CN101578352B - Bulk group VIII/VIB metal catalysts and method of preparing same - Google Patents

Bulk group VIII/VIB metal catalysts and method of preparing same Download PDF

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CN101578352B
CN101578352B CN200780045649.3A CN200780045649A CN101578352B CN 101578352 B CN101578352 B CN 101578352B CN 200780045649 A CN200780045649 A CN 200780045649A CN 101578352 B CN101578352 B CN 101578352B
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acid
catalyst
catalyst precursor
sulfuration
amorphous
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CN101578352A (en
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柏传盛
E-M·埃尔-马基
J·埃尔克斯
侯治国
J·M·麦康纳齐
P·S·文卡塔拉曼
J·吴
韩军
D·贾昆塔
A·哈格迈尔
V·索科洛夫斯基
A·F·小沃尔普
D·M·洛
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Abstract

Bulk metallic catalysts comprised of a Group VIII metal and a Group VIB metal and methods for synthesizing bulk metallic catalysts are provided. The catalysts are prepared by a method wherein precursors of both metals are mixed and interacted with at least one organic acid, such as glyoxylic acid, dried, calcined, and sulfided. The catalysts are used for hydroprocessing, particularly hydrodesulfurization and hydrodenitrogenation, of hydrocarbon feedstocks.

Description

Bulk group VIII/VIB metal catalysts and preparation method thereof
Technical field
The present invention relates to the bulk metal catalyst and the corresponding catalyst precursor that contain at least one group VIII metal and at least one group vib metal.This catalyzer is manufactured by following method: in the method, the reagent (for example metal-salt) containing group VIII and group vib metal for example, is mixed with at least one organic complexing agent (organic acid).Gained mixture is heated and vulcanized.This catalyzer can be used for the hydrotreatment of hydrocarbon feed, particularly hydrogenating desulfurization and hydrodenitrification.
Background technology
More and more stricter environmental regulations requires significantly to reduce the sulphur content of transport fuel.For example, arrive the last of this decade, the maximum sulfur distillating fuel will be limited to 10wppm in Europe and Japan, in North America, be limited to 15wppm.In order to be issued to these super low sulfur requirements expensive situation of changing not being made to by existing refinery, must to design and desulfurization be had to very highly active catalyzer of new generation being low to moderate under middle pressure, especially for the catalyzer distillating fuel.
In one approach, made a compounds relevant to hydrotalcite, for example ammonium nickel molybdate.X-ray diffraction analysis shows, hydrotalcite forms (layering has positively charged sheet and the commutative negatively charged ion in the passage between sheet mutually) mutually by layering, and relevant ammonium nickel molybdate has the molybdate negatively charged ion of being combined with hydroxy nickel oxide sheet in interlayer passage.Referring to, for example, Levin, D., Soled, S.L., and Ying, J.Y., Crystal Structure of an Ammonium Nickel Molybdateprepared by Chemical Precipitation (crystalline structure of the ammonium nickel molybdate of preparing by chemical precipitation), Inorganic Chemistry, the 35th volume, No. 14,4191-4197 page (1996).Teichner and Astier, Appl.Catal.72,321-29 (1991); Ann.Chim.Fr.12,337-43 (1987), and C.R.Acad.Sci.304 (II), #11,563-6 (1987) and Mazzocchia, Solid State Ionics, 63-65 (1993) 731-35 has also reported the preparation of this class material.
United States Patent (USP) 6,162, discloses other method in 350,6,652,738,6,635,599 and 6,534,437, and it relates to for from distillating fuel except a class body group VIII/the group vib trimetallic catalyst of desulfuration.Preferred trimetallic catalyst consists of Ni-Mo-W, and is made by various catalyst precursor compounds.
Although some above-mentioned catalyzer have reached success in various degree, but in this area, still need to have more active catalyzer, to manufacture the transport fuel with ultra-low sulfur, especially for low-voltage hydrogenation, process, for example, be less than 500psig or be less than the catalyzer of the hydrogen dividing potential drop of 1000psig.
Brief summary of the invention
In one embodiment, bulk metal catalyst precursor composition is provided, it comprises group VIII metal, group vib metal and about 10 % by weight to the component based on organic compound of about 60 % by weight, and this catalyst precursor composition has 16 meters squared per gram or less, preferably 10 meters squared per gram or the less surface-area based on BET.In another embodiment, provide the sulphurized catalyst by above-mentioned bulk metal catalyst precursor composition sulfuration is formed.
In an embodiment again, provide the method for preparing bulk group VIII/VIB metal catalysts precursor.The method comprises at least one group VIII metal reagent and at least one group vib metal reagent and the merging of at least one organic complexing agent, forms thus mixture.This mixture is heated to about 250 ℃ to about 450 ℃, to form the catalyst precursor that contains at least 10 % by weight carbon.Then under cure conditions, this catalyst precursor is vulcanized, to produce the sulphurized catalyst that contains at least 10 % by weight carbon.
In an embodiment again, provide the method for hydrotreatment hydrocarbon feed.The method comprises makes described raw material contact with the bulk metal catalyst of sulfuration, the bulk metal catalyst of this sulfuration is by forming catalyst precursor sulfuration, this catalyst precursor comprises group VIII metal, group vib metal and about 10 % by weight to the component based on organic compound of about 60 % by weight, and this catalyst precursor composition has 16 meters squared per gram or less, preferably 10 meters squared per gram or the less surface-area based on BET.
In an embodiment again, the catalyst precursor composition that comprises group VIII metal, group vib metal, carbon and oxygen is provided, carbon content is that about 10 % by weight are to about 25 % by weight, the ratio of group VIII and group vib metal is about 0.2 to about 0.6, and the surface-area of said composition is about 10 meters squared per gram or less.
In an embodiment again, the bulk metal catalyst of the component based on organic compound that comprises group VIII metal, group vib metal and at least about 10 % by weight is provided, and wherein at least a portion group vib metal is the metallic sulfide stacked body form with about 1.2 to about 2.0 stacks as high.
The using method of above-mentioned catalyzer is provided in other embodiments.
Accompanying drawing summary
Fig. 1 provides X-ray diffraction (XRD) figure of body CoMo catalyst precursor according to an embodiment of the invention and contrast CoMo catalyzer.
Fig. 2 a and 2b provide to the temperature programmed oxidation(TPO) (TPO) of catalyst precursor according to an embodiment of the invention and have analyzed relevant data.
Fig. 3 a and 3b provide the temperature programmed reduction(TPR) (H with catalyst precursor according to an embodiment of the invention 2-TPR) analyze relevant data.
Fig. 4 provides catalyst precursor according to an embodiment of the invention and the XRD figure of sulphurized catalyst.
Fig. 5 provides the TEM of sulphurized catalyst according to an embodiment of the invention.
Fig. 6 a and 6b provide the TEM figure of sulphurized catalyst according to an embodiment of the invention.
Fig. 7 provides to the TPO of sulphurized catalyst according to an embodiment of the invention and has studied relevant data.
Fig. 8 has described the hydrodesulfurization activity data of various catalyzer.
Fig. 9 has described the hydrodenitrogenationactivity activity data of various catalyzer.
Figure 10 has described hydrogenating desulfurization and the hydrodenitrogenationactivity activity data of various catalyzer.
Figure 11 has described along with being used to form the amount of organic complexing agent of catalyst precursor and the catalyst activity that changes.
Figure 12 to 16 provides the result of the additional TPO research of body catalyst precursor.
Figure 17 and 18 has described the diffuse-reflectance Fourier transform infrared spectroscopy result of the research of the catalyst precursor to heating according to various heat protocol.
The catalyst precursor that Figure 19 has described to heat in different atmosphere 13c NMR spectrum.
Figure 20 has described the possible complexing configuration of the metal in catalyst precursor of the present invention.
Figure 21 has described to stand the Raman spectrum of the catalyst precursor of various heat protocol.
Figure 22 has described the XRD of the catalyst precursor calcined under differing temps.
Figure 23 has described along with being used to form the amount of organic complexing agent of catalyst precursor and the catalyst activity that changes.
Figure 24 has described the relative reactivity at the catalyst precursor of differing temps calcining.
Figure 25 has described corresponding catalyst after catalyst precursor and sulfuration 13c NMR graphic representation.
Detailed Description Of The Invention
Catalyzer of the present invention is different from the conventional catalyst that is usually used in for example hydrogenating desulfurization of hydrotreatment (HDS).The ordinary method of the HDS activity of the catalyzer that improvement comprises group vib and group VIII metal (for example CoMo catalyzer) is that group vib and group VIII active ingredient are deposited on alumina supporter.This can improve the dispersion of active ingredient and produce extra HDS active.Unlike this, catalyzer of the present invention is by heating by comprise approximately 40 % by weight to the group VIII metal of about 90 % by weight and the catalyst precursor of group vib metal based on body catalyst particle gross weight the body catalyst forming.Weight metal is measured with metal oxide.The surplus of catalyst precursor weight is the material based on organic compound.In one embodiment, group vib metal is Mo or W.In another embodiment, group VIII metal is Co or Ni.In an embodiment again, group vib metal is that Mo and group VIII metal are Co.In an embodiment again, group VIII metal is base metal.
Based on X-ray diffraction, find out, group VIII metal and group vib metal in the catalyst precursor after heating do not have long-range order, and this is common in being mainly the material of crystalline oxides.Replace, in some embodiments, find metal in catalyst precursor by organic complexing agent complexing.Metal and organic complexing agent complexing when metal and complexing agent mix.After one or more heating stepses, the character of complex compound may change, because organic complexing agent one or more conversions or reaction may occur and forms the component based on organic compound.In another embodiment, this catalyst precursor, except having the feature with the metal of organic complexing agent complexing, also can have some crystallizations or nanocrystal feature (based on XRD).
The X-ray diffraction data that provide in the application Fig. 4 produce under the following conditions.Use PANalytical, Inc. manufactures and is furnished with the X-ray powder diffraction analysis of the PANalytical X-pert PRO MPD acquisition sample of X-Cellerator detector.The Cu target under 45kV and 40mA is used in 2 θ scannings.Diffractogram obtains to the scope of 70 ° of 2 θ at 20 ° to 70 ° and 20 °.Step-length is 0.2 degree, and the time of every step is 480 seconds.All the other the X-ray diffraction data and the collection of illustrative plates that in the application, provide produce under the following conditions.The X-ray powder diffraction analysis of using Bruker AXS to manufacture and being furnished with the Bruker D4Endeavor acquisition sample of Vantec-1 high-speed detector.The Cu target under 35kV and 45mA is used in this 2 θ scanning.Diffractogram obtains to the scope of 70 ° of 2 θ at 2 °.Step-length is that the time of 0.01794 degree and every step is 0.1 second.
In this application, " amorphous " catalyzer or catalyst precursor refer to following catalyzer or catalyst precursor: its shortage long-range order or periodicity to have the peak that can for example fully distinguish with the ground unrest in this spectrum by measuring peak intensity to the ratio of ground unrest in x-ray diffraction pattern.Nanocrystal catalyzer or catalyst precursor refer to catalyzer or the catalyst precursor that has certain degree of crystallinity but have the grain-size that is less than 100 nanometers.The x-ray diffraction pattern that use produces according to above-mentioned condition carries out this mensuration.Along with granularity is shunk, the more and more broadening of X-beta ray spectrum, for example, when grain-size < 100 nanometer, produce and have the peak of broadening or seem the XRD figure that does not have peak.Amorphous or nano junction crystalline phase also may be included in the crystallization phases of distinguishable grain-size > 100 nanometers in XRD.Be not limited by any particular theory, it is believed that the high reactivity of the catalyst system of various embodiments according to the present invention is from amorphous and/or nanocrystal component.
In one embodiment, the body catalyst particle of the present invention that the sulfuration by catalyst precursor particle forms can have the characteristic x-ray diffraction pattern of non-crystalline material.Long-range order finds conventionally in the crystallization phases of group VIII and group vib metal oxide and/or sulfide, but conventionally it is believed that and in body catalyst formed according to the present invention, do not have long-range order.Especially, the XRD of catalyzer of the present invention and catalyst precursor spectrum does not show the crystallization phases of CoMo oxide compound, or only weak the crystallization CoMo oxide compound feature that shows.Be not limited by any particular theory, it is believed that component based on organic compound of organic complexing agent and/or gained interrupts or suppressed the crystallization of the oxide compound of group vib and group VIII metal.It is believed that at least a portion body catalyst particle has the structure of certain class complexing of continuous participation and the component based on organic compound, and do not form the crystalline oxides with long-range order.Under the length specification that is not easy to differentiate at XRD, this structure may be amorphous and/or crystallization.Complexation property can be different from the complexing existing in catalyst precursor.In addition, at least a portion metal existing in this catalyzer can be metallic sulfide form, rather than complexing metal or amorphous/small-crystalline metal oxide.
Body catalyst precursor composition of the present invention obtains by metal reagent being mixed with organic complex component, then heating and/or mix, and has about 16 meters squared per gram or less relatively low surface-area (measuring by Brunauer-Ernett-Teller method or BET).In another embodiment, this body catalyst precursor composition has and is less than about 10.0 meters squared per gram or is less than about 9.0 meters squared per gram or is less than about 7.5 meters squared per gram or is less than about 5.0 meters squared per gram or is less than about 4.0 meters squared per gram or is less than about 3.0 meters squared per gram or is less than the surface-area (measuring by BET) of about 2.5 meters squared per gram.In an embodiment again, this body catalyst precursor composition has the surface-area of at least about 0.05 meters squared per gram or at least about 0.1 meters squared per gram or at least about 0.25 meters squared per gram.In a preferred embodiment, this body catalyst precursor composition has about 0.1 meters squared per gram to the surface-area of about 10.0 meters squared per gram.
Group VIII metal is typically about 1 to 10 to about 10 to 1 with the mol ratio of group vib metal.With fractional value, represent, this mol ratio is typically about 0.1 to about 10.Preferably, it is about 3 that the ratio of group VIII metal and group vib metal is less than, and is more preferably less than about 2.Preferably, it is about 0.33 that the ratio of group VIII metal and group vib metal is greater than, more preferably greater than about 0.5.
If catalyst composition also contains any annexing ingredient conventionally existing in hydrotreating catalyst; acidic components for example; for example phosphorus or boron compound; additional transition metal, rare earth metal, main group metal be Si or Al or its mixture for example, and this catalyst composition is in protection scope of the present invention.Suitable additional transition metal is, for example, and rhenium, ruthenium, rhodium, iridium, chromium, vanadium, iron, platinum, palladium, cobalt, nickel, molybdenum, zinc, niobium or tungsten.If this catalyst composition cures, all these metals exist with sulfur form conventionally.Sulfuration before, one or more metals of at least a portion can with catalyst precursor in the described material complexing based on organic compound.After sulfuration, believe at least a portion metal sulphide still in some way with catalyzer in the directly or indirectly combination of the described material (for example carbon) based on organic compound.
By the group VIII of organic complexing agent complexing and the controlled heat of group vib precursor compound with being preferably organic acid form, prepare bulk metal catalyst of the present invention.This organic complexing agent is preferably metal link base or sequestrant.This organic complexing agent is preferably bitooth ligand.This organic complexing agent is preferably adapted at forming in solution metal-ligand complex.
At the solution by containing group VIII metal, group vib metal and organic complexing agent, form in the embodiment of catalyst precursor, group VIII compound and group vib compound are all preferably the water-soluble salts under suitable predetermined concentration, to produce desirable mol ratio as above.Preferred group VIII metal is Co and Ni, and wherein Co most preferably.This group VIII metal is base metal preferably.Preferred group vib metal is Mo and W, and wherein Mo most preferably.The limiting examples of suitable Co precursor compound comprises carbonate, nitrate, vitriol, acetate, muriate, oxyhydroxide, propionic salt, glycinate, hydroxyl carbonate, acetylacetate, acetylacetonate, metal Co (0), oxidation Co, aqua oxidation Co, carboxylic acid Co (particularly oxoethanoic acid Co), citric acid Co, glyconic acid Co, tartrate Co, glycine Co, lactic acid Co, naphthenic acid Co, oxalic acid Co, formic acid Co and composition thereof, comprises above-mentioned ammonium or amine form.Preferred molybdenum and tungsten precursor compound comprise molybdate (and the peroxide molybdate of basic metal or ammonium, two molybdates, three molybdates, four molybdates, seven molybdates, octamolybdate or 14 molybdates), molybdic acid, phospho-molybdic acid, phospho-wolframic acid, Mo-P heteropolyanion compound, W-Si heteropolyanion compound, Co-Mo-W heteropolyanion compound, the tungstate of basic metal or ammonium (and metatungstate, para-tungstate, hexatungstate or Polytungstate), acetylacetonate and composition thereof.In other embodiments, can use any suitable group VIII or group vib metal reagent to prepare group VIII or group vib metallic solution.
Organic acid is the preferred type of organic complexing agent.The limiting examples that is applicable to organic complexing agent herein comprises pyruvic acid, levulinic acid, 2-ketogulonic acid, ketogluconic acid, Thiovanic acid, 4-ethanoyl butyric acid, 1, 3-β-ketoglutaric acid, 3-oxo propionic acid, 4-ketobutyric acid, 2, 3-diformyl succinic acid, 5-oxopentanoic acid, 4-oxopentanoie acid, glyoxylic acid ethyl ester, oxyacetic acid, glucose, glycine, oxaminic acid, oxoethanoic acid 2-oxime, ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA), N-methylamino oxalic acid, iminodiethanoic acid, dihydroxy acetic acid, oxysuccinic acid, glyconic acid, methyl ethyl diketone and citric acid.Preferred organic acid is oxoethanoic acid, oxosuccinic acid, 2-ketogulonic acid, α-ketoglutaric acid, 2-ketone butyric acid, pyruvic acid, ketogluconic acid, Thiovanic acid and oxyacetic acid.Most preferably oxoethanoic acid and oxosuccinic acid.
In another embodiment, this organic complexing agent is that contain-COOH functional group is selected from carboxylic acid-COOH, hydroxamic acid-NOH-C=O, hydroxyl-OH, ketone group-C=O, amine-NH with at least one 2, acid amides-CO-NH 2, imines-CNOH, epoxy group(ing)=COC=or mercaptan-SH the organic acid of additional functionality.This organic complexing agent is preferably bitooth ligand.
The method of preparing catalyzer of the present invention comprises a plurality of steps.First step is mixing step, wherein at least one group VIII metal reagent, at least one group vib metal reagent and at least one organic complexing agent is combined.In one embodiment, one or more metal reagents and organic complexing agent can for example, provide with solution (aqueous solution) form.In another embodiment, one or more metal reagents and organic complexing agent can provide with slurry form.In an embodiment again, one or more metal reagents and organic complexing agent can provide with solid material form.Those of skill in the art will recognize that other form that organic complexing agent and metal reagent are provided is also feasible, and can to each reagent and/or organic complexing agent, use any suitable form (solution, slurry, solid etc.) in synthetic given.
Metal reagent and organic complexing agent are mixed to form precursor mixture.In one or more embodiment of metal reagent or organic complexing agent is provided with solution or slurry form, mixing can comprise to be added this metal reagent and organic complexing agent in single container to.If provide one or more of metal reagent and organic complexing agent with solid form, mixing can comprise the temperature that this organic complexing agent is heated to be enough to melting complexing agent.This can make organic complexing agent by any solid metal reagent solvation.
Temperature in mixing process is preferably envrionment temperature to solvent boiling point.This preparation can be carried out in any suitable manner.For example, in relating to the embodiment of solution and/or slurry, can prepare independent solution (or slurry) by each catalyst component.That is to say, can be formed on group VIII metallic compound and the group vib metal in suitable solvent in suitable solvent.The limiting examples of suitable solvent comprises water and C 1to C 3alcohol.Other suitable solvent can comprise polar solvent, for example alcohol, ether and amine.Water is preferred solvent.Group VIII metallic compound and group vib compound are also preferably water miscible, and are preferably formed solution separately, or form the single solution that contains these two kinds of metals.Organic complexing agent can be prepared in suitable solvent (preferably water).These three kinds of solvent compositions can mix with any order.That is to say, all three kinds can be blended together simultaneously, or can successively they be mixed with any order.In one embodiment, preferably first in water medium, two kinds of metal components are mixed, then add organic complexing agent.
Processing condition in mixing step are not crucial conventionally.For example can under their natural pH value (if adopting suspension or solution), add all components at ambient temperature.The common boiling point that preferably makes temperature keep below water, 100 ℃, to guarantee easily to operate component in mixing step process.But, if needed, can use temperature or different pH value higher than water boiling point.At organic complexing agent, be to have in the acid of conjugate base/acid or the embodiment of alkali, can regulate the pH value of mixture to reach desired form to order about acid/soda balance.For example, if organic complexing agent is acid, the pH value of this solution that can raise is so that balance is more tending towards forming conjugate base.If the reaction in mixing step is carried out at elevated temperatures, preferably the suspension adding and solution are preheated to the temperature of the rising that substantially equals temperature of reaction in mixing step.
Should select the amount of metal precursor and organic complexing agent in mixing step, to realize the preferred ratio of metal and material based on organic compound in the catalyst precursor after heating.These preferred ratios have produced highly active body catalyst.For example, in mixing solutions (or other mixture of metal reagent and organic complexing agent), organic acid should reach with the ratio of total metal the minimum level that produces high activated catalyst.
In one embodiment, the material based on organic compound of at least about 10 % by weight is provided in the catalyst precursor that in mixing solutions, the amount of organic complexing agent used should be enough to form afterwards in heating, or at least about 20 % by weight, or at least about 25 % by weight, or at least about 30 % by weight.In another embodiment, the material based on organic compound that is less than about 60 % by weight is provided in the catalyst precursor that in mixing solutions, the amount of organic complexing agent used should form afterwards in heating, or be less than about 40 % by weight, or be less than about 35 % by weight, or be less than about 30 % by weight.Preferably, in mixing solutions, the amount of organic complexing agent used is enough to provide the material based on organic compound of about 20 % by weight to about 35 % by weight in gained catalyst precursor.The desired amount of the material based on organic compound in catalyst precursor can be based on organic complexing agent in mixing solutions and metal ratio and the thermal activation condition realization based on being used to form catalyst precursor.Term " material based on organic compound " refers to the carbon compound existing in the catalyzer after catalyst precursor after heating or sulfuration.This is material derived from organic complexing agent based on organic compound, but can form catalyzer and modification due to heating and/or the sulfuration of this precursor of catalyst precursor.Point out, the final form of the described material based on organic compound can comprise traditionally the carbon that is not regarded as " organic ", for example graphite carbon or amorphous carbon.Term used herein " material based on organic compound " only shows this carbon source from organic complexing agent and/or is used to form another organic carbon source of catalyst precursor.
For the present invention, by under the following conditions catalyst precursor being carried out to temperature programmed oxidation(TPO), measure the weight percent of the material based on organic compound described in catalyst precursor.Sample through super-dry and heating is used to the temperature programmed oxidation(TPO) of TGA/MS.By collecting TGA/MS data with Mettler TGA 851 thermobalances of being furnished with the quadrupole mass spectrometer coupling of secondary electron multiplier.The 14.3%O in He that 20 to 25 milligrams of samples are being flowed 2in (77 cc/min), under a normal atmosphere total pressure, with 4 ℃/min, from envrionment temperature, be heated to 700 ℃.In TGA/MS experiment, via kapillary, eluting gas is carried to MS instrument, and analyzes specific m/e fragment, for example 18 (H 2o), 44 (CO 2), 64 (SO 2), as degradation production and with the mark of the character mutual relationship of weight/heat effect.
The weight percent of the material losing in TPO program process has represented the weight percent of the described material based on organic compound.Surplus material in catalyst precursor is considered to the metal of the oxide form of certain type.The weight percent of the metal for clarity sake, existing in catalyst precursor represents with the metal oxide of typical oxide chemistry metering.For example, the weight of cobalt and molybdenum is respectively with CoO and MoO 3calculate.
Can carry out similar calculating, to determine the weight percent of the component based on organic compound in the catalyzer forming afterwards in sulfuration.According to aforesaid method, by TPO, measure again the weight percent of the component based on organic compound.Residuals weight in catalyzer is equivalent to the metal of certain forms, for example oxide compound, oxysulfide or sulfide.
In mixing solutions, the amount of organic complexing agent used also should be enough in this solution, form metal-organic complex under reaction conditions.At complexing agent, be in organic acid embodiment, the ratio of organic acid hydroxy-acid group and metal can be at least about 1 (meaning the hydroxy-acid group and the atoms metal that there are roughly the same quantity), or at least about 2, or at least about 3.In another embodiment, the ratio of hydroxy-acid group and metal can be 12 or less, or 10 or less, or 8 or less.
In another embodiment, in mixing solutions, the mol ratio of organic complexing agent used and metal is about 6.0 or less, or about 5.5 or less, or about 5.0 or less, or about 4.8 or less, or about 4.6 or less.In another embodiment, in mixing solutions, organic complexing agent used and the mol ratio of metal are about 1.5 or larger, or about 2 or larger, or about 2.5 or larger, or about 3.0 or larger, or about 3.5 or larger.
In a preferred embodiment, the mol ratio of group VIII metal and group vib metal is at least about 0.1, or at least about 0.2, or at least about 0.33, or at least about 0.5.In another preferred embodiment, the mol ratio of group VIII metal and group vib metal is about 0.9 or less, or about 0.6 or less.
The second step of preparing in the method for catalyzer of the present invention is heating steps.In one embodiment, this heating steps is for dewatering from mixture.In another embodiment, this heating steps is used to form the component based on organic compound in catalyst precursor.Should the component based on organic compound be the product that organic complexing agent heating used in mixing solutions is obtained.This organic complexing agent can be similar to the component based on organic compound substantially, or the component based on organic compound can represent the degradation production of certain type of organic complexing agent.Or, not being limited by any particular theory, the heating of organic complexing agent may cause complexing agent crosslinked, forms the described component based on organic compound.
According to heat protocol, in a plurality of stages, heat and/or the dry protection scope of the present invention that falls into.In one embodiment, the first stage of heat protocol is part drying stage, preferably in vacuum drying oven, at the temperature of about 40 ℃ to about 60 ℃, carries out amount working lipe.Working lipe, amount was equivalent to be enough to except anhydrating to the time of gel formation degree.Conventionally, believe and will form gel during to about 90% water removing about 80%.Mixture at metal reagent and organic complexing agent is in the embodiment of solution or slurry form, the mixture that preferably stirs metal reagent and organic complexing agent component under about envrionment temperature reaches working lipe, to guarantee heating substantially all even dissolvings of all components before.Or, with solid form, providing in the embodiment of organic complexing agent, initial heat-up stage can be equivalent to for making the heating of organic complexing agent melting.The temperature of the mixture time quantum of can remaining valid, so that the organic complexing agent of melting mixes by metal reagent solvation and/or with metal reagent.
In one embodiment, in heat protocol, next heating or drying stage are that temperature is risen to about 110 ℃ to about 130 ℃, 110 ℃ to about 120 ℃ of preferably approximatelies, to drive away extra water to can carry out the degree of heat in the situation that not causing solution boil over and splash.Now gel can change into solidify material.Form amount working lipe of drying material, from gel formation to solidify material, can be for the several seconds to be to a few hours, preferably approximately 1 minute is to a couple of days, and more preferably about 1 minute to 24 hours, more more preferably about 5 minutes to about 10 hours.This gel solidify and be cooled to room temperature after also can be black rubber-like solid material form.Can make this gel or solidify material reach envrionment temperature storage, in order to heating under comparatively high temps in the future.Or this gel or solidify material are at this stage useful as catalysts precursor.
Before or after thermal activation, solid material grind into powder is fallen into protection scope of the present invention.This grinding can be carried out before any heating steps under about 275 ℃ or higher temperature, maybe this grinding can be heated to about 275 ℃ or higher after carry out.Can use any suitable grinding technique to grind this solid material.
This catalyst precursor can stand the further heating phase with the material in decomposed catalyst precursor.This additional heating phase can be about 100 ℃ to about 500 ℃, 250 ℃ to about 450 ℃ of preferably approximatelies, more preferably about 300 ℃ to about 400 ℃, more preferably the temperature of about 300 ℃ to about 340 ℃ is carried out amount working lipe again.Measure as about 0.5 to about 24 hours this working lipe, and preferably approximately 1 was to about 5 hours.In another embodiment, can realize heating by the temperature in stove being risen to about 325 ℃ from room temperature in 1 hour.In one embodiment, heat (comprising possible decomposition) under can for example, for example, existing in the combination of mobile oxygen-containing gas (air), mobile rare gas element (nitrogen) or oxygen-containing gas and rare gas element.In the atmosphere that can exist in stove when heat-processed starts in another embodiment,, heat.This can be called as static conditions, wherein in heat-processed, to this stove, does not provide extra gas supply.Atmosphere in static conditions process in stove can be oxygen-containing gas or rare gas element.Preferably for example, under existing, heats inert atmosphere (nitrogen).Be not limited by any particular theory, by this, add the partially decomposed product that thermogenetic material may represent organic complexing agent, so that metal and the material based on organic compound or component complexing.
As mentioned above, heating steps can carry out in many ways.This heating steps can start from one or more initial heat-up stage at a lower temperature, then under about 275 ℃ or higher temperature, heats.In other embodiments, heat protocol can only comprise about 130 ℃ or lower temperature, or heat protocol can comprise and make immediately temperature rise to about 275 ℃ or higher, or approximately 325 ℃ or higher.Preferably, can control and design preparation condition, so that mixing solutions explosive vaporization does not occur in whole heat protocol, splashes or interrupt.This class embodiment is usually included in the initial heating lower than the temperature of 100 ℃.But in another embodiment, this heat protocol can be included in the condition that causes rapid evaporation when catalyst precursor still contains remarkable water gaging.This can cause the boiling of the mixture that is used to form catalyst precursor or splash.Although be used to form catalyst precursor mixture boiling or to splash be inconvenient, believe and under these conditions, still form catalyst precursor of the present invention.
Contrast with the conventional hydrotreating catalyst conventionally comprising by the carrier of at least one group VIII metal and at least one group vib metal impregnation, catalyzer of the present invention is body catalyst.
Be not limited by any particular theory, believe that described organic complexing agent and/or the gained component based on organic compound plays a role in the unexpected high reactivity of final catalyzer.Believe that this organic complexing agent and/or the gained component based on organic compound contributes to the stabilization of metallics, and/or directly and metal active site interact and prevent metal agglomeration.In other words, this organic complexing agent and/or the component based on organic compound have strengthened the dispersion of avtive spot.When the component based on organic compound with being less than the amount of required scope forms catalyst precursor, the activity of gained catalyzer is lower.
The body fine catalyst precursor composition of the present invention obtaining after grinding and heating can directly be formed as the shape that is applicable to required catalysis end-use.Or this body powder can mix with conventional adhesive material, is then shaped to desired shape.If use tackiness agent, it can introduce before or after the decomposition (heating) that is used to form the mixture of catalyst precursor.The example of possible tackiness agent comprises can be available from Active Minerals International of Hunt Valley, the Actigel clay of MD; Can be available from Nyacol Nano Technologies, Inc.of Ashland, the Nyacol2034DI of MA; Or can for example, available from the Si-resin of Dow Corning, Q-2230.In an embodiment again, can in the mixture for the synthesis of catalyst precursor, add adhesive precursor, for example silicic acid, acetic acid silicon or aluminum acetate.
Third step in catalyzer preparation of the present invention is vulcanisation step.Sulfuration is conventionally by making catalyst precursor composition for example, contact to carry out with sulfocompound (elementary sulfur, hydrogen sulfide or polysulfide).Sulfuration also can adopt the polysulfide hydrocarbon stream of dimethyl disulfide (as be mixed with) and the combination of hydrogen to carry out in liquid phase.Sulfuration can be after being prepared bulk catalyst composition but is carried out before adding tackiness agent (if you are using).
If this catalyst composition, for fixed-bed process, preferably vulcanizes after forming step.Sulfuration can ex situ or original position carry out.For ex situ sulfuration, in reactor, vulcanizing separately before in sulphurized catalyst is loaded into hydrotreater.Original position sulfuration is preferred, and for original position sulfuration, in the same reactor for hydrotreatment, vulcanizes.
In one embodiment, vulcanisation step can be liquid curing.In this embodiment, can be by catalyst exposure be vulcanized body catalyst in the raw material that is mixed with 1.36 % by weight dimethyl disulfide.Or the addition content of dimethyl disulfide can be 0.5 to 2.5 % by weight.This catalyzer can be under the pressure of 500psig contacts with charging under the hydrogen flow velocity of 1.0 LHSV and 700scf/B.This catalyzer preferably contacts initial period in the temperature of 425 °F (218 ℃) with charging, for example 18 hours, then at 625 °F (329 ℃), contacts the second period, for example 24 hours.In other embodiments, can use other conventional vulcanization process.
In relating to another embodiment of liquid curing, can use than the more harsh temperature and pressure condition of the final processing conditions of expection this catalyst vulcanization.For example, if sulphurized catalyst is used for the press working raw material at 150psig, sulfuration can be carried out under comparatively high temps, to reduce, realizes the required time of catalyst vulcanization.
In various embodiments, the catalyzer forming after sulfuration be considered to have at least partly relate to metal by the component complexing based on organic compound or with another interactional structure of component based on organic compound.The character of the component based on organic compound in sulphurized catalyst can be different from the organic complexing agent that is used to form catalyst precursor in the component based on organic compound in catalyst precursor and original mixture.Need explanation, in the following example, the carbon in sulphurized catalyst and sulphur class material appear in temperature programmed oxidation(TPO) research and are oxidized and leave catalyzer in the similar time.A kind of possible explanation to these TPO researchs is, at least a portion catalyst structure, to have complexing (or interaction of some other types) between the component based on organic compound and metal.
In one embodiment, the carbon content of the catalyzer after sulfuration is at least 10 % by weight or at least 12 % by weight.In another embodiment, the carbon content of the catalyzer after sulfuration is 25 % by weight or still less or 20 % by weight or still less.
After sulfuration, at least a portion metal in catalyzer is sulfur form.Especially, group vib metal can form and be considered to have MeS 2the stacked body of the metal sulphide of stoichiometric ratio, wherein Me represents group vib metal.For example, if Mo is group vib metal, can form MoS 2stacked body.In catalyzer formed according to the present invention, the average stacks as high of the group vib metal of sulfuration is about 1.2 to about 2.In another embodiment, average stack thickness is at least 1.2, or at least 1.3, or at least 1.4, or at least 1.5.In an embodiment again, average stacks as high is 2.2 or less, or 2.1 or less, or 2.0 or less, or 1.9 or less.Be not limited by any particular theory, believe that lower stacks as high is indirectly corresponding to the activity improving.
Catalyst composition of the present invention is specially adapted to the charging of hydrotreatment hydrocarbon.The example of hydroprocessing process comprises hydrogenation, hydrogenating desulfurization, hydrodenitrification, Hydrodearomatization and the mild hydrocracking of unsaturates.Preferably hydrogenating desulfurization and hydrodenitrification.Conventional hydroprocessing condition comprises that the hydrogen pressure, 0.1 of temperature, 5 to 250 bar of about 250 ℃ to 450 ℃ is to 10h -1liquid hourly space velocity and 90 to 1780m 3/ m 3the hydrogen of (500 to 10000SCF/B) is processed gas velocity.
Can implement the raw material that the present invention processes is those petroleum feedings streams that seethe with excitement within the scope of overhead product.This boiling range is typically about 140 ℃ to about 360 ℃, and comprises middle runnings and light gas oil stream.The limiting examples of preferred distillate flow comprises diesel oil fuel, jet fuel and heating oil.This raw material can contain the nitrogen of the organic nitrogen compound form of significant quantity, the nitrogen of 10wppm at least for example, and even higher than 1000wppm.This raw material can also contain about 0.1 % by weight to 3 % by weight or higher significant sulphur content.
Hydrotreatment of the present invention also comprises for slurry and boiling bed hydrogenation facture except desulfuration and nitrogen compound, and the hydrogenation of the aromatic molecules for example, existing in light mineral fuel (oil middle runnings), particularly light catalytic cycle cracked oil (LCCO).Overhead product derived from oil, coal, pitch, tar sand or shale oil is suitable charging equally.It is known adopting the hydroprocessing process of the dispersed catalyst slurry mixing with hydrocarbon charging.For example, the United States Patent (USP) 4,557,821 of authorizing the people such as Lopez discloses use circulation slurry catalyst hydrogenation and has processed heavy oil.Other patent that discloses slurry hydrotreatment comprises United States Patent (USP) 3,297,563; 2,912,375; With 2,700,015.Slurry hydroprocessing process of the present invention can be used for processing various chargings, comprises the middle runnings from mineral fuel, for example light catalytic cycle cracked oil (LCCO).
Hydrogenation conditions be included in the temperature range of about 100 ℃ to about 350 ℃ and about 5 normal atmosphere (506kPa) to 300 normal atmosphere (30,390kPa) hydrogen, for example 10 to 275 normal atmosphere (1,013kPa to 27, reaction in pressure 579kPa).In one embodiment, this temperature is in the scope of 180 ℃ to 320 ℃, and pressure is 15, and 195kPa to 20, in the scope of 260kPa hydrogen.Under standard conditions (25 ℃, 1 normal atmosphere), hydrogen is typically about 20 to 200 with the input material volume ratio that enters reactor, for water-white resin, is 100 to 200.
The processing condition that are applicable to the application of catalyzer described herein can extensively change according to raw material to be processed.Therefore,, along with charging boiling point improves, the harsh property of condition also improves.Following table (table 1) is for the representative condition of a series of chargings of illustration.
Table 1
Charging Typical case's boiling range, ℃ Temperature, ℃ Pressure, bar Air speed, V/V/HR H 2Gas velocity SCF/B
Petroleum naphtha 25-210 100-370 10-60 0.5-10 100-2,000
Diesel oil 170-350 200-400 15-110 0.5-4 500-6,000
Heavy gas oil 325-475 260-430 15-170 0.3-2 1000-6,000
Lubricating oil 290-550 200-450 6-210 0.2-5 100-10,000
Residual oil 10-50％＞575 340-450 65-1100 0.1-1 2,000-10,000
Although the present invention as herein described shows the hydrodenitrogenationactivity activity of raising, most HDN catalyzer also show hydrogenating desulfurization (HDS) and hydrogenation activity.Therefore, Catalyst And Method as herein described can be used for nitrogenous and charging sulphur, and is particularly useful for the charging that nitrogen content is high.
The following example is used for illustrating and unrestricted the present invention.
embodiment 1-catalyst precursor is synthetic
Controlled heat legal system by is according to an embodiment of the invention for body CoMo catalyzer.By four hydration Ammonium Heptamolybdates (AHM) of appropriate amount are dissolved in distilled water, the preparation 1M Mo aqueous solution.Also, by four hydration cobaltous acetates of appropriate amount are dissolved in distilled water, prepare the 1M Co aqueous solution.By with 1: 1 dilution 50% aqueous glyoxylic acid of distilled water, prepare 4.5M glyoxylic acid solution.
By above-mentioned three kinds of solution of appropriate amount are mixed, prepare mixture.Gained solution has blush.In solution, the ratio of Mo and Co is 2: 1.Prepare two kinds of body catalyst precursor mixtures.Catalyst precursor mixture has the mol ratio of 4.8 oxoethanoic acid/(Mo+Co), and is marked as catalyst precursor A.Prepare the second catalyst precursor mixture, its oxoethanoic acid/(Mo+Co) mol ratio is 6, and mark is made catalyst precursor B.Catalyst precursor mixture, about 4 hours of 55 ℃ of heating, is then reheated to about 4 hours at 120 ℃.The result of each catalyst precursor is black viscous substance.Then this black viscous substance is cooled to room temperature, this its, solidifies.By this curing atrament grind into powder and be contained in tube furnace, at this, in one hour, temperature is risen to about 325 ℃ from room temperature roughly.Then in air, this catalyst precursor composition is heated about 4 hours at about 325 ℃.
Use agate mortar and pestle that the sample of these two kinds of catalyst precursor powder is rolled into fine powder.By a part of precursor powder sulfuration, produce catalyst fines.
Measure the catalyst precursor composition of catalyst precursor A and catalyst precursor B and similarly but do not use BET surface-area and the carbon content of the CoMo catalyst precursor (comparative catalyst 1) that organic acid makes.Result is presented in following table 2.X-ray diffraction shows, two kinds of body catalyst precursor samples of the present invention are all amorphous in nature, and do not show the long-range order of conventionally observing in XRD when crystallization phases macroparticle.Comparative catalyst 1 x-ray diffraction pattern demonstrates crystallization MoO 3and CoMoO 4, they are regarded as the not desirable catalyst precursor of hydroprocessing process conventionally.It is believed that the residual carbon in catalyst precursor of the present invention interrupted the crystallization of CoMo oxide compound, so that do not have CoMo oxide crystal, or as not existing to the small-crystalline of introducing crystallization property in XRD spectrum almost or completely.
Table 2
Catalyzer BET SA (meters squared per gram) Carbon content (% by weight)
Catalyst precursor A CoMo-6-Gly 15.6 23.8
Catalyst precursor B CoMo-4.8-Gly ＜1 21.9
[0090]
The CoMo that comparative catalyst 1 does not use organic acid to make 20 0.22
From upper table 2, can find out, body CoMo-6-Gly and CoMo-4.8-Gly catalyst precursor have relatively low surface-area.Especially, catalyst precursor CoMo-4.8 has the surface-area that is less than 1 meters squared per gram.After heating, two kinds of catalyst precursors of the present invention all contain the carbon of the significant quantity of about 22 to 24 % by weight.The heating condition that the carbon content of catalyst precursor of the present invention stands with this catalyzer, the i.e. metal ratio of the time of heat protocol and temperature and oxoethanoic acid/(Mo+Co) and changing.Carbon content in body CoMo catalyst precursor affects the form of CoMo and the gained Investigation On Hydrodesulfurizationof of Catalysts Derived of sulphurized catalyst in this class precursor.
embodiment 1B-additional catalyst precursor synthesis example
Use the 1M solution of four hydration Ammonium Heptamolybdates and four hydration cobaltous acetates to form additional catalyst precursor.By the 1M Mo of appropriate amount and Co solution are mixed with the solution that contains 25 % by weight oxoethanoic acids, form the solution that contains 5.7 % by weight AHM, 4.0 % by weight cobaltous acetates and 17.3 % by weight oxoethanoic acids.The mol ratio of R/ (Co+Mo) is 4.8.After heating, the solid yield of this solution is about 8.6%.
Individually, by the 1M Mo of appropriate amount and Co solution are mixed with the solution that contains 50 % by weight oxoethanoic acids, form the solution that contains 12.8 % by weight AHM, 9.1 % by weight cobaltous acetates and 39.1 % by weight oxoethanoic acids.The mol ratio of R/ (Co+Mo) is 4.8.After heating, the solid yield of this solution is about 19.4%.
embodiment 1C
This embodiment relates to the synthetic of body three metal NiCoMo.By controlled heat legal system according to the present invention for body three metal NiCoMo catalyzer.By 200 milligrams of NiO, 200 milligrams of Co (OH) 2with 1 gram of H 2moO 4in each comfortable independent container, dissolve/be suspended in water.In each container, add 50 % by weight glyoxylic acid solutions, so that the acid concentration in each container is 15 % by weight.Merge Ni, Co and Mo solution, and add 6 milliliters of 30%H in the solution merging 2o 2.This sample is heated 4 hours at 250 ℃, to produce body three metal NiCoMo catalyst precursors.
embodiment 2-catalyst precursor characterizes
Synthetic according to an embodiment of the invention CoMo based catalyst precursors is carried out to X-ray diffraction (XRD) analysis.Gained XRD spectrum is presented in Fig. 1.As shown in fig. 1, CoMo based catalyst precursors has amorphous XRD spectrum.It is believed that the component based on organic compound in CoMo catalyst precursor interrupted crystallisation process, produce the CoMo catalyst precursor that there is no the crystallization phases that can detect.In another embodiment of the present invention, crystallization phases may be able to detect in catalyst precursor, but only as a part for catalyst precursor, thereby generation has the XRD of certain crystallization property and certain amorphous characteristic, composes.This is different from the XRD spectrum of the body CoMo material (comparative catalyst 1) that does not use organic complexing agent but make similarly at other side and catalyst precursor of the present invention.The XRD stave of this body contrast CoMo material reveals crystal habit, comprises seeming representing MoO 3and CoMoO 4peak.
the temperature programmed oxidation(TPO) of embodiment 3-catalyst precursor
Carry out temperature programmed oxidation(TPO) (TPO) research, to understand according to the character of the component based on organic compound of the synthetic catalyst precursor of the program of catalyst A in embodiment 1.Fig. 2 a shows, when catalyst precursor stands the rising temperature of the highest 650 ℃, catalyst precursor loses about 30 % by weight weight.Fig. 2 b has shown the mass spectral characteristi that the product that generated by catalyst precursor sample changes along with temperature.The primary product generating in TPO research process is CO 2and H 2o.Based on Fig. 2 a and 2b, it is believed that at 650 ℃, from catalyst precursor sample, removed all carbon.TPO studies the research of the temperature programmed reduction(TPR) described in 4 in conjunction with the embodiments and shows, the component based on organic compound at least comprises carbon, hydrogen and oxygen.
the temperature programmed reduction(TPR) of embodiment 4-catalyst precursor
Fig. 3 has shown according to the temperature programmed reduction(TPR) analysis (H of the synthetic catalyst precursor of the program of catalyst A in embodiment 1 2-TPR) result.This H 2-TPR analyzes at 5%H 2in/He atmosphere, carry out, rate temperature change is 10 ℃/min.H 2-TPR result of study is presented in Fig. 3 a and 3b.Fig. 3 a has shown the total weight loss recording by thermogravimetric analysis.While reaching 700 ℃ to sample, removed almost 40% of precursor example weight.As shown in Fig. 3 b, the H of this weight loss for discharging from precursor sample 2o, CO 2with CO form.The material discharging from sample is considered to represent that component and/or some metal oxides removed based on organic compound are converted into compared with low-oxidation-state.
Also will point out, Fig. 2 a, 2b, 3a and 3b show, before reaching the temperature that approaches 400 ℃, removing of the component based on organic compound is considerably less.Based on this, the sulfuration of catalyst precursor (it also occurs in reducing environment) preferably should be less than about 400 ℃, preferably be less than at the temperature of about 350 ℃ and carry out.For example, a preferred curing temperature is about 325 ℃.
embodiment 5-catalyst characterization
To being similar to the body catalyst precursor of the present invention of catalyst precursor A, impose body sulfuration.Obtained high reactivity material.Fig. 4 has shown the catalyst precursor while making, the x-ray diffraction pattern of the corresponding catalyst after sulfuration, and directly by AHM and H 2the body MoS that S makes 2to comparison.Fig. 4 shows, with body MoS 2unique diffraction peak compare, described vulcanizing material is amorphous substantially, and/or with respect to the resolving power of XRD only containing small-particle.This conforms to the TEM Photomicrograph (it demonstrates small crystalline size) of sulphurized catalyst.It is believed that these small-crystallines represent metallic sulfide, may also comprise metal carbon sulfide.In another embodiment, at least a portion sulphurized catalyst of the present invention can have the crystallization property that can detect by XRD.In this embodiment, gained XRD spectrum can have certain crystallization property and certain amorphous characteristic.
the sulfuration of embodiment 6-catalyst precursor
According to the program of embodiment 1, to produce the catalyst precursor that is similar to catalyst precursor A.Then by liquid phase sulfuration program according to an embodiment of the invention, this catalyst precursor is vulcanized.Fig. 5 provides TEM Photomicrograph and the stacks as high analysis of gained sulphurized catalyst.TEM data show MoS in sulphurized catalyst 2the average stacks as high of stacked body is about 1.5.
Fig. 6 a and 6b have described the TEM data of the sulphurized catalyst of two kinds of additional type.Use the standby catalyzer corresponding with Fig. 6 a and 6b of gas phase sulfuration legal system, with by the catalyst precursor sulfuration according to making with mode like catalyst precursor category-A.By at 10%H 2s/H 2in 232 ℃ by catalyst precursor sulfuration 18 hours then 321 ℃ of revulcanization 12 hours, prepare the catalyzer corresponding with Fig. 6 a.The catalyzer corresponding with Fig. 6 b is at 10%H 2s/H 2in 600 ℃ sulfuration 4 hours.
For the catalyzer in Fig. 6 a, the TEM data presentation of gas phase sulphurized catalyst go out 1.6 on average record stacks as high, for the catalyzer in Fig. 6 b, be 2.2.In addition, the gas phase sulphurized catalyst shown in Fig. 6 a and 6b seems not sample homogeneous as shown in Figure 5.This effect is more remarkable for the catalyzer in Fig. 6 b vulcanizing under comparatively high temps.
the temperature programmed oxidation(TPO) of embodiment 7-sulphurized catalyst
Fig. 7 has described the TPO result of study of the sulphurized catalyst made according to an embodiment of the invention.By being similar to the liquid phase sulfuration of the catalyst precursor of catalyst precursor A, prepare sulphurized catalyst.Point out CO 2and SO 2peak is all in the temperature range of 400 to 600 ℃.Be not limited by any particular theory, in this temperature range, believe body CoMoS 2heat release changes into cobalt oxide and molybdenum oxide, and discharges SO 2.CO 2with SO 2in identical temperature range, discharge and carbon sulfide phase (CoMoS for example xc y, wherein carbon is structurally a part for sulfide phase) formation conform to.Also to point out H 2o is at high temperature released, and may associate with rest part or the surperficial SH group of component based on organic compound.
embodiment 8-heating steps variant
With Kaolinite Preparation of Catalyst precursor like catalyst precursor category-A, different is, in four kinds of different atmospheres, four kinds of different samples are carried out to different heating step, i.e. air, nitrogen, mixed atmosphere (mixture of air and nitrogen) and without the atmosphere (static heating) of airflow.At mixed atmosphere, add and hanker, stove was risen to about 325 ℃ from about room temperature in nitrogen atmosphere in one hour, and at 325 ℃, keep again 2 hours under nitrogen, then during about 2 hours, this atmosphere is transformed into air gradually.Finally process in air and at 325 ℃, carry out 2 hours.Long-pending and the carbon content to each sample surface measurements, and the results are shown in following table 3.
Table 3
The surface-area of body CoMo catalyst precursor and C content
CoMo-Catalysts for Preparing Glyoxylic BET SA (meters squared per gram) C content (% by weight)
Air heating under 617 °F 9.7 22.0
Hybrid Heating under 617 °F ＜0.5 22.8
N under 617 °F 2Heating 0.7 22.7
Static state heating under 617 °F 0.8 22.0
From upper table 3, can find out, body CoMo catalyst precursor has relatively low surface-area.Except the body CoMo catalyst precursor heating in air (its have be less than 10 meters squared per gram surface-area), other catalyst precursor has the surface-area that is less than 1 meters squared per gram.At air and/or nitrogen and/or mixed atmosphere (air and N 2mixture) and/or without after heating in the atmosphere (static atmosphere) of airflow, the carbon of the significant quantity that all catalyst precursors contain about 22 to 23 % by weight.
embodiment 9-hydrogenating desulfurization and hydrodenitrification
Fig. 8 has shown the CoMo catalyzer made according to an embodiment of the invention and the relative hydrodesulfurization activity of commercial catalyst.Commercial catalyst is can be available from Albemarle CatalystsCompany LP of Houston, TX's 757 (KF-757 tM) catalyzer.This KF-757 tMcatalyzer is included in Co and the Mo on alumina supporter.By the catalyst precursor that basis and the similar method of method of catalyst precursor A are made, vulcanize, prepare CoMo catalyzer of the present invention.But, at 325 ℃, at nitrogen, under the existence of non-air, the catalyst precursor for this embodiment is heated.The hydrodesulfurization corresponding with data in Fig. 8 carried out at 220psig pressure.As shown in Figure 8, the relative reactivity of bulk metal catalyst of the present invention is KF-757 tMthe active roughly twice of catalyzer.
Fig. 9 has shown catalyzer of the present invention and KF-757 tMthe analog of hydrodenitrogenationactivity activity.With KF-757 tMcompare, catalyzer of the present invention also shows the hydrodenitrogenationactivity activity of twice.The method corresponding with Fig. 9 also carried out at 220psig.
Figure 10 has shown catalyzer of the present invention and the KF-757 of the hydroprocessing process for carrying out at 500psig tMhydrogenating desulfurization and the comparison of hydrodenitrogenationactivity activity.As shown in Figure 10, under this elevated pressures, catalyzer according to an embodiment of the invention shows and KF-757 for the hydrogenating desulfurization under 500psig tMsimilar activity value, and for the hydrodenitrification under 500psig, also show the activity of 5 times.
In another example, measure catalyzer of the present invention (being equivalent to the catalyst A in embodiment 1) at low H 2pressure is with respect to KF-757 tMrelative reactivity.In phase reactor, at 329 ℃, 200psig H 2with 700SCF/B H 2lower this hydrotreated feed of processing.Initial hydrotreated feed provides in following table 4 with the character of the raw material of processing.
Table 4
Charging KF-757 TM Body CoMo-C
S，ppm 4500 55 16
N，ppm 39 17 7
API 37.9 38.1 38.2
Aromatics % 25.7 24.8 25.2
As shown in table 4, catalyzer of the present invention shows higher HDS and HDN is active, has reduced aromatics saturability simultaneously.From reducing the angle of the total hydrogen consumption hydrotreatment process, the aromatics of reduction is saturated is useful characteristic.
Also compared the hydrotreatment of same type catalyzer under middle pressure.In phase reactor at 329 ℃, 500psig H 2with 700SCF/B H 2lower processing has the original raw material of the T95 value of 773 °F (412 ℃).About initial feed and the additional detail of the raw material of processing, provide in following table 5.
Table 5
Charging KF-757 TM Body CoMo-C
S，ppm 18600 1420 190
N，ppm 167 60 ＜2
API 32.2 35.4 36.4
[0129]
Aromatics, % by weight 32.8 26.7 24.0
1 ring 15.4 21.4 20.2
2 rings 7.7 3.5 3.0
3+ ring 8.7 1.8 0.8
As shown in Figure 5, catalyzer of the present invention shows more active than the high HDS of commercial catalysts and HDN, and only appropriateness increase of hydrogen consumption.
embodiment 10-is with respect to the activity characterization of organic content
Figure 11 has shown the relative reactivity that uses the body CoMo catalyzer that the organic complexing agent of various amounts makes.Use oxoethanoic acid to manufacture various catalyst precursors as organic complexing agent, produced thus the data in Figure 11.As shown in Figure 11, the ratio of organic complexing agent and metal is less than the catalyst precursor of about 2: 1 and produces and to have obviously more SA catalyzer.The ratio of organic complexing agent and metal is greater than about 2: 1, be preferably greater than the catalyzer of about 3: 1 show 4 to 6 times to ratio the active relative reactivity lower than the catalyzer of about 2: 1.
the change of the precursor composition of embodiment 11-based on heat protocol
Figure 12 and 13 has described to use oxoethanoic acid to make and stand the TPO research of the body CoMo precursor of different heating scheme.In Figure 12, in airflow, at 80 ℃, sample a) is heated 14.5 hours.In airflow at 250 ℃ by sample b) heating 4 hours.In airflow at 325 ℃ by sample c) heating 4 hours.In Figure 13, in nitrogen at 400 ℃ by sample d) heating 4 hours.In nitrogen at 500 ℃ by sample e) heating 4 hours.In nitrogen at 600 ℃ by sample f) heating 4 hours.
Figure 12 and 13 shows, for the catalyst precursor that stands to increase progressively temperature in heat protocol, the quantity of material that can be removed in TPO research process successively decreases.Can find out, be heated to the weight loss that the CoMo catalyst precursor material of 80 ℃ shows about 70 % by weight (Figure 12, a).In air or in nitrogen, (not shown) has approximately 60% weight loss (Figure 12, b) at 250 ℃ of heating catalyst precursor sample of 4 hours.The sample that stood the higher temperature of 325 ℃ before TPO research shows the weight loss (Figure 12, c) of about 30 to 40 % by weight.As shown in Figure 13, temperature further rises to about 600 ℃ of further losses that cause organic materials from about 400.Also as shown in Figure 13, before TPO, catalyst precursor is heated to 550 ℃ or higher temperature under air exists and has produced in TPO research process the not catalyst precursor of bodies lost weight, show in air to have removed organic materials completely in being heated to the process of 550 ℃.But in similar heat protocol, the catalyzer being exposed in nitrogen atmosphere shows certain weight loss really in TPO research process.Even in nitrogen atmosphere at the catalyzer of 600 ℃ of heating, Figure 13 also shows not remove completely organic materials.This shows that heating can be controlled organic materials decomposition better under nitrogen (or other inertia) atmosphere.More generally, based on TPO, research is found out, is used for the heating condition of catalyst precursor by control, can control the amount of the component based on organic compound in catalyst precursor.
For being similar to the TPO research shown in Figure 12 and 13, also use mass spectroscopy to characterize the product discharging from sample.Figure 14 described with a)-c of research) similarly under condition but use N 2h in the TPO process of the body CoMo catalyst precursor that atmosphere replacement air atmosphere is processed 2the evolution of O signal.Figure 15 has described the CO of same sample 2discharge.
Figure 14 and 15 shows, with sample a) the similar precursor of making at the water and the CO that have discharged significant quantity lower than 200 ℃ 2.Be not limited by any particular theory, believe H 2o and CO 2release can and be adsorbed and excessive oxoethanoic acid owing to the water molecules being adsorbed existing in the precursor after 80 ℃ of thermal treatment.In nitrogen, after 250 ℃ of thermal treatment, as was expected, H 2o and CO 2release disappear.During higher than 250 ℃, the H observing 2o and CO 2release be similar to the H through 80 ℃ of heat treated samples 2o and CO 2discharge.The sample that is heated to 325 ℃ in nitrogen is also followed this pattern, during lower than 325 ℃, seldom or not discharges, and at the rest part of temperature range, discharges similarly with other sample.Especially, most of CO that all samples discharges 2all near the temperature 600 ℃.Be not limited by any particular theory, it is believed that near this CO 600 ℃ 2discharge (and H 2respective peaks in O spectrum) show, a part of oxoethanoic acid or gained acetaldehyde acidic group component have strong interaction or the combination with metal site.For heat treated sample in air, observe similar results.
Based on above-mentioned TPO research, in some embodiments, may preferably make catalyst precursor be exposed to higher than at the temperature of about 200 ℃ to 250 ℃.This thermal treatment seems the initial burst release of having removed water and organic materials from catalyst precursor, and this is of value to processing or use below.In other embodiments, can carry out TPO research to the catalyst precursor made from other organic complexing agent, to determine the temperature contrast of the water of original bulk and the release temperature of organic materials.In another embodiment, this catalyst precursor should remain on the temperature lower than about 450 ℃, to avoid the decomposition of strong interactional oxoethanoic acid or its component.Those of skill in the art will recognize that this temperature also can become with the character of selected organic complex.
Figure 16 has described body CoMo catalyst precursor another TPO after 325 ℃ of thermal treatment in different atmosphere that uses oxoethanoic acid to make: airflow, still air, nitrogen/air and nitrogen gas stream.Figure 16 shows, the weight loss (in TPO process) of the body CoMo catalyst precursor obtaining under different atmosphere is not the impact of the atmosphere while being subject to heat-treating very doughtily.For at the lower all four kinds of catalyst precursors that obtain of identical thermal treatment temp (325 ℃), observe similar weight loss.In the temperature higher than 325 ℃, weight loss can be subject to the impact of the atmosphere that exists in catalyst precursor heat-processed.
In a word, TPO result (Figure 12-16) conforms to BET surface area measurement with the as above carbon analysis shown in table 2.
embodiment 12-additional catalyst precursor characterizes
Figure 17 has described in air and nitrogen in the DRIFTS of 325 ℃ of heat treated body CoMoC materials spectrum.On the Nicolet 670FTIR spectrometer of cooled with liquid nitrogen MCT detector, collect diffuse-reflectance fourier transform infrared spectroscopy (DRIFTS) spectrum being furnished with.With 8cm -1resolving power record this spectrum.The powdered sample of body CoMo is loaded in the controlled atmosphere DRIFTS chamber (Thermo Spectra Tech) of being furnished with ZnSe window.This chamber is connected with adding the gas system of dry He and other gas.Use programming stove Quality control temperature.Conventionally by the sample after making in He at 120 ℃ with 2 ℃/min of processing, and keep 1 hour with by sample drying.
As shown in FTIR, the material based on organic compound existing in catalyst precursor is similar.1700 to 1900cm -1scope in observe aldehyde and the distinctive C=O of acid groups vibration, and 1400 to 1650cm -1scope in can see the vibration to the distinctive OCO of carboxyl.The skew of C=O vibration can for example, owing to metal site (Co is or/and Mo part) for example, complexing with organic complexing agent (oxoethanoic acid) functional group (aldehyde and carboxylic acid).Demonstrated other material, for example aliphatic CH 2(at 1970-2880 cm -1) and nitrile/isocyanic ester (2220-2191cm -1).Also demonstrate aromatics type residue=CH (3100cm -1) and the material of have-OH type group (at 3300cm -1).It is believed that various surface masses and organic acid (or complexing agent) associate, thereby form complex compound with metal site.In thermal activation process, also may there is chemical conversion and produce new surface mass.For example, can pass through NH 3the existence of explaining nitrile/isocyanic ester of reacting with oxoethanoic acid.NH 3in the ammonium cation decomposition course that can exist in molybdenum precursor, form.
Figure 18 has compared the DRIFTS spectrum from the body CoMo material in different heat treatment stage.As shown in Figure 17, the key feature of catalyst precursor being observed appears in the whole heat-processed that arrives 325 ℃ and all exists.This shows when 325 ℃ of heat treated sample, although discharge H as shown in Figure 14 and Figure 15 2o and CO 2, but the complex compound forming between organic acid and metal before heating steps is stable or most of maintenance.
Figure 19 has described at air and N 2under at 325 ℃ of heat treated body CoMo catalyst precursors 13c NMR spectrum.Shown in Figure 19 13c NMR data provide the further evidence of organic complexing agent (for example oxoethanoic acid) with metal complex.Under magic angle rotation (MAS) condition, record should 13cNMR spectrum, to avoid chemical shift anisotropy and some dipolar interactions.Aliphatic series CH 2type carbon appears at chemical shift range 0 to 40ppm.Within the scope of 15 to 60ppm, also can observe C-N type carbon.In 190 to 220ppm, observe the C=O of aldehyde group, and within the scope of 170 to 180ppm, observe the C+O of carboxyl.Conventionally within the scope of 120 to 160ppm, observe aromatics carbon.In addition, conventionally at about 40 to the 80ppm carbon of observing in C-O and C-N group.These results conform to FTIR data, and can explain by the complexing of metal and oxoethanoic acid functional group.
Figure 20 described metal how can with the possible configuration of oxoethanoic acid or another carboxylic acid complexing.Organic complexing agent of the present invention, oxoethanoic acid for example, can be with monodentate, bidentate or bridge joint mode and metallic joint.The structure of complex compound can become with the character of organic complexing agent and the acidity (pH) of solution (if complexing is formed in the aqueous solution).The limited example that Figure 20 provides this class complex compound to form.
Figure 21 has described in air the Raman spectrum when catalyst precursor stands higher temperatures thermal treatment in temperature programmed oxidation(TPO) research at 325 ℃ of heat treated body CoMo catalyst precursors.In Figure 21, uppermost spectrum is exposed to the body catalyst precursor at 300 ℃ under existing at air.This spectrum may demonstrate some unordered CoMoO 4, but there is no in addition crystalline oxides.Next spectrum has shown the catalyst precursor that is exposed to 450 ℃.CoMoO 4strength of signal stronger in this spectrum.It is believed that this shows to make Co and Mo start agglomeration owing to removing carbonaceous or the material based on organic compound.At 550 ℃, excessive Mo starts to assemble formation MoO in catalyst precursor 3phase.This is considered to owing to carbonaceous material further loss from precursor.Finally, at 600 ℃, removed quite most of carbonaceous material.Now, as shown in the peak indicating with asterisk (*), crystallization MoO 3phase and β-CoMo 4clearly visible in this spectrum.
This Raman result conforms to Figure 15 with Figure 14, and wherein when temperature is during higher than 450 ℃, strong interactional oxoethanoic acid or its component start to decompose.This also conforms to the X-ray diffraction shown in Figure 22 (XRD) result.
Figure 22 provides body CoMo catalyst precursor (by forming 325 ℃ of thermal treatments in air) and identical but be heated to 600 ℃ of comparisons that reach the XRD result between the sample of 4 hours in air.Catalyst precursor (its corresponding to the curve in this figure a)) for being heated to 325 ℃, does not detect discernible crystallization phases by XRD.The XRD of the sample (at 600 ℃, wherein having removed quite most carbonaceous material from catalyst precursor) of processing through higher temperatures on the contrary, shows definite crystal habit.Peak crystallization in XRD spectrum is owing to MoO 3(with *, indicating) and CoMoO 4crystallization phases.
embodiment 13-is organic/change of metal ratio
With different ratio R/(Co+Mo), form the similar precursor solution of solution a series of and from embodiment 1 and 1B.All samples is all used 1M cobaltous acetate, 1M AHM and the preparation of 4.5M oxoethanoic acid.Following table has shown the solution made and the characterization data of gained catalyst precursor.Point out, for BET surface area measurement, in helium, at 200 ℃, carry out degassed program.In air, with 10 ℃/min of temperature rise rates, from room temperature to 600 ℃, carry out thermogravimetric analysis (TGA).All samples shown in following table 6 has all produced amorphous XRD figure.
Table 6
R/(Co+Mo) BET SA (meters squared per gram) By the solid content (% by weight) of TGA C content (% by weight)
2.40 ＜1 76.7 13.2
2.88 ＜1 75.9 14.8
3.36 ＜1 72.4 16.6
3.84 ＜1 70.2 19.0
4.32 ＜1 68.6 19.6
5.28 14.7 68.9 21.1
5.76 10.6 65.2 23
6.24 3.7 62.3 24.8
6.72 7.8 61.5 25.5
Then by precursor sulfuration more relative hydrodesulfurization activity in upper table.Figure 23 shows, with about 4 or the precursor that forms than metal ratio of higher oxoethanoic acid in corresponding sulphurized catalyst, providing good hydrodesulfurization activity.
For other organic complexing agent, the amount of the needed organic complexing agent of reactivity realize improving can for 0.5 or higher organic complexing agent than the ratio of metal, or 1.0 or higher, or 2.0 or higher, or 3.0 or higher, or 4.0 or higher, or 5.0 or higher.
embodiment 14-is prepared by solid mixture
Also can prepare catalyst precursor of the present invention by solid mixture.In the following example, by mixing and grind the solid of cobaltous acetate, AHM and a glyoxylic acid, Kaolinite Preparation of Catalyst precursor.For the first embodiment, after the mixture grinding, at 325 ℃, calcine 4 hours, and in XRD analysis, show partial crystallization phase.In another preparation, after grinding, mixture is placed 24 hours at 80 ℃ or 95 ℃ in autoclave.Then at 325 ℃, precursor is calcined 4 hours.It is mainly the XRD figure of amorphous that gained catalyst precursor has.In a preparation again, under water smoke exists, blended solid is ground, then calcining.In process of lapping, water smoke has increased about 10 % by weight water in blended solid.This has produced the precursor with basic amorphous XRD figure.Various precursors are described in following table 7.
Table 7
Solids mixing sample BET SA (meters squared per gram) The solid (% by weight) that TGA measures C content (% by weight)
Grind ＜1 70.6 19.2
Grind and be placed in 80 ℃ of autoclaves 10.4 63.5 20.3
Grind and be placed in 95 ℃ of autoclaves 15.4 60.9 20.6
Grind and spraying ＜1 69.7 21.1
embodiment 15-is containing different organic body CoMo-C samples
Use the organism shown in following table to replace oxoethanoic acid Kaolinite Preparation of Catalyst precursor.In other side, according to the method in embodiment 1, prepare precursor.In each embodiment, the ratio of organism and metal is 4.8, but ratio in the second ketoisocaproic embodiment is 2.4.Point out, due to the low carbon content of gained precursor, acetic acid and formic acid represent comparative example.
Precursor BET SA (meters squared per gram) The solid (% by weight) that TGA measures C content (% by weight) XRD
Oxoethanoic acid ＜1 66.3 21.9 Amorphous
Acetylacetonate ＜1 73.3 20 Amorphous
Toxilic acid ＜1 50.0 32 Main amorphous, certain crystallization property (MoO 3Phase)
Acetic acid 22 98.7 0.35 Crystallization (CoMoO 4Phase)
Formic acid 19 100.5 0.14 Crystallization (MoO 3Phase)
Glyconic acid ＜1 24.1 57.9 Amorphous
Glucose ＜1 24.1 60.4 Amorphous
Ketoisocaproic <not recording> 46.3 Amorphous
Ketoisocaproic (2.4) <not recording> 37.4 Amorphous
[0163] embodiment 16-prepares body CoMo-C sample by organic acid mixture
Also can use the mixture of organic complexing agent, for example organic acid mixture, prepares acid catalyst precursor of the present invention.For example, use the combination of oxoethanoic acid and pyruvic acid as organic complex, with cobaltous acetate Kaolinite Preparation of Catalyst precursor together with AHM.Under vacuum at 60 ℃ by this mixture dried overnight, then in air 120 ℃ dry, finally in nitrogen 400 ℃ dry 4 hours.The relative quantity of Co and Mo keeps 1: 2.For each precursor, total organic complexing agent is 4.8 with the ratio of total metal (Co+Mo).Mixing oxoethanoic acid used in organic complexing agent and the ratio of pyruvic acid is presented in following table.Each sample described in table has produced amorphous XRD figure.
Sample XRD C content (% by weight)
CoMo-C (oxoethanoic acid: pyruvic acid=2.65) Amorphous 29.3
CoMo-C (oxoethanoic acid: pyruvic acid=1.20) Amorphous 40.1
CoMo-C (oxoethanoic acid: pyruvic acid=0.57) Amorphous 37.4
embodiment 17-aromatics selectivity
4,6-diethyl dibenzothiophene (DEDBT) is to can be used for studying in hydrodesulfurization process to preserving the optionally model compound of aromatic substance.When 4,6DEDBT is during by hydrogenating desulfurization, form two kinds of primary products:
Figure G2007800456493D00311
C4CHB product requires obviously more H 2just can form, and therefore from machining angle, see more not desirable.With C4CHB Compound Phase ratio, the catalyzer that more promotes C4BP compound formation is preferred.Selectivity of catalyst can be expressed as the ratio between the % by weight of C4CHB and the % by weight of C4BP.
Carry out model compound research to study catalyzer manufactured according to the present invention with respect to the relative aromatics selectivity of commercial catalysts.In dodecane model raw material, mix 1.5 % by weight 4,6 diethyl dibenzothiophene (4,6DEDBT).In phase reactor, at 260 ℃, 250psig H 2and 650SCF/BH 2under flow velocity, process this raw material.Under in being equivalent to embodiment 1, the catalyzer of catalyst A exists, and the commercial catalyst KF-757 manufacturing at Albemarle Catalyst Company individually tMthere is lower this raw material of processing.Use GC-analytical reagent composition charging and product.The raw material of processing according to the present invention has 9 C4CHB/C4BP ratio, and uses KF-757 tMthe raw material of processing has 25 ratio.This shows that catalyzer of the present invention is that the reaction path (being the formation of C4BP) that causes direct desulfurization provides good relative reactivity.
embodiment 18-stays carbon in catalyst precursor and sulphurized catalyst
It is believed that in catalyst precursor and sulphurized catalyst, the component based on organic compound is important for keeping the reactivity of the raising of catalyzer.Figure 24 has shown the relative HDS performance of the catalyst precursor of calcining at various temperatures before sulfuration.In Figure 24, at the catalyst precursor lower than 775 °F (413 ℃) lower calcining, show as KF-757 tMactive roughly 200% the activity of catalyzer.Preferably, catalyst precursor can be in about 625 °F (329 ℃) to about 775 °F (413 ℃) lower calcining.For the temperature higher than 825 °F (440 ℃) for precursor calcining, carbon content may be removed, thus shown in having produced compared with low activity.
Carbon is also stayed in the catalyzer of the present invention after sulfuration.Following table shows the catalyst precursor before sulfuration and uses H 2s/H 2the carbon content of the catalyzer after the sulfuration of 500psig liquid phase.
Body CoMo-C Before sulfuration After sulfuration
% by weight C 22.0 15.4
% by weight S 0 32.0
Catalyst precursor and corresponding sulphurized catalyst 13c NMR can provide sulfuration the rear residual further evidence of carbon.Figure 25 shown catalyzer of the present invention before sulfuration and afterwards overall similarly 13c NMR graphic representation.Point out, 13in C NMR graphic representation, in about 170 to 230ppm regions, (distinctive with the C=O of sour official's energy from aldehyde) substituted and conforms to by sulphur atom with Sauerstoffatom in sulfidation with the variation in about 40 to 80ppm regions (C-O is distinctive).

Claims (12)

1. the bulk metal catalyst of the sulfuration of amorphous, it is by preparing the precursor sulfuration of amorphous, described precursor is by preparing the aqueous solution heating of following substances: the organic complexing agent containing carboxylic acid of group VIII metal, group vib metal and 10 % by weight to 60 % by weight, described catalyst precursor composition has the carbon content of 10 to 25 % by weight and is less than the surface-area based on BET of 10 meters squared per gram, the sulphurized catalyst with at least a portion vib metal is the form of metallic sulfide stacked body, and this stacked body has 1.2 to 2.5 stacks as high.
2. the bulk metal catalyst of the sulfuration of the amorphous of claim 1, wherein said group VIII metal is nickel or cobalt, described group vib metal is molybdenum or tungsten.
3. the bulk metal catalyst of the sulfuration of claim 1 or 2 amorphous, the surface-area of wherein said precursor is at least 0.1 meters squared per gram.
4. the bulk metal catalyst of the sulfuration of the amorphous of claim 1, the carbon content that wherein said catalyst precursor comprises at least 12 % by weight.
5. the bulk metal catalyst of the sulfuration of the amorphous of claim 1, wherein said stacks as high is 2.2 or less.
6. the bulk metal catalyst of the sulfuration of the amorphous of claim 5, wherein said stacks as high is 2.0 or less.
7. the bulk metal catalyst of the sulfuration of the amorphous of claim 1, wherein said compositions table reveals following infrared spectra peak: at the 1400cm of carboxy CO O -1to 1650cm -1scope in the peak at carboxyl frequency place, with at the 1700cm of carbonyl C=O -1to 1900cm -1scope in the peak at carbonyl frequency place.
8. the bulk metal catalyst of the sulfuration of the amorphous of claim 1, wherein the ratio of group VIII metal and group vib metal is 0.3 to 0.6.
9. the bulk metal catalyst of the sulfuration of the amorphous of claim 1, wherein said organic complexing agent is selected from pyruvic acid, levulinic acid, 4-ethanoyl butyric acid, 1, 3-β-ketoglutaric acid, 3-oxo propionic acid, 4-ketobutyric acid, 2, 3-diformyl succinic acid, 5-oxopentanoic acid, 4-oxopentanoie acid, Thiovanic acid, glyoxylic acid ethyl ester, oxyacetic acid, glucose, glyconic acid, glycine, oxaminic acid, oxoethanoic acid, oxoethanoic acid 2-oxime, ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA), N-methylamino oxalic acid, iminodiethanoic acid, citric acid, oxalic acid, 2-ketogulonic acid, ketogluconic acid, α-ketoglutaric acid, 2-ketone butyric acid, methyl ethyl diketone and oxosuccinic acid.
10. the bulk metal catalyst of the sulfuration of the amorphous of claim 1, it by heating and prepare in rare gas element.
The bulk metal catalyst of the sulfuration of the amorphous of 11. claims 1,2,4 to 10 any one, wherein said catalyst precursor composition has the carbon content of 20 to 25 % by weight.
The bulk metal catalyst of the sulfuration of the amorphous of 12. claims 3, wherein said catalyst precursor composition has the carbon content of 20 to 25 % by weight.
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