CN102343270A - Hydrogenation catalyst with active metal ingredient in layering distribution and preparation method thereof - Google Patents
Hydrogenation catalyst with active metal ingredient in layering distribution and preparation method thereof Download PDFInfo
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- CN102343270A CN102343270A CN2010102400354A CN201010240035A CN102343270A CN 102343270 A CN102343270 A CN 102343270A CN 2010102400354 A CN2010102400354 A CN 2010102400354A CN 201010240035 A CN201010240035 A CN 201010240035A CN 102343270 A CN102343270 A CN 102343270A
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Abstract
The invention relates to a hydrogenation catalyst with active metal ingredients in layering distribution and a preparation method thereof. Al2O3 or Al2O3 containing SiO2, TiO2 and ZrO2 is used as a carrier with a pore volume of 0.2-3.0 ml/g and a specific surface area of 20-400 m<2>/g; active metal ingredients in the catalyst particles are in layering distribution; a nucleus layer comprises molybdenum nickel or tungsten nickel active metal ingredients, and a casing layer comprises molybdenum cobalt active metal ingredients, wherein at least one active metal ingredient in the nucleus layer is different from that in the casing layer; calculated by metal oxide weight, an active metal ingredient MoO3 accounts for 3.0-20.0%; CoO accounts for 2.0-8.0%; WO3 accounts for 8.0-18%; and NiO accounts for 2.0-8.0%. The method of the invention has simple operation, controllable process, good repeatability and is apt to large scale production; when used for hydrotreatment and modification of heavy oil, the catalyst has high desulfurization, denitrogenation and carbon residue removal activity and stability.
Description
Technical field
The present invention relates to a kind of active metal component and be hydrogenation catalyst of layer distributed and preparation method thereof.
Background technology
Along with the aggravation of crude oil heaviness, inferiorization trend in the world wide, and the increasingly stringent of environmental regulation, market but increases the demand of light-end products year by year simultaneously, and development heavy oil deep process technology has become the task of top priority of petroleum refining industry.Hydrogen addition technology is faced with great challenge as a kind of main manufacturing process of heavy oil deep processing, presses for to develop hydrogenation technique and the higher hydrogenation catalyst of more optimizing that is applicable to inferior raw material of activity stability.Aspect catalyst, press for to develop and have higher desulfurization, denitrogenation, take off carbon residue, take off the active catalyst with stability of virtue, to improve the quality of products and yield; Further reduce Preparation of Catalyst cost, extension fixture on-stream time simultaneously.
At present industrial usually by the stable metallic solution of preparation, saturated impregnated on the carrier made hydrogenation catalyst through dry, roasting.Introduced a kind of hydrogenization catalyst preparation method like US 4399058, group vib and VIII family slaine mixed with ammoniacal liquor, added ammoniacal liquor and be adjusted to a certain pH value, made metallic solution, again with the saturated inorganic oxide carrier that impregnated in of metallic solution (like Al
2O
3, SiO
2Deng) on, make hydrogenation catalyst after drying, the roasting.
For hydrodesulfurization, the denitrification activity that improves catalyst, usually adopt the method for auxiliary agents such as adding P, B, F or complexing agent, take off the impurity performance with what improve catalyst.Introduced a kind of preparation method of hydrotreatment catalyst like US 4483942A; It is with a certain amount of group vib and VIII family slaine, phosphoric acid, citric acid or malic acid and ammoniacal liquor mixing; Be adjusted to a certain pH value; Obtain metal impregnation solution; Then impregnated alumina or silica-alumina supports are processed catalyst after drying, roasting.
For the catalyst that conventional method obtains, the distribution of active metal component on catalyst granules is often comparatively even.At present, be that the hydrogenization catalyst preparation method that multilayer distributes is reported less about active metal component.
Chinese patent CN101224424A provides a kind of preparation method of double layer noble metal active component catalyst; It adopts the double-coated coating method; Activated alumina, cerium zirconium sosoloid and nitric acid are mixed and made into alumina slurry C0; Then carrier is immersed palladium-impregnated salting liquid after slurry C 0, oven dry, the roasting; Obtain catalyst semi-finished product G1 through after the roasting; Process semi-finished product G2 after semi-finished product G1 immersed slurry C 0, drying, roasting once more, with semi-finished product G2 platinum-impregnated rhodium solution after roasting makes double layer noble metal active component catalyst product.The catalyst of this metal component layering can be brought into play the different effects of every layer of active component, improves the utilization rate of active component greatly.But it is too complicated that the shortcoming of this method is the preparation process, and wayward.
Summary of the invention
The object of the present invention is to provide the active metal component that a kind ofly has higher desulfurization, denitrogenation, takes off carbon residue activity and better stability to be hydrogenation catalyst of layer distributed and preparation method thereof; Its characteristics are that active metal component distributes for double-deck in catalyst granules; Promptly has hud typed characteristic distributions; Stratum nucleare is molybdenum nickel or tungsten nickel active metal component; Shell is a molybdenum cobalt active metal component, and the preparation method is simple.
Active metal component of the present invention is the hydrogenization catalyst preparation method of layer distributed:
The preparation of hydrogenation catalyst: select Al for use
2O
3Or contain SiO
2, TiO
2, ZrO
2Al
2O
3As carrier, with molybdenum and nickel or tungsten and nickel active metallic compound, molybdenum and cobalt active metallic compound difference and/or acid and deionized water or ammoniacal liquor are mixed and made into metal impregnation liquid, adopt the method for saturated spray-stain to prepare hydrogenation catalyst.
Adopt the saturated method that sprays; The preparation process is following: earlier with the solution pre-preg carrier that contains two kinds of reactive metals; Use the carrier of the maceration extract spray-stain pre-preg that contains two kinds of active metal components again; Soaked carrier 80～150 ℃ dry 1～8 hour down, roasting 2～6 hours in 300～650 ℃ air then; The back have at least in a kind of maceration extract a kind of active metal component with before a kind of maceration extract different.
A kind of hydrogenation catalyst by the inventive method preparation is characterized in that:
1) selects Al for use
2O
3Or contain SiO
2, TiO
2, ZrO
2Al
2O
3As carrier;
Pore volume is 0.2～3.0ml/g, is preferably 0.45～1.3ml/g;
Specific area is 20～400m
2/ g is preferably 100～240m
2/ g;
2) active metal component is layer distributed in the catalyst granules, and shell is a molybdenum cobalt active metal component, and stratum nucleare is molybdenum nickel or tungsten nickel active metal component; Internal layer has a kind of reactive metal at least with outer different;
3) by the metal oxide weight, active metal component MoO
3Be 3.0～20.0%, CoO is 2.0～8.0%, WO
3Be 8.0～18%, NiO is 2.0～8.O%.
The carrier that uses in the method for preparing catalyst of the present invention can be to drip ball forming, spin granulation, extrusion modling, compression molding etc., is best to drip ball forming and extrusion modling.Catalyst shape can be spherical, bar shaped (comprising cylindrical, trilobal, quatrefoil etc.), sheet shape, is best with spherical and bar shaped.
The hydrogenation catalyst of the inventive method preparation is mainly used in mink cell focus hydrotreatment and upgrading.The advantage of the inventive method is: the catalyst activity metal component distributes for double-deck, promptly has hud typed characteristic distributions, and shell is a molybdenum cobalt active metal component, and stratum nucleare is molybdenum nickel or tungsten nickel active metal component.The prepared catalyst of the present invention has higher desulfurization, denitrogenation, takes off carbon residue activity and stable, and the preparation process is simple.
The specific embodiment
Embodiment 1
Present embodiment is with Al
2O
3Make carrier, its water absorption rate is 1.10mL/g.Adopt the saturated method of spraying to prepare the catalyst that active metal component is Mo, Co, Ni.
Take by weighing the 150g carrier, spray 82.5ml and contain the 14.9g ammonium molybdate and (contain MoO
382m%) with the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%), spray and finish, spray 82.5ml again and contain the 14.9g ammonium molybdate and (contain MoO
382m%), the ammonia spirit of 13.5g cobalt nitrate (containing CoO 25.2m%), sprayed in 5 minutes.Homogenizing is after 10 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, then 120 ℃ dry 5 hours down, roasting 3 hours in 500 ℃ of air again makes catalyst, is numbered C-1.
Embodiment 2
Present embodiment is to contain 1.5m% SiO
2Al
2O
3Make carrier, its water absorption rate is 1.10mL/g.Adopt the saturated method that sprays to prepare the catalyst that active metal component is Mo, Co, Ni.
Take by weighing the 150g carrier, spray 82.5ml and contain the 14.9g ammonium molybdate and (contain MoO
382m%) with the ammonia spirit of 13.5g cobalt nitrate (containing CoO 25.2m%), in the process of spraying, at the uniform velocity splash into 82.5ml and contain the 14.9g ammonium molybdate and (contain MoO
382m%), sprayed in 5 minutes with the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%).Homogenizing is after 10 minutes in the equipment of spraying, 120 ℃ dry 4 hours down, roasting 3 hours in 500 ℃ of air again makes catalyst, is numbered C-2.
Embodiment 3
Present embodiment is to contain 1.0m% SiO
2, 1.5m% TiO
2Al
2O
3Make carrier, water absorption rate is 1.10mL/g.Adopt the saturated method that sprays to prepare the catalyst that active metal component is Mo, W, Ni.
Take by weighing the 150g carrier, spray 75ml and contain the 14.9g ammonium molybdate and (contain MoO
382m%) with the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%), after having sprayed, then spray 90ml and contain the 14.9g ammonium metatungstate and (contain WO
382m%), flooded in 5 minutes with the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%).Homogenizing is after 20 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out the back in 120 ℃ dry 5 hours down, roasting 3 hours in 500 ℃ of air again makes catalyst, is numbered C-3.
Embodiment 4
Present embodiment is to contain 2.0m% ZrO
2Al
2O
3Make carrier, water absorption rate is 1.10mL/g.Adopt the saturated method of spraying to prepare the catalyst that active metal component is Mo, Co, Ni.
Take by weighing the 150g carrier, spray 82.5ml and contain the 14.9g ammonium molybdate and (contain MoO
382m%) with the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%), spray and finish, spray-stain 82.5ml contains the 14.9g ammonium molybdate and (contains MoO again
382m%), sprayed in 5 minutes with the ammonia spirit of 13.5g cobalt nitrate (containing NiO 25.2m%).Homogenizing is after 20 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out the back in 120 ℃ dry 6 hours down, roasting 3 hours in 500 ℃ of air again makes catalyst, is numbered C-4.
Embodiment 5
Present embodiment is with Al
2O
3Make carrier, water absorption rate is 1.10mL/g.Adopt the saturated method of spraying to prepare the catalyst that active metal component is W, Ni, Co.
Take by weighing the 150g carrier, spray 82.5ml in advance and contain the 14.9g ammonium metatungstate and (contain WO
382m%) with the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%), after having sprayed, spray 82.5ml again and contain the 14.9g ammonium metatungstate and (contain WO
382m%), sprayed in 5 minutes with the ammonia spirit of 13.5g cobalt nitrate (containing NiO25.2m%).Homogenizing is after 10 minutes in the equipment of spraying, 120 ℃ dry 7 hours down, roasting 6 hours in 500 ℃ of air again makes catalyst, is numbered C-5.
Embodiment 6
Present embodiment is to contain 1.5m% TiO
2With 2.0m% ZrO
2Al
2O
3As carrier, water absorption rate is 1.10mL/g.Adopt the saturated method of spraying to prepare the catalyst that active metal component is Mo, W, Co.
Take by weighing the 150g carrier, spray 82.5ml in advance and contain the 14.9g ammonium molybdate and (contain MoO
382m%) with the ammonia spirit of 13.5g cobalt nitrate (containing CoO 25.2m%), spray and finish, spray 82.5ml again and contain the 14.9g ammonium metatungstate and (contain WO
382m%), sprayed in 5 minutes with the ammonia spirit of 13.5g cobalt nitrate (containing CoO 25.2m%).Homogenizing is after 10 minutes in the equipment of spraying, 120 ℃ dry 7 hours down, roasting 6 hours in 500 ℃ of air again makes catalyst, is numbered C-6.
Comparative example 1
Present embodiment is with Al
2O
3Make carrier, water absorption rate is 1.10mL/g.Adopt the saturated method of spraying to prepare the catalyst that active metal component is Mo, Co, Ni.
Take by weighing the 150g carrier, spray 165ml by the saturated absorption amount of solution and contain the 29.8g ammonium molybdate and (contain MoO
382m%), the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%), 13.5g cobalt nitrate (containing CoO 25.2m%).Homogenizing is after 5 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out the back in 120 ℃ dry 3 hours down, roasting 3 hours in 500 ℃ of air again makes catalyst, is numbered C-7.
Comparative example 2
Present embodiment is with Al
2O
3Make carrier, water absorption rate is 1.10mL/g.Adopt the saturated method of spraying to prepare the catalyst that active metal component is Mo, Co, Ni.
Take by weighing the 150g carrier, spray 185ml and contain the 29.8g ammonium molybdate and (contain MoO
382m%), the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%) and 13.5g cobalt nitrate (containing CoO 25.2m%).Homogenizing is after 5 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out the back in 120 ℃ dry 3 hours down, roasting 3 hours in 500 ℃ of air again makes catalyst, is numbered C-8.
Embodiment 8
Adopt characterization methods such as BET, EDX, XRF that catalyst C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9 are characterized, physico-chemical property is seen table 1 in detail.
Table 1 catalyst physical data
Annotate: R is the carrier granular radius, is starting point with the catalyst granules surface.
Can find out that from table 1 among catalyst C-1, C-2, C-3, C-4, C-5, the C-6, particle center and top layer have different activity metal component concentration, and the metal component CONCENTRATION DISTRIBUTION of C-7 and C-8 is comparatively even.
Embodiment 9
Present embodiment is catalyst C-1 and C-4 stability test; And with C-5 carry out desulfurization removing nitric active with the stability contrast; Adopt catalyst grade combo dress scheme; Load metal remover, demetalization desulfurizing agent, the agent of high activity desulfurization removing nitric from the bottom to the top respectively in reactor bed, additional proportion is respectively 40%, 20%, 40%.C-1, C-4, C-5 are as the agent of high activity desulfurization removing nitric.
Metal remover is according to CN100363470C embodiment 1 preparation.
The desulfurizing agent preparation method is following:
Take by weighing 300g Al
2O
3(butt 68m%) powder; Powdered active carbon 9.1g; The blue or green powder 8g in field; The three is mixed, add the acid solution that mixes by 200g water and 15g HAc (acetate), mix and pinched 1.5 hours; Obtain plastic; On banded extruder, be extruded into the cloverleaf pattern strip of φ 1.10～1.35mm, this strip was descended dry 4 hours at 120 ℃, obtained carrier in 4 hours 750 ℃ of following roastings., descended dry 2 hours at 120 ℃ then resulting carrier impregnation reactive metal molybdenum and cobalt with conventional method,, promptly make catalyst 550 ℃ of following roastings 3 hours.MoO in the catalyst
3Content is 11.2m%, and the CoO mass content is 6.6m%, specific area 220m
2/ g, pore volume are 0.65ml/g.
On 100ml small fixed hydrogenation plant, estimate.Estimating feedstock oil is that Saudi Arabia subtracts slag, and character is as shown in table 2.
Table 2 test raw material oil main character
Appreciation condition is as shown in table 3.
Table 3 process conditions
Active and estimation of stability result lists in table 4.Relatively metal removal rate, desulfurization degree, denitrification percent are to be 1.00 to make benchmark and relatively get with 500 hours demetallization per of C-1 catalyst runs.By finding out in the table 4, along with the prolongation of the duration of runs, the grading composition that contains the C-1 catalyst with contain desulfurization degree, the denitrification percent of the grading composition of C-4 catalyst and take off carbon yield all apparently higher than the Comparative Examples catalyst; Corresponding desulfurization degree, denitrification percent, take off the carbon yield attenuation degree all less than contrast medium.We can say that the catalyst activity that the inventive method makes is better than the catalyst that conventional method obtains with stability.
Table 4 catalyst stability contrast experiment
Claims (3)
1. an active metal component is the hydrogenation catalyst of layer distributed, it is characterized in that:
1) with Al
2O
3Or contain SiO
2, TiO
2, ZrO
2Al
2O
3Be carrier; Pore volume is 0.2～3.0ml/g; Specific area is 20～400m
2/ g;
2) active metal component is layer distributed in the catalyst granules, and stratum nucleare is molybdenum nickel or tungsten nickel active metal component, and shell is a molybdenum cobalt active metal component; Stratum nucleare has at least a kind of reactive metal different with shell;
3) by the metal oxide weight, active metal component MoO
3Be 3.0～20.0%, CoO is 2.0～8.0%, WO
3Be 8.0～18%, NiO is 2.0～8.0%.
2. the described active metal component of claim 1 is the hydrogenization catalyst preparation method of layer distributed, it is characterized in that: select Al for use
2O
3Or contain SiO
2, TiO
2, ZrO
2Al
2O
3As carrier, with molybdenum and nickel or tungsten and nickel active metallic compound, molybdenum and cobalt active metallic compound difference and/or acid and deionized water or ammoniacal liquor are mixed and made into metal impregnation liquid, adopt the method for saturated spray-stain to prepare hydrogenation catalyst; Adopted for two steps sprayed method; Stratum nucleare is molybdenum nickel or tungsten nickel active metal component; Shell is a molybdenum cobalt active metal component; Spray that to have at least a kind of active metal component and back to spray liquid in the liquid different in one step of back; Soaked carrier 80～150 ℃ dry 1～8 hour down, roasting 2～6 hours in 300～650 ℃ air then.
3. the described active metal component of claim 1 is the application of the hydrogenation catalyst of layer distributed, it is characterized in that: be used for mink cell focus hydrotreatment and modifying catalyst.
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| CN107345151A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of hydrotreating method of high nitrogen inferior heavy oil |
| CN107345150A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of hydrotreating method of high nitrogen inferior heavy oil |
| CN107345150B (en) * | 2016-05-05 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of hydrotreating method of high nitrogen inferior heavy oil |
| CN107345151B (en) * | 2016-05-05 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of hydrotreating method of high nitrogen inferior heavy oil |
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| CN107511178A (en) * | 2016-06-15 | 2017-12-26 | 中国石油化工股份有限公司 | A kind of modified aluminium oxide supports and preparation method and a kind of hydrogenation catalyst and preparation method and application |
| CN107511178B (en) * | 2016-06-15 | 2020-08-18 | 中国石油化工股份有限公司 | Modified alumina carrier and preparation method thereof, hydrogenation catalyst and preparation method and application thereof |
| CN113430003A (en) * | 2020-03-23 | 2021-09-24 | 中国石油天然气股份有限公司 | Hydrotreating method for lubricating oil base oil |
| CN113430003B (en) * | 2020-03-23 | 2023-02-28 | 中国石油天然气股份有限公司 | Hydrotreating method for base oil of lubricating oil |
| CN114768785A (en) * | 2022-03-29 | 2022-07-22 | 木林森活性炭江苏有限公司 | Production process of activated carbon-based carbon, catalyst using activated carbon-based carbon and production process of catalyst |
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