CN102343270B - 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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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, in poor quality trend in the world wide, and the increasingly stringent of environmental regulation, market but increases year by year to the demand of light-end products 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, in the urgent need to developing the higher hydrogenation catalyst that is applicable to inferior raw material of the hydrogenation technique optimized and activity stability.Aspect catalyst, have higher desulfurization in the urgent need to developing, denitrogenation, take off carbon residue, take off the active catalyst with stability of virtue, to improve the quality of products and yield; Further reduce simultaneously catalyst preparation cost, extension fixture on-stream time.
At present industrial usually by the stable metallic solution of preparation, saturated impregnated on the carrier, hydrogenation catalyst is made in drying, roasting.Introduced a kind of preparation method of hydrogenation catalyst such as 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 (such as 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, to improve the removing impurities matter performance of catalyst.Introduced a kind of preparation method of hydrotreating catalyst such as 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 made catalyst after drying, the 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 preparation method of the hydrogenation catalyst of Multi-layers distributing reports 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-coating 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, make semi-finished product G2 after semi-finished product G1 immersed slurry C 0, drying, roasting again, semi-finished product G2 platinum-impregnated rhodium solution is made double layer noble metal active component catalyst product by roasting.The catalyst of this metal component layering can be brought into play the not same-action of every layer of active component, greatly improves the utilization rate of active component.But it is too complicated that the shortcoming of the method is 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, namely has hud typed characteristic distributions, stratum nucleare is molybdenum nickel or tungsten nickel active metal component, shell is molybdenum cobalt active metal component, and the preparation method is simple.
Active metal component of the present invention is the preparation method of the hydrogenation catalyst of layer distributed:
The preparation of hydrogenation catalyst: select Al
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 respectively and/or acid, and deionized water or ammoniacal liquor is mixed and made into metal impregnation liquid, adopts the method for saturated spray-stain to prepare hydrogenation catalyst.
Adopt the saturated method that sprays, preparation process is as follows: first with the solution pre-preg carrier that contains two kinds of reactive metals, use again the carrier of the maceration extract spray-stain pre-preg that contains two kinds of active metal components, carrier behind the dipping 80～150 ℃ lower dry 1～8 hour, then roasting 2～6 hours in 300～650 ℃ air; Have at least a kind of active metal component different from front a kind of maceration extract in rear a kind of maceration extract.
A kind of hydrogenation catalyst by the inventive method preparation is characterized in that:
1) selects Al
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 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 from 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., to drip ball forming and extrusion modling as best.Catalyst shape can be spherical, bar shaped (comprising cylindrical, trilobal, quatrefoil etc.), sheet shape, take spherical and bar shaped as best.
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, namely has hud typed characteristic distributions, and shell is 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 preparation process is simple.
The specific embodiment
Embodiment 1
The present embodiment is with Al
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%) and the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%), spray completely, spray again 82.5ml 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 spraying equipment, 60 ℃ lower dry 2 hours, then 120 ℃ lower dry 5 hours, again roasting 3 hours in 500 ℃ of air makes catalyst, is numbered C-1.
Embodiment 2
The 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%) and the ammonia spirit of 13.5g cobalt nitrate (containing CoO 25.2m%), at the uniform velocity splashing into 82.5ml in spraying process contains the 14.9g ammonium molybdate and (contains MoO
382m%) and the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%), sprayed in 5 minutes.Homogenizing is after 10 minutes in spraying equipment, 120 ℃ lower dry 4 hours, again roasting 3 hours in 500 ℃ of air makes catalyst, is numbered C-2.
Embodiment 3
The 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%) and 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%) and the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%), flooded in 5 minutes.Homogenizing is after 20 minutes in spraying equipment, 60 ℃ lower dry 2 hours, after taking out in 120 ℃ lower dry 5 hours, again roasting 3 hours in 500 ℃ of air makes catalyst, is numbered C-3.
Embodiment 4
The present embodiment is to contain 2.0m% ZrO
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, Co, Ni.
Take by weighing the 150g carrier, spray 82.5ml and contain the 14.9g ammonium molybdate and (contain MoO
382m%) and the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%), spray completely, spray-stain 82.5ml contains the 14.9g ammonium molybdate and (contains MoO again
382m%) and the ammonia spirit of 13.5g cobalt nitrate (containing NiO 25.2m%), sprayed in 5 minutes.Homogenizing is after 20 minutes in spraying equipment, 60 ℃ lower dry 2 hours, after taking out in 120 ℃ lower dry 6 hours, again roasting 3 hours in 500 ℃ of air makes catalyst, is numbered C-4.
Embodiment 5
The present embodiment is with Al
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 W, Ni, Co.
Take by weighing the 150g carrier, spray in advance 82.5ml and contain the 14.9g ammonium metatungstate and (contain WO
382m%) and the ammonia spirit of 13.5g nickel nitrate (containing NiO 25.2m%), after having sprayed, spray again 82.5ml and contain the 14.9g ammonium metatungstate and (contain WO
382m%) and the ammonia spirit of 13.5g cobalt nitrate (containing NiO25.2m%), sprayed in 5 minutes.Homogenizing is after 10 minutes in spraying equipment, 120 ℃ lower dry 7 hours, again roasting 6 hours in 500 ℃ of air makes catalyst, is numbered C-5.
Embodiment 6
The 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 that sprays to prepare the catalyst that active metal component is Mo, W, Co.
Take by weighing the 150g carrier, spray in advance 82.5ml and contain the 14.9g ammonium molybdate and (contain MoO
382m%) and the ammonia spirit of 13.5g cobalt nitrate (containing CoO 25.2m%), spray completely, spray again 82.5ml and contain the 14.9g ammonium metatungstate and (contain WO
382m%) and the ammonia spirit of 13.5g cobalt nitrate (containing CoO 25.2m%), sprayed in 5 minutes.Homogenizing is after 10 minutes in spraying equipment, 120 ℃ lower dry 7 hours, again roasting 6 hours in 500 ℃ of air makes catalyst, is numbered C-6.
Comparative example 1
The present embodiment is with Al
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, Co, Ni.
Take by weighing the 150g carrier, spray 165ml by the saturated absorption solution amount 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 spraying equipment, 60 ℃ lower dry 2 hours, after taking out in 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyst, is numbered C-7.
Comparative example 2
The present embodiment is with Al
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, 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 spraying equipment, 60 ℃ lower dry 2 hours, after taking out in 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyst, is numbered C-8.
Embodiment 8
Adopt the 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 sees Table 1 in detail.
Table 1 catalyst physical data
Annotate: R is the carrier granular radius, take the catalyst granules surface as starting point.
As can be seen from Table 1, among catalyst C-1, C-2, C-3, C-4, C-5, the C-6, the particle center has different active metal component concentrations from the top layer, and the metal component CONCENTRATION DISTRIBUTION of C-7 and C-8 is comparatively even.
Embodiment 9
The present embodiment is catalyst C-1 and C-4 stability test, and carry out the active and stability contrast of desulfurization removing nitric with C-5, adopt catalyst grade combo dress scheme, load respectively from the bottom to the top metal remover, demetalization desulfurizing agent, the agent of high activity desulfurization removing nitric 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 as follows:
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 is mixed by 200g water and 15g HAc (acetic acid), kneading 1.5 hours, obtain plastic, be extruded into the cloverleaf pattern strip of φ 1.10～1.35mm at banded extruder, this strip was descended dry 4 hours at 120 ℃, obtained carrier in 4 hours 750 ℃ of lower roastings., then descended dry 2 hours at 120 ℃ resulting carrier impregnation reactive metal molybdenum and cobalt with conventional method, 550 ℃ of lower roastings 3 hours, namely make catalyst.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.
Estimate at 100ml small fixed hydrogenation plant.Estimating feedstock oil is the Saudi Arabian Vacuum 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 the results are shown in table 4.Relatively metal removal rate, desulfurization degree, denitrification percent are to make benchmark and relatively get as 1.00 take 500 hours demetallization per of C-1 catalyst runs.As can be seen from 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.Can say, the catalyst activity that the inventive method makes and stability are better than the catalyst that conventional method obtains.
Table 4 catalyst stability contrast experiment
Claims (2)
1. an active metal component is the hydrogenation catalyst of layer distributed, it is characterized in that:
L) 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 tungsten nickel active metal component, and shell is molybdenum cobalt active metal component; Stratum nucleare has at least a kind of reactive metal different from 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. an active metal component claimed in 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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| CN107345158B (en) * | 2016-05-05 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of heavy oil hydrogenation treatment method |
| 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 |
| 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 |
| 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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