CN104667956A - A catalyst for hydrogenation modification of hydrocarbon oil and a preparing method thereof - Google Patents
A catalyst for hydrogenation modification of hydrocarbon oil and a preparing method thereof Download PDFInfo
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Abstract
A catalyst for hydrogenation modification and a preparing method thereof are disclosed. In the catalyst, a carrier comprises aluminum oxide and a molecular sieve, active metal components are Mo, Co and Ni, and distribution situations of concentrations of the active metal components in the cross section of each catalyst particle are that Co0/Co1<Co<1/2>/Co1<1, Ni0/Ni1>Ni<1/2>/Ni1>1 and the Mo is evenly distributed. In the preparing method, the MO is introduced into the catalyst by a conventional method; and the Co and the Ni are introduced by dipping the carrier with a wetting solution containing an absorbent I by adopting an unsaturated dipping method, loading the active metal Co by dipping, dipping with a solution containing an absorbent II by saturated dipping or excessive dipping, and loading the active metal Ni by dipping. The catalyst is used in a diesel oil hydrogenation modification process, has deep hydrodesulfurization activity, and can improve comprehensive properties such as the cetane number under the circumstance that a high diesel oil yield is maintained.
Description
Technical field
The present invention relates to a kind of catalyst for hydro-upgrading and preparation method thereof, particularly a kind of catalyst for hydro-upgrading being suitable for diesel modifying and preparation method thereof.
Background technology
Produce for clean diesel, prior art mainly comprises the technology such as hydrofinishing and MHUG.Hydrofinishing can reduce the sulfur content of upgrading diesel oil, but limited to improving Cetane number and reducing T95 temperature capability.MHUG adopts the catalyst for hydro-upgrading containing molecular sieve (Y zeolite or beta-molecular sieve), by suitably cracking such as the aromatic hydrocarbons in diesel oil, in reduction diesel oil while sulphur nitrogen impurity content, improves the combination properties such as diesel cetane-number.But adopt current catalyst for hydro-upgrading, to improve the combination property (sulphur nitrogen impurity content, Cetane number, T95 temperature, arene content etc.) of diesel oil, the cracking degree that usual needs are higher, diesel yield can be made so lower, and the yield of diesel oil will be kept, the combination property of diesel oil is again less than good improvement.
Sulfur-containing compound in diesel oil distillate and aromatic hydrocarbons, usually exist with the structure of complexity, such as dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene etc., wherein more difficult what remove is the thiophenes such as dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene to hydrogenation, especially with 4,6-dimethyl Dibenzothiophene (4,6-BMDBT) and 2,4,6-trimethyl dibenzothiophenes (2,4,6-BMDBT) class formation is complicated and the sulfur-containing compound of steric effect of having living space is the most difficult removes.Reach the degree of depth and ultra-deep desulfurization, just need to remove these complex structures and sterically hindered large sulfur-containing compound, and these sulfur-containing compounds are usually more difficult under the hydrofinishing operating condition that HTHP etc. is harsh removes, then diesel yield can be reduced by hydrocracking.Therefore, when keeping diesel yield higher, how to remove the impurity in diesel oil, can improve again the combination property of diesel oil simultaneously, this is the current important topic needing research.
Catalyst for hydro-upgrading normally adopts the alumina support containing molecular sieve, and with group vib and group VIII metal for hydrogenation active metals component, wherein active metal component is generally equally distributed in the catalyst.CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, this catalyst consist of aluminium oxide 40 ~ 80wt%, amorphous aluminum silicide 0 ~ 20wt%, Y zeolite 5 ~ 30wt%.CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof, mainly adopt the predecessor of silica-alumina, aluminium oxide and/or aluminium oxide and Y zeolite mixing, shaping and roasting, introduce the hydrogenation metal of effective dose afterwards at shaping species.Above-mentioned catalyst has higher desulfurization and denitrification activity, but the shortcoming such as the amplitude that the yield of diesel product is low, the Cetane number of diesel oil improves is little, condensation point is high and density is large.
CN201110350790.2 discloses a kind of diesel oil hydrogenation modification Catalysts and its preparation method.This catalyst comprises the carrier and hydrogenation active metals component that are made up of modified beta molecular sieve and aluminium oxide, and wherein active metal component is equally distributed in the catalyst.When adopting this catalyst for diesel oil hydrogenation modification, although can reduce the condensation point of diesel oil distillate, improve the Cetane number of upgrading diesel oil, diesel yield is below 97%, still lower.
Summary of the invention
For problems of the prior art, the invention provides a kind of catalyst for hydro-upgrading and preparation method thereof.This catalyst is used for, in diesel oil hydrogenation modification process, having deep hydrodesulfurizationof activity, and can improve the combination properties such as Cetane number when keeping diesel yield higher.
Catalyst for hydro-upgrading of the present invention, carrier comprises aluminium oxide and molecular sieve, and active metal component is Mo, Co and Ni, and wherein the CONCENTRATION DISTRIBUTION of active metal component on the cross section of each catalyst granules is as follows: Co
0/ Co
1< Co
1/2/ Co
1< 1, Ni
0/ Ni
1> Ni
1/2/ Ni
1> 1, Mo is substantially for being uniformly distributed.
In the present invention, the CONCENTRATION DISTRIBUTION formula A of active metal component on the cross section of each catalyst granules
m/ B
nrepresent, on the cross section of i.e. each catalyst granules, the ratio of the concentration of m place elements A and the concentration of n place element B (in the present invention, unit is mol ratio), wherein A represents active metallic element Mo, Co or Ni, B represents active metallic element Mo, Co or Ni, wherein A with B can be identical, also can be different, with any point of catalyst granules cross section outer most edge and outer most edge point for starting point is designated as 0, with the central point of catalyst granules cross section for terminal is designated as 1, connection starting point and terminal obtain straight-line segment, m and n is illustrated respectively in the location point that above-mentioned straight-line segment is chosen, the value of m and n represents the ratio of the length accounting for above-mentioned straight-line segment from starting point to the distance of the location point chosen, the value of m and n is 0 ~ 1, wherein m(or n) value be 0, 1/4, 1/2, 3/4, 0 of the length accounting for above-mentioned straight-line segment from starting point to the distance of the location point chosen is represented respectively when 1, 1/4, 1/2, 3/4, the position (see figure 3) at selected point place when 1, above-mentioned location point is selected (or appearance millet cake) also referred to as outer most edge, 1/4 location point, 1/2 location point, 3/4 location point, central point.In the present invention, in the present invention, in order to express easily, A and B directly adopts active metallic element Mo, Co or Ni to replace, m and n is directly with the location point that the above-mentioned straight-line segment of digitized representation of 0 ~ 1 is determined, represents arbitrary location point on above-mentioned straight-line segment with x1 or x2, such as, Co
0/ Co
1represent that A and B is Co, namely m=0, n=1 represent the ratio of the concentration of catalyst granules cross section outer most edge point place Elements C o and the concentration of central spot Elements C o, Ni
1/2/ Ni
1represent that A and B is Ni, m=1/2, namely n=1 represents on the described straight-line segment on catalyst granules cross section, the ratio of the concentration of selected point position element Ni and the concentration of central spot element Ni when making the distance from outer most edge point to selected point account for 1/2 of above-mentioned straight-line segment length.X1 with x2 in the present invention is being connected the location point (but not comprising outer most edge point and central point) that the straight-line segment that above-mentioned outer most edge point and central point obtain is chosen arbitrarily respectively, and is less than from outer most edge point to the distance of x2 point i.e. 0 < x1 < x2 < 1 from outer most edge point to the distance of x1 point.
In the present invention, relate to and use formula A
m/ B
nit is specific as follows that form represents: Co
0/ Co
1(A and B is Co, m=0, n=1), Co
1/4/ Co
1(A and B is Co, m=1/4, n=1), Co
1/2/ Co
1(A and B is Co, m=1/2, n=1), Co
3/4/ Co
1(A and B is Co, m=3/4, n=1), Co
x1/ Co
1(A and B is Co, m=x1, n=1), Co
x2/ Co
1(A and B is Co, m=x2, n=1), Ni
0/ Ni
1(A and B is Ni, m=0, n=1), Ni
1/4/ Ni
1(A and B is Ni, m=1/4, n=1), Ni
1/2/ Ni
1(A and B is Ni, m=1/2, n=1), Ni
3/4/ Ni
1(A and B is Ni, m=3/4, n=1), Ni
x1/ Ni
1(A and B is Ni, m=x1, n=1), Ni
x2/ Ni
1(A and B is Ni, m=x2, n=1), Mo
0/ Mo
1(A and B is Mo, m=0, n=1), Mo
1/4/ Mo
1(A and B is Mo, m=1/4, n=1), Mo
1/2/ Mo
1(A and B is Mo, m=1/2, n=1), Mo
3/4/ Mo
1(A and B is Mo, m=3/4, n=1).
In catalyst for hydro-upgrading of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Co
0/ Co
1with Co
1/2/ Co
1ratio be 0.2 ~ 0.8, be preferably 0.2 ~ 0.7, Ni
0/ Ni
1with Ni
1/2/ Ni
1ratio 1.5 ~ 2.6, be preferably 1.7 ~ 2.5.
In catalyst for hydro-upgrading of the present invention, the distribution of active metal component on catalyst granules cross section is preferably as follows: Co
0/ Co
1< Co
1/4/ Co
1< Co
1/2/ Co
1.
In catalyst for hydro-upgrading of the present invention, the distribution of active metal component on catalyst granules cross section is preferably as follows: Co
1/2/ Co
1< Co
3/4/ Co
1< 1.
In catalyst for hydro-upgrading of the present invention, the distribution of active metal component on catalyst granules cross section is preferably as follows: Ni
0/ Ni
1> Ni
1/4/ Ni
1> Ni
1/2/ Ni
1.
In catalyst for hydro-upgrading of the present invention, the distribution of active metal component on catalyst granules cross section is preferably as follows: Ni
1/2/ Ni
1> Ni
3/4/ Ni
1> 1.
In catalyst for hydro-upgrading of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Co
0/ Co
1with Co
1/4/ Co
1ratio be 0.30 ~ 0.90, be preferably 0.30 ~ 0.85, Co
1/4/ Co
1with Co
1/2/ Co
1ratio be 0.4 ~ 0.9, be preferably 0.4 ~ 0.87; Ni
0/ Ni
1with Ni
1/4/ Ni
1ratio be 1.2 ~ 1.8, be preferably 1.3 ~ 1.7, Ni
1/4/ Ni
1with Ni
1/2/ Ni
1ratio be 1.1 ~ 1.7, be preferably 1.2 ~ 1.6.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Co
0/ Co
1< Co
x1/ Co
1< Co
x2/ Co
1< 1, wherein 0 < x1 < x2 < 1.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Ni
0/ Ni
1> Ni
x1/ Ni
1> Ni
x2/ Ni
1> 1, wherein 0 < x1 < x2 < 1.
In catalyst for hydro-upgrading of the present invention, on catalyst granules cross section, along described straight-line segment from outer most edge, point is to central point, and active metal component concentration distribution is as follows: the concentration of Co increases substantially gradually, the concentration of Ni reduces substantially gradually, and the concentration of Mo is essentially and is uniformly distributed.
In the present invention, the CONCENTRATION DISTRIBUTION that described " substantially reducing (or gradually increase) gradually along described straight-line segment " refers to described active metallic element, but allows to exist between one or more partial zones along described straight-line segment presenting the trend reducing (or increasing gradually) gradually to the whole interval of central point generally from outer most edge point; In this partial zones, the CONCENTRATION DISTRIBUTION of described active metallic element presents different trend (such as remain constant and/or increase (or reducing gradually) and/or disordered state gradually) along described straight-line segment.Prerequisite is, existence between this kind of partial zones is can to tolerate or negligible to those skilled in the art, or be inevitable for the state-of-art of this area, and the existence between these partial zones does not affect those skilled in the art and the CONCENTRATION DISTRIBUTION of described active metallic element in described whole interval is still judged to be " presenting the trend reducing (or gradually increase) gradually generally ".In addition, the existence between this partial zones does not affect the present invention and expects and be the realization of object acceptable, and be also contained within protection scope of the present invention.
In the present invention, described " concentration of Mo is essentially and is uniformly distributed " refers to the CONCENTRATION DISTRIBUTION of Mo on the whole cross section of each described catalyst granules is uniformity, but allows to exist and can tolerate to those skilled in the art and maybe can ignore or inevitable CONCENTRATION DISTRIBUTION fluctuation (deviation) for the state-of-art of this area.For example, such as, now Mo
0/ Mo
1to be in 1 ± 5% scope and Mo
m/ Mo
1be in 1 ± 5% scope, preferred Mo
0/ Mo
1to be in 1 ± 2% scope and Mo
m/ Mo
1be in 1 ± 2% scope.The fluctuation of this CONCENTRATION DISTRIBUTION does not affect the present invention and expects and be the realization of object acceptable, and be also contained within protection scope of the present invention.
In the present invention, described catalyst for hydro-upgrading is that (solid) is granular, instead of the amorphous state such as powder.As the shape of described particle, the various shapes that catalyst for hydro-upgrading routine in this area uses can be enumerated, such as can enumerate spherical, column etc. further, wherein preferred spherical or column.As described spherical, such as spheroidal and elliposoidal etc. can be enumerated; As described column, cylindric, flat column and profiled-cross-section (such as clover, bunge bedstraw herb etc.) column etc. such as can be enumerated.The granularity of described catalyst for hydro-upgrading is 3 ~ 8mm, is preferably 3 ~ 5mm.
In the present invention, described " cross section of catalyst granules " refers to the whole surface of minimum dimension direction by exposing after the geometric center cutting of its shape along a catalyst granules.Such as, when described catalyst granules is spherical, described cross section refers to the whole surface (such as see Fig. 1) by exposing after the cutting of its centre of sphere along the radius of this ball or short-axis direction.Or when described catalyst granules is column, described cross section refers to the whole surface (such as see Fig. 2) of length dimension direction by exposing after the central point cutting of this length dimension perpendicular to this post.In the present invention, the periphery of described exposed surface is called the outer most edge of this cross section, described geometric center (central point than the centre of sphere as the aforementioned or length dimension) is called the central point on this cross section.
Catalyst for hydro-upgrading of the present invention, with the weight of catalyst for benchmark, the content of carrier is 46wt% ~ 87wt%, be preferably 46% ~ 80%, more preferably surplus, Ni in the content of NiO for 1wt% ~ 8wt%, Mo are with MoO
3meter content be 10wt% ~ 40wt%, Co in the content of CoO for 0.5wt% ~ 6wt%; With the weight of catalyst carrier for benchmark, the content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%.
In catalyst for hydro-upgrading of the present invention, be positioned at the concentration of the Co at catalyst granules cross section outer most edge point place and concentration ratio (mol ratio) the i.e. Co of central spot Co
0/ Co
1be 0.08 ~ 0.80, be positioned at the concentration of the Ni at catalyst granules outer most edge point place and concentration ratio (mol ratio) the i.e. Ni of central spot Ni
0/ Ni
1be 1.2 ~ 7.0.
In catalyst for hydro-upgrading of the present invention, described molecular sieve is Y zeolite and/or beta-molecular sieve.With the weight of catalyst carrier for benchmark, the content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%.Wherein said molecular sieve is hydrogen type molecular sieve.Wherein beta-molecular sieve preferred property is as follows: specific area 450m
2/ g ~ 750m
2/ g, total pore volume 0.30ml/g ~ 0.45ml/g, SiO
2/ Al
2o
3mol ratio 40 ~ 100, the mol ratio of meleic acid amount 0.1 ~ 0.5mmol/g, Gu Jia Lv ∕ non-framework aluminum is 5 ~ 20, B acid/L acid is 0.30 ~ 0.50, Na
2o≤0.15wt%.Beta-molecular sieve of the present invention can adopt existing method to prepare.In the present invention, SiO
2/ Al
2o
3mol ratio adopt chemical determination, meleic acid amount, B acid and L sour employing Pyridine adsorption IR spectra method measure, wherein meleic acid amount be B acid and L acid acid amount with.Sodium oxide content adopts ion emission spectroscopy method to measure.Framework aluminum and non-framework aluminum content adopt NMR method to measure.
In catalyst for hydro-upgrading of the present invention, can not contain adjuvant component in carrier, also can contain adjuvant component, wherein adjuvant component can be one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron etc., adjuvant component in element content in the carrier at below 30wt%, preferred below 20wt%.Described carrier can adopt conventional method to prepare, such as kneading method etc.
The character of catalyst for hydro-upgrading of the present invention is as follows: specific area is 100 ~ 260 m
2/ g, is preferably 120 ~ 220 m
2/ g, pore volume is 0.20 ~ 0.60mL/g, is preferably 0.2 ~ 0.5 mL/g.
The preparation method of catalyst for hydro-upgrading provided by the invention, at least adopt one of with the following method, first method comprises:
(1) with the solution impregnating carrier containing adsorbent I, drying, obtain the carrier containing adsorbent I, the consumption of adsorbent I accounts for 0.1% ~ 10.0% of vehicle weight, described adsorbent I for number-average molecular weight be the polyalcohol of 400 ~ 10000, described dipping adopts saturated dipping or excessive dipping;
(2) with dipping solution impregnation steps (1) gains containing Ni, through super-dry and roasting, catalyst intermediate is obtained;
(3) unsaturated infusion process is adopted, by the catalyst intermediate that the fountain solution impregnation steps (2) containing adsorbent II is obtained, the consumption of adsorbent II accounts for 0.1% ~ 10.0% of vehicle weight, and wherein said adsorbent II is one or more in organic carboxyl acid and its esters;
(4) with dipping solution impregnation steps (3) gains containing Co, through super-dry and roasting,
Wherein active metal Mo before step (1), after step (2) and before step (3), after step (4) at least one step introduce in catalyst for hydro-upgrading;
Second method comprises:
A, adopt unsaturated infusion process, with the fountain solution impregnated carrier containing adsorbent II, the consumption of adsorbent II accounts for 0.1% ~ 10.0% of vehicle weight, and wherein said adsorbent II is one or more in organic carboxyl acid and its esters;
B, the dipping solution impregnation steps A gains of use containing Co, through super-dry and roasting, obtain catalyst intermediate,
C, the solution impregnation catalyst intermediate of use containing adsorbent I, drying, obtain the catalyst intermediate containing adsorbent I, the consumption of adsorbent I accounts for 0.1% ~ 10.0% of vehicle weight, described adsorbent I for number-average molecular weight be the polyalcohol of 400 ~ 10000, described dipping adopts saturated dipping or excessive dipping;
D, the dipping solution impregnation steps C gains of use containing Ni, through super-dry and roasting;
Wherein active metal Mo before steps A, after step B and before step C, after step D at least one step introduce in catalyst for hydro-upgrading.
In the inventive method, carrier can adopt conventional method to prepare, and molecular sieve can be introduced in aluminium oxide kneading process, also can introduce in alumina preparation process.
Described adsorbent I for number-average molecular weight be the polyalcohol of 400 ~ 10000, being preferably number-average molecular weight is the polyalcohol of 1000 ~ 8000, and described polyalcohol can be PTMEG, preferably polyethylene glycol.The addition of polyalcohol accounts for 0.05% ~ 10.0% of vehicle weight, is preferably 0.1% ~ 9.0%.
Described adsorbent II is one or more in organic carboxyl acid and its esters.Described organic acid comprise in acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid, TGA, mercaptopropionic acid, ethylenediamine tetra-acetic acid, nitrilotriacetic acid, ring ethylenediamine tetra-acetic acid etc. one or more.Organic carboxylate be preferably above-mentioned organic carboxyl acid ammonium salt in one or more.
In the inventive method, in the fountain solution containing adsorbent II and the solution containing adsorbent I, water and/or ethanol is adopted to be solvent.
In first method, preferred condition is as follows:
The solution impregnating carrier of step (1) containing adsorbent I, adopts incipient impregnation or excessive dipping, and after dipping terminates, sample through health or without health, then carries out drying, if need health, conditioned time is 1 ~ 12h; Described drying condition is as follows: temperature is 60 DEG C ~ 250 DEG C, drying time 0.5h ~ 20h.
Step (2), with after the dipping solution dipping containing Ni, through health or without health, then carries out drying and roasting.As needed health, conditioned time is 0.5 ~ 6.0h.Described drying condition is as follows: baking temperature is 70 DEG C ~ 200 DEG C, and be preferably 100 DEG C ~ 160 DEG C, drying time is 0.5h ~ 20h, is preferably 1h ~ 6h; Described roasting condition: sintering temperature is 300 DEG C ~ 750 DEG C, be preferably 400 DEG C ~ 650 DEG C, roasting time is 0.5h ~ 20h, is preferably 1h ~ 6h.
In the present invention, the fountain solution of step (3) containing adsorbent II floods, and adopt unsaturated dipping, preferably adopt unsaturated spraying, the immersion liquid amount that wherein unsaturated dipping is used and the volume ratio of catalyst intermediate saturated absorption amount of solution are 0.02 ~ 0.4.Dipping is containing after the fountain solution of adsorbent, and baking temperature is generally 60 DEG C ~ 250 DEG C, is preferably 100 ~ 200 DEG C, and drying time, 0.5h ~ 20h, was preferably 1h ~ 6h.When spraying the fountain solution containing adsorbent, the shower nozzle that atomizing effect is good should be selected, dissolution homogeneity is distributed in catalyst intermediate.After the fountain solution dipping of dipping containing adsorbent terminates, directly can carry out next step, also can be passed through health and carry out next step again, conditioned time is 0.5 ~ 8h.
Step (4) is loaded in catalyst intermediate by infusion process with the dipping solution containing Co and adopts equi-volume impregnating, through health or without health after dipping, then carries out drying.As needed health, conditioned time is 0.5 ~ 6.0h.Described drying condition is as follows: baking temperature is 60 DEG C ~ 300 DEG C, and be preferably 100 DEG C ~ 160 DEG C, drying time is 0.5h ~ 20h, is preferably 1h ~ 6h.Described roasting condition: sintering temperature is 300 DEG C ~ 750 DEG C, be preferably 400 DEG C ~ 650 DEG C, roasting time is 0.5h ~ 20h, is preferably 1h ~ 6h.
In second method, preferred condition is as follows:
In the present invention, the fountain solution of steps A containing adsorbent II floods, and adopt unsaturated dipping, preferably adopt unsaturated spraying, the immersion liquid amount that wherein unsaturated dipping is used and the volume ratio of carrier saturated absorption amount of solution are 0.02 ~ 0.4.Dipping is containing after the fountain solution of adsorbent, and baking temperature is generally 60 DEG C ~ 250 DEG C, is preferably 100 ~ 200 DEG C, and drying time, 0.5h ~ 20h, was preferably 1h ~ 6h.When spraying the fountain solution containing adsorbent, the shower nozzle that atomizing effect is good should be selected, dissolution homogeneity is distributed on carrier.After the fountain solution dipping of dipping containing adsorbent terminates, directly can carry out next step, also can be passed through health and carry out next step again, conditioned time is 0.5 ~ 8h.
Step B is loaded on carrier by infusion process with the dipping solution containing Co and adopts equi-volume impregnating, through health or without health after dipping, then carries out drying.As needed health, conditioned time is 0.5 ~ 6.0h.Described drying condition is as follows: baking temperature is 60 DEG C ~ 300 DEG C, and be preferably 100 DEG C ~ 160 DEG C, drying time is 0.5h ~ 20h, is preferably 1h ~ 6h.Described roasting condition: sintering temperature is 300 DEG C ~ 750 DEG C, be preferably 400 DEG C ~ 650 DEG C, roasting time is 0.5h ~ 20h, is preferably 1h ~ 6h.
When step C use contains the solution impregnation of adsorbent I, adopt incipient impregnation or excessive dipping, after dipping terminates, sample through health or without health, then carries out drying, if need health, conditioned time is 1 ~ 12h; Described drying condition is as follows: temperature is 60 DEG C ~ 250 DEG C, drying time 0.5h ~ 20h.
Step D, with after the dipping solution dipping containing Ni, through health or without health, then carries out drying and roasting.As needed health, conditioned time is 0.5 ~ 6.0h.Described drying condition is as follows: baking temperature is 70 DEG C ~ 200 DEG C, and be preferably 100 DEG C ~ 160 DEG C, drying time is 0.5h ~ 20h, is preferably 1h ~ 6h; Described roasting condition: sintering temperature is 300 DEG C ~ 750 DEG C, be preferably 400 DEG C ~ 650 DEG C, roasting time is 0.5h ~ 20h, is preferably 1h ~ 6h.
In catalyst for hydro-upgrading preparation method of the present invention, active metal, by infusion process load, adopts equi-volume impregnating usually.Dipping method is known by technical staff.Active metal solution manufacturing method is known by technical staff, and its solution concentration regulates by the consumption of each compound, thus prepares the catalyst of specified activity constituent content.The raw material of required active component is generally the compound of the types such as salt, oxide or acid, if cobalt source is from one or more in cobalt nitrate, cobalt carbonate, basic cobaltous carbonate, cobalt chloride, cobalt oxalate.Nickel source is from one or more in nickel nitrate, nickelous carbonate, basic nickel carbonate, nickel chloride, nickel oxalate.In described dipping solution, except active metal component, phosphorus-containing compound can also be contained, as being one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate etc.
In the inventive method, one or more in adjuvant component fluorine, silicon, phosphorus, titanium, zirconium and boron, adopt conventional method to introduce in catalyst, such as can introduce when prepared by carrier in catalyst, also can introduce catalyst after prepared by carrier.Introduce in catalyst after carrier preparation, the method for dipping separately can be adopted to introduce in catalyst, also together can flood with active metal component and introduce in catalyst.
Catalyst for hydro-upgrading of the present invention in the hydro-upgrading of heavy distillate (especially diesel oil) as the application of catalyst for hydro-upgrading.
Described heavy distillate can be diesel oil, wax oil, wherein preferred diesel oil.The total sulfur content of described heavy distillate is generally 0.3wt% ~ 3.0wt%, preferred 0.3wt% ~ 2.5wt%, the sulfur content that wherein difficult de-sulfur-containing compound (with 4,6-dimethyl Dibenzothiophene for meter) is contributed is approximately more than 0.01wt%, is generally 0.01 wt% ~ 0.05wt%.
The present invention, in described application or described hydrogenation modification method, can only use catalyst for hydro-upgrading of the present invention, also can by catalyst for hydro-upgrading of the present invention and other catalyst for hydro-upgrading (than as be known in the art those) according to the ratio needed arbitrarily with the use of, such as employing different catalysts bed grating or used in combination.
According to the present invention, to the operating condition of described hydro-upgrading without any special restriction, the operating condition that this area routine uses can be adopted, such as reaction temperature 260 ~ 400 DEG C, preferably 310 ~ 370 DEG C, reaction stagnation pressure 3 ~ 13MPa, preferably 5 ~ 9MPa, volume space velocity 0.5 ~ 4h during liquid
-1, preferably 1 ~ 2h
-1, hydrogen to oil volume ratio 200:1 ~ 2000:1, preferred 400:1 ~ 1000:1.
In catalyst for hydro-upgrading of the present invention, active metal component Mo is evenly distributed substantially, active metal component Co is the trend increased gradually substantially from catalyst granules outer surface to center, Ni is the trend reduced gradually substantially from catalyst granules outer surface to center, the active metal component of uneven distribution matches with acidic components molecular sieve in carrier, this catalyst is specially adapted in the hydro-upgrading process of diesel oil, while diesel deep desulfurization, improve the combination properties such as the Cetane number of diesel oil when keeping diesel yield higher.
Catalyst for hydro-upgrading prepared by the present invention, Mo adopts conventional method introducing to make it be uniformly distributed in catalyst, the solution of adsorbent I is contained by saturated dipping or excessive dipping, then Ni is flooded, make the trend that the concentration of Ni tapers off from catalyst external surface to center, make the amount of the active phase of Mo-Ni further from outer surface to center in the trend reduced gradually, by the fountain solution of unsaturated dipping containing adsorbent II, a part of adsorption potential on catalyst granules outer surface and marginal position surface is occupied by adsorbent, when dipping contains the solution of active metal Co, decrease the absorption of Co in carrier edge position, make the concentration of active metal Co from outer surface to center in the trend increased gradually, make the amount of the active phase of Mo-Co further from outer surface to center in the trend increased progressively, the active metal component of this uneven distribution is matched with acidic components molecular sieve in carrier, improve the deep hydrodesulfurizationof performance of catalyst, and suitable open loop, isomery, the performances such as cracking, for in the hydro-upgrading process of diesel oil, can while diesel deep desulfurization, the combination properties such as the Cetane number of diesel oil are improved when keeping diesel yield higher.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of spherical catalyst particles cutting mode;
Fig. 2 is the schematic diagram of cylindrical catalyst particle cutting mode;
Fig. 3 is the selected each position point that catalyst granules passes through to cut on rear gained cross section and this cross section, wherein 0 represent any point on this cross section in outer most edge and outer most edge point, 1/4 represents 1/4 location point, 1/2 represents 1/2 location point, 3/4 represents 3/4 location point, and 1 represents central point.
Fig. 4 is the concentration profile of active metal component Ni and Co on this cross section in embodiment 2 gained catalyst C3.Wherein abscissa is each position point on this cross section, and ordinate is the ratio of the concentration of central spot on the concentration at a certain location point place and this cross section.
Detailed description of the invention
The technical scheme that the invention is further illustrated by the following examples, but invention should not be deemed limited in this embodiment.In the present invention, wt% is mass fraction.
In the inventive method, active metal component Mo introduces the method in catalyst for hydro-upgrading, is described for first method, such as can introduce before step (1), also can introduce after step (2) and before the step (3), also can introduce after step (4).When active metal component Mo introduces before the step (1), following at least one method can be adopted: add in carrier component dry glue powder preparation process and then shapingly make containing the carrier of Mo, add when carrier component kneading and compacting to make and add containing the carrier of Mo and the shaping rear employing infusion process of carrier component the carrier made containing Mo.When active metal component Mo introduces after step (2) and before the step (3), infusion process can be adopted to introduce.When active metal component Mo introduces after step (4), infusion process also can be adopted to introduce.When active metal component Mo introduces before the step (1), can adopt one of with the following method:
One, add in the preparation process of aluminum oxide dry glue powder, as introduced with co-precipitation, fractional precipitation mode, then with molecular sieve kneading and compacting, the obtained carrier containing Mo after drying, roasting;
Two, add with kneading form when carrier is shaping: aluminum oxide dry glue powder, molecular sieve are mixed with the compound containing active metal component Mo, then through kneading and compacting, the obtained carrier containing Mo is made in dry, roasting;
Three, by aluminum oxide dry glue powder, molecular sieve kneading and compacting, then carry out drying, roasting makes carrier, afterwards with the solution impregnating carrier containing active metal component Mo, drying, roasting make the carrier containing Mo.
In above-mentioned forming process, can add conventional shaping assistant, one or more in such as extrusion aid, adhesive, peptizing agent etc., addition can be determined by this area knowledge according to Kaolinite Preparation of Catalyst character.Wherein adhesive generally adopts little porous aluminum oxide, is selected from the boehmite of aluminium chloride-Ammonia Process, carbonizatin method or aluminum sulfate method production and the SB alumina powder etc. of Zlegler synthetic reaction accessory substance.
In catalyst for hydro-upgrading preparation method of the present invention, adopt prior art condition containing the drying in the carrier preparation process of Mo and roasting, if baking temperature is 40 DEG C ~ 250 DEG C, drying time is 0.5h ~ 20h; Sintering temperature is 350 DEG C ~ 750 DEG C, and roasting time is 0.5h ~ 20h.
Analytical method of the present invention is as follows:
(1) content (wt%) of active metal component and adjuvant component adopts x ray fluorescence spectrometry to measure.
(2) specific area (m
2/ g) and pore volume (ml/g) adopt BET method to measure.
(3) CONCENTRATION DISTRIBUTION of each active metal component in catalyst granules
In following embodiment and comparative example, employ columniform carrier (but the present invention is obviously not limited to this, also can use other grain shape), catalyst granules obtained thus is also columniform.From the catalyst that each embodiment and comparative example obtain, random selecting catalyst granules is as measurement sample.In order to measure the CONCENTRATION DISTRIBUTION of each active metal component in this catalyst granules, perpendicular to the length dimension direction of this cylindrical particle, being cut by the central point of this length dimension, obtaining two exposed surfaces.Get one of them exposed surface as measurement cross section.
This measurement uses EPMA method, with reference to GB/T15074-2008(Electron probe quantitative analysis method general rule) carry out, electron probe microanalyzer (JXA-8230 type, Jeol Ltd. manufactures) carries out.Measuring condition is: accelerating potential 15kV, beam intensity 5 × 10
-8a, beam spot diameter, 1 μm, X-ray detects angle: Mo is 38 °, and Ni is 24 °, and Co is 26 °, correction method: ZAF correction method, the standard specimen of use: pure metal oxides standard specimen (is respectively NiO, CoO and MoO
3), precision: be less than 1%, secondary electron image resolution ratio: 3nm(LaB
6), linear system: Ni and Co adopts K
αlinear system, Mo adopts L
αlinear system.
Measuring method is: in the outer most edge of this cross section, choose arbitrarily a location point as 0, using the central point on this cross section as 1, connecting described location point 0 (is in fact the radius of this cross section with the straight-line segment of described location point 1, therefore also referred to as radial direction), the concentration value of measuring gage allocation point place targeted activity metal, then by division calculation, the ratio (being mol ratio in the present invention) of each concentration value is obtained.
Fig. 4 is the concentration profile of active metal in the catalyst C3 of embodiment 2 gained, by evenly choosing 21 location points (comprising location point 0 and location point 1) on this straight-line segment, with these location points for abscissa, the ratio of the concentration value of the corresponding active metal measured to location point 1 place (i.e. central point) with the concentration value of the targeted activity metal (for Ni and Co) of each position point place measurement (uses Ni respectively
m/ Ni
1and Co
m/ Co
1represent) be ordinate, so to draw and to obtain.
(4) total sulfur content in raw material and hydrogenation products adopts ultraviolet fluorescence method to measure (ASTM D5453-1993), and 4,6-BMDBT content adopts GC-AED(gas-chromatography-atom luminescence spectroscopy) measure.
(5) number-average molecular weight Mn adopts GPC method to measure.
Cylindrical vector used in embodiment, wherein carrier lengths is about 3 ~ 5mm.
Embodiment 1
The present embodiment introduces the preparation method of catalyst precarsor.The aluminum oxide dry glue powder specific surface 350m of siliceous, boron
2/ g, pore volume is 0.90ml/g.
Take aluminum oxide dry glue powder 380g that is siliceous, boron, add citric acid and each 6g of sesbania powder, beta-molecular sieve 18g, after mixing, add acid solution 340g, HNO in acid solution
3weight concentration be 1.74%, all the other are distilled water.After rolling 20min, by the circular orifice extrusion of diameter 1.7mm.After 120 DEG C of dry 4h, 500 DEG C of roasting 3h.Obtained carrier strip is designated as S1.With the carrier strip S1 obtained by the solution impregnation containing Mo, after 130 DEG C of dry 4h, 500 DEG C of roasting 2h, obtained catalyst precarsor is designated as S1.
Take aluminum oxide dry glue powder 360g that is siliceous, boron, add citric acid and each 6g of sesbania powder, Y molecular sieve 30g, add acid solution 335g, HNO in acid solution
3weight concentration be that 2.6%, Mo is with MoO
3the weight content of meter is 27.8%, and all the other are distilled water.After rolling 20min, by the circular orifice extrusion of diameter 1.7mm.500 DEG C of roasting 3h after 120 DEG C of dry 4h, obtained catalyst precarsor is designated as S2.
Prepare aluminum oxide dry glue powder that is siliceous, molybdenum.In container, add 1L deionized water, be warming up to 58 DEG C, add 3L containing Al simultaneously
2o
3for the aluminum nitrate solution of 4g/100mL with containing NH
3for the ammonia spirit of 10g/100mL, control ph is 7.8, and feed time is 120min.After stopping is reinforced, system is aging 50min under said temperature and pH value condition, adds SiO
2content is the solution of sodium metasilicate through 100mL of 5.0g, continues aging 60min, then washs 4 times, to Cl
-/ Al
2o
3till <0.5%.Preparation is containing the aqueous solution 1L of molybdenum, wherein MO
3concentration 4.3g/100mL, adds in filter cake, stirs into pasty state, after 120 DEG C of dry 8h, is crushed to granularity and is less than 180 objects and accounts for more than 95%, obtain required dry glue powder.
The character of the aluminum oxide dry glue powder of the siliceous and molybdenum of gained is as follows: specific surface 340m
2/ g, pore volume is 0.88ml/g.
Take siliceous and aluminum oxide dry glue powder 360g that is molybdenum, add citric acid and each 6g of sesbania powder, Y molecular sieve 18g, beta-molecular sieve 9g, after mixing, add acid solution 345g, HNO in acid solution
3weight concentration be 1.74%, all the other are distilled water.After rolling 20min, by the circular orifice extrusion of diameter 1.7mm.500 DEG C of roasting 3h after 120 DEG C of dry 4h.Obtained carrier strip is designated as S3.
Identical with S3 carrier preparation process, just do not add molecular sieve, the carrier made is designated as S4.
The physico-chemical property of used carrier in table 1 embodiment
In the present embodiment, in Ni, P and Co used, P maceration extract, Ni predecessor is nickel nitrate, and Co predecessor is cobalt nitrate, and P predecessor is phosphoric acid.
Embodiment 2
Take tartaric acid 18g, stirring and dissolving in 45g water, obtained fountain solution I.Get S1 carrier 30 as one kind 0g, evenly sprayed on S1 by fountain solution I, the time of spraying is 15min.After fountain solution I sprays end, through 100 DEG C of dry 2h, with the above-mentioned carrier of maceration extract incipient impregnation containing Co, P, gained sample average is divided into three parts, wherein the first increment product not health, through 120 DEG C of dry 3h, and 480 DEG C of roasting 2h, the sample of acquisition is designated as B1; Second increment product health 1h, through 120 DEG C of dry 3h, 480 DEG C of roasting 2h, obtained sample is designated as B2; Triplicate sample health 3h, through 120 DEG C of dry 3h, 480 DEG C of roasting 2h, obtained sample is designated as B3.
Take 6g Macrogol 2000 (namely molecular weight is the polyethylene glycol of 2000, lower same), stirring and dissolving in the water measured, obtained solution II.With this solution II incipient impregnation sample B1, B2 and B3 respectively, then carry out the health of 10h, after 120 DEG C of dry 3h, obtained sample is designated as Z1, Z2 and Z3 respectively.
Spray above-mentioned Z1, Z2 and Z3 sample with the maceration extract equal-volume containing Ni, P respectively, directly carry out 120 DEG C of dry 3h without health after spraying end, 480 DEG C of roasting 2h, the catalyst of acquisition is designated as C1, C2 and C3 respectively.
Embodiment 3
Take 24g cetomacrogol 1000, stirring and dissolving in the water measured, obtained solution II.With the sample S2 of this solution II incipient impregnation 300g, then carry out the health of 5h, after 120 DEG C of dry 3h, obtained sample is designated as B4.
Spray B4 sample with the maceration extract equal-volume containing Ni, P, spray gained sample average after terminating and be divided into three parts, the wherein direct 120 DEG C of dry 3h of the first increment product, 480 DEG C of roasting 2h, the sample of acquisition is designated as Z4; Second increment product health 1h, 120 DEG C of dry 3h, 480 DEG C of roasting 2h, obtained sample is designated as Z5; Triplicate sample health 3h, 120 DEG C of dry 3h, 480 DEG C of roasting 2h, obtained sample is designated as Z6.
Take malic acid 2g, stirring and dissolving in 8g ethanol, obtained fountain solution I.Evenly sprayed on Z4 by fountain solution I, the time of spraying is 5min.With the above-mentioned carrier of maceration extract incipient impregnation containing Co, P, dipping terminates rear health 1h, and through 120 DEG C of dry 3h, 480 DEG C of roasting 2h, the catalyst of acquisition is designated as C4.Process Z5 and Z6 respectively by the method identical with process Z4, the catalyst obtained is designated as C5 and C6.
Embodiment 4
Take citric acid and each 3.5g of malonic acid, stirring and dissolving in 20g water, obtained fountain solution I.Get S3 carrier 100g, evenly sprayed on S3 by fountain solution I, the time of spraying is 25min.With containing the above-mentioned carrier of Co, P maceration extract incipient impregnation, dipping terminates rear health 1h, and through 120 DEG C of dry 3h, 480 DEG C of roasting 2h, the sample of acquisition is designated as B5.
Take 2g PEG 8000, stirring and dissolving in the aqueous solution measured, obtained solution II.With this solution II incipient impregnation sample B5, then carry out the health of 5h, after 120 DEG C of dry 3h, obtained sample is designated as Z7.
Spray Z5 sample with the maceration extract equal-volume containing Ni, P, directly through 120 DEG C of dry 3h, 480 DEG C of roasting 2h, the catalyst of acquisition is designated as C7.
Comparative example 1
Get S1 carrier 100g, preparation contains the maceration extract of Ni, Co, P and citric acid and each 3.5g of malonic acid, and after the above-mentioned carrier of incipient impregnation, through 120 DEG C of dry 3h, 480 DEG C of roasting 2h, the sample of acquisition is designated as C8.
Comparative example 2
Get S4 carrier 100g, adopt the preparation method identical with C7 catalyst to prepare, the catalyst of acquisition is designated as C9.
Table 2 embodiment and comparative example catalyst activity metal form
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Composition | |||||||||
| MoO 3，wt％ | 24.0 | 24.1 | 23.8 | 23.9 | 24.0 | 24.1 | 23.9 | 24.0 | 24.1 |
| CoO，wt％ | 2.3 | 2.4 | 2.3 | 2.3 | 2.4 | 2.4 | 2.3 | 2.4 | 2.4 |
| NiO，wt％ | 1.9 | 2.1 | 1.9 | 2.0 | 2.1 | 2.1 | 2.0 | 2.0 | 2.0 |
| P 2O 5，wt％ | 2.8 | 2.7 | 2.8 | 2.7 | 2.8 | 2.7 | 2.7 | 2.7 | 2.7 |
| Carrier * | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
In table 2, the aluminium oxide of carrier * and C1, C2, C3 and C8 and beta-molecular sieve and auxiliary agents of silicon and boron, aluminium oxide and Y molecular sieve and auxiliary agents of silicon and boron in C4, C5 and C6, aluminium oxide, β and Y molecular sieve and auxiliary agents of silicon in C7, the aluminium oxide in C9 and auxiliary agents of silicon.
The CONCENTRATION DISTRIBUTION of elements Mo in catalyst granules in table 3 embodiment and comparative example gained catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Mo 0/Mo 1 | 1.01 | 1.00 | 1.00 | 1.01 | 0.99 | 1.00 | 1.02 | 1.0 | 0.99 |
| Mo 1/4/Mo 1 | 1.01 | 0.98 | 0.98 | 1.00 | 1.00 | 1.02 | 1.01 | 1.01 | 1.02 |
| Mo 1/2/Mo 1 | 1.00 | 0.99 | 1.01 | 0.98 | 0.98 | 0.99 | 1.0 | 0.98 | 1.0 |
| Mo 3/4/Mo 1 | 0.99 | 1.01 | 1.00 | 0.99 | 1.00 | 1.01 | 0.99 | 0.99 | 0.99 |
The CONCENTRATION DISTRIBUTION of Elements C o in catalyst granules in table 4 embodiment and comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Co 0/Co 1 | 0.13 | 0.27 | 0.56 | 0.31 | 0.32 | 0.32 | 0.30 | 0.96 | 0.29 |
| Co 1/4/Co 1 | 0.29 | 0.45 | 0.64 | 0.79 | 0.78 | 0.80 | 0.43 | 0.97 | 0.41 |
| Co 1/2/Co 1 | 0.60 | 0.81 | 0.91 | 0.97 | 0.96 | 0.96 | 0.80 | 1.00 | 0.81 |
| Co 3/4/Co 1 | 0.91 | 0.94 | 0.98 | 0.99 | 0.99 | 1.00 | 0.95 | 0.99 | 0.94 |
The CONCENTRATION DISTRIBUTION of element Ni in catalyst granules in table 5 embodiment and comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Ni 0/Ni 1 | 2.82 | 2.83 | 2.82 | 3.03 | 2.50 | 2.08 | 2.51 | 0.95 | 2.53 |
| Ni 1/4/ Ni 1 | 1.90 | 1.88 | 1.89 | 1.94 | 1.72 | 1.50 | 1.70 | 0.97 | 1.72 |
| Ni 1/2/ Ni 1 | 1.27 | 1.28 | 1.27 | 1.31 | 1.22 | 1.18 | 1.20 | 0.99 | 1.21 |
| Ni 3/4/ Ni 1 | 1.10 | 1.11 | 1.10 | 1.11 | 1.08 | 1.05 | 1.06 | 1.00 | 1.06 |
Embodiment 5
The present embodiment is the henchnmrk test of catalyst.
Catalyst performance evaluation experiment is carried out on 100mL small hydrogenation device, carries out presulfurization before performance evaluation to catalyst.Evaluating catalyst condition is at reaction stagnation pressure 10.0MPa, volume space velocity 1.5 h during liquid
-1, hydrogen-oil ratio 800:1, reaction temperature is 365 DEG C.Henchnmrk test feedstock oil character is in table 6, Evaluation results is in table 7, from data in table, catalyst for hydro-upgrading is prepared with the present invention, catalyst desulphurizing activated apparently higher than comparative example catalyst, under maintenance diesel yield is not less than the condition of 97%, the Cetane number of diesel oil is improved more than 10 units, product quality obtains good improvement.
table 6 feedstock oil character
| Feedstock oil | Catalytic diesel oil |
| Density (20 DEG C), g/cm 3 | 0.9433 |
| Boiling range/DEG C | |
| IBP/10% | 182/250 |
| 30%/50% | 284/310 |
| 70%/90% | 332/347 |
| 95%/EBP | 358/370 |
| Condensation point, DEG C | 5 |
| Sulphur, μ g/g | 8698 |
| 4,6-BMDBT content, μ g/g | 103.6 |
| Nitrogen, μ g/g | 1225 |
| Cetane number | 28 |
| C，wt% | 87.98 |
| H，wt% | 11.12 |
table 7 catalyst performance evaluation result
| Catalyst | C1 | C2 | C3 | C4 |
| Diesel oil | ||||
| Yield, wt% | 98.1 | 98.0 | 98.2 | 97.5 |
| Density (20 DEG C)/g.cm -3 | 0.8341 | 0.8397 | 0.8399 | 0.8387 |
| T95，℃ | 349 | 350 | 350 | 348 |
| Condensation point, DEG C | -20 | -20 | -21 | -22 |
| Cetane number | 46.5 | 46.6 | 46.8 | 47.8 |
| Sulphur, μ g/g | 11 | 10 | 10 | 9 |
Table 7 continues
| Catalyst | C5 | C6 | C7 | C8 | C9 |
| Diesel oil | |||||
| Yield, wt% | 97.5 | 97.6 | 97.8 | 97.6 | 99.6 |
| Density (20 DEG C)/g.cm -3 | 0.8388 | 0.8391 | 0.8393 | 0.8401 | 0.8576 |
| T95，℃ | 347 | 348 | 348 | 350 | 355 |
| Condensation point, DEG C | -22 | -21 | -22 | -19 | 4 |
| Cetane number | 47.7 | 47.6 | 47.7 | 44.8 | 34.9 |
| Sulphur, μ g/g | 9 | 8 | 7 | 19 | 13 |
Claims (25)
1. a catalyst for hydro-upgrading, carrier comprises aluminium oxide and molecular sieve, and active metal component is Co, Mo, Ni, and wherein the CONCENTRATION DISTRIBUTION of active metal component on each catalyst granules cross section is as follows: Co
0/ Co
1< Co
1/2/ Co
1< 1, Ni
0/ Ni
1> Ni
1/2/ Ni
1the concentration of > 1, Mo is essentially and is uniformly distributed;
Wherein, the CONCENTRATION DISTRIBUTION formula A of active metal component on the cross section of each catalyst granules
m/ B
nrepresent, i.e. the ratio of the concentration of m place elements A and the concentration of n place element B on the cross section of each catalyst granules, wherein A represents active metallic element Mo, Co or Ni, and B represents active metallic element Mo, Co or Ni, with any point of catalyst granules cross section outer most edge for starting point is designated as 0, with the central point of catalyst granules cross section for terminal is designated as 1, connection starting point and terminal obtain straight-line segment, m and n is illustrated respectively in the location point that above-mentioned straight-line segment is chosen, the value of m and n represents the ratio of the length accounting for above-mentioned straight-line segment from starting point to the distance of the location point chosen, the value of m and n is 0 ~ 1, in order to express easily, A and B directly adopts active metallic element Mo, Co or Ni replaces, m and n is directly with the location point that the above-mentioned straight-line segment of digitized representation of 0 ~ 1 is determined.
2. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, active metal component, in catalyst granules, at least comprises following a kind of scheme:
(1) Co
0/ Co
1with Co
1/2/ Co
1ratio be 0.2 ~ 0.8;
(2) Ni
0/ Ni
1with Ni
1/2/ Ni
1ratio 1.5 ~ 2.6.
3. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, active metal component, in catalyst granules, at least comprises following a kind of scheme:
(1) Co
0/ Co
1with Co
1/2/ Co
1ratio be 0.2 ~ 0.7;
(2) Ni
0/ Ni
1with Ni
1/2/ Ni
1ratio 1.7 ~ 2.5.
4. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section at least comprises following a kind of scheme:
（1）Co
0/Co
1＜Co
1/4/Co
1＜Co
1/2/Co
1；
（2）Co
1/2/Co
1＜Co
3/4/Co
1＜1；
（3）Ni
0/Ni
1＞Ni
1/4/Ni
1＞Ni
1/2/Ni
1；
（4）Ni
1/2/Ni
1＞Ni
3/4/Ni
1＞1；
(5) Co
0/ Co
1< Co
x1/ Co
1< Co
x2/ Co
1< 1, wherein 0 < x1 < x2 < 1;
(6) Ni
0/ Ni
1> Ni
x1/ Ni
1> Ni
x2/ Ni
1> 1, wherein 0 < x1 < x2 < 1.
5. according to catalyst according to claim 4, it is characterized in that in described catalyst for hydro-upgrading, active metal component, in catalyst granules, at least comprises following a kind of scheme:
(1) Co
0/ Co
1with Co
1/4/ Co
1ratio be 0.3 ~ 0.9;
(2) Co
1/4/ Co
1with Co
1/2/ Co
1ratio be 0.4 ~ 0.9;
(3) Ni
0/ Ni
1with Ni
1/4/ Ni
1ratio be 1.2 ~ 1.8;
(4) Ni
1/4/ Ni
1with Ni
1/2/ Ni
1ratio be 1.1 ~ 1.7.
6. according to catalyst according to claim 4, it is characterized in that in described catalyst for hydro-upgrading, active metal component, in catalyst granules, at least comprises following a kind of scheme:
(1) Co
0/ Co
1with Co
1/4/ Co
1ratio be 0.3 ~ 0.85;
(2) Co
1/4/ Co
1with Co
1/2/ Co
1ratio be 0.4 ~ 0.87;
(3) Ni
0/ Ni
1with Ni
1/4/ Ni
1ratio be 1.3 ~ 1.7;
(4) Ni
1/4/ Ni
1with Ni
1/2/ Ni
1ratio be 1.2 ~ 1.6.
7. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, on catalyst granules cross section, along described straight-line segment from outer most edge, point is to central point, active metal component concentration distribution is as follows: the concentration of Co increases substantially gradually, the concentration of Ni reduces substantially gradually, and the concentration of Mo is essentially and is uniformly distributed.
8., according to catalyst according to claim 1, it is characterized in that described catalyst for hydro-upgrading, with the weight of catalyst for benchmark, the content of carrier be 46wt% ~ 87wt%, Ni in the content of NiO for 1wt% ~ 8wt%, Mo are with MoO
3meter content be 10wt% ~ 40wt%, Co in the content of CoO for 0.5wt% ~ 6wt%; With the weight of catalyst carrier for benchmark, the content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%.
9. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, be positioned at the concentration of Co at catalyst granules cross section outer most edge point place and the concentration ratio of central spot Co and Co
0/ Co
1be 0.08 ~ 0.90, be positioned at the concentration of Ni at catalyst granules cross section outer most edge point place and the concentration ratio of central spot Ni and Ni
0/ Ni
1be 1.2 ~ 7.0.
10., according to catalyst according to claim 1, it is characterized in that described molecular sieve is Y zeolite and/or beta-molecular sieve.
11. according to catalyst according to claim 1, it is characterized in that described molecular sieve is beta-molecular sieve; Wherein beta-molecular sieve character is as follows: specific area 450m
2/ g ~ 750m
2/ g, total pore volume 0.30ml/g ~ 0.45ml/g, SiO
2/ Al
2o
3mol ratio 40 ~ 100, the mol ratio of meleic acid amount 0.1 ~ 0.5mmol/g, Gu Jia Lv ∕ non-framework aluminum is 5 ~ 20, B acid/L acid is 0.30 ~ 0.50, Na
2o≤0.15wt%.
12. according to catalyst according to claim 1, it is characterized in that the character of described catalyst for hydro-upgrading is as follows: specific area is 120 ~ 220 m
2/ g, pore volume is 0.20 ~ 0.60mL/g.
13. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, containing adjuvant component, wherein adjuvant component is one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component in element weight content in the catalyst at below 15wt%.
14. according to catalyst according to claim 1, it is characterized in that containing phosphorus in described catalyst for hydro-upgrading, with P
2o
5meter weight content is in the catalyst 1% ~ 6%.
The preparation method of the arbitrary described catalyst for hydro-upgrading of 15. claim 1 ~ 12, at least adopt one of with the following method, first method comprises:
(1) with the solution impregnating carrier containing adsorbent I, drying, obtains the carrier containing adsorbent I, in the consumption of adsorbent I vehicle weight 0.1% ~ 10.0%, described adsorbent I for molecular weight be the polyalcohol of 400 ~ 10000, described dipping adopts saturated dipping or excessive dipping;
(2) with dipping solution impregnation steps (1) gains containing Ni, through super-dry and roasting, catalyst intermediate is obtained;
(3) unsaturated infusion process is adopted, by the catalyst intermediate that the fountain solution impregnation steps (2) containing adsorbent II is obtained, the consumption of adsorbent II accounts for 0.1% ~ 10.0% of vehicle weight, and wherein said adsorbent II is one or more in organic carboxyl acid and its esters;
(4) with dipping solution impregnation steps (3) gains containing Co, through super-dry and roasting;
Wherein active metal Mo before step (1), after step (2) and before step (3), after step (4) at least one step introduce in catalyst for hydro-upgrading;
Second method comprises:
A, adopt unsaturated infusion process, with the fountain solution impregnated carrier containing adsorbent II, the consumption of adsorbent II accounts for 0.1% ~ 10.0% of vehicle weight, and wherein said adsorbent II is one or more in organic carboxyl acid and its esters;
B, the dipping solution impregnation steps A gains of use containing Co, through super-dry and roasting, obtain catalyst intermediate,
C, the solution impregnation catalyst intermediate of use containing adsorbent I, drying, obtain the catalyst intermediate containing adsorbent I, the consumption of adsorbent I accounts for 0.1% ~ 10.0% of vehicle weight, described adsorbent I for number-average molecular weight be the polyalcohol of 400 ~ 10000, described dipping adopts saturated dipping or excessive dipping;
D, the dipping solution impregnation steps C gains of use containing Ni, through super-dry and roasting;
Wherein active metal Mo before steps A, after step B and before step C, after step D at least one step introduce in catalyst for hydro-upgrading.
16. in accordance with the method for claim 15, it is characterized in that in first method, and in the dipping solution of step (2) and/or step (4), containing phosphorus, phosphorus source is one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate; In catalyst, the introduction volume of phosphorus is with P
2o
5meter accounts for 1% ~ 6% of final catalyst for hydro-upgrading weight; In second method, in the dipping solution of step B and/or step D, containing phosphorus, phosphorus source is one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate; In catalyst, the introduction volume of phosphorus is with P
2o
5meter accounts for 1% ~ 6% of final catalyst for hydro-upgrading weight.
17. in accordance with the method for claim 15, it is characterized in that described adsorbent I to be number-average molecular weight be the polyalcohol of 1000 ~ 8000.
18. according to catalyst according to claim 15, it is characterized in that described polyalcohol is polyethylene glycol.
19. according to catalyst according to claim 15, and it is characterized in that described adsorbent II is for one or more in organic carboxyl acid and its esters, its carbon number is 2 ~ 15.
20. in accordance with the method for claim 15, it is characterized in that described organic acid comprises in acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid, TGA, mercaptopropionic acid, ethylenediamine tetra-acetic acid, nitrilotriacetic acid, ring ethylenediamine tetra-acetic acid one or more; Organic carboxylate is one or more in the ammonium salt of above-mentioned organic carboxyl acid.
21. in accordance with the method for claim 15, it is characterized in that: in the solution containing adsorbent I and the fountain solution containing adsorbent II, adopt water and/or ethanol to be solvent.
22. in accordance with the method for claim 15, it is characterized in that: first method one of at least to adopt in a ~ e:
When a, step (1) use contains the solution impregnation of adsorbent I, adopt incipient impregnation or excessive dipping, after dipping terminates, sample through health or without health, then carries out drying; If need health, conditioned time is 1 ~ 12h; Described drying condition is as follows: temperature is 60 DEG C ~ 250 DEG C, drying time 0.5h ~ 20h;
When b, step (2) are flooded with the dipping solution containing Ni, through health or without health, then carry out drying and roasting; As needed health, conditioned time is 0.5 ~ 6.0h; Described drying condition is as follows: baking temperature is 70 DEG C ~ 200 DEG C, drying time 0.5h ~ 20h; Described roasting condition: sintering temperature is 300 DEG C ~ 750 DEG C, and roasting time is 0.5h ~ 20h;
After the fountain solution dipping of c, step (3) dipping containing adsorbent II terminates, carry out next step again through health, conditioned time is 0.5 ~ 8h; Or step (3) dipping containing adsorbent II fountain solution after, drying carries out next step again, and wherein baking temperature is 60 DEG C ~ 250 DEG C, drying time 0.5h ~ 20h; Or after the fountain solution dipping of step (3) dipping containing adsorbent II terminates, first through health more after drying, then carry out next step, wherein conditioned time is 0.5 ~ 8h, described drying condition is as follows: baking temperature is 60 DEG C ~ 250 DEG C, drying time 0.5h ~ 20h;
Unsaturated dipping described in d, step (3) adopts unsaturated spraying, and the immersion liquid amount that wherein unsaturated dipping is used and the volume ratio of catalyst precarsor saturated absorption amount of solution are 0.02 ~ 0.4;
When e, step (4) pass through infusion process load with the dipping solution containing Co, adopt equi-volume impregnating, through health or without health after dipping, then carry out drying; As needed health, conditioned time is 0.5 ~ 6.0h; Described drying condition: baking temperature is 60 DEG C ~ 300 DEG C, and drying time is 0.5h ~ 20h; Described roasting condition: sintering temperature is 300 DEG C ~ 750 DEG C, and roasting time is 0.5h ~ 20h.
23. in accordance with the method for claim 15, it is characterized in that: second method one of at least to adopt in a ~ e:
After the fountain solution dipping of a, steps A dipping containing adsorbent II terminates, carry out next step again through health, conditioned time is 0.5 ~ 8h; Or steps A dipping containing adsorbent II fountain solution after, drying carries out next step again, and wherein baking temperature is 60 DEG C ~ 250 DEG C, drying time 0.5h ~ 20h; Or after the fountain solution dipping of steps A dipping containing adsorbent II terminates, first through health more after drying, then carry out next step, wherein conditioned time is 0.5 ~ 8h, described drying condition is as follows: baking temperature is 60 DEG C ~ 250 DEG C, drying time 0.5h ~ 20h;
Unsaturated dipping described in b, steps A adopts unsaturated spraying, and the immersion liquid amount that wherein unsaturated dipping is used and the volume ratio of carrier saturated absorption amount of solution are 0.02 ~ 0.4;
When c, step B pass through infusion process load with the dipping solution containing Co, adopt equi-volume impregnating, through health or without health after dipping, then carry out drying; As needed health, conditioned time is 0.5 ~ 6.0h; Described drying condition: baking temperature is 60 DEG C ~ 300 DEG C, and drying time is 0.5h ~ 20h; Described roasting condition: sintering temperature is 300 DEG C ~ 750 DEG C, and roasting time is 0.5h ~ 20h;
When d, step C use contains the solution impregnation of adsorbent I, adopt incipient impregnation or excessive dipping, after dipping terminates, sample through health or without health, then carries out drying; If need health, conditioned time is 1 ~ 12h; Described drying condition is as follows: temperature is 60 DEG C ~ 250 DEG C, drying time 0.5h ~ 20h;
When e, step D flood with the dipping solution containing Ni, through health or without health, then carry out drying and roasting; As needed health, conditioned time is 0.5 ~ 6.0h; Described drying condition is as follows: baking temperature is 70 DEG C ~ 200 DEG C, drying time 0.5h ~ 20h; Described roasting condition: sintering temperature is 300 DEG C ~ 750 DEG C, and roasting time is 0.5h ~ 20h.
The method of 24. 1 kinds of heavy distillate hydro-upgradings, is characterized in that adopting the arbitrary described catalyst for hydro-upgrading of claim 1 ~ 14.
25. in accordance with the method for claim 24, it is characterized in that: described heavy distillate is diesel oil.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108620118A (en) * | 2017-03-24 | 2018-10-09 | 中国石油化工股份有限公司 | A kind of catalyst for hydro-upgrading and preparation method thereof |
| US20210354118A1 (en) * | 2019-02-01 | 2021-11-18 | China University Of Petroleum-Beijing | In situ bifunctional catalyst for deep desulfurization and increasing octane number of gasoline and preparation method thereof |
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| EP0204314B1 (en) * | 1985-06-05 | 1990-11-14 | Nippon Oil Co. Ltd. | Catalyst for hydrotreatment of heavy oils |
| CN102196860A (en) * | 2008-10-23 | 2011-09-21 | 第一毛织株式会社 | Supported catalyst for synthesizing carbon nanotubes, method for preparing thereof and carbon nanotube using the same |
| CN102463149A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Activation method of hydrogenation catalyst |
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| EP0204314B1 (en) * | 1985-06-05 | 1990-11-14 | Nippon Oil Co. Ltd. | Catalyst for hydrotreatment of heavy oils |
| CN102196860A (en) * | 2008-10-23 | 2011-09-21 | 第一毛织株式会社 | Supported catalyst for synthesizing carbon nanotubes, method for preparing thereof and carbon nanotube using the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108620118A (en) * | 2017-03-24 | 2018-10-09 | 中国石油化工股份有限公司 | A kind of catalyst for hydro-upgrading and preparation method thereof |
| CN108620118B (en) * | 2017-03-24 | 2020-03-17 | 中国石油化工股份有限公司 | Hydrogenation modification catalyst and preparation method thereof |
| US20210354118A1 (en) * | 2019-02-01 | 2021-11-18 | China University Of Petroleum-Beijing | In situ bifunctional catalyst for deep desulfurization and increasing octane number of gasoline and preparation method thereof |
| US11998899B2 (en) | 2019-02-01 | 2024-06-04 | China University Of Petroleum-Beijing | Bifunctional catalyst for deep desulfurization and gasoline quality improvement and preparation method therefor |
| US12115522B2 (en) * | 2019-02-01 | 2024-10-15 | China University Of Petroleum-Beijing | In situ bifunctional catalyst for deep desulfurization and increasing octane number of gasoline and preparation method thereof |
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