear resisting property are good, the more rational coal liquefied oil boiling bed hydrogenation treatment catalyst carrier and preparation method thereof of pore structure.
Boiling bed hydrogenation treatment catalyst carrier of the present invention, its component comprises aluminum oxide and/or modified aluminas, and be present in the carrier with fine powder sintering shape, its characteristics are to contain sapphire whisker in the described carrier, 4～500 microns of its length, preferred length 4-200 micron is preferably 10～80 microns, 4～100 microns of diameters, preferred diameter 4-50 micron.The content of described sapphire whisker in carrier is 3wt%～10wt%, 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 0.01～0.2ml/g.
In the carrier of the present invention except containing sapphire whisker, remaining component can be identical with the conventional catalyst carrier with content, preferably contain modified aluminas, described modified aluminas is phosphorus and/or boron modified aluminas, wherein auxiliary agent phosphorus is 2wt%～7wt% in the content of oxide compound in modified aluminas, be preferably 2wt%～6wt%, boron is 2wt%～7wt% in the content of oxide compound in modified aluminas, is preferably 2wt%～6wt%.The content of this modified aluminas in carrier is 10wt%～97wt%.
Also can contain nano silicon in the preferred catalyst carrier for hydrgenating of the present invention, the content in carrier is 0～10wt%, is preferably 2.5wt%～10wt%, is preferably 5wt%-10wt%.The median size of described nano silicon is 10～100nm.
Also can contain other refractory inorganic oxides in the support of the catalyst of the present invention, such as being selected from aluminum oxide, silicon oxide, magnesium oxide, aluminum oxide one magnesium oxide, silica-alumina, silicon oxide-magnesium oxide, titanium oxide-magnesium oxide, zirconium white, silica-alumina-magnesium oxide and the clay one or more.
The specific surface area of the preferred catalyst carrier for hydrgenating of the present invention is 240～360m
2/ g, pore volume are 0.45～0.65ml/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.
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 infrared spectrometer to record, and the sorbent material that uses is pyridine.The median size of nanoparticle is the mean diameter that scanning electron microscope records.
The preparation method of catalyst carrier for hydrgenating of the present invention comprises following process:
(1). aluminum oxide and/or modified aluminas, 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;
The preparation method of used phosphorus of catalyst carrier for hydrgenating of the present invention and/or boron additive modified aluminas is as follows:
Get the material that contains γ one aluminum oxide precursor, get its filter cake, making beating is warming up to 50～90 ℃, preferred 65～75 ℃, add content of phosphorus-containing compound and/or boron-containing compound, and stirred 30～90 minutes at 50～90 ℃, filter, drying makes modified aluminas.The material of the described γ of containing one aluminum oxide precursor can be carborization, aluminum nitrate method, alchlor process, Tai-Ace S 150 method synthetic γ one aluminum oxide precursor, preferably the aluminum oxide precursor of Carbonization Preparation.
Wherein the sapphire whisker powder can adopt following manner to add: (1) adds the sapphire whisker powder in aluminum oxide or modified aluminas preparation process, such as adding in making beating or when adding phosphorus with/boron additive in phosphorus and/or boron modified aluminas preparation process; (2) after sapphire whisker powder and aluminum oxide or modified aluminas 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.
Adoptable binder ingredients is the aperture refractory inorganic oxides in the catalyst carrier for hydrgenating preparation process of the present invention, as in clay, silicon oxide, aluminum oxide, sial, zirconium white and the titanium oxide-magnesium oxide one or more, be preferably little porous aluminum oxide, its character is as follows: 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 support of the catalyst preparation, extrusion aid commonly used can be: one or more in sesbania powder, citric acid, 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, citric acid, 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 diameter of carrier can be slice or the sphere of 0.8～1.2mm.
Adopt the method for dipping to carry active metal component in the boiling bed hydrogenation catalyst carrier of the present invention, be prepared into boiling bed hydrogenation catalyst, can be used for handling the hydrogenation that boiling range is 80～500 ℃ liquefied coal coil last running, being specially adapted to boiling range is the hydrogenation of 90～460 ℃ liquefied coal coil last running.
Boiling bed hydrogenation catalyst carrier of the present invention has following advantage:
1, containing sapphire whisker in the carrier, can increase substantially the physical strength and the wear resisting property of support of the catalyst, is the stability of the catalyzer of carrier thereby improved with it, in the work-ing life of improving catalyzer simultaneously, has reduced production cost.Especially adopt the active oxidation aluminum fiber, under the prerequisite that improves catalyzer physical strength and wear resisting property, improved the hydrogenation activity and the stability of catalyzer.
2, in the material of γ one aluminum oxide precursor, add phosphate builder and carry out modification, can make high-specific surface area, pore distribution concentration, and pore structure with suitable pore size distribution, because the condition of selecting is suitable, auxiliary agent phosphorus can also play certain reaming effect, be beneficial to the diffusion of reaction mass, improve the catalyst reaction performance; And the adding of auxiliary agent boron can also be regulated the acidity of aluminum oxide powder, makes it have suitable acid matter.
3. adopt the nanometer grade silica powder, can make the hole wall of catalyzer 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.
The characteristics of support of the catalyst of the present invention are described below by specific embodiment.
Embodiment 1
The preparation of modified aluminas G-1
Get the filter cake after the aluminum oxide precursor washing of Carbonization Preparation, surveying its butt is 30wt%, gets this filter cake 1500 grams, add 2.5 liters of deionized waters, making beating is warming up to 65 ℃, stirred 1 hour, add 90 gram 85m% phosphoric acid solutions, filter filter cake, add 2.0 liters of deionized waters, making beating, be warming up to 70 ℃, and add 86 gram boric acid, and be 10gNH with concentration
3The ammonia soln of/100ml stirs pH value of solution value modulation 61 hour, and filtration was 110 ℃ of dryings 4 hours, and sample is G-1, and its physico-chemical property sees Table 1.
Embodiment 2
The preparation of modified aluminas G-2.
Get aluminum oxide precursor washing back filter cake 800 grams of Tai-Ace S 150 method preparation, butt is 30wt%, add 3 liters of deionized waters, be warming up to 85 ℃ after stirring, and add 53 gram 85wt% phosphoric acid solutions, filter filter cake, add 2.5 liters of deionized waters, making beating is warming up to 70 ℃, and add 120 gram boric acid, and be 10gNH with concentration
3The ammonia soln of/100ml stirs pH value of solution value modulation 6.5 1 hour, continues stirring 30 minutes, 110 ℃ of dryings 4 hours, and sample G-2, its physico-chemical property sees Table 1.
Table 1 sample physico-chemical property
| The embodiment numbering | 1 | 2 |
| Sample number into spectrum | G-1 | G-2 |
| P 2O 5，wt％ | 2.3 | 1.4 |
| B 2O 3，wt％ | 1.95 | 2.71 |
| Specific surface area, m 2/g | 401 | 456 |
| Pore volume, ml/g | 0.91 | 1.12 |
| Infrared acidity, mmol/g | 0.47 | 0.48 |
Embodiment 3
The preparation of boiling bed hydrogenation catalyst carrier C-1 of the present invention.
With 168 gram G-1,18 gram sapphire whisker (30 microns of length, 6 microns of diameters, specific surface 183m
2/ g, pore volume 0.08ml/g), 19 gram nano silicons (the pure nano silicon of branch that chemical industry company limited in Tianjin produces), 193.5 grams are by SB powder (pore volume 0.46ml/g, specific surface area 260m
2/ g), and by the tackiness agent (butt 30wt%, sour al mole ratio are 0.3) of above-mentioned SB powder preparation, put into rolling machine, grind to can squeezing paste, extrusion, 110 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours make support of the catalyst C-1.The support of the catalyst physico-chemical property sees Table 2.
Embodiment 4
The preparation of boiling bed hydrogenation catalyst carrier C-2 of the present invention.
With 219 gram G-2,32 gram sapphire whisker powder (50 microns of length, 10 microns of diameters, specific surface 150m
2/ g, pore volume 0.18ml/g), 236.52 grams are by SB powder (pore volume 0.46ml/g, specific surface area 260m
2/ g), and by tackiness agent (the butt 30wt% of above-mentioned SB powder preparation, the acid al mole ratio is 0.3), wherein 25.3 restrain nano silicon (the pure nano silicon of branch that chemical industry company limited in Tianjin produces, median sizes＜100nm) be added in the tackiness agent, said mixture is put into rolling machine, grind to can squeezing paste extrusion, 110 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours make support of the catalyst C-2.The support of the catalyst physico-chemical property sees Table 2.
Embodiment 5
The preparation of boiling bed hydrogenation treatment catalyst support C-3 of the present invention.
At embodiment 1, change the add-on of nano silicon into 29.7 grams by 19 grams, the charging capacity of other each material and operational condition are all identical with embodiment 3, i.e. the cost example.
Embodiment 6
The preparation of boiling bed hydrogenation treatment catalyst support C-4 of the present invention.
At embodiment 2, change the add-on of sapphire whisker powder into 16.9 grams by 32 grams, the charging capacity of other each material and operational condition are all identical with embodiment 4, i.e. the cost example.
Embodiment 7
The preparation of boiling bed hydrogenation treatment catalyst support C-5 of the present invention.
Get the filter cake after the aluminum oxide precursor washing of Carbonization Preparation, surveying its butt is 30wt%, gets this filter cake 1500 grams, add 2.5 liters of deionized waters, making beating is warming up to 65 ℃, adds 43 gram sapphire whisker powder (80 microns of length, 40 microns of diameters, specific surface 245m
2/ g, pore volume 0.14ml/g), stirred 1.5 hours, add 81 gram 85wt% phosphoric acid solutions, filter filter cake, adds 2.0 liters of deionized waters, making beating is warming up to 75 ℃, and adds 79 and restrain boric acid, and is 10gNH with concentration
3The ammonia soln of/100ml stirs pH value of solution value modulation 71 hour, and filtration obtains modified oxidized aluminium powder G-3 110 ℃ of dryings 4 hours; With 176 gram G-3,253.44 grams are by SB powder (pore volume 0.46ml/g, specific surface area 260m
2/ g), and by the tackiness agent (butt 30wt%, sour al mole ratio are 0.3) of above-mentioned SB powder preparation, put into rolling machine, grind to can squeezing paste, extrusion, 120 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours make support of the catalyst C-5.The support of the catalyst physico-chemical property sees Table 2.
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 the sapphire whisker powder.The support of the catalyst physico-chemical property sees Table 2.
Table 2 support of the catalyst physico-chemical property
| Embodiment of the invention support of the catalyst | The agent of Comparative Examples reference | |||||
| Bearer number | C-1 | C-2 | C-3 | C-4 | C-5 | J-1 |
| SiO 2，wt％ | 6.1 | 6.4 | 9.3 | 6.3 | - | 6.2 |
| Sapphire whisker, wt% | 6 | 8 | 6 | 4.3 | 4 | - |
| Specific surface area, m 2/g | 286 | 272 | 331 | 305 | 236 | 242 |
| Pore volume, ml/g | 0.50 | 0.53 | 0.57 | 0.55 | 0.53 | 0.52 |
| Average pore diameter, nm | 8.2 | 8.1 | 8.9 | 8.3 | 8.6 | 7.8 |
| Diameter accounts for total pore volume, % for the 4nm-10nm pore volume | 77.8 | 76.9 | 78.3 | 79.1 | 70.7 | 75.9 |
| Infrared acidity, mmol/g | 0.50 | 0.43 | 0.55 | 0.41 | 0.35 | 0.49 |
| Particle diameter, mm | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 |
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 liquefied coal coil.
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 the 960mlMo-Ni-P dipping solution, MoO
3Content is 24.6g/100ml, and NiO content is 4.51g/100ml, and P content is the solution of 1.12g/100ml.
Embodiment 8
This example is the preparation of catalyst A.
With the above-mentioned preparation Mo of support C-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 3.14wt%, MO
3Content be 17.2wt%, P
2O
5Content be 1.54wt%, its character is as follows: specific surface is 224m
2/ g, pore volume are 0.369ml/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 2.97wt%, MO
3Content be 17.5wt%, P
2O
5Content be 1.72wt%, its character is as follows: specific surface is 189m
2/ g, pore volume are 0.342ml/g.
Adopting coal direct liquefaction oil A is the hydrogenation activity of stock oil evaluate catalysts A, B.Stock oil character sees Table 3.Be reflected on 31 the boiling bed hydrogenation device 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 stock oil character
| Project | Stock oil |
| Density, g/cm 3 | 0.9501 |
| Boiling range, ℃ | |
| IBP/10％ | 96/218 |
| 50％/90％ | 277/386 |
| 95％/EP | -/459 |
| The bromine valency, gBr/100ml | 27.7 |
| Sulphur, wt% | 0.23 |
| Nitrogen, wt% | 0.59 |
| Oxygen, wt% | 1.6 |
Table 4 evaluating catalyst result
| Numbering | Catalyst A | Catalyst B |
| Relative desulfurization degree, wt% | 99 | 97 |
| Relative denitrification percent, wt% | 97 | 94 |
| Relative deoxidation rate, wt% | 98 | 97 |
Table 5 live catalyst and 24 hours rear catalyst intensity of reaction and abrasion contrast
| Numbering | Catalyst A | Catalyst B | |
| Intensity, N/mm | Fresh dose | 22 | 15 |
| Reaction back agent | 22 | 12 | |
| Abrasion, wt% | Fresh dose | ＜1 | 1.96 |
| Reaction back agent | 1.10 | 2.17 | |
By above-mentioned experimental result as can be seen, the reaming effect of auxiliary agent phosphorus has improved the specific surface area of aluminum oxide powder effectively, and makes carrier have the pore structure of suitable pore size distribution, and the adding of auxiliary agent boron can also be regulated the acidity of aluminum oxide powder, makes it have suitable acid matter.Support of the catalyst of the present invention be because the adding of nano silicon material can make the hole wall of catalyzer thin and closely knit, under the prerequisite that has improved catalyzer pore volume, specific surface area, raising by a relatively large margin the physical strength and the wear resisting property of support of the catalyst.And adopt the sapphire whisker powder, raising by a larger margin physical strength and the wear resisting property and the water-fast impact property of support of the catalyst, can satisfy the service requirements of ebullated bed to catalyzer.
By evaluation result as can be seen, this catalyzer is used for the liquefied coal coil stable hydrogenation under the ebullated bed operational stage, can remove heteroatomss such as sulphur in the liquefaction oil, nitrogen, oxygen to greatest extent, reduce its alkene and aromaticity content, improve the stability of product, reached the purpose of stable hydrogenation.
Claims (11)
1, a kind of coal liquefied oil boiling bed hydrogenation treatment catalyst carrier, its component comprises aluminum oxide and/or modified aluminas, and be present in the carrier with fine powder sintering shape, it is characterized in that containing sapphire whisker in the described carrier, 4～500 microns of its length, 4～100 microns of diameters, the content in carrier are 3wt%～10wt%.
2, according to the described carrier of claim 1, it is characterized in that 4～200 microns of the length of described sapphire whisker, 4～50 microns of diameters, the content in carrier are 3wt%～8wt%.
3,, it is characterized in that 10～80 microns of the length of described sapphire whisker, 4～50 microns of diameters according to the described carrier of claim 1.
4,, it is characterized in that described sapphire whisker is the active oxidation aluminum fiber, its specific surface 120～280m according to the described carrier of claim 1
2/ g, pore volume are 0.01～0.2ml/g.
5, according to the described carrier of claim 1, it is characterized in that described modified aluminas is the aluminum oxide of phosphorus and/or boron additive modification, phosphorus is 2wt%～7wt% in the content of oxide compound in modified aluminas, boron is 2wt%～7wt% in the content of oxide compound in modified aluminas, and the content of this modified aluminas in carrier is 10wt%～97wt%.
6, according to the described carrier of claim 1, it is characterized in that containing nano silicon in the described carrier, the content in carrier is 2.5wt%～10wt%.
7, according to the described carrier of claim 1, it is characterized in that the median size of described nano silicon is 10～100nm, the content in carrier is 5wt%～10wt%.
8, according to claim 5 or 6 described carriers, the specific surface area that it is characterized in that described catalyst carrier for hydrgenating is 240～360m
2/ g, pore volume are 0.45～0.65ml/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 4nm-10nm, and infrared acidity is 0.35～0.55mmol/g.
9, the preparation method of the arbitrary described carrier of claim 1～8 comprises following process:
(1). aluminum oxide and/or modified aluminas, 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.
10,, it is characterized in that the preparation method of used phosphorus and/or boron additive modified aluminas is as follows according to the described preparation method of claim 9:
Get the material that contains γ one aluminum oxide precursor, get its filter cake, making beating is warming up to 50～90 ℃, adds P contained compound and/or boron-containing compound, and stirs 30～90 minutes at 50～90 ℃, filters, and drying makes modified aluminas; The material of the described γ of containing one aluminum oxide precursor can be carborization, aluminum nitrate method, alchlor process, Tai-Ace S 150 method synthetic γ one aluminum oxide precursor.
11, according to the described preparation method of claim 9, it is characterized in that the adding mode of described sapphire whisker is as follows: (1) adds the sapphire whisker powder in aluminum oxide or modified aluminas preparation process; (2) after direct oxidation aluminum fiber powder and aluminum oxide or modified aluminas 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350374A (en) * | 2011-05-31 | 2012-02-15 | 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 |
| CN108393091A (en) * | 2017-02-08 | 2018-08-14 | 中国石油化工股份有限公司 | Liquefied coal coil hydrotreating catalyst and the preparation method and application thereof |
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2006
- 2006-06-07 CN CN200610027539A patent/CN100580058C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350374A (en) * | 2011-05-31 | 2012-02-15 | 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 |
| 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 |
| CN108393091A (en) * | 2017-02-08 | 2018-08-14 | 中国石油化工股份有限公司 | Liquefied coal coil hydrotreating catalyst and the preparation method and application thereof |
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| CN100580058C (en) | 2010-01-13 |
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