CN104646009B - A kind of inferior heavy oil Hydrobon catalyst and preparation method thereof - Google Patents
A kind of inferior heavy oil Hydrobon catalyst and preparation method thereof Download PDFInfo
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- CN104646009B CN104646009B CN201310597246.7A CN201310597246A CN104646009B CN 104646009 B CN104646009 B CN 104646009B CN 201310597246 A CN201310597246 A CN 201310597246A CN 104646009 B CN104646009 B CN 104646009B
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Abstract
The present invention relates to a kind of inferior heavy oil Hydrobon catalyst and preparation method thereof.Catalyst is using aluminum oxide as carrier, using VIII and VIB elements particularly Ni Mo as active component, and catalyst pore volume is 0.45~0.60cm3/ g, specific surface area is 205~260m2/ g, average pore size is 7.0~12.0nm, and its average pore diameter is in radially gradually to increase from center to outer surface along catalyst granules.The preparation method of catalyst is that the acid solution that the carrier particles after shaping and roasting are increased continuously with concentration is handled.The catalyst surface aperture of the present invention is larger, and duct is open, and diffusion is excellent, with high hydrodesulfurization activity and activity stability.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, particularly inferior heavy oil Hydrobon catalyst
And preparation method thereof.
Background technology
The inferior heavy oil such as impurity content such as wax tailings, residual oil is higher, it usually needs by hydrotreating, (such as residual oil adds
Hydrogen) impurity such as the sulphur of wherein most are removed, to produce vapour, the diesel oil of cleaning by follow-up processing (such as catalytic cracking)
Deng oil product and industrial chemicals.Contain substantial amounts of resin and asphalt in the inferior heavy oils such as residual oil, this moieties molecular weight is big, knot
Structure is complicated, and diffusion is difficult, therefore it is required that catalyst has excellent pore passage structure, to improve the de- impurity activity of catalyst and steady
It is qualitative.
The pore structure of catalyst has important influence to its performance.For catalyst for hydroprocessing of heavy oil, 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, from
And improve the reactivity of catalyst；Metal deposit or reaction coking is avoided to cause catalyst aperture to block and cause catalysis simultaneously
Agent rapid deactivation, to improve the activity stability of catalyst.Therefore the unobstructed catalyst for hydroprocessing of heavy oil in a duct, will
With good reactivity and activity stability.
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 diameter is in gradually to increase to 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
Hydrobon 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；3) carrier obtained by being impregnated again with the solution containing active metal, is made final catalyst.
The present invention catalyst is using aluminum oxide or the aluminum oxide containing auxiliary agent is carrier, its pore volume be 0.45~0.60cm3/ g,
Specific surface area is 205~260m2/ g, average pore diameter is 7.0~12.0nm, it is characterised in that along catalyst granules radial direction therefrom
The heart is in gradually to increase to its average pore diameter of outer surface.
The principle that the present invention makes catalyst duct unimpeded is：Its saturated water absorption is pressed to the carrier particles after shaping and roasting
Isometric spray acid solution.While spray, the concentration of acid solution is continuously adjusted, it is entered from low to high
In the duct of grain.Due to the effect of capillary pressure, the low concentration acid solution first sprayed can spread to carrier granular internal layer, and
Outer layer of the high concentrated acid solution meeting sprayed afterwards closer to carrier granular.Under conditions of higher than room temperature, by acid solution with
Effect between aluminum oxide, is expanded the bore dia in duct.Due to the difference of the acid solutions of priority spray, it is caused
Reaming effect is different, carrier duct is constantly become big from granular center to outer surface, forms open " trumpet type " hole
Road structure, so that the pore volume of carrier increases, duct is unobstructed.
One kind of catalyst is prepared as follows：
(1) boehmite dry glue powder is weighed, extruded moulding after water, peptizing agent and extrusion aid, abundant kneading is added.Into
Appropriate different auxiliary agents can be added during type as needed；After drying, it is put into roaster in 550~750 DEG C of constant temperature 1~8
Hour；
(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) dried, in 460~540 DEG C of roasting temperatures 2 as the strip obtained by (2) 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 auxiliary agent can be the elements such as phosphorus, boron, fluorine, silicon, titanium, zirconium
It is more than one or both of compound.
The shape of catalyst of the present invention can be changed according to different requirements.
Catalyst of the present invention, it is adaptable to the hydrodesulfurization 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 desulfurizing activity and stability are high.
The average pore diameter radial distribution signal of catalyst of the present invention is as shown in Figure 1.
Brief description of the drawings
Fig. 1 is catalyst average pore diameter radial distribution schematic diagram.
Embodiment
The feature of the present invention is further illustrated with embodiment and comparative example below.
Embodiment 1
(1) preparation of carrier
Weigh the macropore boehmite dry glue powder (contents on dry basis 71.5wt%) of Yantai Heng Hui Chemical Co., Ltd.s production
500g, adds sesbania powder 14g, is well mixed.Concentration for 4.0wt% acetum 390g add afore-mentioned materials in, kneading into
Plastic, is then extruded into a diameter of 1.4mm cylinder on preceding crowded formula single-screw extruder.Dried 3.0 hours at 120 DEG C,
Insert again in roaster, 650 DEG C, constant temperature 3 hours are risen to 180 DEG C/h of speed.
(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
Carrier is uniformly sprayed, and acetic acid is uniformly added into foregoing deionized water with the speed of 3.0g/ minutes while shower water.It is sprayed to
After carrier saturated water absorption, 50 DEG C of closed processes 2.0 hours, water purification is washed 2 times.Dried 3.0 hours at 150 DEG C.
(3) preparation of catalyst
Weigh 281.0 grams of technical grade ammonium heptamolybdates and (contain MoO381wt%), 500 grams of concentration are added under agitation is
18wt% ammonia spirit, is stirred to being completely dissolved, and is added 271.0 grams of technical grade nickel nitrates (containing NiO24wt%), is stirred to complete
Fully dissolved, the ammonia spirit for being finally 18w% 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 is weighed, sesbania powder 14g is added, is well mixed.It is 3.5wt%'s concentration
Acetum 400g is added in afore-mentioned materials, and kneading is into plastic.Method extrusion, drying and roasting same as Example 1.Will
250g deionized waters are uniformly sprayed with the speed of 30mL/ minutes to gained alumina support, with 4.0g/ minutes while shower water
Speed be uniformly added into acetic acid into foregoing deionized water.It is sprayed to after carrier saturated water absorption, 60 DEG C of closed processes 3.0 are small
When, water purification is washed 3 times.Dried 3.0 hours at 200 DEG C.It is catalyzed using catalyst preparation conditions in the same manner as in Example 1
Agent B.
Embodiment 3
The addition speed of acetic acid in embodiment 1 is changed to 2.5g/ minutes, other conditions are same as Example 1, must urged
Agent C.
Embodiment 4
In example 2, while Air washer using the speed of 3.0g/ minutes be uniformly added into water concentration as
45wt% salpeter solution.It is sprayed to after carrier saturated water absorption, 45 DEG C of closed processes 2.0 hours, water purification is washed 2 times, 150
DEG C dry 3.0 hours.Catalyst D is obtained using catalyst preparation conditions in the same manner as in Example 1.
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, the second that concentration is 8wt% is sprayed to resulting vehicle
Acid solution is to saturated water absorption, 50 DEG C of closed processes 2.0 hours, and water purification is washed 2 times.Dried 3.0 hours at 150 DEG C.Using with
Identical catalyst preparation conditions obtain catalyst F in embodiment 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 15g, 11g height is mixed into dry glue powder resistance to
Grind after carbon black, abundant kneading, 650 DEG C are calcined 3 hours, obtain carrier.Using with identical catalyst preparation bar in embodiment 1
Part obtains catalyst G.
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 its average pore diameter are from granular center to outer surface in gradually increasing, and duct permeability is preferable；And it is right
Ratio 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, the first reaction is first passed through
Device Hydrodemetalation catalyst, then by each example catalyst of the above in second reactor, take hydrogen One-through design, HDM
Catalyst is with batch industrial products.The process conditions all same that each example catalyst is used is evaluated, is respectively：Reaction pressure (hydrogen
Partial pressure), 16.0MPa；Reaction temperature, 385 DEG C；Total liquid hourly space velocity (LHSV), 0.26h-1；Hydrogen-oil ratio (v), 1000.Single reactor constant temperature
Segment body accumulates 300cm3, metal remover filling 100cm3, each example catalyst 194cm of the above3.Evaluation result is shown in Table 4.
From this example, the inventive method, which obtains catalyst, has higher hydrodesulfurization activity and well activity stabilized
Property.
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 | Husky light often slag |
| Density (20 DEG C)/gcm-3 | 0.98 |
| S,wt% | 3.9 |
The catalyst desulfurizing activity stability evaluation result of table 4
Claims (7)
1. a kind of inferior heavy oil Hydrobon catalyst, using aluminum oxide as carrier, using VIII race and VI B races metal as active component,
Catalyst pore volume is 0.45~0.60cm3/ g, specific surface area is 205~260m2/ g, average pore size is 7.0~12.0nm, and it is special
Levy and be that radially its average pore diameter from center to outer surface is in gradually to increase along catalyst granules；The catalyst is from particle
Average pore diameter average pore diameter small l~5nm compared with particle diameter 90% to surface portion of the heart to the part of particle diameter 50%.
2. according to catalyst described in claim l, it is characterised in that VIII race's element is that Ni, VI B element are Mo, the catalyst with
Weight meter contains NiO2~5%, MoO312~16%.
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 and extrusion aid, abundant kneading extruded moulding and through drying,
Roasting, obtains alumina support；
(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) impregnated with the solution of nickeliferous and molybdenum as the strip obtained by (2) and drying, roasting, final catalyst is made.
4. according to preparation method described in claim 3, it is characterised in that：In step (1) roasting condition of carrier be with l00~
200 DEG C/h of speed rises to 550~750 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 l~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 (3)
DEG C, the time is 2~5 hours.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106914249B (en) * | 2015-12-24 | 2019-11-08 | 中国石油天然气股份有限公司 | Residuum hydrogenating and metal-eliminating catalyst and preparation method thereof |
| CN106914250B (en) * | 2015-12-24 | 2019-07-05 | 中国石油天然气股份有限公司 | Catalyst for hydrotreatment of residual oil and preparation method thereof |
| CN107983326B (en) * | 2016-10-26 | 2020-08-18 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst forming carrier |
| CN107983405B (en) * | 2016-10-26 | 2020-08-18 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN108452846B (en) * | 2017-10-27 | 2020-08-07 | 中国石油天然气股份有限公司 | Gasoline hydrofining catalyst and preparation method thereof |
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| 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 in gradient increase and distribution according to concentration and preparation method thereof |
| CN102861590A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method thereof |
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Patent Citations (3)
| 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 in gradient increase and distribution according to concentration and preparation method thereof |
| CN102861590A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method thereof |
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