CN105983418B - Containing TiO2Macropore residuum hydrogenating and metal-eliminating catalyst preparation method - Google Patents

Containing TiO2Macropore residuum hydrogenating and metal-eliminating catalyst preparation method Download PDF

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CN105983418B
CN105983418B CN201510061806.6A CN201510061806A CN105983418B CN 105983418 B CN105983418 B CN 105983418B CN 201510061806 A CN201510061806 A CN 201510061806A CN 105983418 B CN105983418 B CN 105983418B
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catalyst
metal
macropore
preparation
residuum hydrogenating
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CN105983418A (en
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于双林
赵愉生
程涛
崔瑞利
谭青峰
姚远
张春光
由慧玲
赵元生
范建光
周志远
张志国
王燕
刘佳澎
魏静
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China Petroleum and Natural Gas Co Ltd
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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

Containing TiO2Macropore residuum hydrogenating and metal-eliminating catalyst preparation method
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
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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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