CN105983418B - Containing TiO2Macropore residuum hydrogenating and metal-eliminating catalyst preparation method - Google Patents
Containing TiO2Macropore residuum hydrogenating and metal-eliminating catalyst preparation method Download PDFInfo
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Abstract
One kind containing TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, include the following steps, boehmite, sesbania powder, expanding agent, adhesive and nanometer titanium hydroxide mixed aqueous solution are mixed, forms and is fired into carrier, roast and be made containing TiO after impregnating metal active component2Macropore residuum hydrogenating and metal-eliminating catalyst.
Description
Technical field
The invention belongs to a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, it is suitble to use fixed bed residual hydrogenation equipment
In, major function is to complete residuum hydrogenating and metal-eliminating process, can effectively improve the demetalization performance of catalyst.
Background technique
With the continuous aggravation of crude oil heaviness, in poor quality trend, mink cell focus deep process technology is constantly subjected to refine both at home and abroad
The great attention of oily expert.The key for determining hydrotreating techniques level is catalyst performance levels, especially at heavy-oil hydrogenation
Reason catalyst requirement has required good demetalization, desulfurization, denitrification activity.In heavy oil metal impurities be primarily present in colloid and
In asphalitine, this moieties molecular weight is big, structure is complicated, and diffusion is difficult, therefore it is required that there is catalyst macropore to hold, large aperture
Characteristic, macropore is convenient for diffusion of the macromolecule reactant to catalytic inner, and big pore volume, which helps to improve, holds metal or coke
Charcoal ability.Active metal has good dispersibility and dispersion stabilization in catalyst duct simultaneously, facilitates hydrogenation reaction
Progress.
The characteristics of CN1206037A discloses a kind of residuum hydrogenating and metal-eliminating catalyst, the invention is in aluminium oxide preparation process
In physics expanding agent and chemical enlargement agent is added simultaneously, then active component is loaded on the carrier in a manner of spraying,
The Kong Rongwei 0.80-1.20mL/g of the catalyst, specific surface 110-200m2/ g, can several apertures be 15-20nm.
CN1417300A discloses a kind of hydrodemetallization and preparation method thereof, and the preparation method of the catalyst includes with containing the
The solution of group vib and group VIII metallic compound impregnates a kind of macropore alumina supporter, the preparation method of the alumina support
Including by the mixture extrusion molding of boehmite, acid, water and extrusion aid, molding is fast in 35 minutes at 90-300 DEG C
Speed completes drying, roasts at least 0.5 hour and is made in the atmosphere of moisture vapor at 600-800 DEG C, gained alumina support
Pore size distribution is the 70-90% that the hole that diameter is 10-20nm accounts for total pore volume.The method use acid can reduce Kong Rong.
Application No. is 201010220850.4 Chinese invention patent applications to disclose a kind of macropore hydrogenation processing catalyst
Preparation method, prepared using the boehmite dry glue powder kneading method of two kinds of difference Kong Rong, then supported active metals, wherein
A kind of boehmite Kong Rong great, it is possible to provide the hole of bore dia 30nm-100nm, second of boehmite provide micron-sized
Hole can produce the hydrogenation protecting agent of intensity height, large bulk density, Kong Rong great by adjusting the mixed deterioration ratio of the two, but to quasi-
Boehmite ingredient requirement is high, and technique is relatively cumbersome.
CN102626659A provides a kind of TiO2-Al2O3Meet the preparation method of carrier, this method by titanium hydroxide with
And nonionic surfactant is added in deionized water and mixes, it is 0.5-5 that nitric acid, which is added, and adjusts the PH of colloidal sol, by soluble carbon
The aqueous solution in source is that 1-30h carries out hydro-thermal reaction, reaction knot 100-200 DEG C, reaction pressure 0.1-1.5MPa, reaction time
Beam is centrifugally separating to obtain the carbon particle that partial size is 200-800nm, and carbon particle is added in colloidal sol and is mediated uniformly with boehmite,
Extrusion molding, drying, roasting obtain TiO2-Al2O3Carrier, the method use acid to influence Kong Rong, while preparation process is opposite
It is cumbersome.
CN1103009 discloses a kind of preparation method of catalyst for heavy oil hydrogenation demetal carrier, it is by two kinds of apertures
It is distributed different aluminium hydroxide predecessors, carbon black and surfactant is added as expanding agent, by kneading and compacting, drying, roasting
Burning forms double-hole alumina support.Requirement of this method to predecessor alumina raw material is harsh, needs to be added more surface
Activating agent, industrial application higher cost.
Both at home and abroad to hydrogenation catalyst studies have shown that the type and property of carrier can be important to the generation of the performance of catalyst
It influences.Recent study discovery, with TiO2Modified Al2O3Carrier can obviously improve the Hydrogenation of catalyst, have catalyst
There are higher low temperature active, selective and anti-poisoning capability.
Summary of the invention
The present invention is mainly to provide a kind of containing TiO2Macropore residuum hydrogenating and metal-eliminating catalyst, catalytic hydrodemetallation
Activity is higher.
The shortcomings that present invention is overcome in the prior art reduces acid to the shadow of carrier cellular structure by anacidity kneading process
It rings, obtains TiO2Equally distributed macropore alumina supporter, what carried metal was prepared into contains TiO2Macropore residuum hydrogenating and metal-eliminating is urged
Agent can effectively improve the hydrodemetallization performance of catalyst.
The present invention provides a kind of containing TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, includes the following steps,
Boehmite, sesbania powder, expanding agent, adhesive and nanometer titanium hydroxide mixed aqueous solution are mixed, forms and is fired into load
Body, roasts after impregnating metal active component to be made and contains TiO2Macropore residuum hydrogenating and metal-eliminating catalyst.
It is of the present invention to contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, wherein adhesive is preferred
For methylcellulose, hydroxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, methylol hydroxyl second
One or more of base cellulose, the additional amount of adhesive are the 2%-7% of boehmite quality.
It is of the present invention to contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, wherein by adhesive plus
Enter and nanoscale titanium hydroxide is added in deionized water after mixing, the additional amount of titanium hydroxide is preferably boehmite quality
2%-10%.
It is of the present invention to contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, wherein expanding agent is preferred
For active carbon and/or asphaltic residue powder, active carbon is preferably one of wood activated charcoal, cocoanut active charcoal, apricot shell active carbon
Or it is several, expanding agent mesh number is preferably 100-200 mesh, and the additional amount of expanding agent is preferably the 1%-5% of boehmite quality.
It is of the present invention to contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, wherein sesbania powder adds
Enter amount is preferably boehmite quality 2%~7%.
It is of the present invention to contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, wherein carrier calcination temperature
Preferably 700-950 DEG C of degree, calcining time is preferably 3-10 hours.
It is of the present invention to contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, wherein preferably carry
The Kong Rong of body mesopore pore size 15-80nm accounts for the 40%-60% of total pore volume, what the Kong Rong Zhan of macropore diameter 90-1200nm always held
20%-30%, aperture be less than the hole 15nm Kong Rong account for total pore volume less than 40%.
It is of the present invention to contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, wherein impregnating metal is
Ni salt and Mo salt, in finished catalyst, in terms of catalyst gross mass, Ni and Mo content sum total preferably account for 5%-18%.
It is of the present invention to contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, wherein Mo salt is preferably
One or more of ammonium molybdate, sodium phosphomolybdate, ammonium phosphomolybdate, Ni salt are preferred nickel nitrate, in nickel acetate, basic nickel carbonate
It is one or more of.
It is of the present invention to contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, wherein catalyst roasting
Temperature is preferably 450-600 DEG C, and calcining time is preferably 3-10 hours.
Beneficial effects of the present invention:
In Hydrodemetalation catalyst preparation process of the present invention, acid is not used, the pore structure of carrier will not be caused seriously
It destroys, makes carrier that there is the big pore size distribution concentrated；The present invention is in working process heavy oil residue, catalytic hydrodemetallation, desulfurization
Activity is higher.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Adhesive:
In the present invention, adhesive is not particularly limited, usual adhesive can be enumerated as methylcellulose, methylol
One of cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxymethylhydroxyethyl cellulose or
Several, described adhesive also acts as reaming effect in addition to the bond strength between raising matrix particle.
The additional amount of adhesive:
In the present invention, the additional amount of adhesive is not particularly limited, the additional amount of usual adhesive is to intend thin water aluminium
The 2%-7% of stone quality；
If the additional amount of adhesive is less than the 2% of boehmite quality, since the additional amount of adhesive is very few, cause
Kneading is difficult to form；And the additional amount of adhesive is greater than the 7% of boehmite quality, since adhesive additional amount is excessive, makes
Other beneficial effects are had no without larger impact at wastage of material, and to pore structure.
The additional amount of titanium hydroxide:
In the present invention, the additional amount of titanium hydroxide is not particularly limited, the additional amount of usual titanium hydroxide is thin to intend
The 2%-10% of diaspore quality；
If the additional amount of titanium hydroxide is less than the 2% of boehmite quality, since the additional amount of titanium hydroxide is very few,
It causes not to be obviously improved hydrodemetallization effect；And the additional amount of titanium hydroxide is greater than the 10% of boehmite quality,
Since the additional amount of titanium hydroxide is excessive, wastage of material, and increased costs are caused, other beneficial effects are had no.
Expanding agent:
In the present invention, expanding agent is not particularly limited, usual expanding agent can be enumerated as active carbon and/or asphaltic residue
Powder, active carbon are one or more of wood activated charcoal, cocoanut active charcoal, apricot shell active carbon, and expanding agent mesh number is 100-200
Mesh；
If the mesh number of expanding agent is less than 100 mesh, since mesh number is excessive, cause shaping carrier intensity lower, and expanding agent
Mesh number be greater than 200 mesh cause specific surface excessive since mesh number is excessive and reaming effect be unobvious, have no other beneficial effects.
The additional amount of expanding agent:
In the present invention, the additional amount of expanding agent is not particularly limited, the additional amount of usual expanding agent is to intend thin water aluminium
The 1%-5% of stone quality；
If the additional amount of expanding agent is less than the 1% of boehmite quality, since the additional amount of expanding agent is very few, cause
Reaming effect is unobvious；And the additional amount of expanding agent is greater than the 5% of boehmite quality, due to the additional amount mistake of expanding agent
It is more, wastage of material is caused, and support strength is lower, has no other beneficial effects.
The additional amount of sesbania powder:
In the present invention, the additional amount of sesbania powder is not particularly limited, the additional amount of usual sesbania powder is to intend thin water aluminium
The 2%~7% of stone quality；
If the additional amount of sesbania powder is less than the 2% of boehmite quality, since the additional amount of sesbania powder is very few, cause
Molding effect is bad；And the additional amount of sesbania powder is greater than the 7% of boehmite quality, since the additional amount of sesbania powder is excessive,
Wastage of material is caused, other beneficial effects are had no.
Carrier calcination condition:
In the present invention, carrier calcination condition is not particularly limited, usual carrier calcination condition: temperature 700-950
DEG C, calcining time 3-10 hours；
If carrier calcination temperature is less than 700 DEG C, since maturing temperature is too low, cause specific surface excessively high, and maturing temperature
Greater than 950 DEG C, since maturing temperature is excessively high, causes specific surface too low, have no other beneficial effects；
If calcining time was less than 3 hours, since calcining time is too short, roasting is caused to be not thorough, specific surface hole Rong Bufu
It closes and requires, and calcining time is more than 10 hours, due to overlong time, the time is caused to waste, and has no other beneficial effects.
Ni and Mo content:
In the present invention, Ni and Mo content is not particularly limited, usual impregnating metal is Ni salt and Mo salt, catalyst
In finished product, in terms of catalyst gross mass, Ni and Mo content sum total account for 5%-18%.
If in finished catalyst, in terms of catalyst gross mass, Ni and Mo content are summed up less than 5%, since Ni and Mo contain
It measures very few, causes hydrodemetallization, desulfurization effect poor；And in finished catalyst, in terms of catalyst gross mass, Ni and Mo content are total
It closes and is greater than 18%, since Ni and Mo content is excessive, causes to waste, and be not improved demetalization, desulfurization effect, have no other
Beneficial effect.
Mo salt type:
In the present invention, Mo salt type is not particularly limited, usual Mo salt can be enumerated as ammonium molybdate, sodium phosphomolybdate, phosphorus
One or more of ammonium molybdate.
Ni salt type:
In the present invention, Ni salt type is not particularly limited, usual Ni salt can be enumerated as nickel nitrate, nickel acetate, alkali formula
One or more of nickelous carbonate.
Catalyst roasting condition:
In the present invention, catalyst roasting condition is not particularly limited, usual catalyst roasting condition: temperature 450-
600 DEG C, calcining time 3-10 hours；
If catalyst maturing temperature is less than 450 DEG C, since maturing temperature is too low, cause specific surface excessively high, and roasts temperature
Degree is greater than 600 DEG C, since maturing temperature is excessively high, causes specific surface too low, has no other beneficial effects；
If calcining time was less than 3 hours, since calcining time is too short, cause to roast insufficient, specific surface is excessively high and roasts
Burning the time is more than 10 hours, due to overlong time, the time is caused to waste, has no other beneficial effects.
Technical characterstic of the invention is further described below with reference to specific example:
Embodiment 1:
Macropore boehmite dry glue powder 500g is weighed, 15g sesbania powder and 20g asphaltic residue powder, the wooden activity of 5g is added
Charcoal is uniformly mixed；20 grams of titanium hydroxides and 25g methylcellulose are added in 400g water purification, mixing is slowly added to afore-mentioned materials
In, then kneading is extruded into the cloverleaf pattern that diameter is 1.6mm at plastic on preceding crowded formula single-screw extruder.It is dry at 120 DEG C
Dry 2.5 hours, then be placed in roaster, in 800 DEG C constant temperature 3 hours, obtain carrier.Above-mentioned alumina support 100g is weighed, is added
Enter 150 mlMo-Ni-NH3Solution (contains MoO310wt%, NiO3It 3.5wt%) impregnates, wherein Mo-Ni-NH3The configuration of solution is such as
Under: after addition 24.85g ammonium molybdate stirring and dissolving is complete in the ammonium hydroxide for being 20% to 90ml concentration, 28.35g nickel nitrate is added and stirs
It mixes to being completely dissolved, water is added to mend to 150ml；After the completion of spraying, filter off redundant solution, 120 DEG C drying 3 hours, then at 600 DEG C
Roasting 5 hours, is made Hydrodemetalation catalyst A1 of the invention.
Embodiment 2
Macropore boehmite dry glue powder 500g is weighed, 10g sesbania powder is added and 5g asphaltic residue powder is uniformly mixed；By 20
Gram titanium hydroxide and 20g methylcellulose, 5 hydroxymethyl celluloses are added in 400g water purification, and mixing is slowly added in afore-mentioned materials,
Then kneading is extruded into the cloverleaf pattern that diameter is 1.6mm at plastic on preceding crowded formula single-screw extruder.In 120 DEG C of dryings
2.5 hours, then be placed in roaster, in 700 DEG C constant temperature 10 hours, obtain carrier.Above-mentioned alumina support 100g is weighed, is added
Enter 150mlMo-Ni-NH3Solution (contains MoO34wt%, NiO3It 1wt%) impregnates, wherein Mo-Ni-NH3The configuration of solution is as follows:
After addition 24.85g ammonium molybdate stirring and dissolving is complete in the ammonium hydroxide for being 20% to 90ml concentration, the stirring of 28.35g nickel nitrate is added
To being completely dissolved, water is added to mend to 150ml；After the completion of spraying, filter off redundant solution, 120 DEG C drying 3 hours, then at 600 DEG C
Roasting 3 hours, is made Hydrodemetalation catalyst A2 of the invention.
Embodiment 3
Macropore boehmite dry glue powder 500g is weighed, 35g sesbania powder and 20g asphaltic residue powder, 5g apricot shell activity is added
Charcoal is uniformly mixed；50 grams of titanium hydroxides and 10g methylcellulose are added in 4000g water purification, mixing is slowly added to afore-mentioned materials
In, then kneading is extruded into the cloverleaf pattern that diameter is 1.6mm at plastic on preceding crowded formula single-screw extruder.It is dry at 120 DEG C
Dry 2.5 hours, then be placed in roaster, in 950 DEG C constant temperature 3 hours, obtain carrier.Above-mentioned alumina support 100g is weighed, is added
Enter 150 mlMo-Ni-NH3Solution (contains MoO313wt%, NiO3It 5wt%) impregnates, wherein Mo-Ni-NH3The configuration of solution is such as
Under: to 90ml concentration be 20% ammonium hydroxide in be added 33.7g ammonium molybdate stirring and dissolving it is complete after, be added 42g nickel nitrate stir to
It is completely dissolved, water is added to mend to 150ml；After the completion of spraying, filter off redundant solution, 120 DEG C drying 3 hours, then roasted at 450 DEG C
10 hours, Hydrodemetalation catalyst A3 of the invention is made.
Embodiment 4
Macropore boehmite dry glue powder 500g is weighed, 25g sesbania powder and 15g asphaltic residue powder, 5g apricot shell activity is added
Charcoal, 5 cocoanut active charcoals are uniformly mixed；10 grams of titanium hydroxides and 35g methylcellulose are added in 400g water purification, are mixed slow
It is added in afore-mentioned materials, then kneading is extruded into the clover that diameter is 1.6mm at plastic on preceding crowded formula single-screw extruder
Shape.It is 2.5 hours dry at 120 DEG C, then be placed in roaster, in 800 DEG C constant temperature 6 hours, obtain carrier.Weigh above-mentioned aluminium oxide
150mlMo-Ni-NH is added in carrier 100g3Solution (contains MoO310wt%, NiO3It 3.5wt%) impregnates, wherein Mo-Ni-NH3
The configuration of solution is as follows: after addition 24.85g ammonium molybdate stirring and dissolving is complete in the ammonium hydroxide for being 20% to 90ml concentration, being added
28.35g nickel nitrate is stirred to being completely dissolved, and water is added to mend to 150ml；After the completion of spraying, redundant solution is filtered off, 120 DEG C of dryings 3 are small
When, then roasted 5 hours at 500 DEG C, Hydrodemetalation catalyst A4 of the invention is made.
Comparative example 1:
According to method described in Chinese patent CN1103009, prepares carrier and 150 mlMo-Ni-NH are added3Solution
(contain MoO310wt%, NiO33.5wt%) impregnate, filter off redundant solution, 120 DEG C drying 3 hours, then roast at 600 DEG C 5 small
When, catalyst B1 is made.
Comparative example 2
According to method described in Chinese patent CN1103009,20g titanium hydroxide is added in carrier preparation process, carries
Body preparation completes that 150mlMo-Ni-NH is added3Solution (contains MoO310wt%, NiO3It 3.5wt%) impregnates, filters off redundant solution,
120 DEG C drying 3 hours, then roasted 5 hours at 600 DEG C, catalyst B2 be made.
Comparative example 3:
According to method described in Chinese patent CN102626659A, prepares carrier and 150 mlMo-Ni-NH3 of addition are molten
Liquid (contains MoO310wt%, NiO33.5wt%) impregnate, filter off redundant solution, 120 DEG C drying 3 hours, then roast 5 at 600 DEG C
Hour, catalyst B3 is made.
Comparative example 4
Macropore boehmite dry glue powder 500g is weighed, 15g sesbania powder and 20g asphaltic residue powder, the wooden activity of 5g is added
Charcoal is uniformly mixed；25g methylcellulose is added in 400g water purification, mixing is slowly added in afore-mentioned materials, and kneading is at plastic
Then body is extruded into the cloverleaf pattern that diameter is 1.6mm on preceding crowded formula single-screw extruder.It is 2.5 hours dry at 120 DEG C, then
Be placed in roaster in, in 800 DEG C constant temperature 3 hours, obtain carrier.Above-mentioned alumina support 100g is weighed, 150mlMo-Ni- is added
NH3Solution (contains MoO310wt%, NiO3It 3.5wt%) impregnates, wherein Mo-Ni-NH3The configuration of solution is as follows: to 90ml concentration
For be added in 20% ammonium hydroxide 24.85g ammonium molybdate stirring and dissolving it is complete after, 28.35g nickel nitrate is added and stirs to being completely dissolved,
Water is added to mend to 150ml；After the completion of spraying, filter off redundant solution, 120 DEG C drying 3 hours, then roasted 5 hours at 600 DEG C, system
Obtain Hydrodemetalation catalyst B4 of the invention.
Comparative example 5
Macropore boehmite dry glue powder 500g is weighed, 15g sesbania powder and 20g asphaltic residue powder, the wooden activity of 5g is added
Charcoal is uniformly mixed；20 grams of titanium hydroxides and 25g citric acid are added in 400g water purification, mixing is slowly added in afore-mentioned materials, is mixed
Plastic is pinched into, the cloverleaf pattern that diameter is 1.6mm is then extruded on preceding crowded formula single-screw extruder.At 120 DEG C dry 2.5
Hour, then be placed in roaster, in 800 DEG C constant temperature 3 hours, obtain carrier.Above-mentioned alumina support 100g is weighed, is added
150mlMo-Ni-NH3Solution (contains MoO310wt%, NiO3It 3.5wt%) impregnates, wherein Mo-Ni-NH3The configuration of solution is as follows:
After addition 24.85g ammonium molybdate stirring and dissolving is complete in the ammonium hydroxide for being 20% to 90ml concentration, the stirring of 28.35g nickel nitrate is added
To being completely dissolved, water is added to mend to 150ml；After the completion of spraying, filter off redundant solution, 120 DEG C drying 3 hours, then at 600 DEG C
Roasting 5 hours, is made Hydrodemetalation catalyst B5 of the invention.
Embodiment and comparative example effect:
Embodiment and comparative example catalyst physico-chemical property are as shown in table 1,
1 embodiment of table and comparative example catalyst property
Seen from table 1, comparative example, the B5 and A1 from table are much higher than using the specific surface and Kong Rong of catalyst obtained by this patent
Comparison from the point of view of, what methylcellulose played is not only cementation, and there are also reaming effects.
Using certain poor residuum as raw material, oil property is as shown in table 1, under identical reaction conditions (reaction pressure
134.0MPa；380 DEG C of temperature；Volume space velocity 0.25h when liquid-1；Hydrogen to oil volume ratio 1000) 3 kinds of different catalysts of comparison plus hydrogen
Reaction effect, the results are shown in Table 2.
2 raw material oil property of table
Catalyst result in 1 embodiment and comparative example of table
| Catalyst number | A1 | A2 | A3 | A4 | B1 | B2 | B3 | B4 | B5 |
| De- (Ni+V) % | 90.3 | 90.2 | 90.1 | 90.3 | 86.0 | 87.6 | 82.0 | 80.5 | 88.0 |
| Desulfurization degree % | 91.2 | 91.0 | 91.5 | 91.0 | 89.5 | 89.0 | 87.0 | 88.3 | 87.5 |
As can be seen from Table 2, the obvious excellent and comparative example of its desulfurization demetalization performance of the catalyst in this patent embodiment
Prepared catalyst, and there is B4 and A1 to find out, titanium hydroxide is most important to the performance for improving catalyst.
Claims (6)
1. one kind contains TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, which is characterized in that include the following steps, it will
Boehmite, sesbania powder, expanding agent, adhesive and the mixing of nanometer titanium hydroxide mixed aqueous solution, form and are fired into carrier,
It roasts to be made after impregnating metal active component and contains TiO2Macropore residuum hydrogenating and metal-eliminating catalyst, carrier calcination temperature 700-950
DEG C, calcining time 3-10 hours；
Expanding agent is active carbon and/or asphaltic residue powder, and active carbon is wood activated charcoal, in cocoanut active charcoal, apricot shell active carbon
One or more, expanding agent mesh number be 100-200 mesh；
Adhesive be methylcellulose, hydroxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose,
One or more of hydroxymethylhydroxyethyl cellulose；
Wherein, the additional amount of adhesive is the 2%-7% of boehmite quality,
The additional amount of titanium hydroxide is the 2%-10% of boehmite quality,
The additional amount of expanding agent is the 1%-5% of boehmite quality,
The additional amount of sesbania powder is the 2%~7% of boehmite quality.
2. according to claim 1 contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, it is characterised in that:
Adhesive is added in deionized water, nanoscale titanium hydroxide is added after mixing.
3. according to claim 1 contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, it is characterised in that:
The Kong Rong of carrier mesopore pore size 15-80nm accounts for the 40%-60% of total pore volume, what the Kong Rong Zhan of macropore diameter 90-1200nm always held
20%-30%, aperture be less than the hole 15nm Kong Rong account for total pore volume less than 40%.
4. according to claim 1 contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, it is characterised in that:
Impregnating metal is Ni salt and Mo salt, and in finished catalyst, in terms of catalyst gross mass, Ni and Mo content sum total account for 5%-18%.
5. according to claim 1 contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, it is characterised in that:
Mo salt is one or more of ammonium molybdate, sodium phosphomolybdate, ammonium phosphomolybdate, and Ni salt is nickel nitrate, in nickel acetate, basic nickel carbonate
One or more.
6. according to claim 1 contain TiO2The preparation method of macropore residuum hydrogenating and metal-eliminating catalyst, it is characterised in that:
450-600 DEG C of catalyst maturing temperature, calcining time 3-10 hours.
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| CN108236940A (en) * | 2016-12-27 | 2018-07-03 | 中国石油天然气股份有限公司 | The preparation method of catalyst for hydrotreatment of residual oil carrier |
| CN107456979A (en) * | 2017-09-18 | 2017-12-12 | 北京欧奏普尔环保设备有限公司 | macroporous catalyst preparation method |
| CN111001412A (en) * | 2019-11-27 | 2020-04-14 | 浙江石油化工有限公司 | Titanium-containing residual oil hydrotreating catalyst and preparation method thereof |
| CN115245830B (en) * | 2021-04-27 | 2024-05-28 | 中国石油天然气股份有限公司 | Poor-quality residual oil hydrodemetallization catalyst and preparation method thereof |
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| CN101890371A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Titanium dioxide-aluminum oxide composite carrier and preparation method thereof |
| CN102649069A (en) * | 2011-02-24 | 2012-08-29 | 中国石油化工股份有限公司 | Hydrogenated active protective agent taking alumina containing IVB group metal as carrier, as well as preparation and application of hydrogenated active protective agent |
| CN102698757A (en) * | 2012-05-31 | 2012-10-03 | 中国石油化工股份有限公司 | Cracking C9 hydrogenation catalyst and preparation method thereof |
| CN103480428A (en) * | 2012-06-12 | 2014-01-01 | 中国石油化工股份有限公司 | Hydrated alumina molded matter and preparation method thereof, alumina molded matter and applications of hydrated alumina molded matter and alumina molded matter |
| CN103657667A (en) * | 2013-11-26 | 2014-03-26 | 陕西延长石油(集团)有限责任公司研究院 | Preparation method for novel heavy oil hydrogenization demetallization catalyst adopting macroporous structures |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101890371A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Titanium dioxide-aluminum oxide composite carrier and preparation method thereof |
| CN102649069A (en) * | 2011-02-24 | 2012-08-29 | 中国石油化工股份有限公司 | Hydrogenated active protective agent taking alumina containing IVB group metal as carrier, as well as preparation and application of hydrogenated active protective agent |
| CN102698757A (en) * | 2012-05-31 | 2012-10-03 | 中国石油化工股份有限公司 | Cracking C9 hydrogenation catalyst and preparation method thereof |
| CN103480428A (en) * | 2012-06-12 | 2014-01-01 | 中国石油化工股份有限公司 | Hydrated alumina molded matter and preparation method thereof, alumina molded matter and applications of hydrated alumina molded matter and alumina molded matter |
| CN103657667A (en) * | 2013-11-26 | 2014-03-26 | 陕西延长石油(集团)有限责任公司研究院 | Preparation method for novel heavy oil hydrogenization demetallization catalyst adopting macroporous structures |
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