CN104646005A - 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 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000295 fuel oil Substances 0.000 title claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 34
- 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 20
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 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
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 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
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000005406 washing Methods 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
- 239000008187 granular material Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 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
- 239000007921 spray Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012535 impurity 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
- 230000008859 change Effects 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
- 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
- 230000008021 deposition Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 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
- 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
- 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
- -1 clean vapour Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 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
- 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002156 mixing Methods 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
- 238000012856 packing Methods 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
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 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
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 larger surface orifice, wide pore channel, excellent diffusion performance and high hydrodemetallizationActivity and activity stability.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, particularly inferior heavy oil Hydrodemetalation catalyst and preparation method thereof.
Background technology
Inferior heavy oil contains the metal impurities such as higher Ni, V as residual oil etc., usually needs to remove through hydrotreatment, so that through follow-up processing (as catalytic cracking), produces oil product and the industrial chemicals such as clean vapour, diesel oil.Research shows, in the inferior heavy oil such as residual oil, metal impurities are mainly present in resin and asphalt, and this part molecular weight of material is large, complex structure, diffusion difficulty, therefore require that catalyst has excellent pore passage structure, be convenient to the diffusion of macromolecular reaction thing, reaction and deposition.
The pore structure of catalyst has important impact to its performance.For mink cell focus hydrogenation conversion catalyst, need that there is unobstructed duct and larger pore volume.Unobstructed diffusion and the reaction being conducive to macromolecule hydrocarbon material in mink cell focus in duct, to improve the reactivity of catalyst; Avoid metal impurities to deposit simultaneously or react coking causing catalyst aperture block and cause rapid catalyst deactivation, promote that metal impurities are to catalyst duct inside deposition, improve metal-holding capacity and the activity stability of catalyst.Therefore the mink cell focus Hydrodemetalation catalyst that a duct is unobstructed, will have good reactivity and activity stability.
In order to improve the pore volume of alumina support and obtain unimpeded duct, generally adopt the method adding expanding agent at present, such as US4,448,896 patent Introductions for raw material, and add carbon powder as expanding agent with a kind of boehmite, obtain alumina support through kneading, extrusion, drying and roasting.Its shortcoming is: add a small amount of carbon powder, then easily form " ink bottle " nibs; Add too much carbon powder, then cause support strength obviously to reduce.
Patent US4,066,574, US4,113,661 and US4,341,625 preparation methods describing a kind of alumina support, namely in Alpha-alumina monohydrate, first add aqueous solution of nitric acid, fully add a certain amount of ammonia spirit again after effect, reach the object expanding carrier pore volume.Although the method can play reaming effect, carrier hole diameter is single distribution by particle exterior surface to center, is unfavorable for the effect playing particle surfaces externally and internally substantially.
Summary of the invention
The object of this invention is to provide a kind of method making the directed reaming of catalyst, though catalyst average pore diameter along particle radial by center to outer surface in increasing gradually; Another object of the present invention is to provide the unobstructed inferior heavy oil Hydrodemetalation catalyst in a kind of duct.
The main points of the inventive method are: 1) first carry out peptization, extruded moulding, drying and roasting to boehmite; 2) acid solution that the particle concentration after shaping and roasting increases continuously is processed, and closed processes, washing and drying under higher than the condition of room temperature; And repeatedly 3) again with the carrier that the solution impregnation containing active metal obtains, obtained final catalyst.
Carrier of the present invention can be alumina support, and also can be the alumina support containing auxiliary agent, its pore volume be 0.71 ~ 0.85mL/g, and specific area is 90 ~ 150m
2/ g, average pore diameter is 19.0 ~ 30.0nm, it is characterized in that along catalyst granules radial direction its average pore diameter from center to outer surface be increase gradually.
The present invention makes the unimpeded principle in carrier duct be: to the particle after shaping and roasting by its saturated water absorption equal-volume spray acid solution.While spray, the concentration of continuous adjustment of acidity solution, makes it enter into the duct of particle from low to high.Due to the effect of capillary pressure, the low concentration acid solution first sprayed can spread to carrier granular internal layer, and the high concentrated acid solution then sprayed can closer to the skin of carrier granular.Higher than under the condition of room temperature, by the effect between acid solution and aluminium oxide, the bore dia in duct is expanded.Due to the difference of the successively acid solutions of spray, cause its reaming effect different, finally make carrier duct from granular center to outer surface, constantly become large, form open " trumpet type " pore passage structure, thus make that the pore volume of carrier increases, duct is open.
The one of catalyst is prepared as follows:
(1) take boehmite dry glue powder, add water, peptizing agent, extrusion aid and expanding agent, extruded moulding after abundant kneading.After drying, roaster is put into 850 ~ 1050 DEG C of constant temperature 2 ~ 5 hours;
(2) to the even shower water of (1) gained carrier, while shower water, in water, acid or acid solution is at the uniform velocity added, until reach the saturated water absorption of carrier; Closed processes 1 ~ 4 hour under 40 ~ 95 DEG C of conditions, with water purification washing 1 ~ 3 time, gained material was 105 ~ 300 DEG C of dryings 2 ~ 6 hours;
(3) repeat to operate 1 ~ 3 time in (2);
(4) by the solution impregnation of the nickeliferous and molybdenum strip by (3) gained, dry, 460 ~ 540 DEG C of roasting temperatures 2 ~ 5 hours, obtained final catalyst.
Acid of the present invention or acid solution are nitric acid, acetic acid or phosphoric acid and solution thereof.
Described extrusion aid is the blue or green powder in field or citric acid.Described expanding agent is polyethylene glycol, polyvinyl alcohol, methylcellulose.
The shape of alumina support of the present invention can change according to different requirements.
Catalyst of the present invention, is applicable to the HDM of inferior heavy oil.
Compared with existing method for preparing catalyst, the advantage of the inventive method is: catalyst pores diameter is open distribution, and surperficial aperture is comparatively large, and duct is unobstructed, and catalyst has high metal removal activity and activity stability.
Accompanying drawing explanation
The average pore diameter radial distribution schematic diagram of Fig. 1 catalyst of the present invention.
Detailed description of the invention
Below further illustrate feature of the present invention with embodiment and comparative example.
Embodiment 1
(1) preparation of carrier
Take boehmite dry glue powder (contents on dry basis 71.2wt%) 500g that three doses, Jiangsu chemical inc produces, add sesbania powder 15g, add methylcellulose 15g, mix.The acetum 450g being 1.0wt% concentration adds in afore-mentioned materials, and kneading is to plastic, and then on front crowded formula single-screw extruder, being extruded into diameter is the cylindrical of 1.4mm.120 DEG C of dryings 3 hours, then insert in roaster, rise to 900 DEG C with the speed of 180 DEG C/h, roasting 3 hours.
(2) process of carrier
Take (1) gained carrier 30 as one kind 0 gram and be placed in rotation vessel, 250g deionized water is evenly sprayed to gained alumina support with the speed of 30mL/ minute, while shower water, in aforementioned deionized water, evenly adds glacial acetic acid with the speed of 6.5g/ minute.Spray is to carrier saturated water absorption, and 50 DEG C of closed processes 1.0 hours, water purification washs 3 times.200 DEG C of dryings 3.0 hours.
(3) (2) described operation 1 time is repeated.
(4) preparation of catalyst
Take 136.4 grams of technical grade ammonium heptamolybdates (containing MoO
381wt%), adding 500 grams of concentration is under agitation the ammonia spirit of 10wt%, is stirred to and dissolves completely, then adds 54.2 grams of technical grade nickel nitrates (containing NiO24w%), be stirred to and dissolve completely, be finally adjusted to 1000mL with the ammonia spirit that concentration is 10wt%.Take and be placed in rotation vessel by (2) gained strip, spray into gained metallic solution until saturated, 120 DEG C of dryings 3.0 hours after taking-up, then 500 DEG C of roastings 3 hours, obtain catalyst A.
Embodiment 2
Aforementioned boehmite dry glue powder 500g, adds sesbania powder 15g, adds polyvinyl alcohol 25g, mix.The acetum 410g being 2.5wt% concentration adds in afore-mentioned materials, kneading 45 minutes.The method extrusion identical with embodiment 1 and drying, 920 DEG C of roastings 3 hours.250g deionized water is evenly sprayed to gained alumina support with the speed of 30mL/ minute, while shower water, in aforementioned deionized water, evenly adds glacial acetic acid with the speed of 8.0g/ minute.Spray is to carrier saturated water absorption, and 70 DEG C of closed processes 2.0 hours, wash 3 times.200 DEG C of dryings 3.0 hours.Repeat above acid treatment process 2 times.Catalyst preparation conditions in the same manner as in Example 1 is adopted to obtain catalyst B.
Embodiment 3
Change carrier calcination temperature in embodiment 1 into 880 DEG C, the speed that adds of acetic acid changes 5.0g/ minute into, and other condition is all identical with embodiment 1, obtains catalyst C.
Embodiment 4
In example 2, in water, evenly add with the speed of 5.0g/ minute the salpeter solution that concentration is 45wt% while Air washer.Other condition is identical with embodiment 2, obtains catalyst D.
Comparative example 1
The step identical with embodiment 1 and condition is shaping, dry and roasting, and do not carry out acid treatment.Catalyst preparation conditions in the same manner as in Example 1 is adopted to obtain catalyst E.
Comparative example 2
The step identical with embodiment 1 and condition is shaping, dry and roasting, to gained carrier spray concentration be the acetic acid solution of 12wt% to saturated water absorption, 50 DEG C of closed processes 1.0 hours, water purification washed 2 times, 200 DEG C of dryings 3.0 hours.Repeat above acid treatment process 1 time.Catalyst preparation conditions in the same manner as in Example 1 is adopted to obtain catalyst F.
Comparative example 3
This comparative example is by US4, and 448,896 methods described prepare Kaolinite Preparation of Catalyst after carrier.
Boehmite dry glue powder 500g as hereinbefore, adds sesbania powder 14g, is mixed into 11g high wear-resistant carbon black, obtains carrier in dry glue powder.Catalyst preparation conditions in the same manner as in Example 1 is adopted to obtain catalyst G.
Embodiment 5
This example is physicochemical property and the Activity evaluation of above each routine catalyst.
Carrier or catalyst from granular center to the average pore diameter assay method of outer surface different piece are: first with the pore volume of low-temperature nitrogen adsorption method (BET) working sample, specific area and average pore diameter, then get a certain amount of sample and be placed in attrition of catalyst instrument, grinding process is carried out to sample, adds a certain amount of quartz sand or alumina particle to increase the rate of wear simultaneously.When sample is reduced to a certain degree through polishing particle diameter, the working sample loss in weight also measures its pore structure again, the pore volume total by sample and surface area equal the relation of each several part sum, can calculate pore volume and the specific area of the part polished off, and then calculate its average pore diameter.Determine the average pore diameter from outer surface to granular center different piece thus.
Each routine carrier physicochemical property is in table 1.The physicochemical property of each routine catalyst is in table 2.From table 1 and table 2, carrier of the present invention and corresponding catalyst pore volume and aperture are all comparatively large, and average pore diameter from granular center to outer surface in increasing gradually, duct permeability is better; And comparative example carrier and catalyst average pore diameter do not change.
Evaluation feedstock oil character is in table 3.
During evaluate catalysts, pass through beds after hydrogen and feedstock oil mixing, take hydrogen One-through design.The process conditions evaluating each routine catalyst employing are all identical, 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 300cm
3, Catalyst packing 200cm
3.Evaluation result is in table 4.
From this example, the inventive method obtains catalyst and has the active and good activity stability of higher HDM.
Table 1 carrier physicochemical property
﹡ refers to the average pore diameter of a carrier part
﹡ ﹡ refers to that on carrier cross section, certain a bit accounts for the percentage of its cross sectional radius apart from the distance of carrier particle exterior surface
Table 2 catalyst physicochemical property
Table 3 feedstock oil character
| Character | Middle East residual oil |
| Density (20 DEG C)/gcm -3 | 0.99 |
| (Ni+V)，μg.g -1 | 103 |
[0059] table 4 catalyst desulfurizing activity stability evaluation result
Claims (9)
1. an inferior heavy oil Hydrodemetalation catalyst take aluminium oxide as carrier, and with VIII and group vib metal for active component, catalyst pore volume is 0.71 ~ 0.85mL/g, and specific area is 90 ~ 150m
2/ g, average pore diameter is 19.0 ~ 30.0nm, it is characterized in that: along catalyst granules radial from center to outer surface its average pore diameter in increasing gradually.
2. according to catalyst described in claim 1, it is characterized in that: the average pore diameter of described catalyst 50% part from granular center to particle diameter is compared with the little 2 ~ 6nm of the average pore diameter of particle diameter 90% to surface portion.
3. according to catalyst described in claim 1, it is characterized in that: VIII element is Ni, VIB element is Mo, described catalyst is by weight containing NiO0.5 ~ 2%, MoO
35 ~ 10%.
4. a preparation method for catalyst described in claim 1, is characterized in that: comprise the following steps:
(1) take boehmite dry glue powder, add water, peptizing agent, extrusion aid and expanding agent, extruded moulding after abundant kneading drying, roasting, obtain alumina support;
(2) to the even shower water of (1) gained carrier, while shower water, in water, acid or acid solution is at the uniform velocity added, until reach the saturated water absorption of carrier; Closed processes under higher than the condition of room temperature, then with water purification washing, and dry;
(3) (2) described operation 1 ~ 3 time is repeated;
(4) by the solution impregnation of nickeliferous and molybdenum by the strip of (3) gained and dry, roasting, obtained final catalyst.
5. according to preparation method described in claim 4, it is characterized in that: described in step (1), expanding agent is polyethylene glycol, polyvinyl alcohol, methylcellulose, its addition is 3 ~ 10% of aluminium oxide contents on dry basis.
6. according to preparation method described in claim 4, it is characterized in that: in step (1), the roasting condition of carrier is rise to 850 ~ 1050 DEG C with the speed of 100 ~ 200 DEG C/h, constant temperature 2 ~ 5 hours.
7. according to preparation method described in claim 4, it is characterized in that: acid described in step (2) is nitric acid, acetic acid or phosphoric acid.
8. according to preparation method described in claim 4, it is characterized in that: described in step (2), closed processes temperature is 40 ~ 95 DEG C, the time is 1 ~ 4 hour; Described baking temperature is 105 ~ 300 DEG C.
9. according to preparation method described in claim 4, it is characterized in that: in step (3), catalyst sintering temperature is 460 ~ 540 DEG C, and the time is 2 ~ 5 hours.
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|---|---|---|---|---|
| CN115888690A (en) * | 2023-01-03 | 2023-04-04 | 中化泉州石化有限公司 | Heavy oil hydrodemetallization catalyst for up-flow reactor and preparation method thereof |
| CN115957740A (en) * | 2023-01-03 | 2023-04-14 | 中化泉州石化有限公司 | Heavy oil hydrotreating catalyst and preparation method thereof |
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| CN1054393C (en) * | 1997-07-22 | 2000-07-12 | 中国石油化工总公司 | Residuum hydrogenating and metal-eliminating catalyst |
| CN101927191B (en) * | 2009-06-26 | 2012-05-30 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115888690A (en) * | 2023-01-03 | 2023-04-04 | 中化泉州石化有限公司 | Heavy oil hydrodemetallization catalyst for up-flow reactor and preparation method thereof |
| CN115957740A (en) * | 2023-01-03 | 2023-04-14 | 中化泉州石化有限公司 | Heavy oil hydrotreating catalyst and preparation method thereof |
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