CN104667982A - A catalyst for hydrogenation modification and a preparing method thereof - Google Patents
A catalyst for hydrogenation modification and a preparing method thereof Download PDFInfo
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- CN104667982A CN104667982A CN201310604965.7A CN201310604965A CN104667982A CN 104667982 A CN104667982 A CN 104667982A CN 201310604965 A CN201310604965 A CN 201310604965A CN 104667982 A CN104667982 A CN 104667982A
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Abstract
A catalyst for hydrogenation modification and a preparing method thereof are disclosed. In the catalyst, a carrier comprises aluminum oxide and a molecular sieve, active metal components are Mo, Co and Ni, distribution situations of concentrations of the active metal components in the cross section of each catalyst particle are that Co0/Co1<Co<1/2>/Co1<1, Ni0/Ni1>Ni<1/2>/Ni1>1, Ni0/Mo0>Ni<1/2>/Mo<1/2>>Ni1/Mo1 and Co0/Mo0<Co<1/2>/Mo<1/2><Co1/Mo1, and the catalyst comprises an organic compound. The preparing method includes dipping with a solution containing an absorbent I by saturated dipping or excessive dipping, dipping with a solution containing the active metal Mo and the active metal Ni, drying, calcinating, dipping with an absorbent II comprising one or more of organic carboxylic acids and salts thereof by unsaturated dipping, and loading the active metal Mo and the active metal Co by dipping or loading the Mo, the Co and the organic compound by dipping. The catalyst is used in a diesel oil hydrogenation modification process, has deep hydrodesulfurization activity, and can improve comprehensive properties such as the cetane number under the circumstance that a high diesel oil yield is maintained.
Description
Technical field
The present invention relates to a kind of catalyst for hydro-upgrading and preparation method thereof, particularly a kind of catalyst for hydro-upgrading being suitable for diesel modifying and preparation method thereof.
Background technology
Produce for clean diesel, prior art mainly comprises the technology such as hydrofinishing and MHUG.Hydrofinishing can reduce the sulfur content of upgrading diesel oil, but limited to improving Cetane number and reducing T95 temperature capability.MHUG adopts the catalyst for hydro-upgrading containing molecular sieve (Y zeolite or beta-molecular sieve), by suitably cracking such as the aromatic hydrocarbons in diesel oil, in reduction diesel oil while sulphur nitrogen impurity content, improves the combination properties such as diesel cetane-number.But adopt current catalyst for hydro-upgrading, to improve the combination property (sulphur nitrogen impurity content, Cetane number, T95 temperature, arene content etc.) of diesel oil, the cracking degree that usual needs are higher, diesel yield can be made so lower, and the yield of diesel oil will be kept, the combination property of diesel oil is again less than good improvement.
Sulfur-containing compound in diesel oil distillate and aromatic hydrocarbons, usually exist with the structure of complexity, such as dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene etc., wherein more difficult what remove is the thiophenes such as dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene to hydrogenation, especially with 4,6-dimethyl Dibenzothiophene (4,6-BMDBT) and 2,4,6-trimethyl dibenzothiophenes (2,4,6-BMDBT) class formation is complicated and the sulfur-containing compound of steric effect of having living space is the most difficult removes.Reach the degree of depth and ultra-deep desulfurization, just need to remove these complex structures and sterically hindered large sulfur-containing compound, and these sulfur-containing compounds are usually more difficult under the hydrofinishing operating condition that HTHP etc. is harsh removes, then diesel yield can be reduced by hydrocracking.Therefore, when keeping diesel yield higher, how to remove the impurity in diesel oil, can improve again the combination property of diesel oil simultaneously, this is the current important topic needing research.
Catalyst for hydro-upgrading normally adopts the alumina support containing molecular sieve, and with group vib and group VIII metal for hydrogenation active metals component, wherein active metal component is generally equally distributed in the catalyst.CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, this catalyst consist of aluminium oxide 40 ~ 80wt%, amorphous aluminum silicide 0 ~ 20wt%, Y zeolite 5 ~ 30wt%.CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof, mainly adopt the predecessor of silica-alumina, aluminium oxide and/or aluminium oxide and Y zeolite mixing, shaping and roasting, introduce the hydrogenation metal of effective dose afterwards at shaping species.Above-mentioned catalyst has higher desulfurization and denitrification activity, but the shortcoming such as the amplitude that the yield of diesel product is low, the Cetane number of diesel oil improves is little, condensation point is high and density is large.
CN201110350790.2 discloses a kind of diesel oil hydrogenation modification Catalysts and its preparation method.This catalyst comprises the carrier and hydrogenation active metals component that are made up of modified beta molecular sieve and aluminium oxide, and wherein active metal component is equally distributed in the catalyst.When adopting this catalyst for diesel oil hydrogenation modification, although can reduce the condensation point of diesel oil distillate, improve the Cetane number of upgrading diesel oil, diesel yield is below 97%, still lower.
Summary of the invention
For problems of the prior art, the invention provides a kind of catalyst for hydro-upgrading and preparation method thereof.This catalyst is used for, in diesel oil hydrogenation modification process, having deep hydrodesulfurizationof activity, and can improve the combination properties such as Cetane number when keeping diesel yield higher.
Catalyst for hydro-upgrading of the present invention, carrier comprises aluminium oxide and molecular sieve, and active metal component is Mo, Co and Ni, and wherein the CONCENTRATION DISTRIBUTION of active metal component on the cross section of each catalyst granules is as follows: Co
0/ Co
1< Co
1/2/ Co
1< 1, Ni
0/ Ni
1> Ni
1/2/ Ni
1> 1, Ni
0/ Mo
0> Ni
1/2/ Mo
1/2> Ni
1/ Mo
1, Co
0/ Mo
0< Co
1/2/ Mo
1/2< Co
1/ Mo
1containing organic matter in described catalyst, described organic matter is selected from organic nitrogen-containing organic compound, one or more in organic compounds containing sulfur and oxygen-containing organic compound that carbon number is 2 ~ 20, organic matter and Mo atomic molar are than being 0.002:1 ~ 2.0:1, be preferably 0.02:1 ~ 1.5:1, more preferably 0.02:1 ~ 1.0:1.
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 or Ni, B represents active metallic element Mo, Co or Ni, wherein A with B can be identical, also can be different, with any point of catalyst granules cross section outer most edge and outer most edge point for starting point is designated as 0, with the central point of catalyst granules cross section for terminal is designated as 1, connection starting point and terminal obtain straight-line segment, m and n is illustrated respectively in the location point that above-mentioned straight-line segment is chosen, the value of m and n represents the ratio of the length accounting for above-mentioned straight-line segment from starting point to the distance of the location point chosen, the value of m and n is 0 ~ 1, wherein m(or n) value be 0, 1/4, 1/2, 3/4, 0 of the length accounting for above-mentioned straight-line segment from starting point to the distance of the location point chosen is represented respectively when 1, 1/4, 1/2, 3/4, the position (see figure 3) at selected point place when 1, above-mentioned location point is selected (or appearance millet cake) also referred to as outer most edge, 1/4 location point, 1/2 location point, 3/4 location point, central point.In the present invention, in the present invention, in order to express easily, A and B directly adopts active metallic element Mo, Co or Ni to replace, m and n is directly with the location point that the above-mentioned straight-line segment of digitized representation of 0 ~ 1 is determined, represents arbitrary location point on above-mentioned straight-line segment with x1 or x2, such as, Co
0/ Co
1represent that A and B is Co, namely m=0, n=1 represent the ratio of the concentration of catalyst granules cross section outer most edge point place Elements C o and the concentration of central spot Elements C o, Ni
1/2/ Ni
1represent that A and B is Ni, m=1/2, namely n=1 represents on the described straight-line segment on catalyst granules cross section, the ratio of the concentration of selected point position element Ni and the concentration of central spot element Ni when making the distance from outer most edge point to selected point account for 1/2 of above-mentioned straight-line segment length, Ni
0/ Mo
0expression A is Ni, B is Mo, m=0, n=0, namely represents the ratio of the concentration of catalyst granules cross section outer most edge point place element Ni and the concentration of this elements Mo.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), Ni
0/ Mo
0(A is Ni, B is Mo, m=0, n=0), Ni
1/4/ Mo
1/4(A is Ni, B is Mo, m=1/4, n=1/4), Ni
1/2/ Mo
1/2(A is Ni, B is Mo, m=1/2, n=1/2), Ni
3/4/ Mo
3/4(A is Ni, B is Mo, m=3/4, n=3/4), Ni
1/ Mo
1(A is Ni, B is Mo, m=1, n=1), Ni
x1/ Mo
x1(A is Ni, B is Mo, m=x1, n=x1), Ni
x2/ Mo
x2(A is Ni, B is Mo, m=x2, n=x2), Co
0/ Mo
0(A is Co, B is Mo, m=0, n=0), Co
1/4/ Mo
1/4(A is Co, B is Mo, m=1/4, n=1/4), Co
1/2/ Mo
1/2(A is Co, B is Mo, m=1/2, n=1/2), Co
3/4/ Mo
3/4(A is Co, B is Mo, m=3/4, n=3/4), Co
1/ Mo
1(A is Co, B is Mo, m=1, n=1), Co
x1/ Mo
x1(A is Co, B is Mo, m=x1, n=x1), Co
x2/ Mo
x2(A is Co, B is 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: Co
0/ Co
1with Co
1/2/ Co
1ratio be 0.2 ~ 0.8, be preferably 0.2 ~ 0.7; Ni
0/ Ni
1with Ni
1/2/ Ni
1ratio 1.5 ~ 2.6, be preferably 1.7 ~ 2.5.
In catalyst for hydro-upgrading of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Ni
0/ Mo
0with Ni
1/2/ Mo
1/2ratio be 1.4 ~ 2.3, be preferably 1.5 ~ 2.2; Co
0/ Mo
0with Co
1/2/ Mo
1/2ratio be 0.10 ~ 0.70, be preferably 0.12 ~ 0.65.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Co
0/ Co
1< Co
1/4/ Co
1< Co
1/2/ Co
1.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Co
1/2/ Co
1< Co
3/4/ Co
1< 1.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Ni
0/ Ni
1> Ni
1/4/ Ni
1> Ni
1/2/ Ni
1.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Ni
1/2/ Ni
1> Ni
3/4/ Ni
1> 1.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Ni
0/ Mo
0> Ni
1/4/ Mo
1/4> Ni
1/2/ Mo
1/2.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Ni
1/2/ Mo
1/2> Ni
3/4/ Mo
3/4> Ni
1/ Mo
1.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Co
0/ Mo
0< Co
1/4/ Mo
1/4< Co
1/2/ Mo
1/2.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Co
1/2/ Mo
1/2< Co
3/4/ Mo
3/4< Co
1/ Mo
1.
In catalyst for hydro-upgrading of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Co
0/ Co
1with Co
1/4/ Co
1ratio be 0.30 ~ 0.90, be preferably 0.30 ~ 0.85; Co
1/4/ Co
1with Co
1/2/ Co
1ratio be 0.4 ~ 0.9, be preferably 0.4 ~ 0.87; Ni
0/ Ni
1with Ni
1/4/ Ni
1ratio be 1.2 ~ 1.8, be preferably 1.3 ~ 1.7; Ni
1/4/ Ni
1with Ni
1/2/ Ni
1ratio be 1.1 ~ 1.7, be preferably 1.2 ~ 1.6.
In catalyst for hydro-upgrading of the present invention, active metal component is in catalyst granules, and preferred version is as follows: Ni
0/ Mo
0with Ni
1/4/ Mo
1/4ratio be 1.1 ~ 1.8, be preferably 1.15 ~ 1.7; Ni
1/4/ Mo
1/4with Ni
1/2/ Mo
1/2ratio be 1.1 ~ 1.8, be preferably 1.15 ~ 1.7; Co
0/ Mo
0with Co
1/4/ Mo
1/4ratio be 0.25 ~ 0.85, be preferably 0.3 ~ 0.8; Co
1/4/ Mo
1/4with Co
1/2/ Mo
1/2ratio be 0.25 ~ 0.85, be preferably 0.3 ~ 0.8.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Co
0/ Co
1< Co
x1/ Co
1< Co
x2/ Co
1< 1, wherein 0 < x1 < x2 < 1.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Ni
0/ Ni
1> Ni
x1/ Ni
1> Ni
x2/ Ni
1> 1, wherein 0 < x1 < x2 < 1.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Ni
0/ Mo
0> Ni
x1/ Mo
x1> Ni
x2/ Mo
x2> Ni
1/ Mo
1, wherein 0 < x1 < x2 < 1.
In catalyst for hydro-upgrading of the present invention, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section is preferably as follows: Co
0/ Mo
0< Co
x1/ Mo
x1< Co
x2/ Mo
x2< Co
1/ Mo
1, wherein 0 < x1 < x2 < 1.
In catalyst for hydro-upgrading of the present invention, on catalyst granules cross section, along described straight-line segment from outer most edge, point is to central point, active metal component concentration distribution is as follows: the concentration of Ni reduces substantially gradually, the concentration of Co increases substantially gradually, the concentration mol ratio of Ni/Mo reduces substantially gradually, and the concentration mol ratio of Co/Mo increases substantially gradually.
In the present invention, the CONCENTRATION DISTRIBUTION that described " substantially reducing (or gradually increase) gradually along described straight-line segment " refers to described active metallic element, but allows to exist between one or more partial zones along described straight-line segment presenting the trend reducing (or increasing gradually) gradually to the whole interval of central point generally from outer most edge point; In this partial zones, the CONCENTRATION DISTRIBUTION of described active metallic element presents different trend (such as remain constant and/or increase (or reducing gradually) and/or disordered state gradually) along described straight-line segment.Prerequisite is, existence between this kind of partial zones is can to tolerate or negligible to those skilled in the art, or be inevitable for the state-of-art of this area, and the existence between these partial zones does not affect those skilled in the art and the CONCENTRATION DISTRIBUTION of described active metallic element in described whole interval is still judged to be " presenting the trend reducing (or gradually increase) gradually generally ".In addition, the existence between this partial zones does not affect the present invention and expects and be the realization of object acceptable, and be also contained within protection scope of the present invention.
In the present invention, described catalyst for hydro-upgrading is that (solid) is granular, instead of the amorphous state such as powder.As the shape of described particle, the various shapes that catalyst for hydro-upgrading routine in this area uses can be enumerated, such as can enumerate spherical, column etc. further, wherein preferred spherical or column.As described spherical, such as spheroidal and elliposoidal etc. can be enumerated; As described column, cylindric, flat column and profiled-cross-section (such as clover, bunge bedstraw herb etc.) column etc. such as can be enumerated.The granularity of described catalyst for hydro-upgrading is generally 3 ~ 8mm, is preferably 3 ~ 5mm.
In the present invention, described " cross section of catalyst granules " refers to the whole surface of minimum dimension direction by exposing after the geometric center cutting of its shape along a catalyst granules.Such as, when described catalyst granules is spherical, described cross section refers to the whole surface (such as see Fig. 1) by exposing after the cutting of its centre of sphere along the radius of this ball or short-axis direction.Or when described catalyst granules is column, described cross section refers to the whole surface (such as see Fig. 2) of length dimension direction by exposing after the central point cutting of this length dimension perpendicular to this post.In the present invention, the periphery of described exposed surface is called the outer most edge of this cross section, described geometric center (central point than the centre of sphere as the aforementioned or length dimension) is called the central point on this cross section.
Catalyst for hydro-upgrading of the present invention, with the weight of catalyst for benchmark, the content of carrier is 55wt% ~ 88wt%, be preferably 55wt% ~ 85wt%, more preferably surplus, Ni in the content of NiO for 1wt% ~ 8wt%, Mo are with MoO
3meter content be 8wt% ~ 32wt%, Co in the content of CoO for 1wt% ~ 8wt%; With the weight of catalyst carrier for benchmark, the content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%.
Can also contain adjuvant component in catalyst for hydro-upgrading of the present invention, one or more in such as fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component for less than 15%, is preferably 1% ~ 10% in element weight content in the catalyst.Preferably containing phosphorus in catalyst for hydro-upgrading of the present invention, with P
2o
5meter weight content is in the catalyst 1% ~ 6%.
In catalyst for hydro-upgrading of the present invention, be positioned at ratio and the Ni of the concentration of catalyst granules cross section outer most edge point place element Ni and the concentration of central spot element Ni
0/ Ni
1be 1.2 ~ 7.0, be preferably 1.5 ~ 5.0, be positioned at ratio and the Co of the concentration of catalyst granules cross section outer most edge point place Elements C o and the concentration of central spot Co
0/ Co
1be 0.1 ~ 0.8, be preferably 0.2 ~ 0.7.
In catalyst for hydro-upgrading of the present invention, be positioned at ratio (mol ratio) the i.e. Ni of the concentration of catalyst granules cross section outer most edge point place element Ni and the concentration of elements Mo
0/ Mo
0be 0.22 ~ 0.80, be positioned at ratio (mol ratio) the i.e. Co of the concentration of catalyst granules cross-section center point place Elements C o and the concentration of elements Mo
1/ Mo
1be 0.20 ~ 0.78.
In catalyst for hydro-upgrading of the present invention, described molecular sieve is Y zeolite and/or beta-molecular sieve.With the weight of catalyst carrier for benchmark, the content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%.Wherein said molecular sieve is hydrogen type molecular sieve.Wherein beta-molecular sieve preferred property is as follows: specific area 450m
2/ g ~ 750m
2/ g, total pore volume 0.30ml/g ~ 0.45ml/g, SiO
2/ Al
2o
3mol ratio 40 ~ 100, the mol ratio of meleic acid amount 0.1 ~ 0.5mmol/g, Gu Jia Lv ∕ non-framework aluminum is 5 ~ 20, B acid/L acid is 0.30 ~ 0.50, Na
2o≤0.15wt%.Beta-molecular sieve of the present invention can adopt existing method to prepare.In the present invention, SiO
2/ Al
2o
3mol ratio adopt chemical determination, meleic acid amount, B acid and L sour employing Pyridine adsorption IR spectra method measure, wherein meleic acid amount be B acid and L acid acid amount with.Sodium oxide content adopts ion emission spectroscopy method to measure.Framework aluminum and non-framework aluminum content adopt NMR method to measure.
In catalyst for hydro-upgrading of the present invention, can not contain adjuvant component in carrier, also can contain adjuvant component, wherein adjuvant component can be one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron etc., adjuvant component in element content in the carrier at below 30wt%, preferred below 20wt%.Described carrier can adopt conventional method to prepare, such as kneading method etc.
The character of catalyst for hydro-upgrading of the present invention is as follows: specific area is 100 ~ 260 m
2/ g, is preferably 120 ~ 220 m
2/ g, pore volume is 0.20 ~ 0.60mL/g, is preferably 0.2 ~ 0.5 mL/g.
In described catalyst for hydro-upgrading, 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, organic matter and Mo atomic molar are than being 0.002:1 ~ 2.0:1, 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 one or more in 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.
In described catalyst for hydro-upgrading, described organic matter to be carbon number be 2 ~ 15 organic acid and its esters in one or more; Comprise 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, ethylenediamine tetra-acetic acid, nitrilotriacetic acid, ring ethylenediamine tetra-acetic acid etc. in described organic acid, organic carboxylate be selected from the ammonium salt of above-mentioned organic carboxyl acid one or more.
The preparation method of catalyst for hydro-upgrading of the present invention, comprising:
(1) with the solution impregnating carrier containing adsorbent I, after drying, obtain the carrier containing adsorbent I, wherein the content of adsorbent I is 0.1% ~ 10.0% of vehicle weight; Described adsorbent I for molecular weight be the polyethylene glycol of 400 ~ 8000, described dipping adopts saturated dipping or excessive dipping;
(2) with dipping solution impregnation steps (1) gains containing Mo, 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, wherein the content of adsorbent II accounts for 0.1% ~ 10.0% of vehicle weight, described adsorbent II is one or more in organic carboxyl acid and its esters, and described dipping adopts unsaturated dipping;
(4) load Mo and 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, obtain catalyst for hydro-upgrading;
B, use, containing Mo, Co and organic dipping solution impregnation steps (3) gains, through super-dry, obtain catalyst for hydro-upgrading;
C, dipping solution impregnation steps (3) gains of use containing Mo, Co, through super-dry or dry and roasting, then flood with organic matter, drying obtains catalyst for hydro-upgrading.
In the inventive method, carrier can adopt conventional method to prepare, and molecular sieve can be introduced in aluminium oxide kneading process, also can introduce in alumina preparation process.
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 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 impregnating carrier, adopts incipient impregnation or excessive dipping.After dipping terminates, sample can be passed through health or without health, if through the general conditioned time of health be 1 ~ 12h.After health terminates, then through drying steps.Described drying condition is as follows: temperature is 60 DEG C ~ 250 DEG C, is preferably 100 ~ 200 DEG C, and drying time, 0.5h ~ 20h, was preferably 1h ~ 6h.
The inventive method, after step (2) uses dipping solution impregnation steps (1) gains containing Mo, Ni, can be passed through health, also can without health, as needed health, conditioned time is 0.5 ~ 6.0h, carry out drying and roasting again, drying condition is as follows: baking temperature is 70 DEG C ~ 300 DEG C, is preferably 100 DEG C ~ 160 DEG C, drying time is 0.5h ~ 20h, be preferably 1h ~ 6h, roasting condition is as follows: sintering temperature is 300 DEG C ~ 750 DEG C, is preferably 400 DEG C ~ 650 DEG C, roasting time is 0.5h ~ 20h, is preferably 1h ~ 6h.
The inventive method, with the fountain solution impregnated catalyst intermediate containing adsorbent II in step (3), dipping wherein preferably adopts unsaturated spraying, and the time of spraying is generally 1min ~ 40min, preferred 2min ~ 20min.The volume of the fountain solution containing adsorbent II used is 0.02 ~ 0.4 with the ratio of the saturated imbibition volume of catalyst intermediate.When spraying the fountain solution containing adsorbent II, the shower nozzle that atomizing effect is good should be selected, dissolution homogeneity is distributed on alumina support.After fountain solution impregnated catalyst intermediate containing adsorbent II, can be passed through drying steps, also can directly enter step (4) without drying steps.Drying condition is as follows: temperature is generally 60 DEG C ~ 250 DEG C, is preferably 100 ~ 200 DEG C, time 0.5h ~ 20h, is preferably 1h ~ 6h.
The inventive method, the dipping solution impregnated catalyst intermediate of step (4) containing Mo, Co, can be passed through health, also can without health, and as needed health, conditioned time is 0.5 ~ 4.0h, then carries out drying.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 100 DEG C ~ 160 DEG C, and drying time, 0.5h ~ 20h, was preferably 1h ~ 6h.Roasting condition described in method C is as follows: burning 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.
Those skilled in the art, according to organic character used, can select the drying condition be suitable for, thus make in final catalyst for hydro-upgrading containing organic matter.
In catalyst for hydro-upgrading preparation method of the present invention, active metal component supports on carrier by infusion process, usually adopts incipient impregnation, and preferably adopt saturated spraying, the time of spraying is generally 5min ~ 40min, preferred 10min ~ 20min.Dipping method is known by technical staff.After active metal component solution impregnating carrier, need through super-dry.Active metal solution manufacturing method is known by technical staff, and its solution concentration regulates by the consumption of each compound, thus prepares the catalyst of specified activity constituent content.The raw material of required active component is generally the compound of the types such as salt, oxide or acid, from one or more in molybdenum oxide, ammonium molybdate, ammonium paramolybdate as molybdenum source, nickel source is from one or more in nickel nitrate, nickelous carbonate, basic nickel carbonate, nickel chloride, nickel oxalate, and cobalt source is from one or more in cobalt nitrate, cobalt carbonate, basic cobaltous carbonate, cobalt chloride, cobalt oxalate.In described dipping solution, except active metal component, phosphorus-containing compound can also be contained, as being one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate etc.Preferably containing phosphorus in catalyst for hydro-upgrading of the present invention, with P
2o
5meter mass content is in the catalyst 1% ~ 6%.
In the inventive method, active metal component Mo is introduced by step (2) and step (4) two step, wherein the mol ratio 0.4 ~ 2.5 of step (2) and the added Mo of step (4).
In the inventive method, one or more in adjuvant component fluorine, silicon, phosphorus, titanium, zirconium and boron, adopt conventional method to introduce in catalyst, such as can introduce when prepared by carrier in catalyst, also can introduce catalyst after prepared by carrier.Introduce in catalyst after carrier preparation, the method for dipping separately can be adopted to introduce in catalyst, also together can flood with active metal component and introduce in catalyst.
Catalyst for hydro-upgrading of the present invention in the hydro-upgrading of heavy distillate (especially diesel oil) as the application of catalyst for hydro-upgrading.
Described heavy distillate can be diesel oil, wax oil, wherein preferred diesel oil.The total sulfur content of described heavy distillate is generally 0.3wt% ~ 3.0wt%, preferred 0.3wt% ~ 2.5wt%, the sulfur content that wherein difficult de-sulfur-containing compound (with 4,6-dimethyl Dibenzothiophene for meter) is contributed is approximately more than 0.01wt%, is generally 0.01 wt% ~ 0.05wt%.
The present invention, in described application or described hydrogenation modification method, can only use catalyst for hydro-upgrading of the present invention, also can by catalyst for hydro-upgrading of the present invention and other catalyst for hydro-upgrading (than as be known in the art those) according to the ratio needed arbitrarily with the use of, such as employing different catalysts bed grating or used in combination.
According to the present invention, to the operating condition of described hydro-upgrading without any special restriction, the operating condition that this area routine uses can be adopted, such as reaction temperature 260 ~ 400 DEG C, preferably 310 ~ 370 DEG C, reaction stagnation pressure 3 ~ 13MPa, preferably 5 ~ 9MPa, volume space velocity 0.5 ~ 4h during liquid
-1, preferably 1 ~ 2h
-1, hydrogen to oil volume ratio 200:1 ~ 2000:1, preferred 400:1 ~ 1000:1.
In catalyst for hydro-upgrading of the present invention, active metal component Co from catalyst granules outer surface to center in the trend increased progressively, the trend that Ni tapers off from catalyst granules outer surface to center, Co/Mo atomic ratio from catalyst granules outer surface to center in the trend increased progressively, 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 matter, this catalyst is specially adapted in the hydro-upgrading process of diesel oil, while diesel deep desulfurization, the combination properties such as the Cetane number of diesel oil are improved when keeping diesel yield higher.
The present invention prepares in the method for catalyst for hydro-upgrading, the fountain solution of adsorbent I is contained by saturated dipping or excessive dipping, then Mo is flooded, after Ni active metal solution, slow down Mo, Ni is to the diffusion velocity at catalyst granules center, 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 component Co from catalyst granules outer surface to center in the trend increased progressively, the trend that Ni tapers off from catalyst granules outer surface to center, Co/Mo atomic ratio from catalyst granules outer surface to center in the trend increased progressively, 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 matter, improve the deep hydrodesulfurizationof performance of catalyst, and suitable open loop, isomery, the performances such as cracking, for in the hydro-upgrading process of diesel oil, can while diesel deep desulfurization, the combination properties such as the Cetane number of diesel oil are improved when keeping diesel yield higher.In addition, the present invention, by controlling the preparation condition of catalyst for hydro-upgrading, makes organic matter be present in final catalyst for hydro-upgrading, 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 C6 particle of embodiment 2 gained.Wherein abscissa is each position point on this cross section, and ordinate is the ratio of the concentration of central spot on the concentration at a certain location point place and this cross section.
Detailed description of the invention
The technical scheme that the invention is further illustrated by the following examples, but invention should not be deemed limited in this embodiment.In the present invention, wt% is mass fraction.
Analytical method of the present invention is as follows:
(1) content (wt%) of active metal component and adjuvant component adopts x ray fluorescence spectrometry to measure.
(2) specific area (m
2/ g) and pore volume (ml/g) adopt BET method to measure.
(3) CONCENTRATION DISTRIBUTION of each active metal component in catalyst granules
In following embodiment and comparative example, employ columniform carrier (but the present invention is obviously not limited to this, also can use other grain shape), catalyst granules obtained thus is also columniform.From the catalyst that each embodiment and comparative example obtain, random selecting catalyst granules is as measurement sample.In order to measure the CONCENTRATION DISTRIBUTION of each active metal component in this catalyst granules, perpendicular to the length dimension direction of this cylindrical particle, being cut by the central point of this length dimension, obtaining two exposed surfaces.Get one of them exposed surface as measurement cross section.
This measurement uses EPMA method, with reference to GB/T15074-2008(Electron probe quantitative analysis method general rule) carry out, electron probe microanalyzer (JXA-8230 type, Jeol Ltd. manufactures) carries out.Measuring condition is: accelerating potential 15kV, beam intensity 5 × 10
-8a, beam spot diameter, 1 μm, X-ray detects angle: 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.
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 C6 of embodiment 2 gained, by evenly choosing 21 location points (comprising location point 0 and location point 1) on this straight-line segment, with these location points for abscissa, the ratio of the concentration value of the corresponding active metal measured to location point 1 place (i.e. central point) with the concentration value of the targeted activity metal (for Ni and Co) of each position point place measurement (uses Ni respectively
m/ Ni
1and Co
m/ Co
1represent) be ordinate, so to draw and to obtain.
(4) total sulfur content in raw material and hydrogenation products adopts ultraviolet fluorescence method to measure (ASTM D5453-1993), and 4,6-BMDBT content adopts GC-AED(gas-chromatography-atom luminescence spectroscopy) measure.
(5) number-average molecular weight Mn adopts GPC method to measure.
In embodiment, the diameter of cylindrical vector used is about 1.2mm, and length is about 3 ~ 5mm, and its physico-chemical property is as shown in table 1:
The physico-chemical property of used carrier in table 1 embodiment
Mo predecessor in the present embodiment in Mo, Ni, P and Mo used, Co, P maceration extract is MoO
3, Ni predecessor is basic nickel carbonate, and Co predecessor is basic cobaltous carbonate, and P predecessor is phosphoric acid.
Embodiment 1
Take 18g 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 S1 carrier of 300g 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.
Spray above-mentioned B1 sample with maceration extract (the first maceration extract) equal-volume containing Mo, Ni, P, 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 15g, stirring and dissolving in 45g water, obtained fountain solution.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 (the second maceration extract) incipient impregnation containing Mo, Co, P, the sample average of gained is divided into three 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; Triplicate sample health 3h, through 120 DEG C of dry 3h, obtained sample is designated as C3.
Embodiment 2
Take 24g cetomacrogol 1000, stirring and dissolving in the water measured, obtained fountain solution I.With the S2 carrier 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 B2.
Spray B2 sample with maceration extract (the first maceration extract) equal-volume containing Mo, Ni, P, after spraying end, gained sample average is divided into three parts, wherein the direct 120 DEG C of dry 3h of the first increment product, after 480 DEG C of roasting 2h, the sample of acquisition is designated as Z2; Second increment product health 1h, 120 DEG C of dry 3h, after 480 DEG C of roasting 2h, obtained sample is designated as Z3; Triplicate sample health 3h, 120 DEG C of dry 3h, after 480 DEG C of roasting 2h, obtained sample is designated as Z4.
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 (the second maceration extract) incipient impregnation containing Mo, Co, P, dipping terminates rear health 1h, and through 120 DEG C of dry 3h, the catalyst of acquisition is designated as C4.The treatment step process Z3 adopting above-mentioned Z2 identical respectively and Z4 sample, the catalyst obtained is designated as C5 and C6 respectively.
Embodiment 3
Take 4g PEG 8000, stirring and dissolving in the aqueous solution measured, obtained fountain solution I.With the S3 carrier 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 B3.
Spray B3 sample with maceration extract (the first maceration extract) equal-volume containing Mo, Ni, P, directly through 120 DEG C of dry 3h, the sample of acquisition is designated as Z5.
Take citric acid and each 7g of malonic acid, stirring and dissolving in 40g water, obtained fountain solution II.Evenly sprayed on Z5 by fountain solution II, the time of spraying is 25min.With containing the above-mentioned sample of Mo, Co, P maceration extract (the second maceration extract) incipient impregnation, dipping terminates rear health 1h, and through 120 DEG C of dry 3h, the catalyst of acquisition is designated as C7.
Prepare the glycerinated aqueous solution, equal-volume sprays part C7 sample, and on the glycerine of introducing and catalyst, the mol ratio of Mo is 0.03:1, and after spraying end, through 120 DEG C of dry 3h, the catalyst of acquisition is designated as C8.
Comparative example 1
Get S1 carrier 100g, after using the above-mentioned carrier of maceration extract (the first maceration extract) incipient impregnation containing Mo, Ni, P, through 120 DEG C of dry 3h, after 480 DEG C of roasting 2h, the sample of acquisition is designated as B8.With maceration extract (the second maceration extract) the incipient impregnation B8 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 C9.
Comparative example 2
Get S4 carrier 100g, adopt the preparation method identical with C4 catalyst to prepare, the sample of acquisition is designated as C10.
Table 2 embodiment and comparative example catalyst form
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 | C10 |
| Composition | ||||||||||
| Mo(is with MoO 3Meter), wt% | 20.5 | 20.3 | 20.4 | 20.3 | 20.3 | 20.4 | 20.3 | 20.2 | 20.4 | 20.4 |
| Co(is in 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 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 P 2O 5Meter), 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 maceration extract/the second maceration extract | 1.0 | 1.0 | 1.0 | 0.8 | 0.8 | 0.8 | 1.2 | 1.2 | 1.0 | 1.0 |
| Character | ||||||||||
| Specific area, m 2/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 aluminium oxide of carrier * and 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 in C7 and C8, the aluminium oxide in C10.
The CONCENTRATION DISTRIBUTION of Elements C o in catalyst granules in table 3 embodiment and comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 | C10 |
| Co 0/Co 1 | 0.15 | 0.28 | 0.51 | 0.34 | 0.33 | 0.34 | 0.33 | 0.38 | 0.98 | 0.33 |
| Co 1/4/Co 1 | 0.31 | 0.48 | 0.62 | 0.78 | 0.80 | 0.78 | 0.45 | 0.50 | 0.99 | 0.80 |
| Co 1/2/Co 1 | 0.62 | 0.80 | 0.92 | 0.95 | 0.96 | 0.95 | 0.82 | 0.84 | 1.00 | 0.96 |
| Co 3/4/Co 1 | 0.90 | 0.94 | 0.98 | 0.99 | 0.99 | 1.00 | 0.96 | 0.96 | 0.99 | 0.99 |
The CONCENTRATION DISTRIBUTION of element Ni in catalyst granules in table 4 embodiment and comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 | C10 |
| Ni 0/Ni 1 | 2.83 | 2.84 | 2.83 | 2.97 | 2.57 | 2.09 | 2.58 | 2.54 | 0.98 | 2.95 |
| Ni /4/Ni 1 | 1.89 | 1.88 | 1.89 | 1.96 | 1.71 | 1.54 | 1.76 | 1.72 | 1.00 | 1.95 |
| Ni 1/2/Ni 1 | 1.27 | 1.26 | 1.26 | 1.32 | 1.26 | 1.16 | 1.20 | 1.19 | 1.00 | 1.31 |
| Ni 3/4/Ni 1 | 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 |
| Ni 0/Mo 0 | 0.43 | 0.41 | 0.42 | 0.43 | 0.40 | 0.38 | 0.40 | 0.38 | 0.21 | 0.43 |
| Ni 1/4/Mo 1/4 | 0.27 | 0.28 | 0.27 | 0.29 | 0.29 | 0.28 | 0.28 | 0.28 | 0.20 | 0.29 |
| Ni 1/2/Mo 1/2 | 0.22 | 0.21 | 0.22 | 0.22 | 0.21 | 0.21 | 0.22 | 0.21 | 0.20 | 0.22 |
| Ni 3/4/Mo 3/4 | 0.18 | 0.17 | 0.17 | 0.18 | 0.17 | 0.16 | 0.17 | 0.16 | 0.21 | 0.18 |
| Ni 1/Mo 1 | 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 |
| Co 0/Mo 0 | 0.06 | 0.08 | 0.12 | 0.07 | 0.08 | 0.07 | 0.07 | 0.06 | 0.23 | 0.07 |
| Co 1/4/Mo 1/4 | 0.15 | 0.17 | 0.18 | 0.19 | 0.19 | 0.20 | 0.14 | 0.14 | 0.22 | 0.19 |
| Co 1/2/Mo 1/2 | 0.30 | 0.28 | 0.26 | 0.32 | 0.31 | 0.31 | 0.26 | 0.27 | 0.22 | 0.32 |
| Co 3/4/Mo 3/4 | 0.37 | 0.36 | 0.31 | 0.34 | 0.34 | 0.35 | 0.33 | 0.34 | 0.22 | 0.34 |
| Co 1/Mo 1 | 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, carries out presulfurization before performance evaluation to catalyst.Evaluating catalyst condition is at reaction stagnation pressure 10.0MPa, volume space velocity 1.5 h during liquid
-1, hydrogen-oil ratio 800:1, reaction temperature is 365 DEG C.Henchnmrk test feedstock oil character is in table 7, Evaluation results is in table 8, from data in table, catalyst for hydro-upgrading is prepared with the present invention, catalyst desulphurizing activated apparently higher than comparative example catalyst, under maintenance diesel yield is not less than the condition of 97%, the Cetane number of diesel oil is improved more than 10 units, product quality obtains good improvement.
table 7 feedstock oil character
| Feedstock oil | Catalytic diesel oil |
| Density (20 DEG C), g/cm 3 | 0.9433 |
| Boiling range/DEG C | |
| IBP/10% | 182/250 |
| 30%/50% | 284/310 |
| 70%/90% | 332/347 |
| 95%/EBP | 358/370 |
| Condensation point, DEG C | 5 |
| Sulphur, μ g/g | 8698 |
| 4,6-BMDBT content, μ g/g | 103.6 |
| Nitrogen, μ g/g | 1225 |
| Cetane number | 28 |
| C，wt% | 87.98 |
| H，wt% | 11.12 |
table 8 catalyst performance evaluation result
| Catalyst | C1 | C2 | C3 | C4 | 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，℃ | 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 |
| Sulphur, μ 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，℃ | 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 |
| Sulphur, μ g/g | 8 | 7 | 6 | 17 | 12 |
Claims (24)
1. a catalyst for hydro-upgrading, carrier comprises aluminium oxide and molecular sieve, and active metal component is Mo, Co and Ni, and wherein the CONCENTRATION DISTRIBUTION of active metal component on each catalyst granules cross section is as follows: Co
0/ Co
1< Co
1/2/ Co
1< 1, Ni
0/ Ni
1> Ni
1/2/ Ni
1> 1, Ni
0/ Mo
0> Ni
1/2/ Mo
1/2> Ni
1/ Mo
1, Co
0/ Mo
0< Co
1/2/ Mo
1/2< Co
1/ Mo
1containing organic matter in described catalyst, described organic matter is selected from organic nitrogen-containing organic compound, one or more in organic compounds containing sulfur and oxygen-containing organic compound that carbon number is 2 ~ 20, organic matter and Mo atomic molar are than being 0.002:1 ~ 2.0:1, be preferably 0.02:1 ~ 1.5:1, more preferably 0.02:1 ~ 1.0:1;
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 or Ni, and B represents active metallic element Mo, Co or Ni, with any point of catalyst granules cross section outer most edge for starting point is designated as 0, with the central point of catalyst granules cross section for terminal is designated as 1, connection starting point and terminal obtain straight-line segment, m and n is illustrated respectively in the location point that above-mentioned straight-line segment is chosen, the value of m and n represents the ratio of the length accounting for above-mentioned straight-line segment from starting point to the distance of the location point chosen, the value of m and n is 0 ~ 1, in order to express easily, A and B directly adopts active metallic element Mo, Co or Ni replaces, m and n is directly with the location point that the above-mentioned straight-line segment of digitized representation of 0 ~ 1 is determined.
2. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, active metal component, in catalyst granules, at least comprises following a kind of scheme:
(1) Co
0/ Co
1with Co
1/2/ Co
1ratio be 0.2 ~ 0.8;
(2) Ni
0/ Ni
1with Ni
1/2/ Ni
1ratio 1.5 ~ 2.6;
(3) Ni
0/ Mo
0with Ni
1/2/ Mo
1/2ratio be 1.4 ~ 2.3;
(4) Co
0/ Mo
0with Co
1/2/ Mo
1/2ratio be 0.10 ~ 0.70.
3. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, active metal component, in catalyst granules, at least comprises following a kind of scheme:
(1) Co
0/ Co
1with Co
1/2/ Co
1ratio be 0.2 ~ 0.7;
(2) Ni
0/ Ni
1with Ni
1/2/ Ni
1ratio 1.7 ~ 2.5;
(3) Ni
0/ Mo
0with Ni
1/2/ Mo
1/2ratio be 1.5 ~ 2.2;
(4) Co
0/ Mo
0with Co
1/2/ Mo
1/2ratio be 0.12 ~ 0.65.
4. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, the CONCENTRATION DISTRIBUTION of active metal component on catalyst granules cross section at least comprises following a kind of scheme:
（1）Co
0/Co
1＜Co
1/4/Co
1＜Co
1/2/Co
1；
（2）Co
1/2/Co
1＜Co
3/4/Co
1＜1；
（3）Ni
0/Ni
1＞Ni
1/4/Ni
1＞Ni
1/2/Ni
1；
（4）Ni
1/2/Ni
1＞Ni
3/4/Ni
1＞1；
（5）Ni
0/Mo
0＞Ni
1/4/Mo
1/4＞Ni
1/2/Mo
1/2；
（6）Ni
1/2/Mo
1/2＞Ni
3/4/Mo
3/4＞Ni
1/Mo
1；
（7）Co
0/Mo
0＜Co
1/4/Mo
1/4＜Co
1/2/Mo
1/2；
（8）Co
1/2/Mo
1/2＜Co
3/4/Mo
3/4＜Co
1/Mo
1；
(9) Co
0/ Co
1< Co
x1/ Co
1< Co
x2/ Co
1< 1, wherein 0 < x1 < x2 < 1;
(10) Ni
0/ Ni
1> Ni
x1/ Ni
1> Ni
x2/ Ni
1> 1, wherein 0 < x1 < x2 < 1;
(11) Ni
0/ Mo
0> Ni
x1/ Mo
x1> Ni
x2/ Mo
x2> Ni
1/ Mo
1, wherein 0 < x1 < x2 < 1;
(12) Co
0/ Mo
0< Co
x1/ Mo
x1< Co
x2/ Mo
x2< Co
1/ Mo
1, wherein 0 < x1 < x2 < 1.
5. according to catalyst according to claim 4, it is characterized in that in described catalyst for hydro-upgrading, active metal component, in catalyst granules, at least comprises following a kind of scheme:
(1) Co
0/ Co
1with Co
1/4/ Co
1ratio be 0.3 ~ 0.9;
(2) Co
1/4/ Co
1with Co
1/2/ Co
1ratio be 0.4 ~ 0.9;
(3) Ni
0/ Ni
1with Ni
1/4/ Ni
1ratio be 1.2 ~ 1.8;
(4) Ni
1/4/ Ni
1with Ni
1/2/ Ni
1ratio be 1.1 ~ 1.7;
(5) Ni
0/ Mo
0with Ni
1/4/ Mo
1/4ratio be 1.1 ~ 1.8;
(6) Ni
1/4/ Mo
1/4with Ni
1/2/ Mo
1/2ratio be 1.1 ~ 1.8;
(7) Co
0/ Mo
0with Co
1/4/ Mo
1/4ratio be 0.25 ~ 0.85;
(8) Co
1/4/ Mo
1/4with Co
1/2/ Mo
1/2ratio be 0.25 ~ 0.85.
6. according to catalyst according to claim 4, it is characterized in that in described catalyst for hydro-upgrading, active metal component, in catalyst granules, at least comprises following a kind of scheme:
(1) Co
0/ Co
1with Co
1/4/ Co
1ratio be 0.3 ~ 0.85;
(2) Co
1/4/ Co
1with Co
1/2/ Co
1ratio be 0.4 ~ 0.87;
(3) Ni
0/ Ni
1with Ni
1/4/ Ni
1ratio be 1.3 ~ 1.7;
(4) Ni
1/4/ Ni
1with Ni
1/2/ Ni
1ratio be 1.2 ~ 1.6;
(5) Ni
0/ Mo
0with Ni
1/4/ Mo
1/4ratio be 1.15 ~ 1.7;
(6) Ni
1/4/ Mo
1/4with Ni
1/2/ Mo
1/2ratio be 1.15 ~ 1.7;
(7) Co
0/ Mo
0with Co
1/4/ Mo
1/4ratio be 0.3 ~ 0.8;
(8) Co
1/4/ Mo
1/4with Co
1/2/ Mo
1/2ratio be 0.3 ~ 0.8.
7. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, on catalyst granules cross section, along described straight-line segment from outer most edge, point is to central point, active metal component concentration distribution is as follows: the concentration of Ni reduces substantially gradually, the concentration of Co increases substantially gradually, and the concentration mol ratio of Ni/Mo reduces substantially gradually, and the concentration mol ratio of Co/Mo increases substantially gradually.
8., according to catalyst according to claim 1, it is characterized in that described catalyst for hydro-upgrading, with the weight of catalyst for benchmark, the content of carrier be 55wt% ~ 88wt%, Ni in the content of NiO for 1wt% ~ 8wt%, Mo are with MoO
3meter content be 8wt% ~ 32wt%, Co in the content of CoO for 1wt% ~ 8wt%; With the weight of catalyst carrier for benchmark, the content of molecular sieve is 3% ~ 35%, and the content of aluminium oxide is 65% ~ 97%.
9. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, at least comprise following a kind of scheme:
(1) ratio being positioned at the concentration of Ni at catalyst granules cross section outer most edge point place and the concentration of the Ni of central spot is 1.2 ~ 7.0,
(2) concentration of Co at catalyst granules cross section outer most edge point place is positioned at and the ratio of the concentration of central spot Co is 0.1 ~ 0.8,
(3) concentration of Ni at catalyst granules cross section outer most edge point place is positioned at and the ratio of the concentration of Mo is 0.22 ~ 0.80,
(4) concentration of Co at catalyst granules cross-section center point place is positioned at and the ratio of the concentration of Mo is 0.20 ~ 0.78.
10., according to catalyst according to claim 1, it is characterized in that described molecular sieve is Y zeolite and/or beta-molecular sieve.
11. according to catalyst according to claim 1, it is characterized in that described molecular sieve is beta-molecular sieve; Wherein beta-molecular sieve character is as follows: specific area 450m
2/ g ~ 750m
2/ g, total pore volume 0.30ml/g ~ 0.45ml/g, SiO
2/ Al
2o
3mol ratio 40 ~ 100, the mol ratio of meleic acid amount 0.1 ~ 0.5mmol/g, Gu Jia Lv ∕ non-framework aluminum is 5 ~ 20, B acid/L acid is 0.30 ~ 0.50, Na
2o≤0.15wt%.
12. according to catalyst according to claim 1, it is characterized in that the character of described catalyst for hydro-upgrading is as follows: specific area is 120 ~ 220 m
2/ g, pore volume is 0.20 ~ 0.60mL/g.
13. according to catalyst according to claim 1, it is characterized in that in described catalyst for hydro-upgrading, containing adjuvant component, wherein adjuvant component is one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component in element weight content in the catalyst at below 15wt%.
14. according to catalyst according to claim 1, it is characterized in that containing phosphorus in described catalyst for hydro-upgrading, with P
2o
5meter weight content is in the catalyst 1% ~ 6%.
The preparation method of the arbitrary described catalyst of 15. claims 1 ~ 12, comprising:
(1), with the solution impregnating carrier containing adsorbent I, after drying, obtain the carrier containing adsorbent I, wherein the consumption of adsorbent I is 0.1% ~ 10.0% of vehicle weight; Described adsorbent I for molecular weight be the polyethylene glycol of 400 ~ 10000, described dipping adopts saturated dipping or excessive dipping;
(2) with dipping solution impregnation steps (1) gains containing Mo, 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, wherein the consumption of adsorbent II accounts for 0.1% ~ 10.0% of vehicle weight, described adsorbent II is one or more in organic carboxyl acid and its esters, and described dipping adopts unsaturated dipping;
(4) load Mo and Co on step (3) gains.
16. in accordance with the method for claim 15, 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, obtain catalyst for hydro-upgrading;
B, use, containing Mo, Co and organic dipping solution impregnation steps (3) gains, through super-dry, obtain catalyst for hydro-upgrading;
C, dipping solution impregnation steps (3) gains of use containing Mo, Co, through super-dry or dry and roasting, then flood with organic matter, drying obtains catalyst for hydro-upgrading.
17. in accordance with the method for claim 15, and it is characterized in that described adsorbent II is for one or more in organic carboxyl acid and its esters, its carbon number is 2 ~ 15.
18. in accordance with the method for claim 15, it is characterized in that described organic acid comprises in acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, chloroacetic acid, TGA, mercaptopropionic acid, ethylenediamine tetra-acetic acid, nitrilotriacetic acid, ring ethylenediamine tetra-acetic acid etc. one or more, organic carboxylate be selected from the ammonium salt of above-mentioned organic carboxyl acid one or more.
19. in accordance with the method for claim 15, it is characterized in that: in the solution containing adsorbent I and the fountain solution containing adsorbent II, adopt water and/or ethanol to be solvent.
20. in accordance with the method for claim 15, it is characterized in that: described method one of at least to adopt in a ~ e:
A, step (1) are with containing adsorbent I solution impregnating carrier, and after dipping terminates, sample is through health or without health, then through drying steps, if through health, conditioned time is 1 ~ 12h; Drying condition described in step (1) is as follows: baking temperature is 60 DEG C ~ 250 DEG C, drying time 0.5h ~ 20h;
After b, step (2) use dipping solution impregnation steps (1) gains containing Mo, Ni, through health or without health, then carry out drying and roasting, as needed health, conditioned time is 0.5 ~ 6.0h; Described drying condition is as follows: baking temperature is 70 DEG C ~ 300 DEG C, and drying time is 0.5h ~ 20h, and roasting condition is as follows: sintering temperature is 300 DEG C ~ 750 DEG C, and roasting time is 0.5h ~ 20h;
With the fountain solution impregnated catalyst intermediate containing adsorbent II in c, step (3), dipping wherein adopts unsaturated spraying, and the time of spraying is 1min ~ 40min; The volume of the fountain solution containing adsorbent II used is 0.02 ~ 0.4 with the ratio of the saturated imbibition volume of catalyst intermediate;
After d, step (3) the fountain solution impregnated catalyst intermediate containing adsorbent II, directly enter step (4) through drying steps or without drying steps; Described drying condition is as follows: temperature is 60 DEG C ~ 250 DEG C, time 0.5h ~ 20h;
E, active metal component Mo are introduced by step (2) and step (4) two step, wherein the mol ratio 0.4 ~ 2.5 of step (2) and the added Mo of step (4).
21. in accordance with the method for claim 16, it is characterized in that: step (4) is with containing the dipping solution of Mo, Co or containing Mo, Co and organic dipping solution impregnated catalyst intermediate, through health or without health, carry out drying again, 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; 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.
22. in accordance with the method for claim 15, 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 catalyst for hydro-upgrading is 1% ~ 6%.
The method of 23. 1 kinds of heavy distillate hydro-upgradings, is characterized in that adopting the arbitrary described catalyst for hydro-upgrading of claim 1 ~ 14.
24. in accordance with the method for claim 23, it is characterized 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229835A (en) * | 1998-03-20 | 1999-09-29 | 中国石油化工集团公司 | Light oil products hydrogenation treatment catalyst containing moly and/or tungsten, and its prepn. method |
| CN1289828A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrorefining catalyst for fraction oil and its preparing process |
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