CN104667982B - A kind of catalyst for hydro-upgrading and preparation method thereof - Google Patents
A kind of catalyst for hydro-upgrading and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of catalyst for hydro-upgrading and preparation method thereof.In this catalyst for hydro-upgrading, carrier includes aluminium oxide and molecular sieve, and active metal component is Mo, Co and Ni, and wherein active metal component concentration distribution situation on each catalyst granules cross section is as follows: Co0/Co1＜ Co1/2/Co1＜ 1, Ni0/Ni1＞ Ni1/2/Ni1＞ 1, Ni0/ Mo0＞ Ni1/2/ Mo1/2＞ Ni1/ Mo1, Co0/Mo0＜ Co1/2/Mo1/2＜ Co1/ Mo1, containing Organic substance in described catalyst.Its preparation method is as follows: carrier contains the solution of adsorbent I by saturated or excessive dipping, the dipping solution containing active metal Mo, Ni again, drying and roasting, then by unsaturation dipping adsorbent II i.e. containing one or more in organic carboxyl acid and its esters, then dip loading Mo, Co active metal or Mo, Co and Organic substance.This catalyst, during diesel oil hydrogenation modification, has deep hydrodesulfurizationof activity, and can improve the combination properties such as Cetane number in the case of keeping diesel yield higher.
Description
Technical field
The present invention relates to a kind of catalyst for hydro-upgrading and preparation method thereof, a kind of catalyst for hydro-upgrading being suitable to diesel modifying and preparation method thereof.
Background technology
For cleaning diesel production, prior art mainly includes the technology such as hydrofinishing and MHUG.Hydrofinishing can reduce the sulfur content of modification diesel oil, but limited with reduction T95 temperature capability to improving Cetane number.MHUG is to use the catalyst for hydro-upgrading containing molecular sieve (Y type molecular sieve or beta-molecular sieve), by suitably cracking such as the aromatic hydrocarbons in diesel oil, in reducing diesel oil while sulfur nitrogen impurity content, improves the combination properties such as diesel cetane-number.But use current catalyst for hydro-upgrading, to improve the combination property (sulfur nitrogen impurity content, Cetane number, T95 temperature, arene content etc.) of diesel oil, typically require higher cracking degree, diesel yield so can be made relatively low, and the yield of diesel oil to be kept, the combination property of diesel oil is again less than well improving.
Sulfur-containing compound in diesel oil distillate and aromatic hydrocarbons, generally exist with complicated structure, such as dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene etc., wherein be hydrogenated with more difficult removing is the thiophenes such as dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene, especially with 4,6-dimethyl Dibenzothiophene (4,6-BMDBT) and 2,4,6-trimethyl dibenzothiophenes (2,4,6-BMDBT) class formation is complicated and has the sulfur-containing compound of space steric effect to be most difficult to removing.The degree of depth to be reached and ultra-deep desulfurization, it is accomplished by removing that these structures are complicated and sterically hindered big sulfur-containing compound, and the generally more difficult removing under the harsh hydrofinishing operating conditions such as High Temperature High Pressure of these sulfur-containing compounds, by being hydrocracked, diesel yield can be reduced.Therefore, in the case of 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 important topic being currently needed for research.
Catalyst for hydro-upgrading is typically with the alumina support containing molecular sieve, and with vib and group VIII metal for hydrogenation active metals component, wherein active metal component is the most equally distributed.CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, this catalyst consist of aluminium oxide 40～80wt%, amorphous silica-alumina 0～20wt%, Y type molecular sieve 5～30wt%.CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof, mainly use predecessor and Y type molecular sieve mixing, molding and the roasting of silica-alumina, aluminium oxide and/or aluminium oxide, introduce the hydrogenation metal of effective dose afterwards at molding species.Above-mentioned catalyst has higher desulfurization and a denitrification activity, but the shortcoming such as the amplitude that the yield of diesel product is low, diesel-fuel cetane number improves is little, condensation point is high and density is big.
CN201110350790.2 discloses a kind of diesel oil hydrogenation modification catalyst and preparation method thereof.This catalyst comprises the carrier being made up of modified beta molecular sieve and aluminium oxide and hydrogenation active metals component, and wherein active metal component is equally distributed in the catalyst.Use this catalyst when diesel oil hydrogenation modification, although the condensation point of diesel oil distillate can be reduced, improve modification diesel-fuel cetane number, but diesel yield is below 97%, the most relatively low.
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, during diesel oil hydrogenation modification, has deep hydrodesulfurizationof activity, and can improve the combination properties such as Cetane number in the case of keeping diesel yield higher.
The catalyst for hydro-upgrading of the present invention, carrier includes aluminium oxide and molecular sieve, and active metal component is Mo, Co and Ni, and wherein active metal component concentration distribution on the cross section of each catalyst granules is as follows: Co0/Co1＜ Co1/2/Co1＜ 1, Ni0/Ni1＞ Ni1/2/Ni1＞ 1, Ni0/Mo0＞ Ni1/2/Mo1/2＞ Ni1/Mo1, Co0/Mo0＜ Co1/2/Mo1/2＜ Co1/Mo1Containing Organic substance in described catalyst, described Organic substance is one or more in organic nitrogen-containing organic compound, organic compounds containing sulfur and the oxygen-containing organic compound of 2 ~ 20 selected from carbon number, Organic substance and Mo atomic molar are than for 0.002:1～2.0:1, it is preferably 0.02:1 ~ 1.5:1, more preferably 0.02:1 ~ 1.0:1.
In the present invention, active metal component concentration distribution formula A on the cross section of each catalyst granulesm/BnRepresent, on the cross section of the most each catalyst granules, at m, at the concentration of elements A and n, the ratio of the concentration of element B is (in the present invention, unit is mol ratio), wherein A represents active metallic element Mo, Co or Ni, B represents active metallic element Mo, Co or Ni, wherein A with B can be identical, it is also possible to different；nullIt is designated as 0 for starting point with any point i.e. outer most edge point of catalyst granules cross section outer most edge，It is designated as 1 for terminal with the central point of catalyst granules cross section，Connect starting point and terminal obtains straight-line segment，M and n is illustrated respectively on above-mentioned straight-line segment the location point 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、The 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 also referred to as outer most edge and selects (or appearance cake)、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 uses active metallic element Mo, Co or Ni to replace, m and n is directly with defined location point on the above-mentioned straight-line segment of digitized representation of 0～1, represents arbitrary location point on above-mentioned straight-line segment with x1 or x2, such as, Co0/Co1Representing that A and B is Co, m=0, n=1 i.e. represent the ratio of the concentration of the concentration of Elements C o and central spot Elements C o, Ni at catalyst granules cross section outer most edge point1/2/Ni1Represent that A and B is Ni, m=1/2, n=1 i.e. represents on the described straight-line segment on catalyst granules cross section, makes when the distance of outer most edge point to selected point accounts for the 1/2 of above-mentioned straight-line segment length the ratio of the concentration of element Ni and the concentration of central spot element Ni, Ni at selected point position0/Mo0Expression A be Ni, B be Mo, m=0, n=0, i.e. represent the ratio of the concentration of element Ni and the concentration of this elements Mo at catalyst granules cross section outer most edge point.The location point (but not including outer most edge point and central point) that x1 and x2 in the present invention arbitrarily chooses respectively on the straight-line segment that the above-mentioned outer most edge point of connection and central point obtain, and the distance of point is less than the distance that is 0 ＜ x1 ＜ x2 ＜ 1 of point from outer most edge point to x2 from outer most edge point to x1.
In the present invention, relate to using formula Am/BnIt is specific as follows that form represents: Co0/Co1(A and B is Co, m=0, n=1), Co1/4/Co1(A and B is Co, m=1/4, n=1), Co1/2/Co1(A and B is Co, m=1/2, n=1), Co3/4/Co1(A and B is Co, m=3/4, n=1), Cox1/Co1(A and B is Co, m=x1, n=1), Cox2/Co1(A and B is Co, m=x2, n=1), Ni0/Ni1(A and B is Ni, m=0, n=1), Ni1/4/Ni1(A and B is Ni, m=1/4, n=1), Ni1/2/Ni1(A and B is Ni, m=1/2, n=1), Ni3/4/Ni1(A and B is Ni, m=3/4, n=1), Nix1/Ni1(A and B is Ni, m=x1, n=1), Nix2/Ni1(A and B is Ni, m=x2, n=1), Ni0/Mo0(A be Ni, B be Mo, m=0, n=0), Ni1/4/Mo1/4(A be Ni, B be Mo, m=1/4, n=1/4), Ni1/2/Mo1/2(A be Ni, B be Mo, m=1/2, n=1/2), Ni3/4/Mo3/4(A be Ni, B be Mo, m=3/4, n=3/4), Ni1/Mo1(A be Ni, B be Mo, m=1, n=1), Nix1/Mox1(A be Ni, B be Mo, m=x1, n=x1), Nix2/Mox2(A be Ni, B be Mo, m=x2, n=x2), Co0/Mo0(A be Co, B be Mo, m=0, n=0), Co1/4/Mo1/4(A be Co, B be Mo, m=1/4, n=1/4), Co1/2/Mo1/2(A be Co, B be Mo, m=1/2, n=1/2), Co3/4/Mo3/4(A be Co, B be Mo, m=3/4, n=3/4), Co1/Mo1(A be Co, B be Mo, m=1, n=1), Cox1/Mox1(A be Co, B be Mo, m=x1, n=x1), Cox2/Mox2(A be Co, B be Mo, m=x2, n=x2).
In catalyst for hydro-upgrading of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Co0/Co1With Co1/2/Co1Ratio be 0.2 ~ 0.8, preferably 0.2 ~ 0.7；Ni0/Ni1With Ni1/2/Ni1Ratio 1.5 ~ 2.6, preferably 1.7 ~ 2.5.
In catalyst for hydro-upgrading of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Ni0/Mo0With Ni1/2/Mo1/2Ratio be 1.4 ~ 2.3, preferably 1.5 ~ 2.2；Co0/Mo0With Co1/2/Mo1/2Ratio be 0.10 ~ 0.70, preferably 0.12 ~ 0.65.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably as follows: Co0/Co1＜ Co1/4/Co1＜ Co1/2/Co1。
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably as follows: Co1/2/Co1＜ Co3/4/Co1＜ 1.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably as follows: Ni0/Ni1＞ Ni1/4/Ni1＞ Ni1/2/Ni1。
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably as follows: Ni1/2/Ni1＞ Ni3/4/Ni1＞ 1.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably as follows: Ni0/Mo0＞ Ni1/4/Mo1/4＞ Ni1/2/Mo1/2。
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably as follows: Ni1/2/Mo1/2＞ Ni3/4/Mo3/4＞ Ni1/Mo1。
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably as follows: Co0/Mo0＜ Co1/4/Mo1/4＜ Co1/2/Mo1/2。
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably as follows: Co1/2/Mo1/2＜ Co3/4/Mo3/4＜ Co1/Mo1。
In catalyst for hydro-upgrading of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Co0/Co1With Co1/4/Co1Ratio be 0.30 ~ 0.90, preferably 0.30 ~ 0.85；Co1/4/Co1With Co1/2/Co1Ratio be 0.4 ~ 0.9, preferably 0.4 ~ 0.87；Ni0/Ni1With Ni1/4/Ni1Ratio be 1.2 ~ 1.8, preferably 1.3 ~ 1.7；Ni1/4/Ni1With Ni1/2/Ni1Ratio be 1.1 ~ 1.7, preferably 1.2 ~ 1.6.
In catalyst for hydro-upgrading of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Ni0/Mo0With Ni1/4/Mo1/4Ratio be 1.1 ~ 1.8, preferably 1.15 ~ 1.7；Ni1/4/Mo1/4With Ni1/2/Mo1/2Ratio be 1.1 ~ 1.8, preferably 1.15 ~ 1.7；Co0/Mo0With Co1/4/Mo1/4Ratio be 0.25 ~ 0.85, preferably 0.3 ~ 0.8；Co1/4/Mo1/4With Co1/2/Mo1/2Ratio be 0.25 ~ 0.85, preferably 0.3 ~ 0.8.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably as follows: Co0/Co1＜ Cox1/Co1＜ Cox2/Co1＜ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably as follows: Ni0/Ni1＞ Nix1/Ni1＞ Nix2/Ni1＞ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably as follows: Ni0/Mo0＞ Nix1/Mox1＞ Nix2/Mox2＞ Ni1/Mo1, wherein 0 ＜ x1 ＜ x2 ＜ 1.
In catalyst for hydro-upgrading of the present invention, active metal component concentration distribution on catalyst granules cross section is preferably as follows: Co0/Mo0＜ Cox1/Mox1＜ Cox2/Mox2＜ Co1/Mo1, 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 to central point, active metal component concentration distribution is as follows: the concentration of Ni substantially gradually decreases, the concentration of Co is substantially gradually increased, the concentration mol ratio of Ni/Mo substantially gradually decreases, and the concentration mol ratio of Co/Mo is substantially gradually increased.
In the present invention, described " substantially gradually decreasing (or being gradually increased) along described straight-line segment " refers to the concentration distribution of described active metallic element and presents the trend gradually decreasing (or being gradually increased) along described straight-line segment in the whole interval from outer most edge point to central point generally, but it is interval to allow to there is one or more local；In this local is interval, the concentration distribution of described active metallic element presents different trend (such as remain constant and/or be gradually increased (or gradually decreasing) and/or disordered state) along described straight-line segment.Premise is, the existence in interval, this kind of local is can to tolerate or negligible to those skilled in the art, or it is inevitable for the state-of-art of this area, and the interval existence in these local have no effect on those skilled in the art and the concentration distribution in described whole interval of the described active metallic element is still judged to " presenting the trend gradually decreasing (or being gradually increased) generally ".It addition, the interval existence in this local has no effect on the present invention expects the realization of purpose, it is acceptable, and within being also contained in protection scope of the present invention.
In the present invention, described catalyst for hydro-upgrading is that (solid) granular rather than the amorphous state such as powder.As the shape of described granule, this area catalyst for hydro-upgrading can be enumerated conventional use of variously-shaped, such as can enumerate spherical, column etc., the most spherical or column further.As described spherical, spheroidal and elliposoidal etc. such as can be enumerated；As described column, cylindric, flat column and profiled-cross-section (such as Herba Trifolii Pratentis, Herba Galii Bungei etc.) column etc. such as can be enumerated.The granularity of described catalyst for hydro-upgrading is generally 3 ~ 8mm, preferably 3 ~ 5mm.
In the present invention, the whole surface that described " cross section of catalyst granules " is exposed after referring to be cut along the minimum dimension direction of a catalyst granules by the geometric center of its shape.Such as, when described catalyst granules is spherical, described cross section refers to pass through the whole surface (such as seeing Fig. 1) of exposure after its centre of sphere cuts along radius or the short-axis direction of this ball.Or, when described catalyst granules is column, described cross section refers to the whole surface (such as seeing Fig. 2) exposed after the length dimension direction being perpendicular to this post is cut by the central point of this length dimension.In the present invention, the periphery of described exposed surface is referred to as the outer most edge of this cross section, described geometric center (than the centre of sphere as the aforementioned or the central point of length dimension) is referred to as the central point on this cross section.
The catalyst for hydro-upgrading of the present invention, on the basis of the weight of catalyst, the content of carrier is 55wt% ~ 88wt%, preferably 55wt% ~ 85wt%, more preferably surplus, and the content that Ni counts with NiO is as 1wt%～8wt%, and Mo is with MoO3The content of meter is 8wt%～32wt%, and the content that Co counts with CoO is as 1wt%～8wt%；On the basis of the weight of catalyst carrier, the content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%.
Can also contain one or more in adjuvant component, such as fluorine, silicon, phosphorus, titanium, zirconium, boron in catalyst for hydro-upgrading of the present invention, adjuvant component weight content in the catalyst in terms of element is less than 15%, preferably 1% ~ 10%.Catalyst for hydro-upgrading of the present invention preferably comprises phosphorus, with P2O5Meter weight content in the catalyst is 1% ~ 6%.
In the catalyst for hydro-upgrading of the present invention, it is positioned at the ratio i.e. Ni of the concentration of the concentration of element Ni and central spot element Ni at catalyst granules cross section outer most edge point0/Ni1It is 1.2～7.0, preferably 1.5 ~ 5.0, it is positioned at the ratio i.e. Co of the concentration of the concentration of Elements C o and central spot Co at catalyst granules cross section outer most edge point0/Co1It is 0.1～0.8, preferably 0.2 ~ 0.7.
In the catalyst for hydro-upgrading of the present invention, it is positioned at ratio (mol ratio) the i.e. Ni of the concentration of the concentration of element Ni and elements Mo at catalyst granules cross section outer most edge point0/Mo0It is 0.22～0.80, is positioned at ratio (mol ratio) the i.e. Co of the concentration of the concentration of Elements C o and elements Mo at catalyst granules cross-section center point1/Mo1It is 0.20～0.78.
In the catalyst for hydro-upgrading of the present invention, described molecular sieve is Y type molecular sieve and/or beta-molecular sieve.On the basis of the weight of catalyst carrier, 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 surface area 450m2/ g～750m2/ g, total pore volume 0.30ml/g～0.45ml/g, SiO2/Al2O3Mol ratio 40～100, meleic acid amount 0.1～0.5mmol/g, the mol ratio of framework aluminum non-framework aluminum is 5～20, and B-acid/L acid is 0.30～0.50, Na2O≤0.15wt%.Beta-molecular sieve of the present invention can use existing method to prepare.In the present invention, SiO2/Al2O3Mol ratio uses chemical determination, meleic acid amount, B-acid and L acid to use Pyridine adsorption IR spectra method to measure, and wherein meleic acid amount is B-acid and the sum of L acid acid amount.Sodium oxide content uses ion emission spectroscopy method to measure.Framework aluminum and non-framework aluminum content use NMR method to measure.
In the catalyst for hydro-upgrading of the present invention, can not contain adjuvant component in carrier, it is also possible to containing adjuvant component, wherein adjuvant component can be one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron etc., adjuvant component in terms of element content in the carrier at below 30wt%, preferably below 20wt%.Described carrier can use conventional method to prepare, such as kneading method etc..
The character of the catalyst for hydro-upgrading of the present invention is as follows: specific surface area is 100～260 m2/ g, preferably 120 ~ 220 m2/ g, pore volume is 0.20～0.60mL/g, preferably 0.2 ~ 0.5 mL/g.
In described catalyst for hydro-upgrading, containing Organic substance, described Organic substance be carbon number be one or more in organic compounds containing nitrogen, organic compounds containing sulfur and the oxygen-containing organic compound of 2 ~ 20, Organic substance and Mo atomic molar are than for 0.002:1～2.0:1, it is preferably 0.02:1 ~ 1.5:1, more preferably 0.02:1 ~ 1.0:1.
Described organic compounds containing nitrogen is the Organic substance including at least a covalent bond nitrogen-atoms, in organic compounds containing nitrogen, carbon number is 2 ~ 20, concrete such as one or more in ethylenediamine, hexamethylene diamine etc., it is preferably in addition to the nitrogen-atoms comprising at least one covalent bond, also including at least a hydroxyl or the organic compound of carboxy moiety, as: ethanolamine, diethanolamine, triethanolamine, one or more in ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and ring ethylenediaminetetraacetic acid etc..
Described organic compounds containing sulfur is the Organic substance including at least a covalent bond sulphur atom, and in organic compounds containing sulfur, carbon number is generally 2 ~ 20.Such as sulphonic acids (general formula R-SO3H) R therein is the alkyl containing 2 ~ 20 carbon atoms, such as one or more in benzenesulfonic acid, DBSA, p-methyl benzenesulfonic acid etc..Organic compounds containing sulfur can contain the group replacement of one or more carboxyls, carbonyl, ester, ether, hydroxyl, sulfydryl, such as one or more in TGA, mercaptopropionic acid, dimercaptopropanol, BAL etc..In addition to above-mentioned sulfur-containing compound, sulfone and sulfoxide compound can be comprised, such as one or more in dimethyl sulfoxide, dimethyl sulfone etc..
Described oxygen-containing organic compound is at least to contain a carbon atom and the Organic substance of an oxygen atom.Preferably containing at least two oxygen atoms and the organic compound of two carbon atoms, oxygen-containing organic compound carbon number is preferably 2 ~ 20.Oxygen-containing part can be carboxyl, carbonyl, hydroxylic moiety or combinations thereof.These materials can be one or more in acids, alcohols, ethers, saccharide, ketone, phenols, aldehydes and lipid.As follows: one or more in acetic acid, oxalic acid, malonic acid, tartaric acid, malic acid, citric acid, ethylene glycol, propylene glycol, butanediol, glycerol, diethylene glycol, dipropylene glycol, 2,2'-ethylenedioxybis(ethanol)., three butanediols, tetraethylene glycol (TEG), Polyethylene Glycol, glucose, fructose, lactose, maltose, sucrose etc..
In described catalyst for hydro-upgrading, described Organic substance be carbon number be 2～15 organic acid and its esters in one or more；One or more in described organic acid includes acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid, TGA, mercaptopropionic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ring ethylenediaminetetraacetic acid etc., one or more in the ammonium salt of above-mentioned organic carboxyl acid of organic carboxylate.
The preparation method of the catalyst for hydro-upgrading of the present invention, including:
(1) with the solution impregnating carrier containing adsorbent I, after drying, obtaining the carrier containing adsorbent I, wherein the content of adsorbent I is the 0.1% ~ 10.0% of vehicle weight；Described adsorbent I is the Polyethylene Glycol that molecular weight is 400～8000, and described dipping uses saturated dipping or excess dipping；
(2) with dipping solution impregnation steps (1) gains containing Mo, Ni, through being dried and roasting, catalyst intermediate is obtained,
(3) with the fountain solution impregnated catalyst intermediate containing adsorbent II, obtain the catalyst intermediate containing adsorbent II, wherein the content of adsorbent II accounts for the 0.1% ~ 10.0% of vehicle weight, described adsorbent II is one or more in organic carboxyl acid and its esters, and described dipping uses unsaturation dipping；
(4) on step (3) gains, Mo and Co is loaded, preferably at least employing following one method:
A, with dipping solution impregnation steps (3) gains containing Mo, Co, through being dried, obtain catalyst for hydro-upgrading；
B, with containing Mo, Co and organic dipping solution impregnation steps (3) gains, through being dried, obtain catalyst for hydro-upgrading；
C, with dipping solution impregnation steps (3) gains containing Mo, Co, through being dried or being dried and roasting, then impregnate with Organic substance, drying obtains catalyst for hydro-upgrading.
In the inventive method, carrier can use conventional method to prepare, and molecular sieve can introduce in aluminium oxide kneading process, it is also possible to introduces in aluminium oxide preparation process.
In the inventive method, adsorbent I be number-average molecular weight be the polyhydric alcohol of 400～10000, preferably number-average molecular weight be the polyhydric alcohol of 1000～8000, described polyhydric alcohol can be PTMEG, preferably Polyethylene Glycol.
Described adsorbent II is one or more in organic carboxyl acid and its esters, and its carbon number is not more than 15, generally 2～15.Described organic acid includes one or more in acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid etc., TGA, mercaptopropionic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ring ethylenediaminetetraacetic acid etc..One or more in the ammonium salt of the preferred above-mentioned organic carboxyl acid of organic carboxylate.
The inventive method, solution containing adsorbent I and containing in the fountain solution of adsorbent II, using water and/or ethanol is solvent.
The inventive method, step (1), with containing adsorbent I solution impregnating carrier, uses incipient impregnation or excess dipping.Dipping terminate after, sample can through health preserving or without health preserving, if through the general conditioned time of health preserving be 1～12h.After health preserving terminates, drying step.Described drying condition is as follows: temperature is 60 DEG C～250 DEG C, preferably 100～200 DEG C, drying time 0.5h～20h, preferably 1h～6h.
The inventive method, step (2) is with after dipping solution impregnation steps (1) gains containing Mo, Ni, can be through health preserving, also can be without health preserving, as needed health preserving, conditioned time is 0.5～6.0h, being dried and roasting, drying condition is as follows again: baking temperature is 70 DEG C～300 DEG C, preferably 100 DEG C～160 DEG C, drying time is 0.5h～20h, being preferably 1h～6h, roasting condition is as follows: sintering temperature is 300 DEG C～750 DEG C, preferably 400 DEG C～650 DEG C, roasting time is 0.5h～20h, preferably 1h～6h.
The inventive method, with the fountain solution impregnated catalyst intermediate containing adsorbent II in step (3), dipping therein sprays preferably with unsaturation, and the time of spraying is generally 1min～40min, preferably 2min～20min.The ratio of volume imbibition saturated with the catalyst intermediate volume of the fountain solution containing adsorbent II used is 0.02 ~ 0.4.When spraying the fountain solution containing adsorbent II, the shower nozzle that atomizing effect is good should be selected, make solution evenly spread on alumina support.After fountain solution impregnated catalyst intermediate containing adsorbent II, can be through drying steps, it is also possible to be directly entered step (4) without drying steps.Drying condition is as follows: temperature is generally 60 DEG C～250 DEG C, preferably 100～200 DEG C, time 0.5h～20h, preferably 1h～6h.
The inventive method, the step (4) the dipping solution impregnated catalyst intermediate containing Mo, Co, can be through health preserving, it is possible to without health preserving, as needed health preserving, conditioned time is 0.5～4.0h, then is dried.Method A, method B or the drying condition described in method C are as follows: baking temperature is 70 DEG C～300 DEG C, preferably 100 DEG C～160 DEG C, drying time 0.5h～20h, preferably 1h～6h.Roasting condition described in method C is as follows: burning temperature is 300 DEG C～750 DEG C, and preferably 400 DEG C～650 DEG C, roasting time is 0.5h～20h, preferably 1h～6h.
Those skilled in the art are according to organic character used, it is possible to select suitable drying condition, so that containing Organic substance in final catalyst for hydro-upgrading.
In catalyst for hydro-upgrading preparation method of the present invention, active metal component is to support on carrier by infusion process, generally uses incipient impregnation, sprays preferably with saturated, and the time of spraying is generally 5min～40min, preferably 10min～20min.Dipping method is known to technical staff.After active metal component solution impregnating carrier, need through being dried.Active metal solution manufacturing method is known to technical staff, and its solution concentration can be regulated 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, as molybdenum source is generally from one or more in molybdenum oxide, ammonium molybdate, ammonium paramolybdate, nickel source is from one or more in nickel nitrate, nickelous carbonate, basic nickel carbonate, Nickel dichloride., nickel oxalate, and cobalt source is from one or more in cobalt nitrate, cobalt carbonate, basic cobaltous carbonate, cobaltous chloride, cobalt oxalate.In described dipping solution, in addition to active metal component, it is also possible to containing phosphorus-containing compound, as one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate etc..The catalyst for hydro-upgrading of the present invention preferably comprises phosphorus, with P2O5Meter mass content in the catalyst is 1% ~ 6%.
In the inventive method, active metal component Mo is introduced by step (2) and step (4) two step, wherein the mol ratio 0.4～2.5 of Mo added by step (2) and step (4).
In the inventive method, one or more in adjuvant component fluorine, silicon, phosphorus, titanium, zirconium and boron, use conventional method to introduce in catalyst, such as can introduce when prepared by carrier in catalyst, it is also possible to after prepared by carrier, introduce catalyst.Introduce in catalyst after prepared by carrier, the method for individually dipping can be used to introduce in catalyst, it is also possible to together impregnate in introducing catalyst with active metal component.
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%, preferably 0.3wt% ~ 2.5wt%, and the sulfur content that wherein difficult de-sulfur-containing compound (with 4,6-dimethyl Dibenzothiophene is meter) is contributed is about more than 0.01wt%, and usually 0.01
wt%~0.05wt%。
The present invention, in described application or described hydrogenation modification method, can only use the catalyst for hydro-upgrading of the present invention, can also by the 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 arbitrarily needed with the use of, such as use different catalysts bed grating or be used in mixed way.
According to the present invention, the operating condition of described hydro-upgrading is not had any special restriction, operating condition commonly used in the art can be used, such as reaction temperature 260 ~ 400 DEG C, reacts stagnation pressure 3 ~ 13MPa by preferably 310 ~ 370 DEG C, 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, preferably 400:1 ~ 1000:1.
In catalyst for hydro-upgrading of the present invention, active metal component Co is incremental trend from catalyst granules outer surface to center, the trend that Ni tapers off from catalyst granules outer surface to center, Co/Mo atomic ratio is incremental trend from catalyst granules outer surface to center, the trend that Ni/Mo atomic ratio tapers off from catalyst granules outer surface to center, the active metal component of this uneven distribution matches with acidic components molecular sieve in carrier, and containing Organic substance, during this catalyst is particularly well-suited to the hydro-upgrading of diesel oil, while diesel deep desulfurization, the combination properties such as diesel-fuel cetane number are improved in the case of keeping diesel yield higher.
nullThe present invention is prepared in the method for catalyst for hydro-upgrading，The fountain solution containing adsorbent I by saturated dipping or excess dipping，Then Mo is impregnated、After Ni active metal solution，Slow down Mo、Ni is to the diffusion velocity at catalyst granules center，By the unsaturation dipping fountain solution containing adsorbent II，The a part of adsorption potential making carrier granular marginal position surface is adsorbed agent and occupies，Dipping Mo Han active metal、During the solution of Co，Decrease Mo、Co is in the absorption of carrier edge position，Making active metal component Co is incremental trend from catalyst granules outer surface to center，The trend that Ni tapers off from catalyst granules outer surface to center，Co/Mo atomic ratio is incremental trend from catalyst granules outer surface to center，The trend that Ni/Mo atomic ratio tapers off from catalyst granules outer surface to center，And the active metal component of this uneven distribution matches with acidic components molecular sieve in carrier，And containing Organic substance，Improve the deep hydrodesulfurizationof performance of catalyst，And suitable open loop、Isomery、The performances such as cracking，During the hydro-upgrading of diesel oil，Can be while diesel deep desulfurization，The combination properties such as diesel-fuel cetane number are improved in the case of keeping diesel yield higher.Additionally, the present invention is by controlling the preparation condition of catalyst for hydro-upgrading, Organic substance is made to be present in final catalyst for hydro-upgrading, after active metal sulfuration, it is possible to form more lamination number, make the hydrogenation activity of catalyst be 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 granule cutting mode；
Fig. 3 is catalyst granules by each position point selected by gained cross section after cutting and this cross section, wherein 0 any point represented on this cross section in outer most edge i.e. outer most edge point, 1/4 represents 1/4 location point, and 1/2 represents 1/2 location point, 3/4 represents 3/4 location point, and 1 represents central point.
Fig. 4 be embodiment 2 gained catalyst C6 granule in active metal component Ni and Co concentration profile on this cross section.Wherein abscissa is each position point on this cross section, and vertical coordinate is the concentration at a certain location point and the ratio of the concentration of central spot on 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.
Analysis method of the present invention is as follows:
(1) content (wt%) of active metal component and adjuvant component uses X-ray fluorescence spectroscopy to measure.
(2) specific surface area (m2/ g) and pore volume (ml/g) use BET method measure.
(3) each active metal component concentration distribution in catalyst granules
In below example and comparative example, employing the carrier (but present invention is obviously not limited to this, it is possible to use other grain shape) of cylinder, the catalyst granules thus obtained is also round cylindricality.A catalyst granules is randomly selected as measuring samples from the catalyst that each embodiment and comparative example are obtained.In order to measure the concentration distribution in this catalyst granules of each active metal component, it is perpendicular to the length dimension direction of this cylindrical particle, is cut by the central point of this length dimension, it is thus achieved that two exposed surfaces.Take 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) is carried out.Measuring condition is: accelerating potential 15kV, beam intensity 5 × 10-8A, beam spot diameter, 1 m, X-ray detection angle: Mo is 38 °, and Ni is 24 °, and Co is 26 °, correction method: ZAF correction method, the standard specimen of use: pure metal oxides standard specimen (respectively NiO, CoO, MoO3And WO3), precision: less than 1%, secondary electron image resolution: 3nm(LaB6), linear system: Ni and Co uses KαLinear system, Mo uses LαLinear system.
Measuring method is: arbitrarily choose a location point in the outer most edge of this cross section as 0, using the central point on this cross section as 1, connect straight-line segment (the substantially radius of this cross section of described location point 0 and described location point 1, therefore the most radially), measure the concentration value of targeted activity metal at the point of assigned position, then by calculating, it is thus achieved that the ratio (being mol ratio in the present invention) of each concentration value.
Fig. 4 be embodiment 2 gained catalyst C6 in the concentration profile of active metal, it is by uniformly choosing 21 location points (including location point 0 and location point 1) on this straight-line segment, with these location points as abscissa, the ratio of the concentration value of the corresponding active metal that the concentration value of the targeted activity metal (as a example by Ni and Co) measured at each position point is measured to (i.e. central point) at location point 1 (uses Ni respectivelym/Ni1And Com/Co1Represent) it is vertical coordinate, so draw and obtain.
(4) total sulfur content in raw material and hydrogenation products is to use ultraviolet fluorescence method to measure (ASTM
D5453-1993), 4,6-BMDBT content are to use GC-AED(gas chromatogram-atom luminescence spectroscopy) measure.
(5) number-average molecular weight Mn uses 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
In the present embodiment, the Mo predecessor in Mo, Ni, P and Mo, Co, P impregnation liquid used is MoO3, Ni predecessor is basic nickel carbonate, and Co predecessor is basic cobaltous carbonate, and P predecessor is phosphoric acid.
Embodiment 1
Weigh 18g Macrogol 2000 (i.e. molecular weight is the Polyethylene Glycol of 2000, lower same), stirring and dissolving in the water measured, prepare fountain solution I.Impregnating the S1 carrier of 300g with this fountain solution I, then carry out the health preserving of 10h, after 120 DEG C of dry 3h, the sample prepared is designated as B1.
Spray above-mentioned B1 sample with impregnation liquid (the first impregnation liquid) equal-volume containing Mo, Ni, P, directly carry out 120 DEG C of dry 3h after spraying end without health preserving, after 480 DEG C of roasting 2h, it is thus achieved that sample be designated as Z1.
Weigh tartaric acid 15g, stirring and dissolving in 45g water, prepare fountain solution.Uniformly being 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 impregnation liquid (the second impregnation liquid) the above-mentioned carrier of incipient impregnation containing Mo, Co, P, the sample average of gained is divided into three parts, wherein first part of sample not health preserving, through 120 DEG C of dry 3h, it is thus achieved that sample be designated as C1；Second sample health preserving 1h, through 120 DEG C of dry 3h, prepared sample is designated as C2；Triplicate sample health preserving 3h, through 120 DEG C of dry 3h, prepared sample is designated as C3.
Embodiment 2
Weigh 24g cetomacrogol 1000, stirring and dissolving in the water measured, prepare fountain solution I.With the S2 carrier of this fountain solution I incipient impregnation 300g, then carrying out the health preserving of 5h, after 120 DEG C of dry 3h, the sample prepared is designated as B2.
Spray B2 sample with impregnation liquid (the first impregnation liquid) equal-volume containing Mo, Ni, P, after spraying end, gained sample average be divided into three parts, wherein first part of direct 120 DEG C of dry 3h of sample, after 480 DEG C of roasting 2h, it is thus achieved that sample be designated as Z2；Second sample health preserving 1h, 120 DEG C of dry 3h, after 480 DEG C of roasting 2h, the sample prepared is designated as Z3；Triplicate sample health preserving 3h, 120 DEG C of dry 3h, after 480 DEG C of roasting 2h, the sample prepared is designated as Z4.
Weigh malic acid 1.0g, stirring and dissolving in 6g ethanol, prepare fountain solution II.Uniformly being sprayed on Z2 by fountain solution II, the time of spraying is 5min.With impregnation liquid (the second impregnation liquid) the above-mentioned sample of incipient impregnation containing Mo, Co, P, dipping terminates rear health preserving 1h, through 120 DEG C of dry 3h, it is thus achieved that catalyst be designated as C4.Being respectively adopted process step process Z3 identical for above-mentioned Z2 and Z4 sample, the catalyst obtained is designated as C5 and C6 respectively.
Embodiment 3
Weigh 4g PEG 8000, stirring and dissolving in the aqueous solution measured, prepare fountain solution I.With the S3 carrier of this fountain solution I incipient impregnation 200g, then carrying out the health preserving of 5h, after 120 DEG C of dry 3h, the sample prepared is designated as B3.
Spray B3 sample, directly through 120 DEG C of dry 3h with impregnation liquid (the first impregnation liquid) equal-volume containing Mo, Ni, P, it is thus achieved that sample be designated as Z5.
Weigh citric acid and each 7g of malonic acid, stirring and dissolving in 40g water, prepare fountain solution II.Uniformly being sprayed on Z5 by fountain solution II, the time of spraying is 25min.With containing Mo, Co, P impregnation liquid (the second impregnation liquid) the above-mentioned sample of incipient impregnation, dipping terminates rear health preserving 1h, through 120 DEG C of dry 3h, it is thus achieved that catalyst be designated as C7.
Preparing glycerinated aqueous solution, equal-volume sprays part C7 sample, and on the glycerol of introducing and catalyst, the mol ratio of Mo is 0.03:1, after spraying end, through 120 DEG C of dry 3h, it is thus achieved that catalyst be designated as C8.
Comparative example 1
Take S1 carrier 100g, after impregnation liquid (the first impregnation liquid) the above-mentioned carrier of incipient impregnation containing Mo, Ni, P, after 120 DEG C of dry 3h, 480 DEG C of roasting 2h, it is thus achieved that sample be designated as B8.With impregnation liquid (the second impregnation liquid) the incipient impregnation B8 containing Mo, Co, P, after 120 DEG C of dry 3h, 480 DEG C of roasting 2h, it is thus achieved that catalyst be designated as C9.
Comparative example 2
Take S4 carrier 100g, use the preparation method identical with C4 catalyst to prepare, it is thus achieved that sample be designated as C10.
Table 2 embodiment forms with comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 | C10 |
| Composition | ||||||||||
| Mo(is with MoO3Meter), wt% | 20.5 | 20.3 | 20.4 | 20.3 | 20.3 | 20.4 | 20.3 | 20.2 | 20.4 | 20.4 |
| Co(is in terms of CoO), wt% | 2.2 | 2.1 | 2.0 | 2.1 | 2.1 | 2.2 | 2.1 | 2.2 | 2.1 | 2.0 |
| Ni(is in terms of NiO), wt% | 2.2 | 2.2 | 2.3 | 2.3 | 2.2 | 2.3 | 2.3 | 2.3 | 2.3 | 2.2 |
| P(is with P2O5Meter), wt% | 2.3 | 2.2 | 2.3 | 2.3 | 2.2 | 2.2 | 2.2 | 2.2 | 2.2 | 2.3 |
| Carrier | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| The mol ratio of Mo added by first impregnation liquid/the second impregnation liquid | 1.0 | 1.0 | 1.0 | 0.8 | 0.8 | 0.8 | 1.2 | 1.2 | 1.0 | 1.0 |
| Character | ||||||||||
| Specific surface area, m2/g | 174 | 172 | 173 | 175 | 176 | 171 | 174 | 172 | 173 | 171 |
| Pore volume, mL/g | 0.36 | 0.35 | 0.36 | 0.35 | 0.36 | 0.36 | 0.35 | 0.36 | 0.36 | 0.35 |
In table 2, the carrier * i.e. aluminium oxide of C1, C2, C3 and C9 and beta-molecular sieve, aluminium oxide and Y molecular sieve in C4, C5 and C6, aluminium oxide and β and Y molecular sieve, the aluminium oxide in C10 in C7 and C8.
The concentration distribution in catalyst granules of table 3 embodiment and Elements C o in comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 | C10 |
| Co0/Co1 | 0.15 | 0.28 | 0.51 | 0.34 | 0.33 | 0.34 | 0.33 | 0.38 | 0.98 | 0.33 |
| Co1/4/Co1 | 0.31 | 0.48 | 0.62 | 0.78 | 0.80 | 0.78 | 0.45 | 0.50 | 0.99 | 0.80 |
| Co1/2/Co1 | 0.62 | 0.80 | 0.92 | 0.95 | 0.96 | 0.95 | 0.82 | 0.84 | 1.00 | 0.96 |
| Co3/4/Co1 | 0.90 | 0.94 | 0.98 | 0.99 | 0.99 | 1.00 | 0.96 | 0.96 | 0.99 | 0.99 |
Table 4 embodiment and element Ni in the comparative example catalyst concentration distribution in catalyst granules
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 | C10 |
| Ni0/Ni1 | 2.83 | 2.84 | 2.83 | 2.97 | 2.57 | 2.09 | 2.58 | 2.54 | 0.98 | 2.95 |
| Ni/4/Ni1 | 1.89 | 1.88 | 1.89 | 1.96 | 1.71 | 1.54 | 1.76 | 1.72 | 1.00 | 1.95 |
| Ni1/2/Ni1 | 1.27 | 1.26 | 1.26 | 1.32 | 1.26 | 1.16 | 1.20 | 1.19 | 1.00 | 1.31 |
| Ni3/4/Ni1 | 1.09 | 1.08 | 1.10 | 1.12 | 1.09 | 1.07 | 1.07 | 1.07 | 0.99 | 1.12 |
Ni/Mo(mol ratio in table 5 embodiment and comparative example catalyst) concentration distribution in catalyst particles particle diameter
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 | C10 |
| Ni0/Mo0 | 0.43 | 0.41 | 0.42 | 0.43 | 0.40 | 0.38 | 0.40 | 0.38 | 0.21 | 0.43 |
| Ni1/4/Mo1/4 | 0.27 | 0.28 | 0.27 | 0.29 | 0.29 | 0.28 | 0.28 | 0.28 | 0.20 | 0.29 |
| Ni1/2/Mo1/2 | 0.22 | 0.21 | 0.22 | 0.22 | 0.21 | 0.21 | 0.22 | 0.21 | 0.20 | 0.22 |
| Ni3/4/Mo3/4 | 0.18 | 0.17 | 0.17 | 0.18 | 0.17 | 0.16 | 0.17 | 0.16 | 0.21 | 0.18 |
| Ni1/Mo1 | 0.16 | 0.15 | 0.15 | 0.16 | 0.15 | 0.15 | 0.15 | 0.15 | 0.22 | 0.16 |
Co/Mo(mol ratio in table 6 embodiment and comparative example catalyst) concentration distribution in catalyst granules
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 | C10 |
| Co0/Mo0 | 0.06 | 0.08 | 0.12 | 0.07 | 0.08 | 0.07 | 0.07 | 0.06 | 0.23 | 0.07 |
| Co1/4/Mo1/4 | 0.15 | 0.17 | 0.18 | 0.19 | 0.19 | 0.20 | 0.14 | 0.14 | 0.22 | 0.19 |
| Co1/2/Mo1/2 | 0.30 | 0.28 | 0.26 | 0.32 | 0.31 | 0.31 | 0.26 | 0.27 | 0.22 | 0.32 |
| Co3/4/Mo3/4 | 0.37 | 0.36 | 0.31 | 0.34 | 0.34 | 0.35 | 0.33 | 0.34 | 0.22 | 0.34 |
| Co1/Mo1 | 0.44 | 0.40 | 0.34 | 0.36 | 0.36 | 0.37 | 0.39 | 0.39 | 0.23 | 0.36 |
Embodiment 4
The present embodiment is the henchnmrk test of catalyst.
Catalyst performance evaluation experiment is carried out on 100mL small hydrogenation device, before performance evaluation, catalyst is carried out presulfurization.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 raw oil character is shown in Table 7, Evaluation results is shown in Table 8, from data in table, catalyst for hydro-upgrading is prepared by the present invention, catalyst desulphurizing activated apparently higher than comparative example catalyst, under conditions of keeping diesel yield not less than 97%, diesel-fuel cetane number being improved more than 10 units, product quality has obtained good improvement.
Table
7
Raw oil character
| Raw oil | Catalytic diesel oil |
| Density (20 DEG C), g/cm3 | 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 |
| Sulfur, g/g | 8698 |
| 4,6-BMDBT content, g/g | 103.6 |
| Nitrogen, 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 | C5 |
| Diesel oil | |||||
| Yield, wt% | 98.1 | 98.0 | 98.2 | 97.5 | 97.5 |
| Density (20 DEG C)/g.cm-3 | 0.8396 | 0.8390 | 0.8395 | 0.8379 | 0.8383 |
| T95, DEG C | 349 | 350 | 350 | 348 | 347 |
| Condensation point, DEG C | -21 | -21 | -20 | -22 | -22 |
| Cetane number | 46.8 | 47.5 | 47.0 | 48.3 | 48.0 |
| Sulfur, g/g | 10 | 9 | 10 | 7 | 8 |
Table 8 continues
| Catalyst | C6 | C7 | C8 | C9 | C10 |
| Diesel oil | |||||
| Yield, wt% | 97.6 | 97.8 | 98.2 | 97.7 | 99.5 |
| Density (20 DEG C)/g.cm-3 | 0.8385 | 0.8388 | 0.8367 | 0.8412 | 0.8572 |
| T95, DEG C | 348 | 348 | 348 | 350 | 355 |
| Condensation point, DEG C | -21 | -22 | -23 | -19 | 4 |
| Cetane number | 47.9 | 48.0 | 48.4 | 45.0 | 35.0 |
| Sulfur, g/g | 8 | 7 | 6 | 17 | 12 |
Claims (26)
1. a catalyst for hydro-upgrading, carrier includes aluminium oxide and molecular sieve, and active metal component is Mo, Co and Ni, and wherein active metal component concentration distribution on each catalyst granules cross section is as follows: Co0/Co1＜ Co1/2/Co1＜ 1, Ni0/Ni1＞ Ni1/2/Ni1＞ 1, Ni0/Mo0＞ Ni1/2/Mo1/2＞ Ni1/Mo1, Co0/Mo0＜ Co1/2/Mo1/2＜ Co1/Mo1Containing Organic substance in described catalyst, described Organic substance is one or more in organic nitrogen-containing organic compound, organic compounds containing sulfur and the oxygen-containing organic compound of 2～20 selected from carbon number, and Organic substance and Mo atomic molar ratio is for 0.002:1～2.0:1；
Wherein, active metal component concentration distribution formula A on the cross section of each catalyst granulesm/BnRepresenting, the ratio of the concentration of element B at the concentration of elements A and n m on the cross section of the most each catalyst granules, wherein A represents active metallic element Mo, Co or Ni, and B represents active metallic element Mo, Co or Ni；It is designated as 0 for starting point with any point of catalyst granules cross section outer most edge, it is designated as 1 for terminal with the central point of catalyst granules cross section, connect starting point and terminal obtains straight-line segment, m and n is illustrated respectively on above-mentioned straight-line segment the location point 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 uses active metallic element Mo, Co or Ni replaces, m and n is directly with defined location point on the above-mentioned straight-line segment of digitized representation of 0～1；
Wherein, described catalyst for hydro-upgrading, on the basis of the weight of catalyst, the content of carrier is 55wt%～88wt%, and the content that Ni counts with NiO is as 1wt%～8wt%, and Mo is with MoO3The content of meter is 8wt%～32wt%, and the content that Co counts with CoO is as 1wt%～8wt%；On the basis of the weight of catalyst carrier, the content of molecular sieve is 3%～35%, and the content of aluminium oxide is 65%～97%.
2., according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, Organic substance and Mo atomic molar are than for 0.02:1～1.5:1.
3., according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, Organic substance and Mo atomic molar are than for 0.02:1～1.0:1.
4., according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, active metal component, in catalyst granules, at least includes following a kind of scheme:
(1) Co0/Co1With Co1/2/Co1Ratio be 0.2～0.8；
(2) Ni0/Ni1With Ni1/2/Ni1Ratio 1.5～2.6；
(3) Ni0/Mo0With Ni1/2/Mo1/2Ratio be 1.4～2.3；
(4) Co0/Mo0With Co1/2/Mo1/2Ratio be 0.10～0.70.
5., according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, active metal component, in catalyst granules, at least includes following a kind of scheme:
(1) Co0/Co1With Co1/2/Co1Ratio be 0.2～0.7；
(2) Ni0/Ni1With Ni1/2/Ni1Ratio 1.7～2.5；
(3) Ni0/Mo0With Ni1/2/Mo1/2Ratio be 1.5～2.2；
(4) Co0/Mo0With Co1/2/Mo1/2Ratio be 0.12～0.65.
6., according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, active metal component concentration on catalyst granules cross section is distributed and at least includes following a kind of scheme:
(1) Co0/Co1＜ Co1/4/Co1＜ Co1/2/Co1；
(2) Co1/2/Co1＜ Co3/4/Co1＜ 1；
(3) Ni0/Ni1＞ Ni1/4/Ni1＞ Ni1/2/Ni1；
(4) Ni1/2/Ni1＞ Ni3/4/Ni1＞ 1；
(5) Ni0/Mo0＞ Ni1/4/Mo1/4＞ Ni1/2/Mo1/2；
(6) Ni1/2/Mo1/2＞ Ni3/4/Mo3/4＞ Ni1/Mo1；
(7) Co0/Mo0＜ Co1/4/Mo1/4＜ Co1/2/Mo1/2；
(8) Co1/2/Mo1/2＜ Co3/4/Mo3/4＜ Co1/Mo1。
7., according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, active metal component concentration on catalyst granules cross section is distributed and at least includes following a kind of scheme:
(1) Co0/Co1＜ Cox1/Co1＜ Cox2/Co1＜ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1；
(2) Ni0/Ni1＞ Nix1/Ni1＞ Nix2/Ni1＞ 1, wherein 0 ＜ x1 ＜ x2 ＜ 1；
(3) Ni0/Mo0＞ Nix1/Mox1＞ Nix2/Mox2＞ Ni1/Mo1, wherein 0 ＜ x1 ＜ x2 ＜ 1；
(4) Co0/Mo0＜ Cox1/Mox1＜ Cox2/Mox2＜ Co1/Mo1, wherein 0 ＜ x1 ＜ x2 ＜ 1.
8., according to the catalyst described in claim 6 or 7, it is characterised in that in described catalyst for hydro-upgrading, active metal component, in catalyst granules, at least includes following a kind of scheme:
(1) Co0/Co1With Co1/4/Co1Ratio be 0.3～0.9；
(2) Co1/4/Co1With Co1/2/Co1Ratio be 0.4～0.9；
(3) Ni0/Ni1With Ni1/4/Ni1Ratio be 1.2～1.8；
(4) Ni1/4/Ni1With Ni1/2/Ni1Ratio be 1.1～1.7；
(5) Ni0/Mo0With Ni1/4/Mo1/4Ratio be 1.1～1.8；
(6) Ni1/4/Mo1/4With Ni1/2/Mo1/2Ratio be 1.1～1.8；
(7) Co0/Mo0With Co1/4/Mo1/4Ratio be 0.25～0.85；
(8) Co1/4/Mo1/4With Co1/2/Mo1/2Ratio be 0.25～0.85.
9., according to the catalyst described in claim 6 or 7, it is characterised in that in described catalyst for hydro-upgrading, active metal component, in catalyst granules, at least includes following a kind of scheme:
(1) Co0/Co1With Co1/4/Co1Ratio be 0.3～0.85；
(2) Co1/4/Co1With Co1/2/Co1Ratio be 0.4～0.87；
(3) Ni0/Ni1With Ni1/4/Ni1Ratio be 1.3～1.7；
(4) Ni1/4/Ni1With Ni1/2/Ni1Ratio be 1.2～1.6；
(5) Ni0/Mo0With Ni1/4/Mo1/4Ratio be 1.15～1.7；
(6) Ni1/4/Mo1/4With Ni1/2/Mo1/2Ratio be 1.15～1.7；
(7) Co0/Mo0With Co1/4/Mo1/4Ratio be 0.3～0.8；
(8) Co1/4/Mo1/4With Co1/2/Mo1/2Ratio be 0.3～0.8.
10. according to the catalyst described in 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 to central point, active metal component concentration distribution is as follows: the concentration of Ni substantially gradually decreases, the concentration of Co is substantially gradually increased, and the concentration mol ratio of Ni/Mo substantially gradually decreases, and the concentration mol ratio of Co/Mo is substantially gradually increased.
11. according to the catalyst described in claim 1, it is characterised in that in described catalyst for hydro-upgrading, at least includes following a kind of scheme:
(1) being positioned at the concentration of Ni at catalyst granules cross section outer most edge point is 1.2～7.0 with the ratio of the concentration of the Ni of central spot,
(2) being positioned at the concentration of Co at catalyst granules cross section outer most edge point is 0.1～0.8 with the ratio of the concentration of central spot Co,
(3) being positioned at the concentration of Ni at catalyst granules cross section outer most edge point is 0.22～0.80 with the ratio of the concentration of Mo,
(4) ratio being positioned at the concentration of the Co at catalyst granules cross-section center point and the concentration of Mo is 0.20～0.78.
12. according to the catalyst described in claim 1, it is characterised in that described molecular sieve is Y type molecular sieve and/or beta-molecular sieve.
13. according to the catalyst described in claim 1, it is characterised in that described molecular sieve is beta-molecular sieve；Wherein beta-molecular sieve character is as follows: specific surface area 450m2/ g～750m2/ g, total pore volume 0.30ml/g～0.45ml/g, SiO2/Al2O3Mol ratio 40～100, meleic acid amount 0.1～0.5mmol/g, the mol ratio of framework aluminum non-framework aluminum is 5～20, and B-acid/L acid is 0.30～0.50, Na2O≤0.15wt%。
14. according to the catalyst described in claim 1, it is characterised in that the character of described catalyst for hydro-upgrading is as follows: specific surface area is 120～220 m2/ g, pore volume is 0.20～0.60mL/g.
15. according to the catalyst described in claim 1, it is characterized in that in described catalyst for hydro-upgrading, containing adjuvant component, one or more during wherein adjuvant component is fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component in terms of element weight content in the catalyst at below 15wt%.
16. according to the catalyst described in claim 1, it is characterised in that containing phosphorus in described catalyst for hydro-upgrading, with P2O5Meter weight content in the catalyst is 1%～6%.
The preparation method of the arbitrary described catalyst of 17. claim 1～14, including:
(1) with the solution impregnating carrier containing adsorbent I, after drying, obtaining the carrier containing adsorbent I, wherein the consumption of adsorbent I is the 0.1%～10.0% of vehicle weight；Described adsorbent I is the Polyethylene Glycol that molecular weight is 400～10000, and described dipping uses saturated dipping or excess dipping；
(2) with dipping solution impregnation steps (1) gains containing Mo, Ni, through being dried and roasting, catalyst intermediate is obtained,
(3) with the fountain solution impregnated catalyst intermediate containing adsorbent II, obtain the catalyst intermediate containing adsorbent II, wherein the consumption of adsorbent II accounts for the 0.1%～10.0% of vehicle weight, described adsorbent II is one or more in organic carboxyl acid and its esters, and described dipping uses unsaturation dipping；
(4) on step (3) gains, Mo and Co is loaded.
18. in accordance with the method for claim 17, it is characterised in that step (4) at least uses following a kind of method:
A, with dipping solution impregnation steps (3) gains containing Mo, Co, through being dried, obtain catalyst for hydro-upgrading；
B, with containing Mo, Co and organic dipping solution impregnation steps (3) gains, through being dried, obtain catalyst for hydro-upgrading；
C, with dipping solution impregnation steps (3) gains containing Mo, Co, through being dried or being dried and roasting, then impregnate with Organic substance, drying obtains catalyst for hydro-upgrading.
19. in accordance with the method for claim 17, it is characterised in that described adsorbent II is one or more in organic carboxyl acid and its esters, and its carbon number is 2～15.
20. in accordance with the method for claim 17, it is characterized in that described organic acid includes one or more in acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid, TGA, mercaptopropionic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ring ethylenediaminetetraacetic acid, one or more in the ammonium salt of above-mentioned organic carboxyl acid of organic carboxylate.
21. in accordance with the method for claim 17, it is characterised in that: solution containing adsorbent I and containing in the fountain solution of adsorbent II, using water and/or ethanol is solvent.
22. in accordance with the method for claim 17, it is characterised in that: described method at least uses one of a～e:
A, step (1) are with containing adsorbent I solution impregnating carrier, and after dipping terminates, sample is through health preserving or without health preserving, drying step, if through health preserving, 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；
B, step (2), with after dipping solution impregnation steps (1) gains containing Mo, Ni, through health preserving or without health preserving, then are dried and roasting, and as needed health preserving, 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；
With the fountain solution impregnated catalyst intermediate containing adsorbent II in c, step (3), dipping therein uses unsaturation to spray, and the time of spraying is 1min～40min；The ratio of volume imbibition saturated with the catalyst intermediate volume of the fountain solution containing adsorbent II used is 0.02～0.4；
After d, step (3) are containing the fountain solution impregnated catalyst intermediate of adsorbent II, it is directly entered 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, active metal component Mo are introduced by step (2) and step (4) two step, wherein the mol ratio 0.4～2.5 of Mo added by step (2) and step (4).
23. in accordance with the method for claim 18, it is characterized in that: the step (4) dipping solution containing Mo, Co or containing Mo, Co and organic dipping solution impregnated catalyst intermediate, through health preserving or without health preserving, then be dried, as needed health preserving, conditioned time is 0.5～4.0h；Method A, method B or the drying condition described in method C are as follows: baking temperature is 70 DEG C～300 DEG C, drying time 0.5h～20h；Roasting condition described in method C 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 the dipping solution described in step (2) and/or step (4), in addition to active metal component, possibly together with phosphorus, one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate of phosphorus source；The addition of phosphorus is with P2O5It is 1%～6% that meter makes its mass content in catalyst for hydro-upgrading.
The method of 25. 1 kinds of heavy distillate hydro-upgradings, it is characterised in that use the arbitrary described catalyst for hydro-upgrading of claim 1～16.
26. in accordance with the method for claim 25, it is characterised in that: described heavy distillate is diesel oil.
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| 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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| 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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