CN103801313B - A kind of catalyst for hydrogenation of fraction oil and preparation method thereof - Google Patents
A kind of catalyst for hydrogenation of fraction oil and preparation method thereof Download PDFInfo
- Publication number
- CN103801313B CN103801313B CN201310527896.4A CN201310527896A CN103801313B CN 103801313 B CN103801313 B CN 103801313B CN 201310527896 A CN201310527896 A CN 201310527896A CN 103801313 B CN103801313 B CN 103801313B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- active metal
- acid
- ratio
- metal component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of hydrotreating catalyst and preparation method thereof.This hydrotreating catalyst, adopts alumina-based supports, and active metal component is Mo, Co and Ni, and wherein active metal component distribution situation in catalyst granules is as follows: Co0/Co1< Co1/2/Co1< 1, Mo0/Mo1< Mo1/2/Mo1< 1, the concentration of Ni is substantially uniformly distributed, its preparation method is to adopt the unsaturated infusion process fountain solution oxide impregnation alumina-based support containing adsorbent, then dip loading active metal component Mo, Co, and Ni introduces in hydrotreating catalyst in conventional manner.The hydrotreating catalyst of the present invention is particularly suitable as deep hydrodesulfurizationof of diesel oil catalyst.
Description
Technical field
The preparation method that the present invention relates to a kind of hydrotreating catalyst, particularly a kind of preparation method being suitable to catalyst for hydro-processing heavy distillate.
Background technology
Requirement heavy distillate (particularly diesel oil) cleaned along with society is more and more higher, and the deep hydrodesulfurizationof technology of heavy distillate just seems more and more important.Sulfur-containing compound in heavy distillate mainly has aliphatic sulfides, thioether, dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene etc., wherein more difficult elimination is the thiophenes such as dibenzothiophenes, alkyl benzothiophenes and methyldibenzothiophene, especially with 4,6-dimethyl Dibenzothiophene (4,6-BMDBT) with 2,4,6-trimethyl dibenzothiophenes (2,4,6-BMDBT) class formation is complicated and have the sulfur-containing compound of space steric effect to be most difficult to elimination.Reach the degree of depth and ultra-deep desulfurization, it is necessary to remove that these structures are complicated and sterically hindered big sulfur-containing compound, and the generally also more difficult elimination under the harsh operating conditions such as High Temperature High Pressure of these sulfur-containing compounds.Therefore, the heavy distillate degree of depth and ultra-deep desulfurization have significant difference with conventional hydrodesulfurization in reaction mechanism, and this just requires there is particular/special requirement in the design of deep hydrodesulfurizationof catalyst.
Hydrotreating catalyst is typically with alumina-based supports, and with vib and group VIII metal for hydrogenation active metals component, wherein active metal component is usually equally distributed in the catalyst.CN99103007.9 discloses a kind of light-end products hydrotreating catalyst containing molybdenum and/or tungsten.This catalyst contains load tungsten oxide on the alumina support and/or molybdenum oxide, nickel oxide and cobalt oxide, the content of described tungsten oxide and/or molybdenum oxide is that 4 weight % are to less than 10 weight %, the content of nickel oxide is 1～5%, the content of cobalt oxide is 0.01～1 weight %, and the ratio of nickel and cobalt total atom number and the total atom number of nickel, cobalt, tungsten and/or molybdenum is 0.3～0.9.Compared with prior art, this catalyst has relatively low tenor and but has higher low temperature active.This catalyst is particularly well-suited to the hydro-sweetening process of light-end products.
CN99113281.5 discloses a kind of catalyst for hydrorefining distillate oil and preparation method thereof.This catalyst is with aluminium oxide or silicon-containing alumina for carrier, with W, Mo, Ni for active component, adds phosphate builder.By adopting segmentation total immersion technology so that the Metal Distribution on catalyst is more uniform, and the activity of catalyst, particularly hydrodenitrogenationactivity activity is greatly improved.
The hydrotreating catalyst of these prior aries belongs to the Hydrobon catalyst of routine, can not be effectively adapted to the hydrodesulfurization of heavy distillate (especially diesel oil).Therefore, prior art is still required for a kind of hydrotreating catalyst, is particularly suited for the hydrodesulfurization (especially deep hydrodesulfurizationof) of heavy distillate (especially diesel oil).
Summary of the invention
For problems of the prior art, the invention provides a kind of hydrotreating catalyst and preparation method thereof.This catalyst has higher hydrodesulfurization activity.
The hydrotreating catalyst of the present invention, adopts alumina-based supports, 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, Mo0/Mo1< Mo1/2/Mo1The concentration of < 1, Ni is substantially uniformly distributed.
In the present invention, active metal component CONCENTRATION DISTRIBUTION formula A on the cross section of each catalyst granulesm/BnRepresent, namely on the cross section of each catalyst granules, the ratio of the concentration of the concentration of m place elements A and n place 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 and B can be identical, it is also possible to different；It is designated as 0 for starting point with any point of catalyst granules cross section outer most edge and outer most edge point, 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 selects (or appearance 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, and 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/Co1Represent that A and B is Co, m=0, n=1 and namely represents 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, Ni1/2/Ni1Represent that A and B is Ni, m=1/2, namely n=1 represents on the described straight-line segment on catalyst granules cross section, make the distance from outer most edge point to selected point account for above-mentioned straight-line segment length 1/2 time selected point position element Ni the ratio of concentration of concentration and central spot element Ni.Co0/Mo0Expression A is Co, B is Mo, m=0, n=0, namely represents the ratio of the concentration of catalyst granules cross section outer most edge point place Elements C o and the concentration of this elements Mo.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 put from outer most edge point to x1 is less than the distance i.e. 0 < x1 < x2 < 1 of point from outer most edge point to x2.
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), Mo0/Mo1(A and B is Mo, m=0, n=1), Mo1/4/Mo1(A and B is Mo, m=1/4, n=1), Mo1/2/Mo1(A and B is Mo, m=1/2, n=1), Mo3/4/Mo1(A and B is Mo, m=3/4, n=1), Mox1/Mo1(A and B is Mo, m=x1, n=1), Mox2/Mo1(A and B is Mo, m=x2, n=1), Co0/Mo0(A is Co, B is Mo, m=0, n=0)..
In hydrotreating catalyst of the present invention, active metal component is in catalyst granules, it is preferable that scheme is as follows: Co0/Co1With Co1/2/Co1Ratio be 0.2 ~ 0.8, it is preferred to 0.2 ~ 0.7；Mo0/Mo1With Mo1/2/Mo1Ratio be 0.2 ~ 0.8, it is preferred to 0.2 ~ 0.7.
In hydrotreating catalyst of the present invention, active metal component is in catalyst granules, it is preferable that scheme is as follows: Co0/Mo0Ratio be 0.07 ~ 2.0, it is preferred to 0.08 ~ 1.2.
In hydrotreating catalyst of the present invention, active metal component distribution on catalyst granules cross section is preferably as follows: Co0/Co1< Co1/4/Co1< Co1/2/Co1。
In hydrotreating catalyst of the present invention, active metal component distribution on catalyst granules cross section is preferably as follows: Co1/2/Co1< Co3/4/Co1< 1.
In hydrotreating catalyst of the present invention, active metal component distribution on catalyst granules cross section is preferably as follows: Mo0/Mo1< Mo1/4/Mo1< Mo1/2/Mo1。
In hydrotreating catalyst of the present invention, active metal component distribution on catalyst granules cross section is preferably as follows: Mo1/2/Mo1< Mo3/4/Mo1< 1.
In hydrotreating catalyst of the present invention, active metal component is in catalyst granules, it is preferable that scheme is as follows: Co0/Co1With Co1/4/Co1Ratio be 0.30 ~ 0.90, it is preferred to 0.30 ~ 0.85；Co1/4/Co1With Co1/2/Co1Ratio be 0.4 ~ 0.9, it is preferred to 0.4 ~ 0.87；Mo0/Mo1With Mo1/4/Mo1Ratio be 0.30 ~ 0.90, it is preferred to 0.30 ~ 0.85；Mo1/4/Mo1With Mo1/2/Mo1Ratio be 0.4 ~ 0.9, it is preferred to 0.4 ~ 0.87.
In hydrotreating catalyst 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 hydrotreating catalyst of the present invention, active metal component CONCENTRATION DISTRIBUTION on catalyst granules cross section is preferably as follows: Mo0/Mo1< Mox1/Mo1< Mox2/Mo1< 1, wherein 0 < x1 < x2 < 1.
In hydrotreating catalyst of the present invention, on catalyst granules cross section, along described straight-line segment from outer most edge point to central point, active metal component concentration distribution is as follows: the concentration of Co is substantially gradually increased, the concentration of Mo is substantially gradually increased, and the concentration of Ni is substantially uniformly distributed.
In the present invention, described " being substantially gradually increased along described straight-line segment " refers to the CONCENTRATION DISTRIBUTION of described active metallic element and presents, in from outer most edge point to the whole interval of central point, the trend being gradually increased along described straight-line segment generally, but it is interval to allow there is one or more local；In this interval, local, the CONCENTRATION DISTRIBUTION of described active metallic element presents different trend (such as remain constant and/or gradually decrease and/or disordered state) along described straight-line segment.Premise is, the existence in interval, this kind of local is can 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 described active metallic element CONCENTRATION DISTRIBUTION in described whole interval is still judged to " presenting the trend being gradually increased generally ".Expect be the realization of purpose acceptable, and be also contained within protection scope of the present invention it addition, the interval existence in this local has no effect on the present invention.
In the present invention, described " concentration of Ni is substantially uniformly distributed " refers to Ni CONCENTRATION DISTRIBUTION on the whole cross section of each described catalyst granules is uniformity, but allows existence can tolerate to those skilled in the art and maybe can ignore or inevitable CONCENTRATION DISTRIBUTION fluctuation (deviation) for the state-of-art of this area.For example, such as, now Ni0/Ni1It is in 1 ± 5% scope and Nim/Ni1It is in 1 ± 5% scope, it is preferable that Ni0/Ni1It is in 1 ± 2% scope and Nim/Ni1It is in 1 ± 2% scope.The fluctuation of this CONCENTRATION DISTRIBUTION has no effect on the present invention and expects and be the realization of purpose acceptable, and be also contained within protection scope of the present invention.
In the present invention, described hydrotreating catalyst is that (solid) is granular, rather than the amorphous state such as powder.Shape as described granule, it is possible to enumerate this area hydrotreating catalyst conventional use of variously-shaped, such as can enumerate spherical, column etc., wherein preferably 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 hydrotreating catalyst is 3 ~ 8mm, it is preferred to 3 ~ 5mm.
In the present invention, described " cross section of catalyst granules " refers to the whole surface by exposing after the cutting of the geometric center of its shape, the minimum dimension direction along a catalyst granules.Such as, when described catalyst granules is spherical, described cross section refers to the radius along this ball or the short-axis direction whole surface (such as referring to Fig. 1) by exposing after the cutting of its centre of sphere.Or, when described catalyst granules is column, described cross section refers to the whole surface (such as referring to Fig. 2) by exposing after the central point cutting of this length dimension, the length dimension direction being perpendicular to this post.In the present invention, the periphery of described exposed surface is called the outer most edge of this cross section, described geometric center (central point than the centre of sphere as the aforementioned or length dimension) is called the central point on this cross section.
Hydrotreating catalyst provided by the invention, with the weight of catalyst for benchmark, the content of alumina-based supports is 46wt% ~ 87wt%, it is preferred to surplus, Mo is with MoO3The content of meter is that 10wt%～40wt%, Co are with the CoO content counted for 0.5wt%～6wt%, Ni with the NiO content counted for 1wt%～8wt%.
In described hydrotreating catalyst, it is positioned at concentration ratio (mol ratio) the i.e. Mo of concentration and the Mo at grain center points place of the Mo at the outer most edge point place of catalyst granules cross section0/Mo1It is 0.20～0.90, is positioned at concentration ratio (mol ratio) the i.e. Co of concentration and the central spot Co of the Co at the outer most edge point place of catalyst granules cross section0/Co1It is 0.08～0.80.
Can also containing adjuvant component in hydrotreating catalyst of the present invention, one or more in such as fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component counts weight content in the catalyst for less than 15% with element, it is preferred to 1% ~ 10%.Hydrotreating catalyst of the present invention preferably comprises phosphorus, with P2O5Meter weight content in the catalyst is 1% ~ 6%.
In the hydrotreating catalyst of the present invention, described alumina-based supports refers to aluminium oxide for key component, can without adjuvant component, can also containing adjuvant component, wherein adjuvant component can be one or more in silicon, phosphorus, titanium, zirconium, boron etc., adjuvant component in element content in alumina-based supports at below 30wt%, it is preferable that below 20wt%.Described alumina-based supports can adopt conventional method to prepare.The character of described alumina-based supports is preferably as follows: specific surface area is 100～500m2/ g, it is preferred to 150 ~ 400m2/ g, pore volume is 0.25～1.0mL/g, it is preferred to 0.3 ~ 0.9mL/g.
The character of the hydrotreating catalyst of the present invention is as follows: specific surface area is 100～260m2/ g, it is preferred to 120 ~ 220m2/ g, pore volume is 0.20～0.60mL/g, it is preferred to 0.2 ~ 0.5mL/g.
In described hydrotreating catalyst, containing Organic substance, described Organic substance is carbon number be 2 ~ 20 organic compounds containing nitrogen, one or more in organic compounds containing sulfur and oxygen-containing organic compound.
In the hydrotreating catalyst of the present invention, Organic substance and Mo atomic molar are than for 0.002:1～2.0:1, it is preferred to 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, specifically one or more in ethylenediamine, hexamethylene diamine etc., it is preferably except the nitrogen-atoms comprising at least one covalent bond, also including at least the organic compound of a hydroxyl or carboxy moiety, such 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, 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 TGA, mercaptopropionic acid, dimercaptopropanol, BAL etc..Except above-mentioned sulfur-containing compound, it is possible to comprise sulfone and sulfoxide compound, one or more in dimethyl sulfoxide, dimethyl sulfone etc..
Described oxygen-containing organic compound is the Organic substance at least containing a carbon atom and an oxygen atom.Preferably comprising at least two oxygen atom 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 their combination.These materials can be one or more in acids, alcohols, ethers, saccharide, ketone, phenols, aldehydes and lipid.It is preferred that as follows: 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, 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..
The preparation method of hydrotreating catalyst provided by the invention, wherein active metal component Ni introduces in catalyst before step (1) and/or after step (2), active metal component Mo introduces the mode in catalyst: or whole Mo and Co is introduced in catalyst, or part Mo is with Co introduced in catalyst, and remainder Mo and Ni is introduced in catalyst；The process that active metal Co and all or part of Mo introduces in catalyst includes:
(1) adopting the unsaturated infusion process fountain solution oxide impregnation alumina-based support containing adsorbent, the consumption of adsorbent accounts for the 0.1% ~ 10% of alumina-based supports weight, adsorbent is carbon number be 2～15 organic carboxyl acid and its esters in one or more；
(2) dip loading active metal component Mo, Co on step (1) gains.
In the inventive method, part Mo is with Co introduced in catalyst, and remainder Mo and Ni is introduced in catalyst；Wherein the former introduce Mo amount with the latter introduce Mo amount mol ratio be 0.4 ~ 2.5.
In the inventive method, part Mo introduces before the step (1) in catalyst with Ni, the step (2) solution impregnation step (1) gains containing active metal component Mo, Co, drying or dry and roasting, obtains hydrotreating catalyst.
In the inventive method, part Mo introduces in catalyst with Ni after step (2), specific as follows:
(1) the unsaturated infusion process fountain solution oxide impregnation alumina-based support containing adsorbent is adopted, the consumption of wherein said adsorbent accounts for the 0.1% ~ 10.0% of alumina-based supports weight, adsorbent is carbon number be 2～15 organic carboxyl acid and its esters in one or more；
(2) with solution impregnation step (1) gains containing active metal component Mo, Co, drying and roasting,
(3), after dip loading active metal Mo, Ni on step (2) gains, drying or dry and roasting, hydrotreating catalyst is obtained.
Described adsorbent 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 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, in the fountain solution containing adsorbent, adopting water and/or ethanol is solvent.
The described fountain solution containing adsorbent can also comprise alcohol, wherein alcohol is one or more in the alcohol of below C5, can being one or more in monohydric alcohol, polyhydric alcohol, concrete alcohol comprises one or more in ethylene glycol, propylene glycol, glycerol, tetramethylolmethane, xylitol etc..The addition of described alcohol accounts for the 0.1% ~ 10% of alumina-based supports weight.
In the present invention, dipping, containing the fountain solution of adsorbent, adopts unsaturated dipping, it is desirable to adopt unsaturated spraying, and wherein the volume ratio of dip amount used by unsaturated dipping and alumina-based supports saturated absorption amount of solution is 0.02 ~ 0.4.Dipping is containing after the fountain solution of adsorbent, it is possible to drying, it is also possible to direct impregnation contains the solution of active metal Mo, Co, and wherein baking temperature is generally 60 DEG C～250 DEG C, it is preferred to 100～200 DEG C, drying time 0.5h～20h, it is preferred to 1h～6h.When spraying the fountain solution containing adsorbent, the shower nozzle that atomizing effect is good should be selected, make solution evenly spread in alumina-based supports.The dipping fountain solution dipping containing adsorbent can be directly entered next step, it is possible to carry out next step again through health preserving after terminating, and conditioned time is 0.5～8h.
The inventive method, in step (2), after impregnating with the dipping solution containing Mo, Co, can through health preserving, it is possible to without health preserving, as needed health preserving, conditioned time is 0.5～8.0h, then is dried.Described drying condition is as follows: baking temperature is 60 DEG C～250 DEG C, it is preferred to 70 ~ 200 DEG C, it is preferred to 100～200 DEG C, drying time 0.5h～20h, it is preferred to 1h～6h.Can carrying out roasting after dry, described roasting condition is as follows: burning temperature is 300 DEG C～750 DEG C, it is preferred to 400 DEG C～650 DEG C, roasting time is 0.5h～20h, it is preferred to 1h～6h.
The inventive method, the drying condition described in step (3) is as follows: baking temperature is 60 DEG C～250 DEG C, it is preferred to 70 ~ 200 DEG C, it is preferred to 100～200 DEG C, drying time 0.5h～20h, it is preferred to 1h～6h.Can carrying out roasting after dry, described roasting condition is as follows: burning temperature is 300 DEG C～750 DEG C, it is preferred to 400 DEG C～650 DEG C, roasting time is 0.5h～20h, it is preferred to 1h～6h.
In hydrotreating catalyst preparation method of the present invention, active metal Mo, Co load in alumina-based supports by infusion process, generally adopt incipient impregnation.Dipping method known to the skilled person which.After the solution impregnation alumina-based supports containing active metal, it is necessary to through super-dry.Active metal solution manufacturing method known to the skilled person which, its solution concentration can be regulated by the consumption of each compound, thus preparing 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, cobalt source is from one or more in cobalt nitrate, cobalt carbonate, basic cobaltous carbonate, cobaltous chloride, cobalt oxalate.Tungsten source is ammonium metatungstate.Nickel source is from one or more in nickel nitrate, nickelous carbonate, basic nickel carbonate, Nickel dichloride., nickel oxalate.In the solution containing active metal Mo, Ni of the step (2) solution containing active metal component Mo, Co and/or step (3), containing phosphorus, phosphorus source is one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate, and the introduction volume of phosphorus is with P2O5Meter accounts for the 1% ~ 6% of final hydrotreating catalyst weight.
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, it is also possible to introducing catalyst after prepared by carrier.Introduce after prepared by carrier in catalyst, it is possible to adopt the method for individually dipping to introduce in catalyst, it is also possible to together to impregnate in introducing catalyst with active metal component.
Can containing Organic substance in described hydrotreating catalyst, Organic substance is selected from for one or more in organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic compound that carbon number is 2 ~ 20.
In the hydrotreating catalyst of the present invention, Organic substance and Mo and W atomic molar are than for 0.002:1～2.0:1, it is preferred to 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, specifically one or more in ethylenediamine, hexamethylene diamine etc., it is preferably except the nitrogen-atoms comprising at least one covalent bond, also including at least the organic compound of a hydroxyl or carboxy moiety, such 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, 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 TGA, mercaptopropionic acid, dimercaptopropanol, BAL etc..Except above-mentioned sulfur-containing compound, it is possible to comprise sulfone and sulfoxide compound, one or more in dimethyl sulfoxide, dimethyl sulfone etc..
Described oxygen-containing organic compound is the Organic substance at least containing a carbon atom and an oxygen atom.Preferably comprising at least two oxygen atom 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 their combination.These materials can be one or more in acids, alcohols, ethers, saccharide, ketone, phenols, aldehydes and lipid.It is preferred that as follows: 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, 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..
The mode that described Organic substance introduces in catalyst can adopt usual manner to introduce, it is possible to individually impregnates introducing, it is also possible to introduces with active metal solution total immersion, and after introducing Organic substance, general drying processes and can obtain containing organic hydrotreating catalyst.
Hydrotreating catalyst of the present invention in the hydrodesulfurization (especially deep hydrodesulfurizationof) of heavy distillate (especially diesel oil) as the application of Hydrobon catalyst.
Described heavy distillate can be diesel oil, wax oil, wherein preferred diesel oil.The total sulfur content of described heavy distillate is generally 0.3wt% ~ 3.0wt%, preferred 0.3wt% ~ 2.5wt%, the sulfur content that wherein difficult de-sulfur-containing compound (with 4,6-dimethyl Dibenzothiophene for meter) is contributed is about more than 0.01wt%, is usually 0.01wt% ~ 0.05wt%.
Adopt hydrotreating catalyst of the present invention as Hydrobon catalyst, the total sulfur content of described heavy distillate can be reduced to 0.05wt% or lower, it is preferably decreased to 0.005wt% or lower, especially can remove the de-sulfur-containing compound of described difficulty of more than 80wt% (preferred more than 90wt%).
The present invention, in described application or described hydrodesulfurizationprocess process, can only use the hydrotreating catalyst of the present invention, can also by the hydrotreating catalyst of the present invention and other hydrotreating catalysts (than as be known in the art those) according to the ratio arbitrarily needed with the use of, such as adopt different catalysts bed grating or mixing to use.
According to the present invention, the operating condition of described hydrodesulfurization do not had any special restriction, it is possible to adopt operating condition commonly used in the art, such as can enumerate reaction temperature 260 ~ 400 DEG C, it is preferable that 310 ~ 370 DEG C, react stagnation pressure 3 ~ 13MPa, preferably 5 ~ 9MPa, volume space velocity 0.5 ~ 4h during liquid-1, it is preferable that 1 ~ 2h-1, hydrogen to oil volume ratio 200:1 ~ 2000:1, it is preferable that 400:1 ~ 1000:1.
In hydrotreating catalyst of the present invention, active metal component Co and Mo is from catalyst granules outer surface to center in the trend being gradually increased, and Ni is substantially uniformly distributed, it is preferable that containing Organic substance.This catalyst is particularly well-suited in hydrodesulfurization, improves the activity and selectivity of hydrodesulfurization, and especially elimination has the thiophene sulfocompounds of sterically hindered difficult elimination.
Hydrotreating catalyst prepared by the present invention, by the unsaturated dipping fountain solution containing adsorbent, the adsorbed agent of a part of adsorption potential making carrier particle exterior surface and marginal position surface occupies, dipping is containing active metal Mo, during the solution of Co, decrease Mo, Co is in the absorption of carrier edge position, the active metal Mo of dipping after making, the concentration of Co is the trend being gradually increased from outer surface to center, the amount making Mo-Co activity phase further is the trend being gradually increased from outer surface to center, Ni is uniformly distributed in each catalyst granules, particularly it is collectively incorporated in catalyst with part Mo, so by controlling Mo, Co, the CONCENTRATION DISTRIBUTION of Ni different metal, make it cooperate, thus improving the activity and selectivity of catalyst, especially elimination has the thiophene sulfocompounds of sterically hindered difficult elimination.Additionally, the present invention is by controlling the preparation condition of hydrotreating catalyst, Organic substance is made to be present in final hydrotreating catalyst, 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 the selected each position point that catalyst granules passes through after cutting on gained cross section and this cross section, wherein 0 any point represented on this cross section in outer most edge and 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 is active metal component Ni and Co concentration profile on this cross section in embodiment 3 gained catalyst C4.Wherein abscissa is each position point on this cross section, and vertical coordinate is concentration and the ratio of the concentration of central spot on this cross section at a certain location point place.
Detailed description of the invention
In the inventive method, the method introducing active metal Ni and part Mo before the step (1), can adopt following at least one method: add in carrier component dry glue powder preparation process then reshaping make the alumina-based supports containing Ni and Mo, add the alumina-based supports made containing Ni and Mo and carrier component molding when carrier component kneading and compacting after adopt infusion process to add the alumina-based supports made containing Ni and Mo.Illustrate for aluminium oxide as carrier component:
One, add in the preparation process of aluminum oxide dry glue powder, as introduced with co-precipitation, fractional precipitation mode, then molding, prepare the alumina support containing Ni and Mo after drying, roasting；
Two, adding with kneading form when carrier molding: aluminum oxide dry glue powder is mixed homogeneously with the active metal component compound containing Mo and Ni, then through kneading and compacting, the alumina support containing Ni and Mo is made in dry, roasting；
Three, by aluminum oxide dry glue powder kneading and compacting, being then dried, carrier is made in roasting, afterwards with the solution impregnation of alumina carrier containing Mo and Ni active metal component, drying, roasting make the alumina support containing Ni and Mo.
In above-mentioned forming process, it is possible to adding conventional shaping assistant, one or more in such as extrusion aid, binding agent, peptizer etc., addition can be determined by this area knowledge according to preparing catalyst property.Wherein binding agent is generally adopted little porous aluminum oxide, the boehmite produced selected from aluminum chloride-Ammonia Process, carbonizatin method or aluminum sulfate method and the SB alumina powder etc. of Zlegler synthetic reaction by-product.
In hydrotreating catalyst preparation method of the present invention, the dry and roasting in the carrying alumina production procedure containing Ni and Mo adopts prior art condition, and if baking temperature is 40 DEG C～250 DEG C, drying time is 0.5h～20h；Sintering temperature is 350 DEG C～750 DEG C, and roasting time is 0.5h～20h.
According to the preparation method of hydrotreating catalyst provided by the invention, it specifically comprises the following steps that
I, the preparation alumina-based supports containing Mo and Ni；
II, being added to the water by required adsorbent, selectively add alcohol, prepare fountain solution, the volume of described fountain solution accounts for the 2%～40% of the saturated liquid absorption of catalyst precarsor；
III, spraying fountain solution in alumina-based supports with the shower nozzle that atomizing effect is good, the volume according to fountain solution, the time of spraying is 1min～40min；
IV, step III gained sample carries out next step again preferably through health preserving, and conditioned time is 0.5～8h.
V, step IV gained sample is preferably through carrying out next step more after drying, and baking temperature is generally 60 DEG C～250 DEG C, and 0.5h～20h, controlled drying condition and made adsorbent be present in catalyst drying time；
VI, adopt equi-volume impregnating, with the active metal solution impregnation step V gained sample containing Mo, Co, dry 0.5h～20h at 70 DEG C～300 DEG C temperature, control drying condition and make adsorbent be present in catalyst, obtain hydrotreating catalyst.
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 adopts X-ray fluorescence spectroscopy to measure.
(2) specific surface area (m of catalyst2/ g) and pore volume (ml/g) adopt BET method to 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 obtain.In order to measure each active metal component CONCENTRATION DISTRIBUTION in this catalyst granules, 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) carries out.Measuring condition is: accelerating potential 15kV, beam intensity 5 × 10-8A, beam spot diameter, 1 μm, X ray detection angle: W is 53 °, and Mo is 38 °, and Ni is 24 °, and Co is 26 °, correction method: ZAF correction method, the standard specimen of use: pure metal oxides standard specimen (respectively NiO, CoO, MoO3And WO3), precision: less than 1%, secondary electron image resolution: 3nm(LaB6), linear system: Ni and Co adopts KαLinear system, Mo adopts LαLinear system, W adopts MαLinear 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 also referred to as radially), the concentration value of measuring gage allocation point place targeted activity metal, then pass through division calculation, it is thus achieved that the ratio (being mol ratio in the present invention) of each concentration value.
Fig. 4 be embodiment 3 gained catalyst C4 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 for abscissa, the ratio of the concentration value of the corresponding active metal that the concentration value of the targeted activity metal (for Ni and Co) measured with each position point place is measured to location point 1 place (i.e. central point) (uses Ni respectivelym/Ni1And Com/Co1Represent) for vertical coordinate, so draw and obtain.
(4) catalyst is relatively desulphurizing activated
Relatively desulphurizing activated=100 × [(1/S1)0.65-(1/S0)0.65]/[(1/Sc1)0.65-(1/S0)0.65], S in formula1And Sc1Represent the sulfur content adopted in catalyst of the present invention or reference agent gained hydrogenation products, S respectively0Represent the sulfur content adopted in catalyst of the present invention or the raw materials used oil of reference agent.Wherein sulfur content is in S, and unit is μ g/g.
Total sulfur content in raw material and hydrogenation products is to adopt ultraviolet fluorescence method to measure (ASTMD5453-1993), and 4,6-BMDBT content are to adopt GC-AED(gas chromatogram-atom luminescence spectroscopy) measure.
(5) number-average molecular weight Mn adopts GPC method to measure.
Column type carrier used in embodiment, wherein carrier lengths is about 3 ~ 5mm.
Embodiment 1
The preparation method that the present embodiment introduces catalyst precarsor.The aluminum oxide dry glue powder specific surface 350m of siliceous, boron2/ g, pore volume is 0.90ml/g.
Weigh aluminum oxide dry glue powder 400g siliceous, boron, add citric acid and each 6g of sesbania powder, after mix homogeneously, add acid solution 345g, HNO in acid solution3Weight concentration be 1.74%, all the other are distilled water.After rolling 20min, by the circular orifice extrusion of diameter 1.7mm.After 120 DEG C of dry 4h, 500 DEG C of roasting 3h.The carrier strip prepared is designated as S1.With the carrier strip S1 obtained by the solution impregnation containing Mo, Ni, after 130 DEG C of dry 4h, 500 DEG C of roasting 2h, the prepared alumina-based supports containing Mo and Ni is designated as Z1.
Weigh aluminum oxide dry glue powder 400g siliceous, boron, add citric acid and each 6g of sesbania powder, add acid solution 345g, HNO in acid solution3Weight concentration be 2.6%, Mo is with MoO3The weight content of meter is 12.9%, and Ni is with the NiO weight content counted for 2.9%, and all the other are distilled water.After rolling 20min, by the circular orifice extrusion of diameter 1.7mm.500 DEG C of roasting 3h after 120 DEG C of dry 4h, the prepared alumina-based supports containing Mo and Ni is designated as Z2.
Prepare the aluminum oxide dry glue powder of siliceous, molybdenum and nickel.In container, add 1L deionized water, be warming up to 58 DEG C, be simultaneously introduced 3L containing Al2O3For the aluminum nitrate solution of 4g/100mL with containing NH3For the ammonia spirit of 10g/100mL, controlling pH value is 7.8, and feed time is 120min.After stopping is reinforced, system is aging 50min when said temperature and pH value, adds SiO2Content is the solution of sodium metasilicate through 100mL of 4.2g, continues aging 60min, is washed out 4 times, to Cl-/Al2O3< till 0.5%.Preparation aqueous solution 1L, wherein MO containing molybdenum and nickel3Concentration 1.8g/100mL, NiO concentration 0.4g/100mL, adds in filter cake, stirs into pasty state, after 120 DEG C of dry 8h, be crushed to granularity and account for more than 95% less than 180 purposes, obtain required dry glue powder.
The character of siliceous, the molybdenum of gained and the aluminum oxide dry glue powder of nickel is as follows: specific surface 330m2/ g, pore volume is 0.85ml/g.
Weigh the aluminum oxide dry glue powder 400g of siliceous, molybdenum and nickel, add citric acid and each 6g of sesbania powder, after mix homogeneously, add acid solution 345g, HNO in acid solution3Weight concentration be 1.74%, all the other are distilled water.After rolling 20min, by the circular orifice extrusion of diameter 1.7mm.500 DEG C of roasting 3h after 120 DEG C of dry 4h.The alumina-based supports containing Mo and Ni prepared is designated as Z3.
The composition of the table 1 alumina-based supports containing Mo and Ni and character
| Catalyst precarsor | Z1 | Z2 | Z3 |
| Si, wt% | 1.33 | 1.34 | 1.36 |
| B, wt% | 1.66 | 1.63 | - |
| NiO, wt% | 2.87 | 2.95 | 2.78 |
| MO3, wt% | 12.5 | 12.9 | 12.2 |
| Specific surface area, m2/g | 218 | 221 | 225 |
| Pore volume, mL/g | 0.52 | 0.53 | 0.53 |
| Saturated liquid absorption, mL/100g | 60 | 61 | 61 |
Embodiment 2
Weigh citric acid 5.0g, stirring and dissolving in 45g water, prepare fountain solution.Taking Z1300g, be uniformly sprayed on Z1 by fountain solution, spraying time is 10min.Fountain solution sprays after terminating, sample average is divided into three parts, wherein first part of direct 100 DEG C of dry 2h of sample, with impregnation liquid (the first impregnation liquid) the above-mentioned sample of incipient impregnation containing Mo, Co, P and mercaptopropionic acid, the mercaptopropionic acid introduced and the mol ratio of Mo are 0.02:1, after 120 DEG C of dry 3h, it is thus achieved that finished product be designated as C1；Second sample health preserving 1h, through the post-processing step identical with C1, through 120 DEG C of dry 3h, prepared finished product is designated as C2；Triplicate sample health preserving 5h, through the post-processing step identical with C1, through 120 DEG C of dry 3h, prepared finished product is designated as C3.
Embodiment 3
Weigh oxalic acid 0.8g, stirring and dissolving in 4g ethanol, prepare fountain solution.Taking Z2100g, be uniformly sprayed on precursor by fountain solution, spraying time is 4min.Fountain solution sprays and terminates rear health preserving 0.5h.Sample is through 110 DEG C of dry 2h, and after impregnation liquid (the first impregnation liquid) the above-mentioned sample of incipient impregnation containing Mo, Co, P and ethylene glycol, the ethylene glycol of introducing and the mol ratio of Mo are 0.2:1, after 120 DEG C of dry 3h, it is thus achieved that finished product be designated as C4.
Embodiment 4
Weigh malonic acid 6g, stirring and dissolving in 20g water, prepare fountain solution.Taking Z3100g, be uniformly sprayed on Z3 by fountain solution, spraying time is 25min.Fountain solution sprays and terminates rear health preserving 1h, sample is through 100 DEG C of dry 2h, and with impregnation liquid (the first impregnation liquid) the above-mentioned sample of incipient impregnation containing Mo, Co, P and dimethyl sulfone, the dimethyl sulfone of introducing and the mol ratio of Mo are 0.3:1, after 120 DEG C of dry 3h, it is thus achieved that finished product be designated as C5.
Comparative example 1
Take Z1100g, with the above-mentioned carrier of impregnation liquid incipient impregnation containing Mo, Co, P, oxalic acid and ethylene glycol, its mesoxalic acid 0.8g, the ethylene glycol introduced and the mol ratio of Mo are 0.2:1, after the above-mentioned carrier of incipient impregnation, through 120 DEG C of dry 3h, it is thus achieved that catalyst be designated as C6.
Table 2 embodiment and comparative example catalyst activity metal composition
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 |
| Mo(is with MoO3Meter), wt% | 24.3 | 24.3 | 24.4 | 24.6 | 24.5 | 24.3 |
| Co(is in CoO), wt% | 2.4 | 2.3 | 2.3 | 2.4 | 2.3 | 2.3 |
| Ni(is in NiO), wt% | 2.1 | 1.9 | 2.0 | 2.1 | 1.9 | 2.0 |
| P(is with P2O5Meter), wt% | 2.7 | 2.8 | 2.7 | 2.7 | 2.8 | 2.8 |
| Mo and the first impregnation liquid introduced in carrier introduces the mol ratio of Mo | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 |
Table 3 embodiment and elements Mo CONCENTRATION DISTRIBUTION in catalyst granules in comparative example gained catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 |
| Mo0/Mo1 | 0.55 | 0.66 | 0.78 | 0.71 | 0.63 | 1.0 |
| Mo1/4/Mo1 | 0.64 | 0.73 | 0.82 | 0.77 | 0.69 | 1.01 |
| Mo1/2/Mo1 | 0.82 | 0.90 | 0.93 | 0.94 | 0.89 | 0.98 |
| Mo3/4/Mo1 | 0.95 | 0.97 | 0.98 | 0.99 | 0.98 | 0.99 |
Table 4 embodiment and Elements C o CONCENTRATION DISTRIBUTION in catalyst granules in comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 |
| Co0/ Co1 | 0.15 | 0.27 | 0.49 | 0.32 | 0.24 | 1.0 |
| Co1/4/ Co1 | 0.31 | 0.43 | 0.60 | 0.80 | 0.41 | 0.99 |
| Co1/2/ Co1 | 0.64 | 0.79 | 0.86 | 0.95 | 0.72 | 1.01 |
| Co3/4/ Co1 | 0.93 | 0.94 | 0.98 | 0.99 | 0.90 | 1.0 |
Table 5 embodiment and element Ni CONCENTRATION DISTRIBUTION in catalyst granules in comparative example catalyst
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | C6 |
| Ni0/Ni1 | 1.01 | 1.0 | 1.01 | 1.01 | 0.99 | 1.02 |
| Ni/4/Ni1 | 1.0 | 1.02 | 0.99 | 1.02 | 0.98 | 1.0 |
| Ni1/2/Ni1 | 0.99 | 1.01 | 1.0 | 1.00 | 1.01 | 0.99 |
| Ni3/4/Ni1 | 1.02 | 0.99 | 0.98 | 1.01 | 1.0 | 1.0 |
From table 2, table 3, table 4 and table 5, adopt catalyst C1～C5 prepared by the present invention, active metal Mo, Co are radially gradually increased along catalyst granules from edge to centre concentration, and comparative example catalyst C6 active metal Mo, Co are radially to locate the concentration on each position essentially identical, preparing catalyst unlike the present invention is obvious Gradient distribution.Found by C1, C2 and C3, spray terminate rear conditioned time by controlling fountain solution, it is possible to adjust active metal at catalyst granules distributed density radially；Find out from C2, C4 and C5, also can be adjusted active metal Mo, Co by the change in volume of fountain solution at catalyst granules distributed density radially.Therefore the preparation method of catalyst of the present invention is compared with comparative example catalyst, active metal can be adjusted easily at catalyst granules distributed density radially, make Mo, Co that hydrodesulfurization activity is higher higher in granular center concentration, make reactant molecule in the diffusion process at catalyst granules center, first pass through hydrogenation saturated after, reaction in Mo, Co active sites that direct desulfurization activity is higher again, thus improving the deep desulfuration performance of catalyst.
Embodiment 5
The present embodiment is activity rating of catalyst experiment.
Catalyst activity evaluation experimental carries out on 100mL small hydrogenation device, before activity rating, catalyst is carried out presulfurization.Evaluating catalyst condition is at reaction stagnation pressure 6.5MPa, volume space velocity 2.0h during liquid-1, hydrogen-oil ratio 500:1, reaction temperature is 335 DEG C.Active appraisal experiment raw oil character is in Table 6, Activity evaluation is in Table 7, and table 8 provides the content of the difficult de-sulfur-containing compound of typical case in hydrogenation products, from data in table, hydrotreating catalyst is prepared, catalyst desulphurizing activated apparently higher than comparative example catalyst by the present invention.
Table 6 raw oil character
| Raw oil | Atmosphere 3rd side cut diesel oil |
| Density (20 DEG C), g/cm3 | 0.8533 |
| Boiling range, DEG C | |
| IBP | 217 |
| EBP | 375 |
| S, wt% | 1.78 |
| N, μ g/g | 140 |
Table 7 catalyst activity evaluation result
| Catalyst | C1 | C2 | C3 | C4 | C5 | C6 |
| Relatively desulphurizing activated, % | 118 | 125 | 120 | 117 | 127 | 100 |
The content of the difficult de-sulfur-containing compound of typical case in table 8 raw material and hydrogenation products
| Raw material/hydrogenation products | Raw material | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products |
| Catalyst | C1 | C2 | C3 | C4 | C5 | C6 | |
| 4,6-BMDBT, μ g/g | 215 | 14.2 | 12.7 | 13.7 | 14.0 | 12.3 | 21.9 |
Embodiment 6
Employing the alumina support of cylinder in embodiment 6 and comparative example 2, diameter is about 1.2mm, and length is about 3 ~ 5mm, and its physico-chemical property is as shown in table 9.
The physico-chemical property of alumina support used in table 9 embodiment and comparative example
| Project | Alumina support |
| Specific surface area, m2/g | 298 |
| Pore volume, mL/g | 0.64 |
| Bulk density, g/100ml | 63 |
| Saturated liquid absorption, ml/100g | 75 |
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.
Weigh citric acid 1.6g, stirring and dissolving in 15g water, prepare fountain solution.Taking alumina support 100g, uniformly sprayed on the alumina support by fountain solution, spraying time is 10min, and fountain solution sprays after terminating, and obtains sample.Above-mentioned same method is adopted to prepare three parts of sample.Fountain solution spray terminate after, first part of direct 100 DEG C of dry 2h of sample, with impregnation liquid (being called the first impregnation liquid) the above-mentioned carrier of incipient impregnation containing Mo, Co, P, after 120 DEG C of dry 3h, 480 DEG C of roasting 2h, it is thus achieved that semi-finished product be designated as BD1；Fountain solution sprays and terminates rear second sample health preserving 1h, and through the post-processing step identical with catalyst BD1, prepared semi-finished product are designated as BD2；Fountain solution sprays and terminates rear triplicate sample health preserving 5h, and through the post-processing step identical with catalyst BD1, prepared semi-finished product are designated as BD3.
Respectively with impregnation liquid (being called the second impregnation liquid) the above-mentioned BD1 of incipient impregnation, BD2 and the BD3 containing Mo, Ni, P, after 120 DEG C of dry 3h, 480 DEG C of roasting 2h, it is thus achieved that catalyst be designated as CD1, CD2 and CD3 respectively.
Comparative example 2
Take alumina support 100g, after the above-mentioned carrier of impregnation liquid incipient impregnation containing Mo, Co, P, after 120 DEG C of dry 3h, 480 DEG C of roasting 2h, it is thus achieved that semi-finished product be designated as BD4.With the 69mL impregnation liquid incipient impregnation BD4 containing Mo, Ni, P, after 120 DEG C of dry 3h, 480 DEG C of roasting 2h, it is thus achieved that catalyst be designated as CD4.
Table 10 embodiment and comparative example catalyst activity metal component composition
| Catalyst is numbered | CD1 | CD2 | CD3 | CD4 |
| Composition | ||||
| MoO3, wt% | 25.2 | 25.5 | 25.4 | 25.5 |
| CoO, wt% | 2.4 | 2.3 | 2.4 | 2.3 |
| NiO, wt% | 2.6 | 2.5 | 2.6 | 2.5 |
| P2O5, wt% | 2.8 | 2.7 | 2.7 | 2.8 |
| Aluminium oxide | Surplus | Surplus | Surplus | Surplus |
| First containing Mo impregnation liquid and second containing the mol ratio of Mo in Mo impregnation liquid | 1.0 | 1.0 | 1.0 | 1.0 |
Table 11 embodiment and elements Mo CONCENTRATION DISTRIBUTION in catalyst granules in comparative example gained catalyst semi-finished product
| Catalyst is numbered | BD1 | BD2 | BD3 | BD4 |
| Mo0/Mo1 | 0.13 | 0.28 | 0.55 | 1.01 |
| Mo1/4/Mo1 | 0.32 | 0.42 | 0.62 | 0.99 |
| Mo1/2/Mo1 | 0.67 | 0.79 | 0.86 | 1.0 |
| Mo3/4/Mo1 | 0.89 | 0.94 | 0.96 | 1.01 |
Table 12 embodiment and elements Mo CONCENTRATION DISTRIBUTION in catalyst granules in comparative example gained catalyst
| Catalyst is numbered | CD1 | CD2 | CD3 | CD4 |
| Mo0/Mo1 | 0.56 | 0.65 | 0.77 | 0.99 |
| Mo1/4/Mo1 | 0.66 | 0.71 | 0.82 | 1.01 |
| Mo1/2/Mo1 | 0.83 | 0.89 | 0.92 | 0.98 |
| Mo3/4/Mo1 | 0.95 | 0.97 | 0.98 | 1.00 |
Table 13 embodiment and Elements C o CONCENTRATION DISTRIBUTION in catalyst granules in comparative example catalyst
| Catalyst is numbered | CD1 | CD2 | CD3 | CD4 |
| Co0/ Co1 | 0.14 | 0.26 | 0.50 | 0.98 |
| Co1/4/ Co1 | 0.30 | 0.44 | 0.61 | 0.99 |
| Co1/2/ Co1 | 0.64 | 0.78 | 0.85 | 1.02 |
| Co3/4/ Co1 | 0.92 | 0.94 | 0.98 | 1.01 |
Table 14 embodiment and element Ni CONCENTRATION DISTRIBUTION in catalyst granules in comparative example catalyst
| Catalyst is numbered | CD1 | CD2 | CD3 | CD4 |
| Ni0/Ni1 | 1.0 | 1.01 | 0.99 | 1.01 |
| Ni/4/Ni1 | 1.02 | 1.02 | 0.98 | 0.99 |
| Ni1/2/Ni1 | 1.01 | 1.00 | 1.01 | 1.0 |
| Ni3/4/Ni1 | 0.99 | 1.01 | 1.0 | 0.98 |
Embodiment 7
The present embodiment is activity rating of catalyst experiment.
Catalyst activity evaluation experimental carries out on 100ml small hydrogenation device, before activity rating, catalyst is carried out presulfurization.Evaluating catalyst condition is at reaction stagnation pressure 6.0MPa, volume space velocity 2.0h during liquid-1, hydrogen-oil ratio 500:1, reaction temperature is 340 DEG C.Active appraisal experiment raw oil character is in Table 6, and Activity evaluation is in Table 15 and 16, from data in table, prepares hydrotreating catalyst by the present invention, catalyst desulphurizing activated apparently higher than comparative example catalyst.
Table 15 catalyst activity evaluation result
| Catalyst | CD1 | CD2 | CD3 | CD4 |
| Relatively desulphurizing activated, % | 127 | 136 | 131 | 100 |
The content of difficult de-sulfur-containing compound in table 16 raw oil and hydrotreatment products
| Raw material/hydrogenation products | Raw material | Hydrogenation products | Hydrogenation products | Hydrogenation products | Hydrogenation products |
| Catalyst is numbered | CD1 | CD2 | CD3 | CD4 | |
| 4,6-BMDBT, μ g/g | 215 | 15.9 | 14.6 | 15.3 | 23.1 |
Claims (32)
1. a hydrotreating catalyst, adopts alumina-based supports, and active metal component is Co, Mo, Ni, and wherein active metal component CONCENTRATION DISTRIBUTION on each catalyst granules cross section is as follows: Co0/Co1< Co1/2/Co1< 1, Mo0/Mo1< Mo1/2/Mo1The concentration of < 1, Ni is for being uniformly distributed；
Wherein, active metal component CONCENTRATION DISTRIBUTION formula A on the cross section of each catalyst granulesm/BnRepresenting, i.e. the ratio of the concentration of the concentration of m place elements A and 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；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 adopts active metallic element Mo, Co or Ni to replace, and m and n is directly with defined location point on the above-mentioned straight-line segment of the digitized representation of 0～1；
With the weight of catalyst for benchmark, Mo is with MoO3The content of meter is that 10wt%～40wt%, Co are with the CoO content counted for 0.5wt%～6wt%, Ni with the NiO content counted for 1wt%～8wt%.
2. the catalyst described in claim 1, it is characterised in that in described hydrotreating catalyst, 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) Mo0/Mo1With Mo1/2/Mo1Ratio be 0.2 ~ 0.8；
(3) Co0/Mo0Ratio be 0.07 ~ 2.0.
3. the catalyst described in claim 1, it is characterised in that in described hydrotreating catalyst, 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) Mo0/Mo1With Mo1/2/Mo1Ratio be 0.2 ~ 0.7；
(3) Co0/Mo0Ratio be 0.08 ~ 1.2.
4. the catalyst described in claim 1, it is characterised in that in described hydrotreating catalyst, active metal component CONCENTRATION DISTRIBUTION on catalyst granules cross section 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) Mo0/Mo1< Mo1/4/Mo1< Mo1/2/Mo1；
(4) Mo1/2/Mo1< Mo3/4/Mo1< 1.
5. the catalyst described in claim 1, it is characterised in that in described hydrotreating catalyst, active metal component CONCENTRATION DISTRIBUTION on catalyst granules cross section at least includes following a kind of scheme:
(1) Co0/Co1< Cox1/Co1< Cox2/Co1< 1, wherein 0 < x1 < x2 < 1；
(2) Mo0/Mo1< Mox1/Mo1< Mox2/Mo1< 1, wherein 0 < x1 < x2 < 1.
6. the catalyst described in claim 4, it is characterised in that in described hydrotreating catalyst, 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) Mo0/Mo1With Mo1/4/Mo1Ratio be 0.3 ~ 0.9；
(4) Mo1/4/Mo1With Mo1/2/Mo1Ratio be 0.4 ~ 0.9.
7. the catalyst described in claim 4, it is characterised in that in described hydrotreating catalyst, 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) Mo0/Mo1With Mo1/4/Mo1Ratio be 0.3 ~ 0.85；
(4) Mo1/4/Mo1With Mo1/2/Mo1Ratio be 0.4 ~ 0.87.
8. the catalyst described in claim 1, it is characterized in that in described hydrotreating catalyst, on catalyst granules cross section, along described straight-line segment from outer most edge point to central point, active metal component concentration distribution is as follows: the concentration of Co is gradually increased, the concentration of Mo is gradually increased, the even concentration distribution of Ni.
9. the catalyst described in claim 1, it is characterised in that described hydrotreating catalyst, with the weight of catalyst for benchmark, the content of alumina-based supports is that 46wt% ~ 87wt%, Mo are with MoO3The content of meter is that 10wt%～40wt%, Co are with the CoO content counted for 0.5wt%～6wt%, Ni with the NiO content counted for 1wt%～8wt%.
10. the catalyst described in claim 1, it is characterised in that in described hydrotreating catalyst, is positioned at mol ratio and the Mo of the Mo and granular center place Mo of catalyst granules outer surface0/Mo1It is 0.08～0.90, is positioned at mol ratio and the Co of the Co and center Co of catalyst granules outer surface0/Co1It is 0.08～0.80.
11. the catalyst described in claim 1, it is characterised in that the character of described hydrotreating catalyst is as follows: specific surface area is 120～220m2/ g, pore volume is 0.20～0.60mL/g.
12. the catalyst described in claim 1, it is characterized in that in described hydrotreating catalyst, containing Organic substance, described Organic substance is carbon number be 2 ~ 20 organic compounds containing nitrogen, one or more in organic compounds containing sulfur and oxygen-containing organic compound.
13. according to the arbitrary described catalyst of claim 1 ~ 12, it is characterised in that the Organic substance contained in described hydrotreating catalyst and Mo atomic molar ratio is for 0.002:1～2.0:1.
14. according to the arbitrary described catalyst of claim 1 ~ 12, it is characterised in that the Organic substance contained in described hydrotreating catalyst and Mo atomic molar ratio is for 0.02:1 ~ 1.0:1.
15. the catalyst described in claim 1, it is characterized in that in described hydrotreating catalyst, alumina-based supports is with aluminium oxide for key component, without adjuvant component or containing adjuvant component, wherein adjuvant component is one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component in element content in alumina-based supports at below 30wt%.
16. the catalyst described in claim 1, it is characterized in that in described hydrotreating catalyst, containing adjuvant component, wherein adjuvant component is one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron, adjuvant component in element weight content in the catalyst at below 15wt%.
17. the catalyst described in claim 1, it is characterised in that containing phosphorus in described hydrotreating catalyst, with P2O5Meter weight content in the catalyst is 1% ~ 6%.
18. the preparation method of the arbitrary described catalyst of claim 1 ~ 15, wherein active metal component Ni introduces in catalyst before step (1) and/or after step (2), active metal component Mo introduces the mode in catalyst: or whole Mo and Co is introduced in catalyst, or part Mo is with Co introduced in catalyst, and remainder Mo and Ni is introduced in catalyst；
The process that active metal Co and all or part of Mo introduces in catalyst includes:
(1) adopting the unsaturated infusion process fountain solution oxide impregnation alumina-based support containing adsorbent, the consumption of adsorbent accounts for the 0.1% ~ 10% of alumina-based supports weight, adsorbent is carbon number be 2～15 organic carboxyl acid and its esters in one or more；
(2) dip loading active metal component Mo, Co on step (1) gains.
19. in accordance with the method for claim 18, it is characterised in that: part Mo is with Co introduced in catalyst, and remainder Mo and Ni is introduced in catalyst, and wherein the former introduces the mol ratio that Mo amount and the latter introduce Mo amount is 0.4 ~ 2.5.
20. the method described in claim 18 or 19, it is characterized in that: part Mo introduced in catalyst with Ni before step (1), the step (2) solution impregnation step (1) gains containing active metal component Mo, Co, drying or dry and roasting, obtain hydrotreating catalyst.
21. the method described in claim 18 or 19, it is characterised in that: part Mo introduces in catalyst with Ni after step (2), specific as follows:
(1) the unsaturated infusion process fountain solution oxide impregnation alumina-based support containing adsorbent is adopted, the consumption of wherein said adsorbent accounts for the 0.1% ~ 10.0% of alumina-based supports weight, adsorbent is carbon number be 2～15 organic carboxyl acid and its esters in one or more；
(2) with solution impregnation step (1) gains containing active metal component Mo, Co, drying and roasting,
(3), after dip loading active metal Mo, Ni on step (2) gains, drying or dry and roasting, hydrotreating catalyst is obtained.
22. in accordance with the method for claim 18, it is characterised in that described adsorbent 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；Organic carboxylate is one or more in the ammonium salt of above-mentioned organic carboxyl acid.
23. in accordance with the method for claim 18, it is characterized in that the described fountain solution containing adsorbent comprises alcohol, wherein alcohol is one or more in ethylene glycol, propylene glycol, glycerol, tetramethylolmethane, xylitol, and the addition of described alcohol accounts for the 0.1% ~ 10.0% of alumina-based supports weight.
24. in accordance with the method for claim 18, it is characterised in that the unsaturated dipping of step (1) adopts and unsaturated sprays method, wherein the volume ratio of dip amount used by unsaturated dipping and alumina-based supports saturated absorption amount of solution is 0.02 ~ 0.4.
25. in accordance with the method for claim 18, it is characterised in that through health preserving after step (1) dipping, conditioned time is 0.5～8h, or through dry after step (1) dipping, described baking temperature is 60 DEG C～250 DEG C, and drying time, 0.5h～20h, then carried out step (2) again.
26. in accordance with the method for claim 18, it is characterized in that in the step (2) solution containing active metal component Mo, Co, containing phosphorus, phosphorus source is one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate, and the introduction volume of phosphorus is with P2O5Meter accounts for the 1% ~ 6% of final hydrotreating catalyst weight.
27. in accordance with the method for claim 19, it is characterized in that in the solution containing active metal Mo, Ni of the step (2) solution containing active metal component Mo, Co and/or step (3), containing phosphorus, phosphorus source is one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate, and the introduction volume of phosphorus is with P2O5Meter accounts for the 1% ~ 6% of final hydrotreating catalyst weight.
28. in accordance with the method for claim 20, it is characterised in that described drying condition is as follows: baking temperature is 70 DEG C～300 DEG C, and drying time is 0.5h～20h, described roasting condition: sintering temperature is 300 DEG C～750 DEG C, and roasting time is 0.5h～20h.
29. in accordance with the method for claim 21, it is characterized in that the drying condition described in step (2) or step (3) is as follows: baking temperature is 70 DEG C～300 DEG C, drying time is 0.5h～20h, described roasting condition: sintering temperature is 300 DEG C～750 DEG C, and roasting time is 0.5h～20h.
30. in accordance with the method for claim 18, it is characterised in that: containing Organic substance in described hydrotreating catalyst, the mol ratio making the Organic substance in hydrotreating catalyst and Mo atom is 0.002:1～2:1；One or more in organic compounds containing nitrogen, organic compounds containing sulfur and oxygen-containing organic compound of Organic substance.
31. the method for a heavy distillate hydrodesulfurization, it is characterised in that adopt the arbitrary described hydrotreating catalyst of claim 1 ~ 17.
32. the method described in claim 31, it is characterised in that: described heavy distillate is diesel oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310527896.4A CN103801313B (en) | 2012-11-08 | 2013-10-31 | A kind of catalyst for hydrogenation of fraction oil and preparation method thereof |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104428508 | 2012-11-08 | ||
| CN201210442850 | 2012-11-08 | ||
| CN201210442850.8 | 2012-11-08 | ||
| CN201310527896.4A CN103801313B (en) | 2012-11-08 | 2013-10-31 | A kind of catalyst for hydrogenation of fraction oil and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103801313A CN103801313A (en) | 2014-05-21 |
| CN103801313B true CN103801313B (en) | 2016-06-29 |
Family
ID=50698986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310527896.4A Active CN103801313B (en) | 2012-11-08 | 2013-10-31 | A kind of catalyst for hydrogenation of fraction oil and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103801313B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107297215B (en) * | 2016-04-16 | 2019-08-06 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4760045A (en) * | 1985-06-05 | 1988-07-26 | Nippon Oil Co., Ltd. | Catalyst for hydrotreatment of heavy oils and method for its preparation |
| CN101279289A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN101279291A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catlayst |
| CN101927176A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst showing gradient increase and distribution of concentration of active metal and acid additive and preparation method thereof |
-
2013
- 2013-10-31 CN CN201310527896.4A patent/CN103801313B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4760045A (en) * | 1985-06-05 | 1988-07-26 | Nippon Oil Co., Ltd. | Catalyst for hydrotreatment of heavy oils and method for its preparation |
| CN101279289A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN101279291A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catlayst |
| CN101927176A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst showing gradient increase and distribution of concentration of active metal and acid additive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103801313A (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101491766B (en) | Preparation method of hydrogenation catalyst | |
| CN103801314B (en) | A kind of hydrotreating catalyst, its manufacture method and application thereof | |
| JP2018516165A (en) | Hydrotreating catalyst containing metal organic sulfide on doped support | |
| CN104588028B (en) | Hydrogenation catalyst and preparation method thereof | |
| CN104588114B (en) | Catalyst for hydrogenating hydrocarbon oil and preparation method thereof | |
| CN103801348B (en) | A kind of catalyst for hydrogenating hydrocarbon oil and preparation method thereof | |
| CN104588031B (en) | Distillate oil hydrotreatment catalyst and preparation method thereof | |
| CN103801313B (en) | A kind of catalyst for hydrogenation of fraction oil and preparation method thereof | |
| Silvy | Scale-up of a NiMoP/γAl2O3 catalyst for the hydrotreating and mild hydrocracking of heavy gasoil | |
| CN104667962B (en) | A catalyst for diesel oil hydrogenation modification and a preparing method thereof | |
| CN104667956B (en) | A catalyst for hydrogenation modification of hydrocarbon oil and a preparing method thereof | |
| CN104588029B (en) | Hydrotreatment catalyst and preparation method thereof | |
| CN104588030B (en) | Hydrocarbon oil hydrotreatment catalyst and preparation method thereof | |
| CN114433233B (en) | Hydrodenitrogenation catalyst, and preparation method and application thereof | |
| CN104667960B (en) | A catalyst for diesel oil hydrogenation modification and a preparing method thereof | |
| CN104667982B (en) | A kind of catalyst for hydro-upgrading and preparation method thereof | |
| CN103801311B (en) | A kind of preparation method of hydrotreating catalyst | |
| CN104667983B (en) | A catalyst for hydrogenation modification and a preparing method thereof | |
| CN114433232A (en) | Hydrogenation carbon residue removal catalyst and preparation method and application thereof | |
| CN104588116B (en) | Hydrotreatment catalyst and preparation method thereof | |
| CN112717965A (en) | Hydrogenation pretreatment catalyst, and preparation method and application thereof | |
| CN104667959B (en) | A catalyst for diesel oil hydrogenation modification and a preparing method thereof | |
| CN104667961B (en) | Catalyst for hydro-upgrading and preparation method thereof | |
| CN103801403B (en) | A kind of hydrotreating catalyst and preparation method thereof | |
| CN104588115B (en) | Hydrotreatment catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |