CN105582948A - Residual oil hydrodemetallization catalyst and preparation method thereof - Google Patents
Residual oil hydrodemetallization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a residual oil hydrodemetallization catalyst and a preparation method thereof. The catalyst includes an alumina carrier, active metals and carbon, and particularly includes, by weight, 6.0-15% of Mo and/or W, 1.0-4.0% of Co and/or Ni and 1-15%, preferably 5-10%, of the carbon, wherein the active metals are counted on the basis of oxides and the carbon is counted on the basis of element. The content of carbon is gradually reduced from the center to the external surface of a catalyst granule. The preparation method includes the following steps: 1) preparing polyol and/or monosaccharide water solutions in at least two different concentrations; 2) spray-impregnating the alumina carrier with the water solutions according to the sequence from high concentration to low concentration; 3) performing hydrothermal carbonization treatment in a sealed container, and drying the alumina carrier; 4) impregnating the alumina carrier with the active components, and drying the alumina carrier; and 5) performing oxygen-free high-temperature treatment to obtain the hydrodemetallization catalyst. In the catalyst, the content of carbon is gradually distributed, so that the active components are easy to sulfurize completely, thereby significantly improve the demtallization and desulfurization activity of the catalyst.
Description
Technical field
The invention belongs to catalyst preparation field, relate to particularly a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof.
Background technology
The most common hydrogenation catalyst is generally taking aluminium oxide, silica etc. as carrier at present, the loaded catalyst taking metals such as Co, Ni, Mo, W as active component. Active component adopts the method for dipping or kneading to load on carrier, then makes catalyst through super-dry, roasting. When humectant after dipping is dried, active component in maceration extract is along with the evaporation gradually of solvent, in carrier hole, easily form larger active specy particle, cause the part duct in carrier blocked, the migration of solvent in evaporation process simultaneously also can make Active components distribution inhomogeneous, finally affects the activity of catalyst. In addition, in roasting process, active metal component is easily had an effect and is formed very strong M-O-Al key with alumina support, causes active component form Spinel and lose activity, thereby or makes the active component cannot complete cure reduction catalyst activity.
CN101439289A discloses a kind of preparation method of hydrogenation catalyst. This catalyst metal components is made up of one or both metal ingredients in one or both and Mo, the W that comprise in Co, Ni, taking urea or ammoniacal liquor as reaction promoter, adopt the method for reaction in-situ in carrier hole to make metal active constituent generate nickel molybdate (cobalt) or wolframic acid nickel (cobalt) compounds, thereby can avoid reacting of metal and carrier, make metal active constituent more easily cure simultaneously, can improve the activity of hydrogenation catalyst. But catalyst different activities component interphase interaction prepared by the method has formed new compound, be unfavorable for active component dispersed and active further raising on carrier, in addition, preparation process is more complicated.
CN102451704A discloses a kind of preparation method of hydrocracking catalyst, and this catalyst is taking amorphous aluminum silicide and aluminium oxide as carrier, and group VIII and group vib metal are hydrogenation activity component, preferably contain active material B2O3. Catalyst of the present invention is by after amorphous aluminum silicide and aluminium oxide mixed-forming, drying processing, then infusion process supported active metal, then drying and roasting and obtain. The method is compared with conventional infusion process, and shaping carrier, without roasting, has been simplified preparation process, and reduce the strong interaction between active metal and carrier, be conducive to Active components distribution, be more conducive to the performance of metal active, also avoided the specific area loss causing because of multistep roasting. But because shaping carrier is without calcination process, the mechanical strength of catalyst is undesirable.
Summary of the invention
For existing technical deficiency, the invention provides a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof, active metallic content and carbon content distribution gradient in catalyst of the present invention, catalyst exterior active component and carrier function are relatively strong, inner active component and carrier function relatively a little less than, the easy complete cure of active component, has significantly improved the metal removal activity of catalyst.
Residuum hydrogenating and metal-eliminating catalyst of the present invention, comprise alumina support, active metal and carbon, taking catalyst weight as benchmark, active metal is in oxide, and the weight content of Mo and/or W is 6.0wt%-15wt%, and Co and/or Ni weight content are 1.0wt%-4.0wt%, carbon is counted 1wt%-15wt% with element, preferably 5wt%-10wt%, alumina support is 66wt% ~ 92wt%, preferably surplus; Specific surface is 160-270m2/ g, pore volume is 0.8-1.2ml/g; Carbon content meets the following conditions: be 50%-90% apart from the carbon content at catalyst granules cross-section center (hereinafter to be referred as center) 1/4R place and the carbon content of catalyst granules cross-section center ratio, be preferably 60%-80%, distance center 1/2R place carbon content is 30%-70% with center carbon content ratio, preferably 40%-60%, distance center 3/4R place carbon content is 10%-50% with center carbon content ratio, preferably 20%-40%, in cross section outer most edge, the carbon content of any point is 5%-40% with center carbon content ratio, preferably 10%-20%; Active metallic content meets the following conditions: distance center 1/4R active metallic content is 80%-100% with center active metallic content ratio, distance center 1/2R place active metallic content is 70%-80% with center active metallic content ratio, distance center 3/4R place active metallic content is with center active metallic content than being 60%-70%, and in cross section outer most edge, the active metallic content of any point is 50%-60% with center active metallic content ratio.
Catalyst of the present invention is that (solid) is granular, instead of the amorphous state such as powder. As the shape of described particle, can enumerate the conventional various shapes that use of this area Hydrodemetalation catalyst, such as can further enumerating spherical and column. As described spherical, such as enumerating spheroidal and elliposoidal etc.; As described column,, flat column cylindric such as enumerating and profiled-cross-section (such as clover, bunge bedstraw herb etc.) column etc.
In the present invention, so-called " cross section of catalyst granules " refers to along the minimum dimension direction of a catalyst granules and cuts the rear whole surface exposing by the geometric center of its shape. Such as, at described catalyst granules while being spherical, described cross section refers to the whole surface (referring to Fig. 1) exposing after by its centre of sphere cutting along the radius of this ball or short-axis direction. Or, in the time that described catalyst granules is column, the whole surface (such as referring to Fig. 2) that described cross section exposes after referring to and cutting by the central point of this length dimension perpendicular to the length dimension direction of this post.
In the present invention, the periphery of described exposed surface is called to the outer most edge of this cross section, described geometric center (such as the central point of the aforesaid centre of sphere or length dimension) is called to the central point on this cross section.
Carbon content and active metallic content on catalyst granules cross section of the present invention are measured by electron probe.
The preparation method of residuum hydrogenating and metal-eliminating catalyst of the present invention, comprises following content:
(1) with aqueous solution of urea oxide impregnation alumina supporter, the alumina support drying processing after dipping;
(2) maceration extract containing polyalcohol and/or monose and active metal component of at least two kinds of variable concentrations of preparation, spray on step (1) alumina support according to concentration order from high to low, make the concentration of polyalcohol and/or monose and active metal component on carrier, form the gradient that ecto-entad is from low to high and distribute; Wherein according to concentration order from high to low, between adjacent two kinds of variable concentrations maceration extracts, the concentration of polyalcohol and/or monose increases with the concentration of active component or to reduce trend identical;
(3) alumina support after step (2) dipping is proceeded to and in airtight container, carry out hydrothermal treatment consists;
(4) dry materials step (3) being obtained, then anaerobic high-temperature process, obtains residuum hydrogenating and metal-eliminating catalyst.
In the inventive method, the mass concentration of the described aqueous solution of urea of step (1) is 20%-40%, and the consumption of aqueous solution of urea is at least the saturated water adsorptive value of alumina support, and dip time is 1-2 hour.
In the inventive method, the described alumina support of step (1) is graininess, can be spherical or cylindricality, and wherein spherical can be spheroidal or elliposoidal, and cylindricality can be cylindrical, square column type or abnormity (clover, bunge bedstraw herb or five tooth balls). Alumina support can adopt commercially available, the aluminium oxide that is suitable for Hydrodemetalation catalyst carrier that also can adopt conventional method to make. In described alumina support, also can add as required one or more in the auxiliary elements such as Si, Ti, Zr, B or F.
In the inventive method, the described polyalcohol of step (2) comprises one or more in xylitol, sorbierite, sweet mellow wine or arabite etc.; Described monose comprises one or more in glucose, ribose or fructose etc.
In the inventive method, the described active component of step (2) is group vib and/or VIII family metallic element, and wherein group vib metallic element is selected from one or more in molybdenum and/or tungsten, and VIII family metallic element is selected from one or more in nickel and/or cobalt.
In the inventive method, the polyalcohol in the described maceration extract of step (2) and/or the concentration of monose are 5-50g/100ml.
In the inventive method, the group vib metal element content in the described maceration extract of step (2) is counted 5-40g/100ml with oxide, and VIII family metal element content is counted 1-10g/100ml with oxide. Wherein, active metal component is selected from soluble compound, as nickel chloride, nickel nitrate, nickelous sulfate, nickel acetate, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, phosphomolybdic acid, ammonium molybdate, ammonium metatungstate and ammonium tungstate etc.
In the inventive method, according to concentration from high to low, the polyalcohol in adjacent twice maceration extract and/or the concentration difference of monose water are 5-30g/100ml to the described maceration extract of step (2), preferably 1-20g/100ml; Group vib metallic element is taking oxide concentration difference as 4-10g/100ml, and VIII family metallic element is taking oxide concentration difference as 0.5-2g/100ml.
In the inventive method, step (2) is preferably prepared the polyalcohol of 2-4 kind variable concentrations and/or the maceration extract of monose and active metal component.
In the inventive method, the described maceration extract consumption at every turn spraying of step (2) is the 10%-60% of alumina support saturated water adsorptive value, preferably 20%-30%, the saturated water adsorptive value that the total consumption of maceration extract repeatedly spraying is alumina support is to guarantee the saturated dipping of alumina support.
In the inventive method, step (2) is preferably prepared the polyalcohol of 3 kinds of variable concentrations and/or monose and active metal component maceration extract and is sprayed, detailed process is as follows: spray for the first time, the concentration of polyalcohol and/or the monose aqueous solution is 30-50g/100ml, group vib metallic element is taking oxide concentration as 18-20g/100ml, VIII family metallic element is taking oxide concentration as 3-4g/100ml, and the consumption of polyalcohol and/or monose and the active metal component aqueous solution is the 20%-30% of alumina support water absorption; Spray for the second time, the mass concentration of polyalcohol and/or the monose aqueous solution is 10-30g/100ml, group vib metallic element is taking oxide concentration as 10-15g/100ml, VIII family metallic element is taking oxide concentration as 1.5-3g/100ml, and the consumption of polyalcohol and/or monose and the active metal component aqueous solution is the 40%-60% of alumina support water absorption; Spray for the third time, the mass concentration of polyalcohol and/or the monose aqueous solution is 5-10g/100ml, group vib metallic element is taking oxide concentration as 5-10g/100ml, VIII family metallic element is taking oxide concentration as 1-1.5g/100ml, and the consumption of polyalcohol and/or monose and the active metal component aqueous solution is the 10%-40% of alumina support water absorption.
In the inventive method, the described hydrothermal treatment consists of step (3) is two sections of hydrothermal treatment consists, is first 100-140 DEG C of hydrothermal treatment consists 5-10 hour in temperature, then be 180-250 DEG C in temperature, preferably 200-230 DEG C, the hydrothermal treatment consists time is 6-12 hour, preferably 8-10 hour.
In the inventive method, described drying condition is dry 6-10 hour at 80-120 DEG C.
In the inventive method, the described anaerobic high-temperature process condition of step (4) is: treatment temperature is 400-600 DEG C, and the processing time is 3-6 hour; Wherein the atmosphere of anaerobic high-temperature process can be nitrogen or inert atmosphere, and wherein inert atmosphere is one or more in helium, neon or argon gas.
Polyalcohol and/or monose and the active metal component aqueous solution spray dip forming alumina support of variable concentrations for the inventive method, in spray dipping process, polyalcohol and/or monose and the active metal component aqueous solution under the capillary force effect of carrier duct by carrier surface gradually to central permeate, during due to multistep spray dipping, in maceration extract, the concentration of polyalcohol and/or monose and active metal component reduces gradually, has ensured that the concentration of polyalcohol and/or monose and active metal component is and is increased progressively distribution by carrier surface to center. Carrier after dipping adopts two sections of hydrothermal treatment consists, and in the time that low-temperature hydrothermal is processed, polyalcohol and/or monose polymerization reaction take place form polymer and be adsorbed onto alumina carrier surface, and when high-temperature water heat treatment, polymer charing forms carbon-coating and is adsorbed onto carrier surface. Because the concentration of polyalcohol and/or monose is and is increased progressively distribution by carrier surface to center, after charing, the thickness of carbon-coating is and increases progressively distribution from carrier surface to center equally, and the thinner inner carbon-coating of the outside carbon-coating of carrier is thicker. When charing, urea is hydrolyzed, the NH of generation3React with group vib and VIII family active component in solution, form precipitation accordingly, precipitation is adsorbed onto on carbon-coating by hydrogen bond action, has prevented the migration of active metal component. Material after hydrothermal treatment consists is in anaerobic high-temperature process, the existence of carbon-coating has effectively stoped the strong interaction between metal component and carrier, because the gradient of carbon-coating thickness distributes, between active metal and carrier, effect weakens from outside to inside gradually, and catalyst activity improves from outside to inside gradually. In HDM process, the inner active metal component content of catalyst is higher, with carrier function relatively a little less than, increased activity, promote the reaction of inside, catalyst duct, effectively avoid, because outer surface active component activity makes demetalization reaction acutely cause catalyst duct to stop up the phenomenon that makes catalysqt deactivation compared with high, in improving catalyst activity, having extended the service life of catalyst.
Brief description of the drawings
Fig. 1 catalyst granules is spherical cross sectional representation.
Fig. 2 catalyst granules is columniform cross sectional representation.
Detailed description of the invention
Further illustrate the effect of the inventive method below in conjunction with embodiment, but be not limited to following examples. The commercially available formed alumina carrier adopting in embodiment, the pore volume of alumina support is 0.8-1.5ml/g, specific area is 160-300m2/ g, the hole that bore dia is 10-20nm accounts for the 70%-90% of total pore volume, and crushing strength is 130-160N/cm, water absorption 1.0g/g. In catalyst of the present invention, carbon and active metallic content are measured by NEC's JXA-8230 electron probe, and the accelerating potential of selecting when mensuration is 15KV, and probe current is 8 × 10-8A, beam spot size is 3 μ m.
Metering system: carbon content and the active metallic content measuring respectively catalyst cross-section center place and be 1/4R, 1/2R, 3/4R and R place with catalyst cross-section center place distance, wherein R is the distance of line segment between any point in cross-section center and cross section outer most edge, then by division calculation, obtain the ratio between each content.
Embodiment 1
Taking pore volume is 0.9ml/g, and specific area is 220m2100 grams of the γ phase cylinder bar shaped alumina supports of/g are put into beaker, are 24% aqueous solution of urea 120ml dipping 1.5 hours to adding mass concentration in beaker, filter redundant solution, by carrier in 110 DEG C dry 5 hours. Dried carrier is placed in to spray and rolls pot, under rotary state, spray impreg sugar alcohol concentration as 40g/100ml, MoO taking atomizing type to the carrier rolling in pot3Concentration is that 18.8g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 3.5g/100ml(nickel source is from nickel chloride) xylitol and active metal aqueous solution 25ml; Then be 20g/100ml by xylitol concentration, MoO3Concentration is that 11g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 1.9g/100ml(nickel source is from nickel chloride) xylitol and active metal aqueous solution 40ml continue spray oxide impregnation alumina supporter; Finally use
Xylitol concentration is 10g/100ml, MoO3Concentration is that 7.5g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 1.3g/100ml(nickel source is from nickel chloride) xylitol and active metal aqueous solution 40ml continue spray oxide impregnation alumina supporter. Humectant is proceeded in autoclave and by autoclave and is placed in baking oven in 110 DEG C of sealing heat treatments 5 hours, be then warming up to 200 DEG C of sealing heat treatments 8 hours, naturally cool to room temperature. Alumina support after hydrothermal treatment consists is dried 6 hours at 120 DEG C. Dried material is roasting 5 hours at 550 DEG C under nitrogen atmosphere, makes Hydrodemetalation catalyst C1 of the present invention, and catalyst property is in table 1.
Embodiment 2
With embodiment 1, just alumina support is clover bar shaped, and the mass concentration of urea is 32%, when spray floods for the first time, is 30g/100ml by the concentration of 30ml sorbierite, MoO3Concentration is that 20g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 3.7g/100ml(nickel source is from nickel chloride) sorbierite and active metal aqueous solution dipping. When spray floods for the second time, be 10g/100ml by the concentration of 50ml sorbierite, MoO3Concentration is that 13g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 3g/100ml(nickel source is from nickel chloride) sorbierite and active metal aqueous solution dipping. When spray floods for the third time, be 5g/100ml by the concentration of 20ml sorbierite, MoO3Concentration is that 9g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 1.25g/100ml(nickel source is from nickel chloride) sorbierite and active metal aqueous solution dipping. When hydrothermal treatment consists, first 130 DEG C of sealing heat treatments 6 hours, be then warming up to 220 DEG C of sealing heat treatments and within 10 hours, make Hydrodemetalation catalyst C2 of the present invention, catalyst property is in table 1.
Embodiment 3
With embodiment 1, just the mass concentration of urea is 40%, adopts spray dipping when spray dipping four times,
When spray floods for the first time, be 50g/100ml by the concentration of 20ml sweet mellow wine, MoO3Concentration is that 19.8g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 4g/100ml(nickel source is from nickel chloride) sweet mellow wine and active metal aqueous solution dipping. When spray floods for the second time, be 30g/100ml by the concentration of 40ml sorbierite, MoO3Concentration is that 15g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 2.6g/100ml(nickel source is from nickel chloride) sorbierite and active metal aqueous solution dipping. When spray floods for the third time, be 30g/100ml by the concentration of 20ml sorbierite, MoO3Concentration is that 10g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 1.5g/100ml(nickel source is from nickel chloride) sorbierite and active metal aqueous solution dipping. When the 4th spray dipping, be 10g/100ml by the concentration of 20ml sorbierite, MoO3Concentration is that 5g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 1g/100ml(nickel source is from nickel chloride) sorbierite and active metal aqueous solution dipping. When hydrothermal treatment consists, first 120 DEG C of sealing heat treatments 8 hours, be then warming up to 240 DEG C of sealing heat treatments and within 6 hours, make Hydrodemetalation catalyst C3 of the present invention, catalyst property is in table 1.
Embodiment 4
With embodiment 1, just the mass concentration of urea is 20%, adopts spray dipping when spray dipping twice, while spraying dipping for the first time, is 40g/100ml by the concentration of 50ml arabite, MoO3Concentration is that 18g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 3g/100ml(nickel source is from nickel chloride) arabite and active metal aqueous solution dipping. When spray floods for the second time, be 20g/100ml by the concentration of 55ml arabite, MoO3Concentration is that 10g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 1.5g/100ml(nickel source is from nickel chloride) arabite and active metal aqueous solution dipping. When hydrothermal treatment consists, first 140 DEG C of sealing heat treatments 7 hours, be then warming up to 180 DEG C of sealing heat treatments and within 12 hours, make Hydrodemetalation catalyst C4 of the present invention, catalyst property is in table 1.
Embodiment 5
With embodiment 1, just alumina support is bunge bedstraw herb bar shaped, and the mass concentration of urea is 28%, and xylitol changes the mixed alcohol of xylitol, arabite, sorbierite and sweet mellow wine that mass ratio is 1:1:1:1 into, MoO in maceration extract when spray floods for the first time3Concentration is that 19g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 3.3g/100ml(nickel source is from nickel chloride). MoO in maceration extract when spray floods for the second time3Concentration is that 12.5g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 2.25g/100ml(nickel source is from nickel chloride). MoO in maceration extract when spray floods for the third time3Concentration is that 5g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 1.5g/100ml(nickel source is from nickel chloride). When hydrothermal treatment consists, first 100 DEG C of sealing heat treatments 10 hours, be then warming up to 250 DEG C of sealing heat treatments and within 6 hours, make Hydrodemetalation catalyst C5 of the present invention, catalyst property is in table 1.
Embodiment 6
With embodiment 1, just the mass concentration of urea is 36%, and xylitol changes glucose into, MoO in maceration extract when spray floods for the first time3Concentration is that 18.4g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 3.5g/100ml(nickel source is from nickel chloride). MoO in maceration extract when spray floods for the second time3Concentration is that 12g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 1.5g/100ml(nickel source is from nickel chloride). MoO in maceration extract when spray floods for the third time3Concentration is that 6g/100ml(molybdenum source is from ammonium molybdate), NiO concentration is that 1g/100ml(nickel source is from nickel chloride). Make Hydrodemetalation catalyst C6 of the present invention, catalyst property is in table 1.
Embodiment 7
With embodiment 1, just xylitol changes glucose, the fructose that mass ratio is 1:1:1:1 into, the aqueous solution dipping of xylitol and sorbierite. Make Hydrodemetalation catalyst C7 of the present invention, catalyst property is in table 1. Comparative example 1
With embodiment 1, just the xylitol of same volume and mass concentration and active metal solution are adopted to the once mode oxide impregnation alumina supporter of spray dipping, make comparative catalyst C8, catalyst property is in table 1.
Comparative example 2
With embodiment 1, just in maceration extract, do not add xylitol, make comparative catalyst C9, catalyst property is in table 1.
Comparative example 3
With embodiment 1, just the humectant after dipping, without hydrothermal treatment consists, makes comparative catalyst C10, and catalyst property is in table 1.
Table 1 catalyst property.
As can be seen from Table 1, catalyst carbon prepared by employing the inventive method and active metal component are in radially distribution gradient of catalyst, be that catalyst outer surface carbon and active metal component content are relatively low, the inner carbon of catalyst and active metal component content are relatively high.
Embodiment 9
The following examples illustrate Hydrodemetalation catalyst provided by the invention and comparative catalyst's catalytic performance.
Taking the listed decompression residuum of table 2 as raw material, the catalytic performance of catalyst C8-C10 prepared by the catalyst C1-C7 that on the hydrogenation reaction device of 200 milliliters prepared by evaluation example 1-7 and comparative example 1-3, the bar that catalyst is long 2 ~ 3 millimeters, catalyst loading amount is 100 milliliters, reaction temperature is 385 DEG C, hydrogen dividing potential drop is 15MPa, and liquid hourly space velocity (LHSV) is 1.0 hours-1, hydrogen to oil volume ratio is 900, reacts after 200 hours and measures the content that generates each impurity in oil, calculates removal efficiency, evaluation result is in table 3.
Table 2 feedstock oil character.
Table 3 catalyst hydrogenation performance comparison.
| C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 | C10 | |
| Nickel removal, wt% | 72.4 | 78.6 | 74.2 | 67.5 | 73.2 | 73.4 | 72.7 | 50.3 | 42.9 | 42.8 |
| Vanadium removal, wt% | 80.6 | 83.4 | 80.3 | 73.8 | 79.3 | 79.8 | 79.4 | 52.7 | 54.4 | 53.7 |
| Desulfurization, wt% | 56.9 | 62.1 | 59.3 | 52.7 | 58.3 | 57.9 | 59.7 | 46.1 | 43.2 | 46.2 |
Can be found out by table 3 data, compared with comparative catalyst, catalyst provided by the invention has higher HDM activity and hydrodesulfurization activity.
Above-described embodiment and the prepared catalyst of comparative example are carried out to activity rating, and the temperature rise of operation 5000h is in table 3.
Table 4 reaction temperature lift-off value.
Find out from the result of table 4, react after 5000 hours, adopt Hydrodemetalation catalyst provided by the invention, in order to keep high demetallization per, desired reaction temperature increase rate is far smaller than comparative catalyst, and this illustrates that Hydrodemetalation catalyst provided by the invention has higher activity stability.
Claims (15)
1. a residuum hydrogenating and metal-eliminating catalyst, it is characterized in that: comprise alumina support, active metal and carbon, taking catalyst weight as benchmark, active metal is in oxide, the weight content of Mo and/or W is 6.0wt%-15wt%, Co and/or Ni weight content are 1.0wt%-4.0wt%, and carbon is counted 1wt%-15wt% with element, and alumina support is 66wt% ~ 92wt%; Carbon content meets the following conditions: be 50%-90% apart from the carbon content at catalyst granules cross-section center (hereinafter to be referred as center) 1/4R place and the carbon content of catalyst granules cross-section center ratio, distance center 1/2R place carbon content is 30%-70% with center carbon content ratio, distance center 3/4R place carbon content is with center carbon content than being 10%-50%, and in cross section outer most edge, the carbon content of any point is 5%-40% with center carbon content ratio; Active metallic content meets the following conditions: distance center 1/4R active metallic content is 80%-100% with center active metallic content ratio, distance center 1/2R place active metallic content is 70%-80% with center active metallic content ratio, distance center 3/4R place active metallic content is with center active metallic content than being 60%-70%, and in cross section outer most edge, the active metallic content of any point is 50%-60% with center active metallic content ratio.
2. according to catalyst claimed in claim 1, it is characterized in that: specific surface is 160-270m2/ g, pore volume is 0.8-1.2ml/g.
3. a preparation method for the residuum hydrogenating and metal-eliminating catalyst described in claim 1 or 2, is characterized in that comprising following content: (1) uses aqueous solution of urea oxide impregnation alumina supporter, the alumina support drying processing after dipping; (2) maceration extract containing polyalcohol and/or monose and active metal component of at least two kinds of variable concentrations of preparation, spray on step (1) alumina support according to concentration order from high to low, make the concentration of polyalcohol and/or monose and active metal component on carrier, form the gradient that ecto-entad is from low to high and distribute; Wherein according to concentration order from high to low, between adjacent two kinds of variable concentrations maceration extracts, the concentration of polyalcohol and/or monose increases with the concentration of active component or to reduce trend identical; (3) alumina support after step (2) dipping is proceeded to and in airtight container, carry out hydrothermal treatment consists; (4) dry materials step (3) being obtained, then anaerobic high-temperature process, obtains residuum hydrogenating and metal-eliminating catalyst.
4. in accordance with the method for claim 3, it is characterized in that: the mass concentration of the aqueous solution of urea described in step (1) is 20%-40%, and the consumption of aqueous solution of urea is at least the saturated water adsorptive value of alumina support, and dip time is 1-2 hour.
5. it is characterized in that in accordance with the method for claim 3: the described polyalcohol of step (2) comprises one or more in xylitol, sorbierite, sweet mellow wine or arabite; Described monose comprises one or more in glucose, ribose or fructose.
6. in accordance with the method for claim 3, it is characterized in that: the described active component of step (2) is group vib and/or VIII family metallic element, and wherein group vib metallic element is selected from molybdenum and/or tungsten, and VIII family metallic element is selected from nickel and/or cobalt.
7. it is characterized in that in accordance with the method for claim 3: the polyalcohol in the maceration extract described in step (2) and/or the concentration of monose are 5-50g/100ml.
8. in accordance with the method for claim 3, it is characterized in that: according to concentration from high to low, the polyalcohol in adjacent twice maceration extract and/or the concentration difference of monose water are 5-30g/100ml to the maceration extract described in step (2).
9. in accordance with the method for claim 3, it is characterized in that: the maceration extract described in step (2) according to concentration from high to low, group vib metallic element in adjacent twice maceration extract is taking oxide concentration difference as 4-10g/100ml, and VIII family metallic element is taking oxide concentration difference as 0.5-2g/100ml.
10. it is characterized in that in accordance with the method for claim 3: the polyalcohol of step (2) preparation 2-4 kind variable concentrations and/or the maceration extract of monose and active metal component.
11. in accordance with the method for claim 3, it is characterized in that: the described maceration extract consumption at every turn spraying of step (2) is the 10%-60% of alumina support saturated water adsorptive value, the saturated water adsorptive value that the total consumption of maceration extract repeatedly spraying is alumina support.
12. in accordance with the method for claim 3, it is characterized in that: the polyalcohol of 3 kinds of variable concentrations of step (2) preparation and/or monose and active metal component maceration extract spray, detailed process is as follows: spray for the first time, the concentration of polyalcohol and/or the monose aqueous solution is 30-50g/100ml, group vib metallic element is taking oxide concentration as 18-20g/100ml, VIII family metallic element is taking oxide concentration as 3-4g/100ml, and the consumption of polyalcohol and/or monose and the active metal component aqueous solution is the 20%-30% of alumina support water absorption; Spray for the second time, the mass concentration of polyalcohol and/or the monose aqueous solution is 10-30g/100ml, group vib metallic element is taking oxide concentration as 10-15g/100ml, VIII family metallic element is taking oxide concentration as 1.5-3g/100ml, and the consumption of polyalcohol and/or monose and the active metal component aqueous solution is the 40%-60% of alumina support water absorption; Spray for the third time, the mass concentration of polyalcohol and/or the monose aqueous solution is 5-10g/100ml, group vib metallic element is taking oxide concentration as 5-10g/100ml, VIII family metallic element is taking oxide concentration as 1-1.5g/100ml, and the consumption of polyalcohol and/or monose and the active metal component aqueous solution is the 10%-40% of alumina support water absorption.
13. in accordance with the method for claim 3, it is characterized in that: the described hydrothermal treatment consists of step (3) is two sections of hydrothermal treatment consists, first being 100-140 DEG C of hydrothermal treatment consists 5-10 hour in temperature, is then 180-250 DEG C in temperature, and the hydrothermal treatment consists time is 6-12 hour.
14. in accordance with the method for claim 3, it is characterized in that: described drying condition is dry 6-10 hour at 80-120 DEG C.
15. in accordance with the method for claim 3, it is characterized in that: the described anaerobic high-temperature process condition of step (4) is: treatment temperature is 400-600 DEG C, and the processing time is 3-6 hour; Wherein the atmosphere of anaerobic high-temperature process is nitrogen or inert atmosphere, and wherein inert atmosphere is one or more in helium, neon or argon gas.
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| CN101928592A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Grading combination of hydrogenation catalyst |
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| CN1289647A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing catalyst with non-uniform distribution of active metals |
| CN101927176A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal and acid additive concentration in gradient increasing distribution and preparation method thereof |
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