CN104667964A - A catalyst for diesel oil hydrogenation modification and a preparing method thereof - Google Patents
A catalyst for diesel oil hydrogenation modification and a preparing method thereof Download PDFInfo
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Abstract
A hydrogenation modification catalyst and a preparing method thereof are disclosed. In the catalyst, a carrier comprises aluminum oxide and a molecular sieve, active metal components are Mo, W, 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, Mo0/Mo1<Mo<1/2>/Mo1<1, Ni0/Ni1>Ni<1/2>/Ni1>1 and W0/W1>W<1/2>/W1>1. The preparing method includes dipping with a wetting solution containing an absorbent I by adopting an unsaturated dipping method, loading the active metal Mo and the active metal Co by dipping, dipping with a solution containing an absorbent II by a saturated dipping method or an excessive dipping method, and loading the active metal W and 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, W, 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, Mo
0/ Mo
1< Mo
1/2/ Mo
1< 1, Ni
0/ Ni
1> Ni
1/2/ Ni
1> 1, W
0/ W
1> W
1/2/ W
1> 1.
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, Ni or W, B represents active metallic element Mo, Co, Ni or W, 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, Ni or W 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), Mo
x1/ Mo
1(A and B is Mo, m=x1, n=1), Mo
x2/ Mo
1(A and B is Mo, m=x2, n=1), W
0/ W
1(A and B is W, m=0, n=1), W
1/4/ W
1(A and B is W, m=1/4, n=1), W
1/2/ W
1(A and B is W, m=1/2, n=1), W
3/4/ W
1(A and B is W, m=3/4, n=1), W
x1/ W
1(A and B is W, m=x1, n=1), W
x2/ W
1(A and B is W, m=x2, 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; Mo
0/ Mo
1with Mo
1/2/ Mo
1ratio be 0.2 ~ 0.8, be preferably 0.2 ~ 0.7, W
0/ W
1with W
1/2/ W
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: Mo
0/ Mo
1< Mo
1/4/ Mo
1< Mo
1/2/ Mo
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: Mo
1/2/ Mo
1< Mo
3/4/ Mo
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, the distribution of active metal component on catalyst granules cross section is preferably as follows: W
0/ W
1> W
1/4/ W
1> W
1/2/ W
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: W
1/2/ W
1> W
3/4/ W
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; Mo
0/ Mo
1with Mo
1/4/ Mo
1ratio be 0.30 ~ 0.90, be preferably 0.30 ~ 0.85; Mo
1/4/ Mo
1with Mo
1/2/ Mo
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; W
0/ W
1with W
1/4/ W
1ratio be 1.2 ~ 1.8, be preferably 1.3 ~ 1.7; W
1/4/ W
1with W
1/2/ W
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: Mo
0/ Mo
1< Mo
x1/ Mo
1< Mo
x2/ Mo
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, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: W
0/ W
1> W
x1/ W
1> W
x2/ W
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, active metal component concentration distribution is as follows: the concentration of Co increases substantially gradually, the concentration of Mo increases substantially gradually, the concentration of Ni reduces substantially gradually, and the concentration of W reduces substantially gradually.
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 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 45wt% ~ 84wt%, and be preferably 45% ~ 80%, more preferably surplus, Mo is with MoO
3meter content be 6wt% ~ 26wt%, Co in the content of CoO for 1wt% ~ 8wt%, W are with WO
3meter content be 6wt% ~ 28wt%, Ni in the content of NiO for 1wt% ~ 8wt%; 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, Ni/W atomic ratio is 0.11 ~ 4.1, and being preferably 0.13 ~ 3.9, Co/Mo atomic ratio is 0.07 ~ 2.5, is preferably 0.08 ~ 2.3.
In catalyst for hydro-upgrading of the present invention, be positioned at the concentration of outer most edge point place Mo of catalyst granules cross section and the concentration ratio of central spot Mo and Mo
0/ Mo
1be 0.08 ~ 0.80, be positioned at the concentration of outer most edge point place Co of catalyst granules cross section and the concentration ratio of central spot Co and Co
0/ Co
1be 0.08 ~ 0.80.
In catalyst for hydro-upgrading of the present invention, be positioned at the concentration of outer most edge point place W of catalyst granules cross section and the concentration ratio of central spot W and W
0/ W
1be 1.2 ~ 7.0, be positioned at the concentration of outer most edge point place Ni of catalyst granules cross section and the concentration ratio of central spot Ni and 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.
Can also contain adjuvant component in catalyst for hydro-upgrading of the present invention, one or more in such as fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component for less than 15%, is preferably 1% ~ 10% in element weight content in the catalyst.Preferably containing phosphorus in catalyst for hydro-upgrading of the present invention, with P
2o
5meter weight content is in the catalyst 1% ~ 6%.
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 of the present invention, at least adopt one of with the following method, first method comprises:
(1) with the solution impregnating carrier containing adsorbent I, after drying, obtain the carrier containing adsorbent I, wherein adsorbent I consumption is 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 W, Ni, through super-dry and roasting, catalyst intermediate is obtained,
(3) with the fountain solution impregnated catalyst intermediate containing adsorbent II, obtain the catalyst intermediate containing adsorbent II, the consumption of described adsorbent II is 0.1% ~ 10.0% of vehicle weight, described adsorbent II is one or more in organic carboxyl acid and its esters, and described dipping adopts unsaturated dipping;
(4) with dipping solution impregnation steps (3) gains containing Co, Mo, through super-dry and roasting, catalyst for hydro-upgrading is obtained;
Second method comprises:
A, the fountain solution impregnated carrier of use containing adsorbent II, obtain the carrier containing adsorbent II, the consumption of described adsorbent II is 0.1% ~ 10.0% of vehicle weight, and described adsorbent II is one or more in organic carboxyl acid and its esters, and described dipping adopts unsaturated dipping;
B, the dipping solution impregnation steps A gains of use containing Co, Mo, through super-dry and roasting, obtain catalyst intermediate;
C, the solution impregnation catalyst intermediate of use containing adsorbent I, after drying, obtain the catalyst intermediate containing adsorbent I, wherein adsorbent I consumption is 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 W, Ni, through super-dry and roasting, obtain catalyst.
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.
In the inventive method, adsorbent I to be number-average molecular weight be 400 ~ 10000 polyalcohol, being preferably number-average molecular weight is the polyalcohol of 1000 ~ 8000, and described polyalcohol can be PTMEG, preferably polyethylene glycol.
In the inventive method, described adsorbent II is one or more in organic carboxyl acid and its esters, and its carbon number is not more than 15, is generally 2 ~ 15.Described organic acid comprise in acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid etc., TGA, mercaptopropionic acid, ethylenediamine tetra-acetic acid, nitrilotriacetic acid, ring ethylenediamine tetra-acetic acid etc. one or more.One or more in the ammonium salt of the preferred above-mentioned organic carboxyl acid of organic carboxylate.
The inventive method, in the solution containing adsorbent I and the fountain solution containing adsorbent II, adopts water and/or ethanol to be solvent.
In the inventive method, the optimum condition that first method adopts is as follows:
The inventive method, step (1), with containing adsorbent I solution impregnating carrier, adopts incipient impregnation or excessive dipping.After dipping terminates, sample can be passed through health or without health, if through the general conditioned time of health be 1 ~ 12h.After health terminates, then through drying steps.Described drying condition is as follows: temperature is 60 DEG C ~ 250 DEG C, is preferably 100 ~ 200 DEG C, and drying time, 0.5h ~ 20h, was preferably 1h ~ 6h.
The inventive method, step (2) is with containing W, after dipping solution impregnation steps (1) gains of Ni, can be passed through health, also can without health, as needed health, conditioned time is 0.5 ~ 6.0h, carry out drying and roasting again, drying condition is as follows: baking temperature is 70 DEG C ~ 300 DEG C, be preferably 70 DEG C ~ 200 DEG C, more preferably 100 DEG C ~ 160 DEG C drying times are 0.5h ~ 20h, be preferably 1h ~ 6h, roasting condition is as follows: sintering temperature is 300 DEG C ~ 750 DEG C, be preferably 400 DEG C ~ 650 DEG C, roasting time is 0.5h ~ 20h, be preferably 1h ~ 6h.
The inventive method, with the fountain solution impregnated catalyst intermediate containing adsorbent II in step (3), dipping wherein preferably adopts unsaturated spraying, and the time of spraying is generally 1min ~ 40min, preferred 2min ~ 20min.The volume of the fountain solution containing adsorbent II used is 0.02 ~ 0.4 with the ratio of the saturated imbibition volume of catalyst intermediate.When spraying the fountain solution containing adsorbent II, the shower nozzle that atomizing effect is good should be selected, dissolution homogeneity is distributed on carrier.After fountain solution impregnated carrier containing adsorbent II, can be passed through drying steps, also can directly enter step (4) without drying steps.Drying condition is as follows: temperature is generally 60 DEG C ~ 250 DEG C, is preferably 100 ~ 200 DEG C, time 0.5h ~ 20h, is preferably 1h ~ 6h.
The inventive method, the dipping solution impregnated catalyst intermediate of step (4) containing Mo, Co, can be passed through health, also can without health, and as needed health, conditioned time is 0.5 ~ 4.0h, then carries out drying.Described drying condition is as follows: baking temperature is 70 DEG C ~ 300 DEG C, is preferably 70 DEG C ~ 200 DEG C, more preferably 100 DEG C ~ 160 DEG C, and drying time, 0.5h ~ 20h, was preferably 1h ~ 6h.Described roasting condition is as follows: sintering temperature is 300 DEG C ~ 750 DEG C, and be preferably 400 DEG C ~ 650 DEG C, roasting time is 0.5h ~ 20h, is preferably 1h ~ 6h.
In the inventive method, the optimum condition that second method adopts is as follows:
The inventive method, with the fountain solution impregnated carrier containing adsorbent II in steps A, dipping wherein preferably adopts unsaturated spraying, and the time of spraying is generally 1min ~ 40min, preferred 2min ~ 20min.The volume of the fountain solution containing adsorbent II used is 0.02 ~ 0.4 with the ratio of the saturated imbibition volume of carrier.When spraying the fountain solution containing adsorbent II, the shower nozzle that atomizing effect is good should be selected, dissolution homogeneity is distributed on carrier.After fountain solution impregnated carrier containing adsorbent II, can be passed through drying steps, also directly can enter step B without drying steps.Drying condition is as follows: temperature is generally 60 DEG C ~ 250 DEG C, is preferably 100 ~ 200 DEG C, time 0.5h ~ 20h, is preferably 1h ~ 6h.
The inventive method, when step B floods with the dipping solution containing Mo, Co, can be passed through health, also can without health, and as needed health, conditioned time is 0.5 ~ 4.0h, then carries out drying.Described drying condition is as follows: baking temperature is 70 DEG C ~ 300 DEG C, is preferably 70 DEG C ~ 200 DEG C, more preferably 100 DEG C ~ 160 DEG C, and drying time, 0.5h ~ 20h, was preferably 1h ~ 6h.Described roasting condition is as follows: sintering temperature is 300 DEG C ~ 750 DEG C, and be preferably 400 DEG C ~ 650 DEG C, roasting time is 0.5h ~ 20h, is preferably 1h ~ 6h.
The inventive method, step C, with containing adsorbent I solution impregnation catalyst intermediate, adopts incipient impregnation or excessive dipping.After dipping terminates, sample can be passed through health or without health, if through the general conditioned time of health be 1 ~ 12h.After health terminates, then through drying steps.Described drying condition is as follows: temperature is 60 DEG C ~ 250 DEG C, is preferably 100 ~ 200 DEG C, and drying time, 0.5h ~ 20h, was preferably 1h ~ 6h.
The inventive method, after step D uses the dipping solution impregnation steps C gains containing W, Ni, can be passed through health, also can without health, as needed health, conditioned time is 0.5 ~ 6.0h, carry out drying and roasting again, drying condition is as follows: baking temperature is 70 DEG C ~ 300 DEG C, is preferably 70 DEG C ~ 200 DEG C, more preferably 100 DEG C ~ 160 DEG C drying times are 0.5h ~ 20h, be preferably 1h ~ 6h, roasting condition is as follows: sintering temperature is 300 DEG C ~ 750 DEG C, is 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 component supports on carrier by infusion process, usually adopts incipient impregnation, and preferably adopt saturated spraying, the time of spraying is generally 5min ~ 40min, preferred 10min ~ 20min.Dipping method is known by technical staff.After active metal component solution impregnating carrier, need through super-dry.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, from one or more in molybdenum oxide, ammonium molybdate, ammonium paramolybdate as molybdenum source, nickel source is from one or more in nickel nitrate, nickelous carbonate, basic nickel carbonate, nickel chloride, nickel oxalate, cobalt source is from one or more in cobalt nitrate, cobalt carbonate, basic cobaltous carbonate, cobalt chloride, cobalt oxalate, and tungsten source is generally from ammonium metatungstate.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.Preferably containing phosphorus in catalyst for hydro-upgrading of the present invention, with P
2o
5meter mass content is in the catalyst 1% ~ 6%.
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 Co and Mo is the trend increased gradually from catalyst granules outer surface to center, Ni and W is the trend reduced gradually from catalyst granules outer surface to center, the active metal component of this 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, the fountain solution of adsorbent I is contained by saturated dipping or excessive dipping, then W is flooded, after Ni active metal solution, slow down W, Ni is to the diffusion velocity at catalyst granules center, thus make the W of rear leaching, the concentration of Ni in each catalyst granules is the trend reduced gradually from marginal position to center, and by the fountain solution of unsaturated dipping containing adsorbent II, a part of adsorption potential on carrier granular marginal position surface is occupied by adsorbent, dipping is containing active metal Mo, during the solution of Co, decrease Mo, Co is in the absorption of carrier edge position, make active metal Mo, the concentration of Co is the trend increased gradually from marginal position to center, 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 the catalyst C5 of embodiment 2 gained.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.
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: W is 53 °, and 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, MoO
3and WO
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, W adopts M
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 calculating, 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 C5 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.
In embodiment, the diameter of cylindrical vector used is about 1.2mm, and length is about 3 ~ 5mm, and its physico-chemical property is as shown in table 1:
The physico-chemical property of used carrier in table 1 embodiment
Mo predecessor in the present embodiment in Mo, Co, P maceration extract used is MoO
3, Co predecessor is basic cobaltous carbonate, and P predecessor is phosphoric acid, and in W, Ni maceration extract used, W predecessor is ammonium metatungstate, and Ni predecessor is nickel nitrate.
Embodiment 1
Take tartaric acid 15g, stirring and dissolving in 45g water, obtained fountain solution I.Get S1 carrier 30 as one kind 0g, evenly sprayed by fountain solution I on S1 carrier, 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 Mo, Co, P, gained sample average is divided into three parts, wherein the first increment product not health, through 120 DEG C of dry 3h, after 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, after 480 DEG C of roasting 2h, obtained sample is designated as B2, triplicate sample health 3h, and through 120 DEG C of dry 3h, after 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 W, Ni respectively, directly carry out 120 DEG C of dry 3h without health after spraying end, after 480 DEG C of roasting 2h, the catalyst of acquisition is designated as C1, C2 and C3 respectively.
Embodiment 2
Take 24g cetomacrogol 1000, stirring and dissolving in the water measured, obtained fountain solution II.With the S2 carrier of this fountain 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 above-mentioned B4 sample with the maceration extract equal-volume containing W, Ni, after spraying end, sample average is divided into three parts, wherein the direct 120 DEG C of dry 3h of the first increment product, after 480 DEG C of roasting 2h, the catalyst of acquisition is designated as Z4; Second increment product health 1h, through the post-processing step identical with catalyst Z 4, obtained catalyst is designated as Z5; Triplicate sample health 3h, through the post-processing step identical with catalyst Z 4, obtained catalyst is designated as Z6.
Take malic acid 1.0g, stirring and dissolving in 6g ethanol, obtained fountain solution I.Evenly sprayed respectively on sample Z4, Z5 and Z6 by fountain solution I, the time of spraying is 5min.Respectively with the above-mentioned carrier of maceration extract incipient impregnation containing Mo, Co, P, dipping terminates rear health 1h, and through 120 DEG C of dry 3h, after 480 DEG C of roasting 2h, the sample of acquisition is designated as C4, C5 and C6.
Embodiment 3
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 by fountain solution I on S3 carrier, the time of spraying is 25min.With containing the above-mentioned carrier of Mo, Co, P maceration extract incipient impregnation, flood and terminate rear health 1h, through 120 DEG C of dry 3h, after 480 DEG C of roasting 2h, the sample obtained 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 Z7 sample with the maceration extract equal-volume containing W, Ni, directly through 120 DEG C of dry 3h, after 480 DEG C of roasting 2h, the catalyst of acquisition is designated as C7.
Comparative example 1
Get S1 carrier 100g, after using the above-mentioned carrier of maceration extract incipient impregnation containing Mo, Co, P, through 120 DEG C of dry 3h, after 480 DEG C of roasting 2h, the sample of acquisition is designated as B6.With the maceration extract incipient impregnation B6 containing W, Ni, through 120 DEG C of dry 3h, after 480 DEG C of roasting 2h, the catalyst of acquisition is designated as C8.
Comparative example 2
Get S4 carrier 100g, adopt the preparation method identical with C7 catalyst to prepare, the sample of acquisition is designated as C9.
Table 2 embodiment and comparative example catalyst form
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Catalyst forms | |||||||||
| WO 3，wt％ | 19.5 | 19.5 | 19.1 | 19.5 | 19.3 | 19.5 | 19.3 | 19.4 | 19.5 |
| MoO 3，wt％ | 13.1 | 13.4 | 13.2 | 13.4 | 13.2 | 13.3 | 13.6 | 13.3 | 13.4 |
| CoO，wt％ | 2.4 | 2.3 | 2.3 | 2.2 | 2.3 | 2.4 | 2.3 | 2.4 | 2.4 |
| NiO，wt％ | 2.7 | 2.7 | 2.6 | 2.6 | 2.6 | 2.6 | 2.6 | 2.5 | 2.5 |
| P 2O 5，wt％ | 1.48 | 1.48 | 1.46 | 1.46 | 1.47 | 1.45 | 1.45 | 1.47 | 1.47 |
| Carrier * | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Character | |||||||||
| Specific area, m 2/g | 167 | 165 | 163 | 162 | 162 | 165 | 164 | 163 | 163 |
| Pore volume, mL/g | 0.33 | 0.33 | 0.33 | 0.34 | 0.33 | 0.33 | 0.34 | 0.34 | 0.34 |
In table 2, the aluminium oxide of carrier * and C1, C2, C3 and C8 and beta-molecular sieve, aluminium oxide and Y molecular sieve in C4, C5 and C6, aluminium oxide and β and Y molecular sieve in C7, the aluminium oxide in C9.
The CONCENTRATION DISTRIBUTION of elements Mo in catalyst granules in table 3 embodiment and comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Mo 0/Mo 1 | 0.12 | 0.29 | 0.56 | 0.35 | 0.34 | 0.35 | 0.28 | 0.99 | 0.29 |
| Mo 1/4/Mo 1 | 0.31 | 0.41 | 0.66 | 0.69 | 0.71 | 0.70 | 0.39 | 0.98 | 0.38 |
| Mo 1/2/Mo 1 | 0.65 | 0.78 | 0.90 | 0.88 | 0.89 | 0.88 | 0.79 | 1.0 | 0.79 |
| Mo 3/4/Mo 1 | 0.89 | 0.93 | 0.98 | 0.97 | 0.98 | 0.98 | 0.94 | 1.01 | 0.95 |
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 | 0.14 | 0.27 | 0.54 | 0.34 | 0.33 | 0.35 | 0.30 | 0.98 | 0.29 |
| Co 1/4/ Co 1 | 0.31 | 0.45 | 0.65 | 0.73 | 0.75 | 0.76 | 0.44 | 0.99 | 0.45 |
| Co 1/2/ Co 1 | 0.65 | 0.79 | 0.89 | 0.88 | 0.90 | 0.89 | 0.81 | 1.02 | 0.80 |
| Co 3/4/ Co 1 | 0.92 | 0.94 | 0.98 | 0.98 | 1.00 | 0.99 | 0.95 | 1.01 | 0.94 |
The CONCENTRATION DISTRIBUTION of element W in catalyst granules in table 5 embodiment and comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| W 0/W 1 | 2.76 | 2.73 | 2.72 | 2.83 | 2.49 | 2.23 | 2.51 | 0.99 | 2.55 |
| W 1/4/W 1 | 1.78 | 1.79 | 1.77 | 1.84 | 1.66 | 1.48 | 1.67 | 1.02 | 1.69 |
| W 1/2/W 1 | 1.23 | 1.25 | 1.23 | 1.30 | 1.21 | 1.16 | 1.20 | 1.01 | 1.21 |
| W 3/4/W 1 | 1.08 | 1.07 | 1.07 | 1.09 | 1.07 | 1.06 | 1.07 | 0.99 | 1.07 |
The CONCENTRATION DISTRIBUTION of element Ni in catalyst granules in table 6 embodiment and comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Ni 0/ Ni 1 | 2.80 | 2.82 | 2.78 | 2.97 | 2.56 | 2.25 | 2.56 | 0.98 | 2.59 |
| Ni /4/ Ni 1 | 1.88 | 1.87 | 1.85 | 1.96 | 1.71 | 1.49 | 1.75 | 1.0 | 1.77 |
| Ni 1/2/ Ni 1 | 1.25 | 1.25 | 1.23 | 1.34 | 1.25 | 1.18 | 1.22 | 0.99 | 1.23 |
| Ni 3/4/ Ni 1 | 1.08 | 1.10 | 1.10 | 1.12 | 1.09 | 1.06 | 1.07 | 0.98 | 1.07 |
Embodiment 4
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 7, Evaluation results is in table 8, 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 7 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 8 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 | 0.8396 | 0.8390 | 0.8395 | 0.8379 |
| T95，℃ | 349 | 350 | 350 | 348 |
| Condensation point, DEG C | -21 | -21 | -20 | -22 |
| Cetane number | 46.8 | 47.5 | 47.0 | 48.3 |
| Sulphur, μ g/g | 10 | 9 | 10 | 7 |
Table 8 continues
| Catalyst | C5 | C6 | C7 | C8 | C9 |
| Diesel oil | |||||
| Yield, wt% | 97.5 | 97.6 | 97.8 | 97.6 | 99.5 |
| Density (20 DEG C)/g.cm -3 | 0.8383 | 0.8385 | 0.8388 | 0.8410 | 0.8572 |
| T95，℃ | 347 | 348 | 348 | 350 | 355 |
| Condensation point, DEG C | -22 | -21 | -22 | -23 | 4 |
| Cetane number | 48.0 | 47.9 | 48.0 | 48.4 | 34.6 |
| Sulphur, μ g/g | 8 | 8 | 7 | 16 | 11 |
Claims (26)
1. a catalyst for hydro-upgrading, carrier comprises aluminium oxide and molecular sieve, and active metal component is Co, Mo, Ni, W, 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, Mo
0/ Mo
0< Mo
1/2/ Mo
1/2< Mo
1/ Mo
1, Ni
0/ Ni
1> Ni
1/2/ Ni
1> 1, W
0/ W
0> W
1/2/ W
1/2> W
1/ W
1;
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, Ni or W, and B represents active metallic element Mo, Co, Ni or W, 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, Ni or W 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) Mo
0/ Mo
1with Mo
1/2/ Mo
1ratio be 0.2 ~ 0.8;
(3) Ni
0/ Ni
1with Ni
1/2/ Ni
1ratio 1.5 ~ 2.6;
(4) W
0/ W
1with W
1/2/ W
1ratio be 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) Mo
0/ Mo
1with Mo
1/2/ Mo
1ratio be 0.2 ~ 0.7;
(3) Ni
0/ Ni
1with Ni
1/2/ Ni
1ratio 1.7 ~ 2.5;
(4) W
0/ W
1with W
1/2/ W
1ratio be 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）W
0/W
0＞W
1/4/W
1/4＞W
1/2/W
1；
（6）W
1/2/W
1/2＞W
3/4/W
3/4＞1；
（7）Mo
0/Mo
0＜Mo
1/4/Mo
1/4＜Mo
1/2/Mo
1；
（8）Mo
1/2/Mo
1/2＜Mo
3/4/Mo
3/4＜1；
(9) Co
0/ Co
1< Co
x1/ Co
1< Co
x2/ Co
1< 1, wherein 0 < x1 < x2 < 1;
(10) Mo
0/ Mo
0< Mo
x1/ Mo
1< Mo
x2/ Mo
1< 1, wherein 0 < x1 < x2 < 1;
(11) Ni
0/ Ni
1> Ni
x1/ Ni
1> Ni
x2/ Ni
1> 1, wherein 0 < x1 < x2 < 1;
(12) W
0/ W
0> W
x1/ W
1> W
x2/ W
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) Mo
0/ Mo
1with Mo
1/4/ Mo
1ratio be 0.3 ~ 0.9;
(4) Mo
1/4/ Mo
1with Mo
1/2/ Mo
1ratio be 0.4 ~ 0.9;
(5) Ni
0/ Ni
1with Ni
1/4/ Ni
1ratio be 1.2 ~ 1.8;
(6) Ni
1/4/ Ni
1with Ni
1/2/ Ni
1ratio be 1.1 ~ 1.7;
(7) W
0/ W
1with W
1/4/ W
1ratio be 1.2 ~ 1.8;
(8) W
1/4/ W
1with W
1/2/ W
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) Mo
0/ Mo
1with Mo
1/4/ Mo
1ratio be 0.3 ~ 0.85;
(4) Mo
1/4/ Mo
1with Mo
1/2/ Mo
1ratio be 0.4 ~ 0.87;
(5) Ni
0/ Ni
1with Ni
1/4/ Ni
1ratio be 1.3 ~ 1.7;
(6) Ni
1/4/ Ni
1with Ni
1/2/ Ni
1ratio be 1.2 ~ 1.6;
(7) W
0/ W
1with W
1/4/ W
1ratio be 1.3 ~ 1.7;
(8) W
1/4/ W
1with W
1/2/ W
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 Mo increases substantially gradually, and the concentration of Ni reduces substantially gradually, and the concentration of W reduces substantially gradually.
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 is that 45wt% ~ 84wt%, Mo are with MoO
3meter content be 6wt% ~ 26wt%, Co in the content of CoO for 1wt% ~ 8wt%, W are with WO
3meter content be 6wt% ~ 28wt%, Ni in the content of NiO for 1wt% ~ 8wt%; 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, Ni/W atomic ratio is 0.11 ~ 4.1, Co/Mo atomic ratio is 0.07 ~ 2.5.
10. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, be positioned at the concentration of outer most edge point place Mo of catalyst granules cross section and the concentration ratio of central spot Mo and Mo
0/ Mo
1be 0.08 ~ 0.80, be positioned at the concentration of outer most edge point place Co of catalyst granules cross section and the concentration ratio of central spot Co and Co
0/ Co
1be 0.08 ~ 0.80.
11. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, is positioned at the concentration of outer most edge point place W of catalyst granules cross section and the concentration ratio of central spot W and W
0/ W
1be 1.2 ~ 7.0, be positioned at the concentration of outer most edge point place Ni of catalyst granules cross section and the concentration ratio of central spot Ni and Ni
0/ Ni
1be 1.2 ~ 7.0.
12. according to catalyst according to claim 1, it is characterized in that described molecular sieve is Y zeolite and/or beta-molecular sieve.
13. 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%.
14. 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.
15. 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%.
16. 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 of 17. claims 1 ~ 14, at least adopt one of with the following method, first method comprises:
(1), with the solution impregnating carrier containing adsorbent I, after drying, obtain the carrier containing adsorbent I, wherein adsorbent I consumption is 0.1% ~ 10.0% of vehicle weight; Described adsorbent I for molecular weight be the polyethylene glycol of 400 ~ 10000, described dipping adopts saturated dipping or excessive dipping;
(2) with dipping solution impregnation steps (1) gains containing W, Ni, through super-dry and roasting, catalyst intermediate is obtained,
(3) with the fountain solution impregnated catalyst intermediate containing adsorbent II, obtain the catalyst intermediate containing adsorbent II, the consumption of adsorbent II accounts for 0.1% ~ 10.0% of vehicle weight, described adsorbent II is one or more in organic carboxyl acid and its esters, and described dipping adopts unsaturated dipping;
(4) with dipping solution impregnation steps (3) gains containing Co, Mo, through super-dry and roasting, catalyst for hydro-upgrading is obtained;
Second method comprises:
A, the fountain solution impregnated carrier of use containing adsorbent II, obtain the carrier containing adsorbent II, the consumption of adsorbent II accounts for 0.1% ~ 10.0% of vehicle weight, and described adsorbent II is one or more in organic carboxyl acid and its esters, and described dipping adopts unsaturated dipping;
B, the dipping solution impregnation steps A gains of use containing Co, Mo, through super-dry and roasting, obtain catalyst intermediate;
C, the solution impregnation catalyst intermediate of use containing adsorbent I, after drying, obtain the carrier containing adsorbent I, wherein adsorbent I consumption is 0.1% ~ 10.0% of vehicle weight; Described adsorbent I for molecular weight be the polyethylene glycol of 400 ~ 10000, described dipping adopts saturated dipping or excessive dipping;
D, the dipping solution impregnation steps C gains of use containing W, Ni, through super-dry and roasting, obtain catalyst.
18. in accordance with the method for claim 17, 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.
19. in accordance with the method for claim 17, it is characterized in that described adsorbent II 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 etc. one or more, organic carboxylate be selected from the ammonium salt of above-mentioned organic carboxyl acid one or more.
20. in accordance with the method for claim 17, it is characterized in that described adsorbent I is polyethylene glycol.
21. in accordance with the method for claim 17, 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 17, it is characterized in that: first method at least adopts at least one scheme in a ~ e:
A, step (1) are with containing adsorbent I solution impregnating carrier, and after dipping terminates, sample is through health or without health, then through drying steps, if through health, conditioned time is 1 ~ 12h; Drying condition described in step (1) is as follows: baking temperature is 60 DEG C ~ 250 DEG C, drying time 0.5h ~ 20h;
After b, step (2) use dipping solution impregnation steps (1) gains containing W, 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 ~ 300 DEG C, and drying time is 0.5h ~ 20h, and roasting condition is as follows: sintering temperature is 300 DEG C ~ 750 DEG C, and roasting time is 0.5h ~ 20h;
Adopt unsaturated spraying when flooding with the fountain solution containing adsorbent II in c, step (3), the time of spraying is 1min ~ 40min; The volume of the fountain solution containing adsorbent II used is 0.02 ~ 0.4 with the ratio of the saturated imbibition volume of catalyst intermediate;
After d, step (3) the fountain solution dipping containing adsorbent II, directly enter step (4) through drying steps or without drying steps; Described drying condition is as follows: temperature is 60 DEG C ~ 250 DEG C, time 0.5h ~ 20h;
E, step (4) the dipping solution impregnated catalyst intermediate containing Mo, Co, through health or without health, then carry out drying, as needed health, conditioned time is 0.5 ~ 4.0h; Described drying condition is as follows: baking temperature is 70 DEG C ~ 300 DEG C, drying time 0.5h ~ 20h; Described roasting condition is as follows: sintering temperature is 300 DEG C ~ 750 DEG C, and roasting time is 0.5h ~ 20h.
23. in accordance with the method for claim 17, it is characterized in that: second method at least adopts at least one scheme in a ~ e:
Adopt unsaturated spraying when flooding with the fountain solution containing adsorbent II in a, steps A, the time of spraying is 1min ~ 40min; The volume of the fountain solution containing adsorbent II used is 0.02 ~ 0.4 with the ratio of the saturated imbibition volume of carrier;
B, steps A directly enter step B through drying steps or without drying steps after containing the fountain solution dipping of adsorbent II; Described drying condition is as follows: temperature is 60 DEG C ~ 250 DEG C, time 0.5h ~ 20h;
When c, step B flood with the dipping solution containing Mo, Co, through health or without health, then carry out drying, as needed health, conditioned time is 0.5 ~ 4.0h; Described drying condition is as follows: baking temperature is 70 DEG C ~ 300 DEG C, drying time 0.5h ~ 20h; Described roasting condition is as follows: sintering temperature is 300 DEG C ~ 750 DEG C, and roasting time is 0.5h ~ 20h.
D, step C are with containing adsorbent I solution impregnation catalyst intermediate, and after dipping terminates, sample is through health or without health, then through drying steps, if through health, conditioned time is 1 ~ 12h; Drying condition described in step C is as follows: baking temperature is 60 DEG C ~ 250 DEG C, drying time 0.5h ~ 20h;
After e, step D use the dipping solution impregnation steps C gains containing W, 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 ~ 300 DEG C, and drying time is 0.5h ~ 20h, and roasting condition is as follows: sintering temperature is 300 DEG C ~ 750 DEG C, and roasting time is 0.5h ~ 20h.
24. in accordance with the method for claim 17, it is characterized in that: in first method, in the dipping solution described in step (2) and/or step (4), except active metal component, also containing phosphorus, phosphorus source is selected from one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate; The addition of phosphorus is with P
2o
5counting the mass content making it in catalyst for hydro-upgrading is 1% ~ 6%; In second method, in the dipping solution described in step B and/or step D, except active metal component, also containing phosphorus, phosphorus source is selected from one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate; The addition of phosphorus is with P
2o
5counting the mass content making it in catalyst for hydro-upgrading is 1% ~ 6%.
The method of 25. 1 kinds of heavy distillate hydro-upgradings, is characterized in that adopting the arbitrary described catalyst for hydro-upgrading of claim 1 ~ 16.
26. in accordance with the method for claim 25, it is characterized in that: described heavy distillate is diesel oil.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229835A (en) * | 1998-03-20 | 1999-09-29 | 中国石油化工集团公司 | Light oil products hydrogenation treatment catalyst containing moly and/or tungsten, and its prepn. method |
| CN1289828A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrorefining catalyst for fraction oil and its preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229835A (en) * | 1998-03-20 | 1999-09-29 | 中国石油化工集团公司 | Light oil products hydrogenation treatment catalyst containing moly and/or tungsten, and its prepn. method |
| CN1289828A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrorefining catalyst for fraction oil and its preparing process |
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