CN104588031A - Distillate oil hydrotreatment catalyst and preparation method thereof - Google Patents
Distillate oil hydrotreatment catalyst and preparation method thereof Download PDFInfo
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- CN104588031A CN104588031A CN201310527145.2A CN201310527145A CN104588031A CN 104588031 A CN104588031 A CN 104588031A CN 201310527145 A CN201310527145 A CN 201310527145A CN 104588031 A CN104588031 A CN 104588031A
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Abstract
The invention discloses a distillate oil hydrotreatment catalyst and a preparation method thereof. The hydrotreatment catalyst comprises an alumina-based carrier and active metal ingredients of Mo, Co, Ni and W. The distribution of the active metal ingredients in the catalyst particles is characterized by comprising Co0/Co1<Co1/2/Co1<1, Mo0/Mo1<Mo1/2/Mo1<1, Ni0/Ni1>Ni1/2/Ni1>1 and W0/W1>W1/2/W1>1, and preferably, the catalyst particles contain organic matters. The preparation method comprises the following steps of carrying out saturated or excess immersion in an adsorbent I-containing solution, carrying out immersion in a solution containing active metals of W and Ni, carrying out drying and roasting, carrying out unsaturated immersion in an adsorbent II containing one or more of organic carboxylic acids and salts thereof, and carrying out immersion for loading active metals of Mo and Co. The hydrotreatment catalyst has good deep-desulphurization activity and is especially suitable for deep desulphurization of diesel oil.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, particularly one and be suitable for hydrotreating catalyst of heavy distillate (particularly diesel oil) deep desulfuration and preparation method thereof.
Background technology
The requirement cleaned heavy distillate (particularly diesel oil) along with society is more and more higher, and the deep hydrodesulfurizationof technology of heavy distillate just seems more and more important.Sulfur-containing compound in heavy distillate mainly contains aliphatic sulfides, thioether, dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene etc., it is wherein more difficult that what remove is the thiophenes such as dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene, especially with 4,6-dimethyl Dibenzothiophene (4,6-BMDBT) with 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 also more difficult under the operating condition that HTHP etc. is harsh removes.Therefore, the heavy distillate degree of depth and ultra-deep desulfurization have significant difference with the hydrodesulfurization of routine in reaction mechanism, and this just requires there is particular/special requirement in the design of deep hydrodesulfurizationof catalyst.
Hydrotreating catalyst normally adopts alumina-based supports, and with group vib and group VIII metal for hydrogenation active metals component, wherein active metal component is generally equally distributed in the catalyst.CN99103007.9 discloses a kind of light-end products hydrotreating catalyst containing molybdenum and/or tungsten.This catalyst contains load tungsten oxide on the alumina support and/or molybdenum oxide, nickel oxide and cobalt oxide, the content of described tungsten oxide and/or molybdenum oxide is that 4 heavy % are to being less than 10 heavy %, the content of nickel oxide is 1 ~ 5%, the content of cobalt oxide is 0.01 ~ 1 heavy %, and nickel and cobalt total atom number are 0.3 ~ 0.9 with the ratio of the total atom number of nickel, cobalt, tungsten and/or molybdenum.Compared with prior art, this catalyst has lower tenor and but has higher low temperature active.This catalyst is specially adapted to the hydro-sweetening process of light-end products.
CN99113281.5 discloses a kind of catalyst for hydrorefining distillate oil and preparation method thereof.This catalyst for carrier, with W, Mo, Ni for active component, adds phosphate builder with aluminium oxide or silicon-containing alumina.By adopting segmentation total immersion technology, make the Metal Distribution on catalyst more even, the activity of catalyst, particularly hydrodenitrogenationactivity activity is greatly improved.
The hydrotreating catalyst of these prior aries all belongs to conventional Hydrobon catalyst, effectively can not be applicable to the hydrodesulfurization of heavy distillate (especially diesel oil).Therefore, prior art still needs a kind of hydrotreating catalyst, is particularly useful for the hydrodesulfurization (especially deep hydrodesulfurizationof) of heavy distillate (especially diesel oil).
Summary of the invention
For problems of the prior art, the invention provides a kind of hydrotreating catalyst and the preparation method with high hydrodesulfurization activity.
Hydrotreating catalyst of the present invention, adopt alumina-based supports, active metal component is Co, Mo, W and Ni, and wherein the concentration 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst 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 hydrotreating catalyst is that (solid) is granular, instead of the amorphous state such as powder.As the shape of described particle, the various shapes that hydrotreating catalyst 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 hydrotreating catalyst 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.
Hydrotreating catalyst of the present invention, with the weight of catalyst for benchmark, the content of alumina-based supports is 45wt% ~ 84wt%, and be 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%.
In hydrotreating catalyst 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 hydrotreating catalyst described in this, 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 hydrotreating catalyst 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.
Can also contain adjuvant component in hydrotreating catalyst 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 hydrotreating catalyst of the present invention, with P
2o
5meter weight content is in the catalyst 1% ~ 6%.
In hydrotreating catalyst of the present invention, described alumina-based supports refers to aluminium oxide to be key component, adjuvant component can not be contained, also adjuvant component can be contained, wherein adjuvant component can be one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron etc., adjuvant component in the content of element in alumina-based supports at below 30wt%, preferred below 20wt%.Described alumina-based supports can adopt conventional method to prepare.The character of described alumina-based supports is preferably as follows: specific area is 100 ~ 500 m
2/ g, is preferably 150 ~ 400 m
2/ g, pore volume is 0.25 ~ 1.0mL/g, is preferably 0.3 ~ 0.9 mL/g.
The character of hydrotreating catalyst 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.
Organic matter can also be contained in described hydrotreating catalyst, organic matter is selected from organic compounds containing nitrogen, one or more in organic compounds containing sulfur and oxygen-containing organic compound that carbon number is 2 ~ 20, the organic matter contained in catalyst is made to be 0.002:1 ~ 2.0:1 with Mo and W atomic molar ratio, be preferably 0.02:1 ~ 1.5:1, more preferably 0.02:1 ~ 1.0:1.
Described organic compounds containing nitrogen is the organic matter at least comprising a covalent bond nitrogen-atoms, in organic compounds containing nitrogen, carbon number is 2 ~ 20, concrete as one or more in ethylenediamine, hexamethylene diamine etc., be preferably except the nitrogen-atoms comprising at least one covalent bond, also at least comprise the organic compound of a hydroxyl or carboxy moiety, as monoethanolamine, diethanol amine, triethanolamine, one or more in ethylenediamine tetra-acetic acid (EDTA), nitrilotriacetic acid (NTA) and ring ethylenediamine tetra-acetic acid etc.
Described organic compounds containing sulfur is the organic matter at least comprising a covalent bond sulphur atom, and in organic compounds containing sulfur, carbon number is generally 2 ~ 20.As sulphonic acids (general formula R-SO
3h) R is wherein the alkyl containing 2 ~ 20 carbon atoms, as one or more in benzene sulfonic acid, DBSA, p-methyl benzenesulfonic acid etc.The group that can contain one or more carboxyl, carbonyl, ester, ether, hydroxyl, sulfydryl in organic compounds containing sulfur replaces, as TGA, mercaptopropionic acid, dimercaprol dimercaptopropanol etc.Except above-mentioned sulfur-containing compound, sulfone and sulfoxide compound can be comprised, as one or more in dimethyl sulfoxide (DMSO), dimethyl sulfone etc.
Described oxygen-containing organic compound is the organic matter at least containing a carbon atom and an oxygen atom.Preferably comprise the organic compound of at least two oxygen atoms and two carbon atoms, oxygen-containing organic compound carbon number is preferably 2 ~ 20.Carboxyl, carbonyl, hydroxylic moiety or their combination is can be containing oxygen part.These materials can be in acids, alcohols, ethers, carbohydrate, ketone, phenols, aldehydes and lipid one or more.Be preferably as follows further: one or more in acetic acid, oxalic acid, malonic acid, tartaric acid, malic acid, citric acid, ethylene glycol, propane diols, butanediol, glycerine, diethylene glycol (DEG), DPG, triethylene glycol, three butanediols, tetraethylene glycol, polyethylene glycol, glucose, fructose, lactose, maltose, sucrose etc.
The preparation method of hydrotreating catalyst of the present invention, comprising:
(1) by the solution impregnation alumina-based supports containing adsorbent I, after drying, obtain the alumina-based supports containing adsorbent I, wherein adsorbent I consumption is 0.1% ~ 10.0% of alumina-based supports 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 alumina-based supports weight, described adsorbent II is one or more in organic carboxyl acid and its esters, and described dipping adopts unsaturated dipping;
(4) dip loading active metal Mo, Co on step (3) gains, preferably at least adopts a kind of following method:
A, dipping solution impregnation steps (3) gains of use containing Mo, Co, through super-dry or dry and roasting, obtain hydrotreating catalyst;
B, use, containing Mo, Co and organic dipping solution impregnation steps (3) gains, through super-dry, obtain hydrotreating catalyst;
C, dipping solution impregnation steps (3) gains of use containing Mo, Co, after super-dry or drying and roasting, with organic matter dipping, drying, obtains hydrotreating catalyst.
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.Described adsorbent II (i.e. organic matter A) 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.
The inventive method, step (1), with containing adsorbent I solution impregnation alumina-based supports, 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 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 alumina support.After fountain solution oxide impregnation alumina-based support 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, step (4), with the dipping solution containing Mo, Co or containing Mo, Co and organic dipping solution impregnated catalyst intermediate, can be passed through health, also can without health, and as needed health, conditioned time is 0.5 ~ 4.0h, then carries out drying.Drying condition described in method a, method b or method c 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.Roasting condition described in method a or method c 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 hydrotreating catalyst 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 hydrotreating catalyst 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.
In the inventive method, organic addition makes it compare for 0.002:1 ~ 2:1 with Mo atomic molar in the catalyst, is preferably 0.02:1 ~ 1.5:1, is preferably 0.02:1 ~ 1.0:1.The kind of organic additive is well-known to those skilled in the art, can be identical with adsorbent II, also can be different, is generally selected from one or more in organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic compound.
Hydrotreating catalyst of the present invention in the hydrodesulfurization (especially deep hydrodesulfurizationof) of heavy distillate (especially diesel oil) as the application of Hydrobon catalyst.
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 ~ 0.05wt%.
Adopt hydrotreating catalyst of the present invention as Hydrobon catalyst, the total sulfur content of described heavy distillate can be reduced to 0.05wt% or lower, preferably be reduced to 0.005wt% or lower, the described difficulty that especially can remove more than 80wt% (preferred more than 90wt%) takes off sulfur-containing compound.
The present invention, in described application or described hydrodesulfurizationprocess process, can only use hydrotreating catalyst of the present invention, also can by hydrotreating catalyst of the present invention and other hydrotreating catalysts (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 hydrodesulfurization without any special restriction, the operating condition that this area routine can be adopted to use, such as can enumerate 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-1, preferably 1 ~ 2h-1 during liquid, hydrogen to oil volume ratio 200:1 ~ 2000:1, preferred 400:1 ~ 1000:1.
In hydrotreating catalyst of the present invention, active metal component Co and Mo is from catalyst granules outer surface to center in the trend increased gradually, Ni and W is the trend reduced gradually from catalyst granules outer surface to center.This catalyst is specially adapted in hydrodesulfurization, improves the activity and selectivity of hydrodesulfurization, especially removes the thiophene sulfocompounds having sterically hindered difficulty and remove.
Hydrotreating catalyst 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, like this by control Mo, Co and W, the distribution of Ni different metal combination in the catalyst in variable concentrations, make it cooperatively interact, give full play to both advantages, thus improve the activity and selectivity of catalyst, especially the thiophene sulfocompounds that there is sterically hindered difficulty and remove is removed.In addition, the present invention, by controlling the preparation condition of hydrotreating catalyst, makes organic matter be present in final hydrotreating catalyst, after active metal sulfuration, can form more lamination number, the hydrogenation activity of catalyst is further enhanced.
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 3 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 of catalyst
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 3 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) catalyst is relatively desulphurizing activated
Relatively desulphurizing activated=100 × [(1/S
1)
0.65-(1/S
0)
0.65]/[(1/Sc
1)
0.65-(1/S
0)
0.65], S in formula
1and Sc
1represent the sulfur content adopted in catalyst of the present invention or reference agent gained hydrogenation products respectively, S
0represent the sulfur content adopted in catalyst of the present invention or the raw materials used oil of reference agent.Wherein sulfur content is in S, and unit is μ g/g.
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 physico-chemical property of column type alumina support used is as shown in table 1, and wherein the diameter of alumina support is about 1.2mm, and length is about 3 ~ 5mm.
The physico-chemical property of alumina support used in table 1 embodiment
| Project | Alumina support |
| Specific area, m 2/g | 298 |
| Pore volume, mL/g | 0.64 |
| Bulk density, g/100mL | 63 |
| Saturated liquid absorption, mL/100g | 75 |
Embodiment 1
Take 12g Macrogol 2000 (namely molecular weight is the polyethylene glycol of 2000, lower same), stirring and dissolving in the water measured, obtained fountain solution I.Flood the alumina support of 200g with this fountain solution I, then carry out the health of 10h, after 120 DEG C of dry 3h, obtained sample is designated as B1 respectively.
Spray above-mentioned B1 sample with the maceration extract equal-volume containing W, Ni, directly carry out 120 DEG C of dry 3h without health after spraying end, after 480 DEG C of roasting 2h, the sample of acquisition is designated as Z1.
Take tartaric acid 10g, stirring and dissolving in 30g water, obtained fountain solution.Get Z1 sample, evenly sprayed on Z1 by fountain solution II, the time of spraying is 15min.After fountain solution II sprays end, through 100 DEG C of dry 2h, with the above-mentioned carrier of maceration extract incipient impregnation containing Mo, Co, P and ethylenediamine tetra-acetic acid (EDTA), EDTA and the Mo introduced and the mol ratio of W are 0.008:1, sample average after dipping is divided into two parts, wherein the first increment product not health, through 120 DEG C of dry 3h, the sample of acquisition is designated as C1; Second increment product health 1h, through 120 DEG C of dry 3h, obtained sample is designated as C2.
Embodiment 2
Take 16g cetomacrogol 1000, stirring and dissolving in the water measured, obtained fountain solution I.With the alumina support of this fountain solution I incipient impregnation 200g, then carry out the health of 5h, after 120 DEG C of dry 3h, obtained sample is designated as B2.
Spray B2 sample with the maceration extract equal-volume containing W, Ni, after spraying end, sample average is divided into two parts, wherein the direct 120 DEG C of dry 3h of the first increment product, after 480 DEG C of roasting 2h, the sample of acquisition is designated as Z2; Second increment product health 3h, 120 DEG C of dry 3h, after 480 DEG C of roasting 2h, obtained sample is designated as Z3.
Take malic acid 1.0g, stirring and dissolving in 6g ethanol, obtained fountain solution II.Evenly sprayed on Z2 by fountain solution II, the time of spraying is 5min.With the above-mentioned sample of maceration extract incipient impregnation containing Mo, Co, P and TGA, the TGA of introducing and the mol ratio of Mo and W are 0.02:1, and dipping terminates rear health 1h, and through 120 DEG C of dry 3h, the catalyst of acquisition is designated as C3.Get Z3 sample, the catalyst obtained through the treatment step identical with Z2 is designated as C4.
Embodiment 3
Take 7.5g PEG 8000, stirring and dissolving in the aqueous solution measured, obtained fountain solution I.With the alumina support of this fountain solution I incipient impregnation 300g, then carry out the health of 5h, after 120 DEG C of dry 3h, obtained sample is designated as B3.
Spray B3 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 sample of acquisition is designated as Z4.
Take citric acid and each 10.5g of malonic acid, stirring and dissolving in 40g water, obtained fountain solution II.Evenly sprayed on Z4 by fountain solution II, the time of spraying is 25min.With containing the above-mentioned sample of Mo, Co, P maceration extract incipient impregnation, dipping terminates rear health 1h, and through 120 DEG C of dry 3h, the catalyst of acquisition is designated as C5.
Prepare the glycerinated aqueous solution, equal-volume sprays part C5 sample, and on the glycerine of introducing and catalyst, the mol ratio of Mo and W is 0.03:1, and after spraying end, through 120 DEG C of dry 3h, the catalyst of acquisition is designated as C6.
After part C5 sample 480 DEG C of roasting 2h, the catalyst of acquisition is designated as C7.
Comparative example 1
Get alumina support 100g, after using the above-mentioned carrier of maceration extract incipient impregnation containing W, Ni, through 120 DEG C of dry 3h, after 480 DEG C of roasting 2h, the sample of acquisition is designated as B4.With the maceration extract incipient impregnation B4 containing Mo, Co, P, 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
All metal total immersions, and add the organic matter contained in catalyst of the present invention.Get alumina support 100g, preparation contains the maceration extract of Mo, W, Ni, Co, P and citric acid 3.5g, after the above-mentioned carrier of incipient impregnation, after 120 DEG C of dry 3h, equal-volume sprays the aqueous solution containing citric acid, malonic acid and glycerine, wherein citric acid and each 3.5g of malonic acid, on the glycerine introduced and catalyst, the mol ratio of Mo and W is 0.03:1, after spraying end, and health 3h, after 120 DEG C of dry 3h, 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 |
| W is with WO 3Meter, wt% | 19.3 | 19.5 | 19.5 | 19.5 | 19.4 | 19.5 | 19.4 | 19.3 | 19.4 |
| Mo is with MoO 3Meter, wt% | 13.3 | 13.1 | 13.4 | 13.6 | 13.2 | 13.3 | 13.2 | 13.4 | 13.3 |
| Co is in CoO, wt% | 2.4 | 2.3 | 2.3 | 2.4 | 2.3 | 2.4 | 2.4 | 2.2 | 2.2 |
| Ni is in NiO, wt% | 2.6 | 2.6 | 2.7 | 2.5 | 2.6 | 2.6 | 2.5 | 2.6 | 2.6 |
| P is with P 2O 5Meter, wt% | 1.46 | 1.45 | 1.48 | 1.47 | 1.47 | 1.46 | 1.46 | 1.45 | 1.45 |
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 | 0.13 | 0.31 | 0.34 | 0.33 | 0.29 | 0.30 | 0.29 | 0.99 | 0.98 |
| Mo 1/4/Mo 1 | 0.30 | 0.42 | 0.70 | 0.71 | 0.40 | 0.39 | 0.40 | 1.0 | 0.99 |
| Mo 1/2/Mo 1 | 0.67 | 0.79 | 0.89 | 0.88 | 0.79 | 0.80 | 0.80 | 0.98 | 1.01 |
| Mo 3/4/Mo 1 | 0.89 | 0.93 | 0.97 | 0.98 | 0.95 | 0.94 | 0.95 | 0.98 | 1.0 |
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 | 0.34 | 0.33 | 0.30 | 0.32 | 0.31 | 0.99 | 0.98 |
| Co 1/4/ Co 1 | 0.31 | 0.45 | 0.73 | 0.75 | 0.44 | 0.45 | 0.45 | 1.01 | 0.99 |
| Co 1/2/ Co 1 | 0.65 | 0.79 | 0.88 | 0.90 | 0.81 | 0.82 | 0.81 | 0.98 | 1.02 |
| Co 3/4/ Co 1 | 0.92 | 0.94 | 0.98 | 1.00 | 0.95 | 0.95 | 0.95 | 1.00 | 1.01 |
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 | 2.77 | 2.79 | 2.83 | 2.48 | 2.54 | 2.45 | 2.55 | 1.01 | 0.99 |
| W 1/4/W 1 | 1.78 | 1.80 | 1.79 | 1.676 | 1.69 | 1.65 | 1.68 | 1.02 | 1.0 |
| W 1/2/W 1 | 1.23 | 1.25 | 1.30 | 1.20 | 1.23 | 1.21 | 1.22 | 0.99 | 0.98 |
| W 3/4/W 1 | 1.09 | 1.08 | 1.07 | 1.07 | 1.09 | 1.08 | 1.09 | 1.0 | 1.01 |
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 | 2.82 | 2.83 | 2.99 | 2.56 | 2.61 | 2.54 | 2.63 | 0.99 | 1.0 |
| Ni /4/ Ni 1 | 1.87 | 1.89 | 1.97 | 1.73 | 1.77 | 1.73 | 1.78 | 1.01 | 1.02 |
| Ni 1/2/ Ni 1 | 1.24 | 1.25 | 1.36 | 1.24 | 1.22 | 1.21 | 1.21 | 0.99 | 1.0 |
| Ni 3/4/ Ni 1 | 1.09 | 1.10 | 1.12 | 1.09 | 1.07 | 1.07 | 1.07 | 1.0 | 0.99 |
From table 3 and table 4, adopt catalyst C1 ~ C7 prepared by the present invention, active metal Co and Mo increases from edge to centre concentration gradually along catalyst granules radial direction, active metal Ni and W reduces from edge to centre concentration gradually along catalyst granules radial direction, and comparative example catalyst C8 and C9 active metal W, Mo, Co, Ni concentration on each position, radial direction place are substantially identical, be the distribution of obvious gradient unlike Kaolinite Preparation of Catalyst of the present invention.Found by C1, C2, spraying the rear conditioned time of end by controlling fountain solution I, the distributed density of active metal Co and Mo in catalyst granules radial direction can be adjusted; Find out from C2, C3 and C5, also can adjust the distributed density of active metal Co and Mo in catalyst granules radial direction by the changes of contents of fountain solution I; Find out from C1, C3, C4 and C5, by the content of fountain solution II and the conditioned time spraying W, Ni rear catalyst, the distributed density of active metal Ni and W in catalyst granules radial direction can be adjusted.Therefore, the inventive method can adjust the distributed density of different activities metal in catalyst granules radial direction easily, improves the deep desulfuration performance of catalyst.
Embodiment 4
The present embodiment is the active appraisal experiment of catalyst.
Catalyst activity evaluation experimental carries out on 100ml small hydrogenation device, carries out presulfurization before activity rating to catalyst.Evaluating catalyst condition is at reaction stagnation pressure 6.0MPa, volume space velocity 2.0 h during liquid
-1, hydrogen-oil ratio 500:1, reaction temperature is 340 DEG C.Active appraisal experiment feedstock oil character is in table 7, Activity evaluation is in table 8, and table 9 provides the content of the difficult de-sulfur-containing compound of typical case in hydrogenation products, from data in table, hydrotreating catalyst is prepared, catalyst desulphurizing activated apparently higher than comparative example catalyst with the present invention.
Table 7 feedstock oil character
| Feedstock oil | Atmosphere 3rd side cut diesel oil |
| Density (20 DEG C), g/cm 3 | 0.8533 |
| Boiling range, DEG C | |
| IBP | 217 |
| EBP | 375 |
| S，wt% | 1.78 |
| N，μg/g | 140 |
Table 8 catalyst activity evaluation result
| Catalyst | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Relatively desulphurizing activated, % | 144 | 139 | 141 | 138 | 133 | 144 | 130 | 100 | 117 |
The content of the difficult de-sulfur-containing compound of typical case in table 9 raw material and hydrogenation products
| Raw material/hydrogenation products | Raw material | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products |
| Catalyst | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 | |
| 4，6- BMDBT，μg/g | 215 | 11.0 | 11.9 | 11.5 | 12.0 | 12.9 | 11.0 | 13.4 | 22.8 | 16.9 |
Claims (30)
1. a hydrotreating catalyst, adopt alumina-based supports, 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 hydrotreating catalyst, 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 hydrotreating catalyst, 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 hydrotreating catalyst, 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 hydrotreating catalyst, 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 hydrotreating catalyst, 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 hydrotreating catalyst, 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 hydrotreating catalyst, with the weight of catalyst for benchmark, the content of alumina-based supports 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%.
9. according to catalyst according to claim 1, it is characterized in that in described hydrotreating catalyst, 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 hydrotreating catalyst, 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 hydrotreating catalyst, 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 the character of described hydrotreating catalyst 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 hydrotreating catalyst, containing organic matter, described organic matter to be carbon number be 2 ~ 20 organic compounds containing nitrogen, one or more in organic compounds containing sulfur and oxygen-containing organic compound, in hydrotreating catalyst, organic matter and Mo and W atomic molar are than being 0.002:1 ~ 2.0:1, are preferably 0.02:1 ~ 1.0:1.
14. according to catalyst according to claim 1, it is characterized in that in described hydrotreating catalyst, alumina-based supports is take aluminium oxide as key component, not containing adjuvant component or containing adjuvant component, wherein adjuvant component is one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component in the content of element in alumina-based supports at below 30wt%.
15. according to catalyst according to claim 1, it is characterized in that in described hydrotreating catalyst, 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 hydrotreating catalyst, 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, comprising:
(1), by the solution impregnation alumina-based supports containing adsorbent I, after drying, obtain the alumina-based supports containing adsorbent I, wherein adsorbent I consumption is 0.1% ~ 10.0% of alumina-based supports 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 alumina-based supports weight, described adsorbent II is one or more in organic carboxyl acid and its esters, and described dipping adopts unsaturated dipping;
(4) dip loading active metal Mo, Co on step (3) gains.
18. in accordance with the method for claim 17, it is characterized in that step (4) at least adopts a kind of following method:
A, dipping solution impregnation steps (3) gains of use containing Mo, Co, through super-dry or dry and roasting, obtain hydrotreating catalyst;
B, use, containing Mo, Co and organic dipping solution impregnation steps (3) gains, through super-dry, obtain hydrotreating catalyst;
C, dipping solution impregnation steps (3) gains of use containing Mo, Co, after super-dry or drying and roasting, with organic matter dipping, drying, obtains hydrotreating catalyst.
19. 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.
20. 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.
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: step (1), with containing adsorbent I solution impregnation catalyst intermediate, is flooded after terminating, sample is through health or without health, again 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.
23. in accordance with the method for claim 17, it is characterized in that: step (2), with containing after dipping solution impregnation steps (1) gains of W, 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 ~ 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: adopt unsaturated spraying when flooding with the fountain solution containing adsorbent II in 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 carrier.
25. in accordance with the method for claim 17, it is characterized in that: after the fountain solution dipping of step (3) 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.
26. in accordance with the method for claim 18, it is characterized in that: the dipping solution of step (4) containing Mo, Co, containing Mo, Co and organic solution impregnation catalyst intermediate, through health or without health, then carries out drying, as needed health, conditioned time is 0.5 ~ 4.0h; Drying condition described in method a, method b or method c is as follows: baking temperature is 70 DEG C ~ 300 DEG C, drying time 0.5h ~ 20h; The roasting condition of method a or method c is as follows: sintering temperature is 300 DEG C ~ 750 DEG C, and roasting time is 0.5h ~ 20h.
27. in accordance with the method for claim 17, it is characterized in that: 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 hydrotreating catalyst is 1% ~ 6%.
28. in accordance with the method for claim 18, it is characterized in that: described organic addition makes the organic matter in final hydrotreating catalyst be 0.002:1 ~ 2:1 with Mo and W atomic molar ratio, and organic matter is selected from one or more in organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic compound.
The method of 29. 1 kinds of heavy distillate hydrodesulfurizations, is characterized in that adopting the arbitrary described hydrotreating catalyst of claim 1 ~ 16.
30. in accordance with the method for claim 29, it is characterized in that: described heavy distillate is diesel oil.
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| CN106669714A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Method for preparing hydrotreating catalyst |
| US11420193B2 (en) | 2017-07-21 | 2022-08-23 | Albemarle Europe Srl | Hydrotreating catalyst with a titanium containing carrier and organic additive |
| US11524278B2 (en) | 2017-07-21 | 2022-12-13 | Albemarle Europe Srl | Hydrotreating catalyst with a titanium containing carrier and sulfur containing organic additive |
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| DE3675582D1 (en) * | 1985-06-05 | 1990-12-20 | Nippon Oil Co Ltd | HYDROGEN TREATMENT CATALYST. |
| CN1102448C (en) * | 1999-09-29 | 2003-03-05 | 中国石油化工集团公司 | Process for preparing catalyst with non-uniform distribution of active metals |
| CN101279289B (en) * | 2007-04-04 | 2010-05-19 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN101439293B (en) * | 2007-11-19 | 2011-03-16 | 中国石油天然气集团公司 | Selective hydrodesulfurization catalyst containing mesoporous molecular screen and preparation method thereof |
| CN102463149B (en) * | 2010-11-04 | 2015-06-17 | 中国石油化工股份有限公司 | Activation method of hydrogenation catalyst |
| CN102994142B (en) * | 2011-09-15 | 2014-11-26 | 中国石油天然气股份有限公司 | Method for hydrofining pyrolysis gasoline |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106669714A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Method for preparing hydrotreating catalyst |
| CN106669714B (en) * | 2015-11-11 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| US11420193B2 (en) | 2017-07-21 | 2022-08-23 | Albemarle Europe Srl | Hydrotreating catalyst with a titanium containing carrier and organic additive |
| US11524278B2 (en) | 2017-07-21 | 2022-12-13 | Albemarle Europe Srl | Hydrotreating catalyst with a titanium containing carrier and sulfur containing organic additive |
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