CN104646005B - Inferior heavy oil hydrodemetallization catalyst and preparation method thereof - Google Patents
Inferior heavy oil hydrodemetallization catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000295 fuel oil Substances 0.000 title claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- 229910001593 boehmite Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 abstract 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000772415 Neovison vison Species 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a poor heavy oil hydrodemetallization catalyst and a preparation method thereof; the catalyst takes alumina as a carrier, VIII group and VIB elements, particularly Ni-Mo, as active components, the pore volume of the catalyst is 0.71-0.85 mL/g, and the specific surface area is 90-150 m2The average pore diameter is 19.0-30.0 nm, and the average pore diameter gradually increases from the center to the outer surface along the radial direction of the catalyst particles; the preparation method of the catalyst comprises the steps of treating the formed and roasted carrier particles by using an acid solution with continuously increased concentration; the catalyst has the advantages of large surface orifice, wide pore channel, excellent diffusion performance, high hydrodemetallization activity and high activity stability.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, particularly inferior heavy oil hydrodemetallisation catalyst
Agent and preparation method thereof.
Background technology
Inferior heavy oil such as residual oil etc. contains the metal impurities such as higher Ni, V, it usually needs taken off by hydrotreating
Remove, to pass through follow-up processing (such as catalytic cracking), produce the oil products such as vapour, the diesel oil of cleaning and industrial chemicals.Study table
Bright, metal impurities are primarily present in resin and asphalt in the inferior heavy oil such as residual oil, and this moieties molecular weight is big, structure is multiple
Miscellaneous, diffusion is difficult, therefore it is required that catalyst has excellent pore passage structure, is easy to the diffusion of macromolecule reactant, reacts and heavy
Product.
The pore structure of catalyst has important influence to its performance.For mink cell focus hydrogenation conversion catalyst, it is necessary to have
There are unobstructed duct and larger pore volume.Duct is unobstructed to be conducive to the diffusion and reaction of macromolecule hydrocarbon material in mink cell focus, with
Improve the reactivity of catalyst；Avoiding metal impurities to deposit or react coking simultaneously causes catalyst aperture to block and cause to urge
Agent rapid deactivation, promotes metal impurities to deposition inside catalyst duct, improves the metal-holding capacity and activity of catalyst
Stability.Therefore the unobstructed mink cell focus Hydrodemetalation catalyst in a duct, will be steady with good reactivity and activity
It is qualitative.
In order to improve the pore volume of alumina support and obtain unimpeded duct, at present generally using the side for adding expanding agent
Method, such as US4,448,896 patent introductions add carbon powder as expanding agent using a kind of boehmite as raw material, through mixed
Pinch, extrusion, drying and roasting obtain alumina support.It has the disadvantage：A small amount of carbon powder is added, then easily forms " ink bottle " type
Hole；Excessive carbon powder is added, then causes support strength substantially to reduce.
Patent US4,066,574, US4,113,661 and US4,341,625 describe a kind of preparation side of alumina support
Method, i.e., first add aqueous solution of nitric acid in Alpha-alumina monohydrate, fully adds a certain amount of ammonia spirit after effect, reaches
To the purpose for expanding carrier pore volume.Although the method can play reaming effect, carrier bore dia is by particle exterior surface into
The heart is in single distribution, is unfavorable for substantially playing the effect of particle surfaces externally and internally.
The content of the invention
It is an object of the invention to provide a kind of method for making catalyst orient reaming, even if catalyst average pore diameter edge
Particle is in radially gradually to increase by center to outer surface；It is a further object of the present invention to provide the inferior heavy oil that a kind of duct is unobstructed
Hydrodemetalation catalyst.
The main points of the inventive method are：1) peptization, extruded moulding, drying and roasting first are carried out to boehmite；2) it is right
The acid solution that particulate matter after shaping and roasting is increased continuously with concentration is handled, and the closed place under conditions of higher than room temperature
Manage, wash and dry；And the carrier obtained by repeatedly 3) being impregnated again with the solution containing active metal, final catalysis is made
Agent.
The carrier of the present invention can be alumina support or the alumina support containing auxiliary agent, and its pore volume is 0.71
~0.85mL/g, specific surface area is 90~150m2/ g, average pore diameter is 19.0~30.0nm, it is characterised in that along catalyst
Radially its average pore diameter from center to outer surface is in gradually to increase to particle.
The principle that the present invention makes carrier duct unimpeded is：It is isometric by its saturated water absorption to the particulate matter after shaping and roasting
Spray acid solution.While spray, the concentration of acid solution is continuously adjusted, the hole for making it enter particle from low to high
In road.Due to the effect of capillary pressure, the low concentration acid solution first sprayed can spread to carrier granular internal layer, then spray
High concentrated acid solution can closer to carrier granular outer layer.Under conditions of higher than room temperature, pass through acid solution and aluminum oxide
Between effect, expanded the bore dia in duct.Due to the difference of the acid solutions of priority spray, its reaming is caused to imitate
Fruit is different, carrier duct is constantly become big from granular center to outer surface, forms open " trumpet type " pore passage structure,
So that the pore volume of carrier increases, duct is open.
One kind of catalyst is prepared as follows：
(1) weigh boehmite dry glue powder, add after water, peptizing agent, extrusion aid and expanding agent, abundant kneading extrusion into
Type.After drying, it is put into roaster in 850~1050 DEG C of constant temperature 2~5 hours；
(2) to the uniform shower water of (1) resulting vehicle, while shower water, acid or acid solution are at the uniform velocity added in water, directly
To the saturated water absorption for reaching carrier；Closed processes 1~4 hour under the conditions of 40~95 DEG C, 1~3 time, gained are washed with water purification
Material is dried 2~6 hours at 105~300 DEG C；
(3) operation 1~3 time in (2) is repeated；
(4) dried, in 460~540 DEG C of roasting temperatures 2 as the strip obtained by (3) with the solution dipping of nickeliferous and molybdenum
~5 hours, final catalyst is made.
Acid or acid solution of the present invention are nitric acid, acetic acid or phosphoric acid and its solution.
Described extrusion aid is the blue or green powder in field or citric acid.The expanding agent is polyethylene glycol, polyvinyl alcohol, Methyl cellulose
Element.
The shape of alumina support of the present invention can be changed according to different requirements.
Catalyst of the present invention, it is adaptable to the HDM of inferior heavy oil.
Compared with existing method for preparing catalyst, this have the advantage that：Catalyst pores diameter is in open distribution,
Surface aperture is larger, and duct is unobstructed, and catalyst has high metal removal activity and activity stability.
Brief description of the drawings
The average pore diameter radial distribution schematic diagram of Fig. 1 catalyst of the present invention.
Embodiment
The feature of the present invention is further illustrated with embodiment and comparative example below.
Embodiment 1
(1) preparation of carrier
Weigh the boehmite dry glue powder (contents on dry basis 71.2wt%) of the three doses of chemical inc's production in Jiangsu
500g, adds sesbania powder 15g, adds methylcellulose 15g, is well mixed.Concentration is added for 1.0wt% acetum 450g
Enter in afore-mentioned materials, kneading to plastic, a diameter of 1.4mm cylinder is then extruded on preceding crowded formula single-screw extruder.
Dry 3 hours, then inserted in roaster at 120 DEG C, 900 DEG C are risen to 180 DEG C/h of speed, be calcined 3 hours.
(2) processing of carrier
Weigh 300 grams of (1) resulting vehicle be placed in rotation vessel in, by 250g deionized waters with the speed of 30mL/ minutes to
Gained alumina support is uniformly sprayed, and is uniformly added into while shower water with the speed of 6.5g/ minutes into foregoing deionized water
Glacial acetic acid.It is sprayed to after carrier saturated water absorption, 50 DEG C of closed processes 1.0 hours, water purification is washed 3 times.3.0 are dried at 200 DEG C
Hour.
(3) (2) described operation 1 time is repeated.
(4) preparation of catalyst
Weigh 136.4 grams of technical grade ammonium heptamolybdates and (contain MoO381wt%), 500 grams of concentration are added under agitation is
10wt% ammonia spirit, is stirred to being completely dissolved, and is added 54.2 grams of technical grade nickel nitrates (containing NiO24w%), is stirred to complete
Dissolving, the ammonia spirit for being finally 10wt% with concentration is adjusted to 1000mL.Weigh and rotation vessel are placed in by strip obtained by (2)
In, gained metallic solution is sprayed into up to saturation, is dried 3.0 hours at 120 DEG C after taking-up, then be calcined 3 hours at 500 DEG C, it must urge
Agent A.
Embodiment 2
Foregoing boehmite dry glue powder 500g, adds sesbania powder 15g, adds polyvinyl alcohol 25g, is well mixed.Dense
Spend and added for 2.5wt% acetum 410g in afore-mentioned materials, kneading 45 minutes.Method extrusion same as Example 1 and dry
Dry, 920 DEG C are calcined 3 hours.250g deionized waters are uniformly sprayed with the speed of 30mL/ minutes to gained alumina support, sprayed
Glacial acetic acid was uniformly added into foregoing deionized water with the speed of 8.0g/ minutes while water drenching.It is sprayed to the water suction of carrier saturation
After rate, 70 DEG C of closed processes 2.0 hours are washed 3 times.Dried 3.0 hours at 200 DEG C.Repeat above acid treatment process 2 times.Adopt
Catalyst B is obtained with catalyst preparation conditions in the same manner as in Example 1.
Embodiment 3
Carrier calcination temperature in embodiment 1 is changed to 880 DEG C, the addition speed of acetic acid is changed to 5.0g/ minutes, other conditions
It is same as Example 1, obtain catalyst C.
Embodiment 4
In example 2, while Air washer using the speed of 5.0g/ minutes be uniformly added into water concentration as
45wt% salpeter solution.Other conditions are same as Example 2, obtain catalyst D.
Comparative example 1
Step same as Example 1 and condition shaping, dry and roasting, and without acid treatment.Using with embodiment 1
Middle identical catalyst preparation conditions obtain catalyst E.
Comparative example 2
Step same as Example 1 and condition shaping, dry and roasting, it is 12wt%'s to spray concentration to resulting vehicle
Acetic acid solution is to saturated water absorption, 50 DEG C of closed processes 1.0 hours, and water purification is washed 2 times, is dried 3.0 hours at 200 DEG C.Repeat
Above acid treatment process 1 time.Catalyst F is obtained using catalyst preparation conditions in the same manner as in Example 1.
Comparative example 3
This comparative example is to prepare to prepare catalyst after carrier by the US4,448,896 methods described.
Boehmite dry glue powder 500g as hereinbefore, adds sesbania powder 14g, 11g height is mixed into dry glue powder resistance to
Carbon black is ground, carrier is obtained.Catalyst G is obtained using catalyst preparation conditions in the same manner as in Example 1.
Embodiment 5
The physicochemical property and Activity evaluation of this example each example catalyst for more than.
The average pore diameter assay method of carrier or catalyst from granular center to outer surface different piece is：First with low temperature
The pore volume, specific surface area and average pore diameter of nitrogen adsorption method (BET) determination sample, then take a certain amount of sample to be placed in catalyst
In abrasion instrument, grinding process is carried out to sample, while adding a certain amount of quartz sand or alumina particle to increase the rate of wear.
When sample reduces to a certain extent by polishing particle diameter, determination sample weight loss simultaneously determines its pore structure again, by sample
Total pore volume and surface area are equal to the relation of each several part sum, can calculate the pore volume and specific surface area of the part polished off,
And then calculate its average pore diameter.Thus the average pore diameter from outer surface to granular center different piece is determined.
Each example carrier physicochemical property is shown in Table 1.The physicochemical property of each example catalyst is shown in Table 2.From Tables 1 and 2, the present invention
Carrier and corresponding catalyst pore volume and aperture are larger, and average pore diameter is in gradually to increase from granular center to outer surface, hole
Road permeability is preferable；And comparative example carrier and catalyst average pore diameter do not change.
Evaluation is shown in Table 3 with raw material oil nature.
When evaluating catalyst, beds are passed through after hydrogen and feedstock oil mixing, take hydrogen once to lead to
Cross mode.The process conditions all same that each example catalyst is used is evaluated, respectively：Reaction pressure (hydrogen dividing potential drop), 16.0MPa；Reaction
Temperature, 385 DEG C；Total liquid hourly space velocity (LHSV), 0.85h-1；Hydrogen-oil ratio (v)：750.Single reactor constant temperature zone volume 300cm3, catalyst
Load 200cm3.Evaluation result is shown in Table 4.
From this example, the inventive method, which obtains catalyst, has the active and good activity of higher HDM
Stability.
The carrier physicochemical property of table 1
﹡ refers to a part of average pore diameter of carrier
﹡ ﹡ refer to the percentage that distance of the certain point away from carrier particle exterior surface on carrier cross section accounts for its cross sectional radius
The catalyst physicochemical property of table 2
The raw material oil nature of table 3
| Property | Middle East residual oil |
| Density (20 DEG C)/gcm-3 | 0.99 |
| (Ni+V), μ g.g-1 | 103 |
The catalyst desulfurizing activity stability evaluation result of table 4
Claims (7)
1. a kind of inferior heavy oil Hydrodemetalation catalyst, using aluminum oxide as carrier, using VIII and group vib metal as activearm
Point, catalyst pore volume is 0.71~0.85mL/g, and specific surface area is 90~150m2/ g, average pore diameter is 19.0~30.0nm,
It is characterized in that：Along catalyst granules, radially its average pore diameter from center to outer surface is in gradually to increase；The catalyst from
Average pore diameter average pore diameter small 2~6nm compared with particle diameter 90% to surface portion of the granular center to the part of particle diameter 50%.
2. according to catalyst described in claim 1, it is characterised in that：VIII element is that Ni, VIB element are Mo, the catalysis
Agent contains NiO 0.5~2%, MoO by weight35~10%.
3. the preparation method of catalyst described in a kind of claim 1, it is characterised in that：Comprise the following steps：
(1) weigh boehmite dry glue powder, add after water, peptizing agent, extrusion aid and expanding agent, abundant kneading extruded moulding simultaneously
Through drying, roasting, alumina support is produced；
(2) to the uniform shower water of (1) resulting vehicle, while shower water, acid or acid solution are at the uniform velocity added in water, until reaching
To the saturated water absorption of carrier；The closed processes under conditions of higher than room temperature, are then washed with water purification, and are dried；
(3) (2) described operation 1~3 time is repeated；
(4) impregnated with the solution of nickeliferous and molybdenum as the strip obtained by (3) and drying, roasting, final catalyst is made；
Expanding agent described in step (1) is polyethylene glycol, and its addition is the 3~10% of aluminum oxide contents on dry basis.
4. according to preparation method described in claim 3, it is characterised in that：In step (1) roasting condition of carrier be with 100~
200 DEG C/h of speed rises to 850~1050 DEG C, constant temperature 2~5 hours.
5. according to preparation method described in claim 3, it is characterised in that：Acid described in step (2) is nitric acid, acetic acid or phosphoric acid.
6. according to preparation method described in claim 3, it is characterised in that：Closed processes temperature described in step (2) is 40~95
DEG C, the time is 1~4 hour；The drying temperature is 105~300 DEG C.
7. according to preparation method described in claim 3, it is characterised in that：Catalyst sintering temperature is 460~540 in step (4)
DEG C, the time is 2~5 hours.
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| CN115888690B (en) * | 2023-01-03 | 2025-05-30 | 中化泉州石化有限公司 | Heavy oil hydrodemetallization catalyst for up-flow reactor and preparation method thereof |
| CN115957740B (en) * | 2023-01-03 | 2025-03-25 | 中化泉州石化有限公司 | A heavy oil hydroprocessing catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206037A (en) * | 1997-07-22 | 1999-01-27 | 中国石油化工总公司 | Residuum hydrogenating and metal-eliminating catalyst |
| CN101927191A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst carrier with acid additive concentration in gradient increasing distribution and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206037A (en) * | 1997-07-22 | 1999-01-27 | 中国石油化工总公司 | Residuum hydrogenating and metal-eliminating catalyst |
| CN101927191A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst carrier with acid additive concentration in gradient increasing distribution and preparation method thereof |
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