CN103055956A - Impregnating solution of hydrogenation catalyst, its preparation method, hydrogenation catalyst and preparation method thereof - Google Patents
Impregnating solution of hydrogenation catalyst, its preparation method, hydrogenation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides an impregnating solution of a hydrogenation catalyst and its preparation method. The method includes: preparing a VIII-th group metal compound and a first organic complexing agent into an aqueous solution A; preparing a VIB-th group metal compound into an aqueous solution B; and mixing the aqueous solution A and the aqueous solution B. Specifically, the ligand of the first organic complexing agent at least contains the coordination atom N. The invention also provides a hydrogenation catalyst and a preparation method thereof. Compared with current catalysts, the hydrogenation catalyst provided in the invention has high hydrodesulfurization activity. For example, a mixed solution of n-decane with a 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) content of 0.59wt% is adopted as the raw material, and hydrodesulfurization activity contrast evaluation is performed on the catalyst provided in the invention and a contrast catalyst. In terms of a contrast catalyst activity of 100, the hydrodesulfurization activity of the catalyst provided in the invention can reach 120.
Description
Technical field
The present invention relates to a kind of preparation method of maceration extract of hydrogenation catalyst and the maceration extract of the hydrogenation catalyst that prepared by the method, and a kind of preparation method of hydrogenation catalyst and the hydrogenation catalyst that prepared by the method.
Background technology
The environmental consciousness that day by day strengthens and more and more stricter environmental regulation force the oil refining circle more to pay attention to the Clean Fuel Production technological development, and how the production super-low sulfur oil product of economical rationality has become oil refining circle current and expected future needs one of problem that emphasis solves in the regular period.Exploitation have high activity more and optionally the novel hydrogenation catalyst then be one of most economical method of production clear gusoline.
As everyone knows, carrier is as one of important component part of hydrogenation catalyst, and its surperficial physico-chemical property is to the dispersion of reactive metal and the catalytic performance important of catalyst.Although modification can weaken carrier-metal strong interaction to carrier (such as aluminium oxide), causes the decentralized photo of active phase to variation.Therefore, there is at present more researcher to propose to improve the method that reactive metal disperses at carrier, with the activity of further raising hydrogenation catalyst.
CN101797512A discloses a kind of high-activity hydrocracking catalyst and preparation method thereof, and wherein, catalyst comprises acidic components, hydrogenation component and carrier, and acidic components are the phosphotungstic acid cesium salt, and hydrogenation component is nickel, and carrier is silica; Catalyst components by mass percentage content is acidic components 10-50%, hydrogenation component 5-10%, and surplus is carrier.Its preparation method mainly comprises: will be added to respectively by water soluble nickel salt, the water-soluble cesiated salt solution that catalyst is set constituent content preparation in the complexing agent aqueous solution to get solution A; To join by the silicon source of the setting cubage gained of silica in the catalyst in the solution A to get solution B; To join in the solution B by the heteropoly acid aqueous solution that the setting constituent content of catalyst is prepared, evaporate to dryness solution, drying, the solid roasting with gained obtains catalyst.
The adding of complexing agent effectively raises the activity of the hydrogenation catalyst for preparing, yet the hydrogenation activity of the hydrogenation catalyst that the method for the Kaolinite Preparation of Catalyst of employing complexing agent obtains still has very large room for promotion.Therefore, how further by introducing complexing agent, improving the dispersity of metal on carrier, thereby promote the metal component of load to be converted into highly active active phase, will become the in the future emphasis direction of research with the activity of further raising hydrogenation catalyst.
Summary of the invention
The object of the present invention is to provide further hydrogenation catalyst that improves of a kind of hydrodesulfurization activity and preparation method thereof.
The invention provides a kind of preparation method of maceration extract of hydrogenation catalyst, the method comprises, group VIII metallic compound and the first organic complexing agent are mixed with water solution A; The group vib metallic compound is mixed with aqueous solution B; Described water solution A and aqueous solution B are mixed; Wherein, contain at least coordination atom N in the ligand of described the first organic complexing agent.
The invention provides a kind of maceration extract of the hydrogenation catalyst that the preparation method of the maceration extract of aforesaid hydrogenation catalyst prepares according to the present invention.
The present invention also provides a kind of preparation method of hydrogenation catalyst, and the method comprises, maceration extract is contacted with shaping carrier; Wherein, described maceration extract is the maceration extract of the aforesaid hydrogenation catalyst of the present invention.
The present invention also provides a kind of preparation method of hydrogenation catalyst, and the method comprises: prepare a kind of maceration extract, and this maceration extract is contacted with shaping carrier; Wherein, the preparation method of described maceration extract is the preparation method of the maceration extract of hydrogenation catalyst of the present invention.
The present invention also provides a kind of hydrogenation catalyst for preparing according to the preparation method of hydrogenation catalyst of the present invention.
Compare with existing catalyst, hydrogenation catalyst hydrodesulfurization activity provided by the invention is high.For example, to contain 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) mixed solution of the n-decane of 0.59 % by weight is raw material, catalyst provided by the invention and comparative catalyst are carried out the hydrodesulfurization activity comparative evaluation, take comparative catalyst's activity as 100, the hydrodesulfurization activity that the invention provides catalyst can reach 120.The present inventor infers it is because generally speaking, the activity of hydrogenation catalyst is relevant with the dispersity of active component on carrier, and when adopting method of the present invention to prepare hydrogenation catalyst, owing in advance group VIII metallic compound and the first organic complexing agent are mixed with water solution A and the group vib metallic compound are mixed with aqueous solution B, then described water solution A and aqueous solution B are mixed; So that in the preparation hydrogenation catalyst process, metal component exists with suitable metal species form (predecessor), and with before shaping carrier contacts, in advance water solution A and aqueous solution B are mixed, make auxiliary agent nickel (and/or cobalt) and molybdenum (and/or tungsten) approaching as much as possible, may be conducive to auxiliary agent nickel (and/or cobalt) acts synergistically with molybdenum (and/or tungsten), form the active phase that more has accessibility, thereby so that the maceration extract that adopts preceding method to prepare is when contacting with carrier, the dispersity of metal component on carrier is better, fully improve the utilization rate of metal, increased substantially thus the activity of hydrogenation catalyst.
Method of the present invention is simple to operation, is suitable for suitability for industrialized production.
The specific embodiment
The invention provides a kind of preparation method of maceration extract of hydrogenation catalyst, the method comprises, group VIII metallic compound and the first organic complexing agent are mixed with water solution A; The group vib metallic compound is mixed with aqueous solution B; Described water solution A and aqueous solution B are mixed; Wherein, contain at least coordination atom N in the ligand of described the first organic complexing agent.
Among the present invention, ligand (usually also claiming part) is definition well known in the art, it generally refers to and contains at least an atom and have a pair or more of lone pair electrons, or contain in the molecule pi-electron can and central atom (metal or metalloid) produce atom, molecule or the ion of keyed jointing.And in the organic complexing agent generally can with central atom (metal or metalloid) keyed jointing be the functional group of organic complexing agent.Therefore, for organic complexing agent of the present invention, ligand generally refers to the functional group that can produce with central atom (metal or metalloid) keyed jointing in the organic complexing agent.Among the present invention, the coordination atom in the ligand of organic complexing agent refers in the ligand of organic complexing agent directly and the atom of central atom keyed jointing.For example, the ligand of organic complexing agent ethylenediamine tetra-acetic acid is functional groups amino and the carboxyl in the ethylenediamine tetra-acetic acid, and the coordination atom in the ligand is nitrogen-atoms in the functional groups amino and the oxygen atom in functional group's carboxyl.Those skilled in the art all can know this, illustrate no longer one by one at this.
Preparation method according to the maceration extract of the aforesaid hydrogenation catalyst of the present invention all can realize purpose of the present invention, optional wider range of the mol ratio of described the first organic complexing agent and group VIII metallic compound, in order further to strengthen the complexing degree of group VIII metallic compound and the first organic complexing agent, thereby so that group VIII metallic compound dispersity is better in the maceration extract, the mol ratio of preferred described the first organic complexing agent and group VIII metallic compound is 0.1-2: 1, and 1-1.8 more preferably: 1.
Preparation method according to the maceration extract of hydrogenation catalyst of the present invention, aforementioned the first organic complexing agent namely can well be realized purpose of the present invention, for the present invention, contain simultaneously coordination atom N and O in the ligand of preferred described the first organic complexing agent, more preferably described the first organic complexing agent is one or more in ammonia carboxylic acid (usually also claiming amino carboxylic acid), ammonia carboxylate (usually also claiming aminocarboxylate) and the organic amine (such as hydramine); In the hydramine of the ammonia carboxylic acid that further preferred described the first organic complexing agent is C2-C18, the ammonia carboxylate of C2-C18 and C2-C18 one or more, one or more in the hydramine of the ammonia carboxylic acid that further preferred described the first organic complexing agent is C6-C14, the ammonia carboxylate of C6-C14 and C2-C12; Particularly preferably described the first organic complexing agent is trans 1,2-1,2-diaminocyclohexane tetraacetic acid, ethylenediamine tetra-acetic acid, aminotriacetic acid and ammonium salt thereof, and monoethanolamine, diethanol amine, triethanolamine, 3-Propanolamine (also claiming normal propyl alcohol amine), monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, N, N-dimethylethanolamine and N, one or more in the N-diethyl ethylene diamine etc.
The present inventor finds in research process, when described the first organic complexing agent is ammonia carboxylic acid such as aforementioned trans 1, during in 2-1,2-diaminocyclohexane tetraacetic acid, ethylenediamine tetra-acetic acid and the aminotriacetic acid one or more, preferably in the process that group VIII metallic compound and the first organic complexing agent is mixed with water solution A, add ammoniacal liquor, thereby can further strengthen the complexing degree of group VIII metallic compound and the first organic complexing agent; Further preferred, in ammonia, the mol ratio of ammoniacal liquor and the first organic complexing agent is 1-50: 1, be preferably 3-30: 1.
Preparation method according to the maceration extract of hydrogenation catalyst of the present invention, for so that in the maceration extract of the hydrogenation catalyst for preparing the dispersity of group vib metallic compound better, preferably in the process that the group vib metallic compound is mixed with aqueous solution B, add the second organic complexing agent and/or the 3rd organic complexing agent, wherein, the second organic complexing agent is that coordination atom only is the organic carboxyl acid of O in the ligand, and the 3rd organic complexing agent is that coordination atom only is the alkylol of O in the ligand.
The present inventor also finds in research process, in the process that the group vib metallic compound is mixed with aqueous solution B, add simultaneously the second organic complexing agent and the 3rd organic complexing agent and can better realize goal of the invention of the present invention, therefore, preferably in the process that the group vib metallic compound is mixed with aqueous solution B, add the second organic complexing agent and the 3rd organic complexing agent, more preferably the mol ratio of described the 3rd organic complexing agent and the second organic complexing agent is 0.01-5: 1, be preferably 0.05-2: 1, be particularly preferably 0.1-1.5: 1.
Preparation method according to the maceration extract of hydrogenation catalyst of the present invention, optional wider range of the mol ratio of described the second organic complexing agent and/or the 3rd organic complexing agent and group vib metallic compound, for the present invention, under the preferable case, the mol ratio of described the second organic complexing agent and/or the 3rd organic complexing agent and group vib metallic compound is 0.1-5: 1, be preferably 0.3-4: 1,1-4 more preferably: 1.
Preparation method according to the maceration extract of hydrogenation catalyst of the present invention, aforementioned the second organic complexing agent namely can well be realized purpose of the present invention, for the present invention, preferred described the second organic complexing agent is alkyl carboxylic acid, alkyl carboxylate, contain in the carboxylate of the carboxylic acid of the carboxylic acid of aldehyde radical, the carboxylate that contains aldehyde radical, hydroxyl and hydroxyl one or more.Among the present invention, described the second organic complexing agent can be various monobasics or polynary alkyl carboxylic acid, monobasic or polynary alkyl carboxylate, monobasic or the polynary carboxylic acid that contains aldehyde radical, monobasic or the polynary carboxylate that contains aldehyde radical, the carboxylate of the carboxylic acid of monobasic or polynary hydroxyl and monobasic or polynary hydroxyl, the more preferably alkyl carboxylic acid of monobasic or binary, the alkyl carboxylate of monobasic or binary, the carboxylic acid that contains aldehyde radical of monobasic or binary, the carboxylate that contains aldehyde radical of monobasic or binary, the carboxylate of the hydroxyl of the carboxylic acid of the hydroxyl of monobasic or binary and monobasic or binary; More preferably one or more in the carboxylate of the hydroxyl of the monobasic of the carboxylic acid of the hydroxyl of the monobasic of the carboxylate that contains aldehyde radical of the monobasic of the carboxylic acid that contains aldehyde radical of the monobasic of the alkyl carboxylate of the monobasic of the alkyl carboxylic acid of described the second organic complexing agent monobasic that is C2-C8 or binary, C2-C8 or binary, C2-C8 or binary, C2-C8 or binary, C2-C8 or binary and C2-C8 or binary, particularly preferably described the second organic complexing agent is one or more in citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, glycolic acid, tartaric acid and malic acid and the ammonium salt thereof.
Preparation method according to the maceration extract of hydrogenation catalyst of the present invention, aforementioned the 3rd organic complexing agent namely can well be realized purpose of the present invention, for the present invention, described the 3rd organic complexing agent can be various monobasics or the polynary alkylol that satisfies aforementioned requirement, be preferably the above alkylol of binary, the further above alkylol of preferred described the 3rd organic complexing agent binary that is C2-C6 and in the polyethylene glycol (preferred number average molecular weight is 600 below) one or more, further preferably described the 3rd organic complexing agent is glycerine, ethylene glycol, polyethylene glycol (preferred number average molecular weight is below 600), trimethylolethane, pentaerythrite, in xylitol and the sorbierite one or more.
Among the present invention, the optional wider range of the amount ratio of water solution A and aqueous solution B, as long as guarantee in described water solution A and the mixed solution of aqueous solution B, the mol ratio of the first organic complexing agent and group VIII metallic compound, the mol ratio of the second organic complexing agent and/or the 3rd organic complexing agent and group vib metallic compound gets final product in claimed range of the present invention, specifically can select according to the consumption of required group VIII metallic compound and the consumption of group vib metallic compound (being the content of required group VIII metal active constituent in the catalyst and the content of group vib metal active constituent), for the present invention, the weight ratio of preferred described water solution A and aqueous solution B is 0.2-2: 1, and 0.6-1.5 more preferably: 1.
The present invention to the kind of described group VIII metallic compound without specific (special) requirements, for example can be for nickel compound containing, cobalt compound, contain ruthenium compound, iron containing compounds, nickel compound containing, rhodium-containing compound, contain palladium compound, contain in the platinum compounds one or more, under the preferable case, in order to make activity of hydrocatalyst of the present invention higher, described group VIII metallic compound is nickel compound containing and/or cobalt compound.
Preparation method according to the maceration extract of hydrogenation catalyst of the present invention, the optional kind of described cobalt compound is wider, the conventional cobalt compound that uses in this area all can be realized purpose of the present invention, for the present invention, preferred described cobalt compound is the anaerobic hydrochlorate that contains the nonmetal oxyacid hydrochlorate of cobalt and/or contain cobalt, more preferably one or more in the soluble complexes of cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt, more preferably cobalt nitrate and/or basic cobaltous carbonate.
Preparation method according to the maceration extract of hydrogenation catalyst of the present invention, the optional kind of described nickel compound containing is wider, the conventional nickel compound containing that uses in this area all can be realized purpose of the present invention, for the present invention, preferred described nickel compound containing is nickeliferous nonmetal oxyacid hydrochlorate and/or nickeliferous anaerobic hydrochlorate, more preferably one or more in the soluble complexes of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel, more preferably nickel nitrate and/or basic nickel carbonate.
The present invention without specific (special) requirements, is preferably molybdate compound and/or Tungstenic compound to the kind of described group vib metallic compound.
Preparation method according to the maceration extract of hydrogenation catalyst of the present invention, the optional kind of described molybdate compound is wider, the conventional molybdate compound that uses in this area all can be realized purpose of the present invention, for the present invention, preferred described molybdate compound is molybdic acid, molybdenum oxide, molybdate, paramolybdate, contain molybdenum heteropolyacid and contain one or more of molybdenum heteropolyacid salt, more preferably one or more in molybdic acid, molybdenum oxide, ammonium molybdate, ammonium paramolybdate and the silicomolybdic acid.
Preparation method according to the maceration extract of hydrogenation catalyst of the present invention, the optional kind of described Tungstenic compound is wider, the conventional Tungstenic compound that uses in this area all can be realized purpose of the present invention, for the present invention, preferred described Tungstenic compound is one or more in wolframic acid, tungstates, metatungstate, ethyl metatungstate, heteropoly acid containing tungsten and the heteropoly acid containing tungsten salt, more preferably one or more in ammonium metatungstate, ethyl ammonium metatungstate, phosphotungstic acid and the silico-tungstic acid.
The invention provides a kind of maceration extract of the hydrogenation catalyst that is prepared by preparation method of the present invention.
The invention provides a kind of preparation method of hydrogenation catalyst, the method comprises, maceration extract is contacted with shaping carrier; Wherein, the maceration extract of the hydrogenation catalyst for preparing for the preparation method according to the maceration extract of the aforesaid hydrogenation catalyst of the present invention of described maceration extract.
The invention provides a kind of preparation method of hydrogenation catalyst, the method comprises: prepare a kind of maceration extract, and this maceration extract is contacted with shaping carrier; Wherein, the preparation method of described maceration extract is the preparation method of the maceration extract of hydrogenation catalyst of the present invention.
In hydrogenation catalyst of the present invention and preparation method thereof, only hydrogenation catalyst and preparation method thereof is described, the specific features according to the hydrogenation catalyst maceration extract for preparing of the maceration extract of hydrogenation catalyst of the present invention that preparation is used in the hydrogenation catalyst no longer is repeated in this description.
Without specific (special) requirements, for example described shaping carrier can be the shaping carrier that is obtained by one or more moulding in heat-resistant inorganic oxide, inorganic silicate and the molecular sieve to the kind of described shaping carrier in the present invention.
The present invention to the kind of described heat-resistant inorganic oxide without specific (special) requirements, can carry out with reference to prior art, for example can be aluminium oxide, silica, titanium oxide, magnesia, silica-alumina, aluminium oxide-magnesia, silica-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, the oxidation titania-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-magnesia, silica-alumina-zirconia, natural zeolite, in the clay one or more, wherein, be preferably aluminium oxide and/or silica.
The present invention without specific (special) requirements, can be the aluminium oxide of pure γ phase structure to the structure of described aluminium oxide, also can be the aluminium oxide of transition state duplex grain structure (aluminium oxide of at least a mixed crystal among γ and δ, the θ).The present invention without specific (special) requirements, for example can be to make through high-temperature roasting the preparation method of the aluminium oxide of described transition state duplex grain structure, and sintering temperature can be 600-1200 ℃, is preferably 700-1100 ℃; Roasting time can be 0.5-12 hour, is preferably 2-8 hour.
The present invention without specific (special) requirements, can be in zeolite or the non-zeolitic molecular sieves one or more to the kind of described molecular sieve.Described zeolite molecular sieve can be in erionite, ZSM-34 zeolite, modenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, L zeolite, y-type zeolite, X-type zeolite, ZSM-3 molecular sieve, ZSM-4 molecular sieve, ZSM-18 molecular sieve, ZSM-20 molecular sieve, ZSM-48 zeolite, ZSM-57 zeolite, faujasite, Beta zeolite and the omega zeolite one or more.Described non-zeolite molecular sieve can be in phosphate aluminium molecular sieve, HTS and SAPO (such as the SAPO) molecular sieve one or more.According to the present invention, described molecular sieve is preferably hydrogen type molecular sieve, and described hydrogen type molecular sieve can be commercially available, also can adopt conventional method preparation.For example, sodium type molecular sieve can be carried out ion-exchange and dry with conventional ammonium ion exchange method, form ammonium type molecular sieve, form hydrogen type molecular sieve through roasting again.
Preparation method according to hydrogenation catalyst of the present invention, can also contain clay in the described shaping carrier, the kind of described clay can need to be selected by root, is preferably in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and the bentonite one or more.
According to the preparation method of hydrogenation catalyst of the present invention, when containing molecular sieve in the described shaping carrier, take the total amount of described carrier as benchmark, the content of described molecular sieve can be the 0.5-100 % by weight, is preferably the 1-20 % by weight.
According to the preparation method of hydrogenation catalyst of the present invention, described shaping carrier can be cloverleaf pattern, butterfly, cylindrical, hollow cylindrical, quatrefoil, asymmetric quatrefoil, five leaf or spherical.
Preparation method according to hydrogenation catalyst of the present invention, method of the present invention can also be introduced auxiliary agent in preparation hydrogenation catalyst process (described auxiliary agent is preferably fluorine, in phosphorus and the boron one or more), introducing the method for auxiliary agent can carry out with reference to prior art, for example can add the compound that contains auxiliary agent with in maceration extract and the process that shaping carrier contacts, also can maceration extract with will contain again the compound of auxiliary agent after shaping carrier contacts and/or contain auxiliary agent compound solution with contact with shaping carrier after maceration extract contacts, those skilled in the art all can know this, not repeat them here.
According to the preparation method of hydrogenation catalyst of the present invention, the described compound that contains auxiliary agent is preferably one or more in the compound of fluorine-containing compound, phosphorous compound and boracic.More preferably, the described compound that contains auxiliary agent is one or more in hydrofluoric acid, hydrofluoride, fluosilicic acid, fluosilicate, ammonium fluoride, phosphoric acid, phosphorous acid, phosphate, phosphite, boric acid, ammonium borate, ammonium metaborate and the tetraboric acid ammonium; Further preferably, the described compound that contains auxiliary agent is one or more in ammonium fluoride, ammonium fluosilicate, phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), boric acid and the tetraboric acid ammonium.
Preparation method according to hydrogenation catalyst of the present invention, introduce optional wider range of the amount of auxiliary agent, can carry out with reference to prior art, under the preferable case, take the total amount of described hydrogenation catalyst as benchmark, in element, the content of the auxiliary agent of introducing is the 0.01-10 % by weight, is preferably 0.1-10 % by weight, 0.5-7.5 % by weight more preferably.Among the present invention, the content of auxiliary agent refers to the content of auxiliary agent in catalyst in element, generally is that catalyst is measured after 4 hours 550 ℃ of roastings.
According to the preparation method of hydrogenation catalyst of the present invention, optional wider range of the condition of described contact, for the present invention, the condition of preferred contact comprises: the temperature of contact is room temperature to 80 ℃, is preferably room temperature to 60 ℃; Time is 0.01-6 hour, is preferably 0.5-4h.The method of described contact can be the known spraying of art technology, dipping, adsorption method, is preferably dipping and absorption.What adopt in the embodiment of the invention is infusion process.
The present invention without specific (special) requirements, can be the various impregnation methods of prior art to the mode of described dipping, for example can be spray dipping, saturated dipping or excessive liquid dipping.
Preparation method according to hydrogenation catalyst of the present invention, under the preferable case, method of the present invention also comprises filters or does not filter (namely can not filter in the time of general saturated dipping, those skilled in the art all can know this), the step of then carrying out drying or drying and roasting.
The present invention, can carry out with reference to prior art without specific (special) requirements the condition of described drying, roasting.For example, the temperature of described drying is generally 100-250 ℃, is preferably 110-180 ℃, and the time is 0.5-10 hour, is preferably 2-8 hour; The temperature of roasting is generally 300-700 ℃, is preferably 300-550 ℃, and the time is 0.5-12 hour, is preferably 1-8 hour.
The invention provides a kind of hydrogenation catalyst that is prepared by the preparation method of hydrogenation catalyst of the present invention.
According to the conventional method in this area, catalyst provided by the invention is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out presulfurization with sulphur, hydrogen sulfide or other sulfur-bearing raw material, described presulfurization can carry out also can carrying out the original position sulfuration in device outside device, to be translated into sulfide type, all can carry out with reference to prior art this, the present invention does not repeat them here without specific (special) requirements.
Compare with existing Hydrobon catalyst, catalyst provided by the invention has higher hydrodesulfurization activity, this catalyst is applicable to the unifining process of oil, coal liquefaction fraction oil, and this catalyst and hydrocracking catalyst are used the hydro-upgrading process that can be used for heavy distillate.
The following examples will further specify the present invention, but not thereby limiting the invention.
Among the embodiment, the butt quality refers in the quality of 600 ℃ of roastings after 4 hours.
Among the embodiment, as not specifying that employed reagent is AR.
Specify among the embodiment as not, all adopt the method for incipient impregnation to flood.
Embodiment 1-9 is used for illustrating the preparation method of catalyst provided by the invention.
Embodiment 1
Take by weighing 10000 gram aluminium hydrate powder (butt 70 % by weight, available from Chang Ling catalyst branch company of China Petrochemical Industry) usefulness banded extruder (manufacturer: South China Science ﹠ Engineering University's science and technology industry head factory, model: F-26 (III)) being extruded into circumscribed circle diameter is 1.6 millimeters cloverleaf pattern bar, then 120 ℃ of dryings 4 hours, 600 ℃ of roastings 4 hours, obtain carrier S 1, the aluminium oxide that characterizes in this carrier through X-ray diffraction is gama-alumina.
The preparation water solution A: take by weighing 25.80 gram ethylenediamine tetra-acetic acids, add 80 ml waters, the ammoniacal liquor of 25 milliliter of 25 % by weight and 9.80 gram basic nickel carbonates (in Ni, 44 % by weight), heating for dissolving is even;
Preparation aqueous solution B: take by weighing 69.07 gram ammonium citrates and 33.76 gram ammonium heptamolybdates (with MoO
3Meter, 80.7 % by weight), adding 90 ml waters, heating for dissolving is even;
Water solution A added among the aqueous solution B mix, the Hou Jiashui that stirs is settled to 257 milliliters, with above-mentioned 200 gram S1 carriers of this solution impregnation 2 hours, then 170 ℃ of dryings 4 hours, obtains catalyst C1.
Embodiment 2
The preparation water solution A: take by weighing 22.15 gram ethylenediamine tetra-acetic acids, add 80 ml waters, the ammoniacal liquor of 25 milliliter of 25 % by weight and 9.80 gram basic nickel carbonates (in Ni, 44 % by weight), heating for dissolving is even;
Preparation aqueous solution B: take by weighing 46.05 gram ammonium citrates and 33.76 gram ammonium heptamolybdates (with MoO
3Meter, 80.7 % by weight), adding 90 ml waters, heating for dissolving is even;
Water solution A added among the aqueous solution B mix, the Hou Jiashui that stirs is settled to 257 milliliters, with the aforementioned S1 carrier of these solution impregnation 200 grams 2 hours, then 180 ℃ of dryings 4 hours, obtains catalyst C2.
Embodiment 3
The preparation water solution A: take by weighing 10.75 gram ethylenediamine tetra-acetic acids, add 60 ml waters, the ammoniacal liquor of 50 milliliter of 25 % by weight and 21.84 gram nickel nitrates (content of nickel nitrate is 98 % by weight), heating for dissolving is even;
Preparation aqueous solution B: take by weighing 23.02 gram ammonium citrates and 33.76 gram ammonium heptamolybdates (with MoO
3Meter, 80.7 % by weight), adding again 85 ml waters, heating for dissolving is even;
Water solution A added among the aqueous solution B mix, the Hou Jiashui that stirs is settled to 257 milliliters, with the aforementioned S1 carrier of these solution impregnation 200 grams 2 hours, then 160 ℃ of dryings 4 hours, obtains catalyst C3.
Embodiment 4
Take by weighing 10000 gram aluminium hydrate powder (butt 70 % by weight, available from Chang Ling catalyst branch company of China Petrochemical Industry) and 4000 the gram Ludox (contain silica 25 % by weight, available from Haiyang Chemical Plant, Qingdao), use banded extruder (manufacturer: South China Science ﹠ Engineering University's science and technology industry head factory after mixing, model: F-26 (III)) being extruded into circumscribed circle diameter is 1.4 millimeters cloverleaf pattern bar, then 120 ℃ of dryings 10 hours, 600 ℃ of roastings 3 hours obtain carrier S 2.
Take by weighing 200 gram carrier S 2, this carrier was flooded 2 hours with 249 milliliters of the aqueous solution that contains 10.0 gram ammonium fluorides (analyze pure, Beijing Chemical Plant's product), then 120 ℃ of dryings 4 hours, 500 ℃ of roastings 2 hours obtain fluorine-containing carrier S 2-1.
The preparation water solution A: take by weighing 25.80 gram ethylenediamine tetra-acetic acids, add 80 ml waters, the ammoniacal liquor of 25 milliliter of 25 % by weight, 9.80 gram basic nickel carbonates (in Ni, 44 % by weight) and 2.05 gram 3-Propanolamines, heating for dissolving is even;
Preparation aqueous solution B: take by weighing 46.05 gram ammonium citrates, 17.43 gram glycerine and 27.25 gram molybdenum trioxides, add 90 ml waters, heating for dissolving is even;
Will aqueous solution B add in the water solution A and mix, the Hou Jiashui that stirs is settled to 257 milliliters, restrains S2-1 carriers 2 hours with this solution impregnation above-mentioned 200, then 160 ℃ of dryings 6 hours, obtains catalyst C4.
Embodiment 5
Take by weighing 10000 gram aluminium hydrate powder (butt 70 % by weight, available from Chang Ling catalyst branch company of China Petrochemical Industry), 3800 gram Ludox (contain silica 25 % by weight, available from Haiyang Chemical Plant, Qingdao) and 100 gram TS-1 molecular sieves (available from Chang Ling catalyst branch company of China Petrochemical Industry), 10 gram Hydrogen Y molecular sieves (available from Chang Ling catalyst branch company of China Petrochemical Industry) and 5 gram Hydrogen Beta molecular sieves (available from Chang Ling catalyst branch company of China Petrochemical Industry), use banded extruder (manufacturer: South China Science ﹠ Engineering University's science and technology industry head factory after mixing, model: F-26 (III)) being extruded into circumscribed circle diameter is 1.4 millimeters cloverleaf pattern bar, then 120 ℃ of dryings 10 hours, 550 ℃ of roastings 5 hours obtain carrier S 3.
Take by weighing 200 gram carrier S 3, this carrier was flooded 2 hours with 249 milliliters of the aqueous solution that contains 13.0 gram ammonium fluorides (analyze pure, Beijing Chemical Plant's product), then 120 ℃ of dryings 4 hours, 500 ℃ of roastings 2 hours obtain fluorine-containing carrier S 3-1.
The preparation water solution A: take by weighing 25.80 gram ethylenediamine tetra-acetic acids, add 75 ml waters, the ammoniacal liquor of 30 milliliter of 25 % by weight and 9.80 gram basic nickel carbonates (in Ni, 44 % by weight), heating for dissolving is even;
Preparation aqueous solution B: take by weighing 46.05 gram ammonium citrates, 1.26 gram citric acids, 17.43 gram glycerine, 1.16 gram glyoxalic acids, 18.51 gram glycolic acid ammoniums, 1.15 gram polyethylene glycol (PEG-400) and 27.25 gram molybdenum trioxides, add 90 ml waters, heating for dissolving is even;
Will aqueous solution B add in the water solution A and mix, the Hou Jiashui that stirs is settled to 257 milliliters, restrains S3-1 carriers 2 hours with this solution impregnation above-mentioned 200, then 150 ℃ of dryings 8 hours, obtains catalyst C5.
Embodiment 6
Take by weighing 200 gram carrier S 3, this carrier was flooded 2 hours with 249 milliliters of the aqueous solution that contains 16.5 gram ammonium fluorides (analyze pure, Beijing Chemical Plant's product), then 120 ℃ of dryings 4 hours, 500 ℃ of roastings 2 hours obtain fluorine-containing carrier S 3-2.
Preparation water solution A: take by weighing 25.80 gram ethylenediamine tetra-acetic acids, 1.28 grams 1,2-1,2-diaminocyclohexane tetraacetic acid, 1.17 gram ethylenediamine tetra-acetic acid two ammoniums and 1.13 gram aminotriacetic acids, add 75 ml waters, the ammoniacal liquor of 30 milliliter of 25 % by weight, 9.80 gram basic nickel carbonates are (in Ni, 44 % by weight) and 4.64 the gram diethanol amine, heating for dissolving is even;
Preparation aqueous solution B: take by weighing 46.05 gram ammonium citrates, 17.43 gram glycerine, 1.56 gram glycolic acids, 21.14 gram glycolic acid ammoniums, 13.63 gram molybdenum trioxides and 24.02 gram ammonium metatungstates (with WO
3Meter, 91.4 % by weight), adding 80 ml waters, heating for dissolving is even;
Water solution A added among the aqueous solution B mix, the Hou Jiashui that stirs is settled to 257 milliliters, with above-mentioned 200 gram S3-2 carriers of this solution impregnation 2 hours, then 150 ℃ of dryings 8 hours, obtains catalyst C6.
Embodiment 7
The preparation water solution A: take by weighing 25.80 gram ethylenediamine tetra-acetic acids, add 75 ml waters, the ammoniacal liquor of 30 milliliter of 25 % by weight and 9.80 gram basic nickel carbonates (in Ni, 44 % by weight), heating for dissolving is even;
Preparation aqueous solution B: take by weighing 27.25 gram molybdenum trioxides, add the ammoniacal liquor of 60 ml waters and 30 milliliter of 25 % by weight, heating for dissolving is even;
Will aqueous solution B add in the water solution A and mix, the Hou Jiashui that stirs is settled to 257 milliliters, restrains aforementioned S3-1 carrier 2 hours with this solution impregnation 200, then 150 ℃ of dryings 8 hours, obtains catalyst C7.
Embodiment 8
The preparation water solution A: take by weighing 18.28 gram ethylenediamine tetra-acetic acids, add 75 ml waters, the ammoniacal liquor of 30 milliliter of 25 % by weight and 9.80 gram basic nickel carbonates (in Ni, 44 % by weight), heating for dissolving is even;
Preparation aqueous solution B: take by weighing 46.05 gram ammonium citrates, 17.43 gram glycerine, 18.51 gram glycolic acid ammoniums and 27.25 gram molybdenum trioxides, add 90 ml waters, heating for dissolving is even;
Will aqueous solution B add in the water solution A and mix, the Hou Jiashui that stirs is settled to 257 milliliters, restrains aforementioned S3-1 carrier 2 hours with this solution impregnation 200, then 150 ℃ of dryings 8 hours, obtains catalyst C8.
Embodiment 9
The preparation water solution A: take by weighing 22.15 gram ethylenediamine tetra-acetic acids, add 80 ml waters, the ammoniacal liquor of 25 milliliter of 25 % by weight and 9.80 gram basic nickel carbonates (in Ni, 44 % by weight), heating for dissolving is even;
Preparation aqueous solution B: take by weighing 27.63 gram ammonium citrates, 1.08 gram glycerine and 33.76 gram ammonium heptamolybdates (with MoO
3Meter, 80.7 % by weight), adding 90 ml waters, heating for dissolving is even;
Water solution A added among the aqueous solution B mix, the Hou Jiashui that stirs is settled to 257 milliliters, with the aforementioned S1 carrier of these solution impregnation 200 grams 2 hours, then 180 ℃ of dryings 4 hours, obtains catalyst C9.
Comparative Examples 1
Take by weighing 22.58 gram ethylenediamine tetra-acetic acids, add 60 ml waters, the ammoniacal liquor of 125 milliliter of 25 % by weight, 9.80 gram basic nickel carbonates (in Ni, 44 % by weight) and 33.76 gram ammonium heptamolybdates are (with MoO
3Meter, 80.7 % by weight) heating for dissolving evenly after, add water and be settled to 257 milliliters, restrain aforementioned S1 carrier 2 hours with this solution impregnation 200, then 180 ℃ of dryings 4 hours, obtain catalyst D1.
Comparative Examples 2
Take by weighing 64.15 gram ammonium citrates, add 180 ml waters, 9.80 gram basic nickel carbonates (in Ni, 44 % by weight) and 33.76 gram ammonium heptamolybdates are (with MoO
3Meter, 80.7 % by weight); After the dissolving, add water and be settled to 257 milliliters, with the aforementioned S1 carrier of this solution impregnation 200 grams 2 hours, then 180 ℃ of dryings 4 hours, obtain catalyst D2.
Comparative Examples 3
Take by weighing 18.56 gram citric acids, add ammoniacal liquor, 9.80 gram basic nickel carbonates (in Ni, 44 % by weight) and the 33.76 gram ammonium heptamolybdates of 60 ml waters, 125 milliliter of 25 % by weight (with MoO
3Meter, 80.7 % by weight); After the dissolving, add water and be settled to 257 milliliters, with the aforementioned S1 carrier of this solution impregnation 200 grams 2 hours, then 180 ℃ of dryings 4 hours, obtain catalyst D3.
Comparative Examples 4
The preparation water solution A: take by weighing 10.75 gram ethylenediamine tetra-acetic acids, add 60 ml waters, the ammoniacal liquor of 50 milliliter of 25 % by weight and 21.84 gram nickel nitrates (content of nickel nitrate is 98 % by weight), heating for dissolving is even, adds water and is settled to 257 milliliters;
Preparation aqueous solution B: take by weighing 23.02 gram ammonium citrates and 33.76 gram ammonium heptamolybdates (with MoO
3Meter, 80.7 % by weight), adding again 85 ml waters, heating for dissolving is even, adds water and is settled to 257 milliliters;
First with the aforementioned S1 carrier of water solution A dipping 200 grams 2 hours, then 160 ℃ of dryings 4 hours; The water solution B was flooded after the above-mentioned drying gained carrier 2 hours again, then 160 ℃ of dryings 4 hours, obtained catalyst D4.
Comparative Examples 5
The preparation water solution A: take by weighing 10.75 gram ethylenediamine tetra-acetic acids, add 60 ml waters, the ammoniacal liquor of 50 milliliter of 25 % by weight and 21.84 gram nickel nitrates (content of nickel nitrate is 98 % by weight), heating for dissolving is even, adds water and is settled to 257 milliliters;
Preparation aqueous solution B: take by weighing 23.02 gram ammonium citrates and 33.76 gram ammonium heptamolybdates (with MoO
3Meter, 80.7 % by weight), adding again 85 ml waters, heating for dissolving is even, adds water and is settled to 257 milliliters;
The aforementioned S1 carrier of elder generation's water solution B dipping 200 grams 2 hours is then 160 ℃ of dryings 4 hours; Flood after the above-mentioned drying gained carrier 2 hours with water solution A again, then 160 ℃ of dryings 4 hours, obtain catalyst D5.
Comparative Examples 6
Take by weighing 10.75 gram ethylenediamine tetra-acetic acids, 23.02 gram ammonium citrates, add 100 ml waters, the ammoniacal liquor of 60 milliliter of 25 % by weight, 33.76 gram ammonium heptamolybdates are (with MoO
3Meter, 80.7 % by weight) and 21.84 gram nickel nitrates (content of nickel nitrate is 98 % by weight), heating for dissolving is even, adds water and is settled to 257 milliliters.With the above-mentioned 200 gram aforementioned S1 carriers 2 hours of this solution impregnation, then 160 ℃ of dryings 4 hours, obtain catalyst D6.
Comparative Examples 7
The preparation water solution A: take by weighing 10.75 gram ethylenediamine tetra-acetic acids, add 60 ml waters, the ammoniacal liquor of 50 milliliter of 25 % by weight and 33.76 gram ammonium heptamolybdates are (with MoO
3Meter, 80.7 % by weight) heating for dissolving is even;
Preparation aqueous solution B: take by weighing 23.02 gram ammonium citrates and 21.84 gram nickel nitrates (content of nickel nitrate is 98 % by weight), add ammoniacal liquor and 50 ml waters of 30 milliliter of 25 % by weight again, heating for dissolving is even; Water solution A is joined among the aqueous solution B, and the Hou Jiashui that stirs is settled to 257 milliliters, with aforementioned 1 carrier of this solution impregnation 200 gram S 2 hours, then 160 ℃ of dryings 4 hours, obtains catalyst D7.
Comparative Examples 8
The preparation water solution A: take by weighing 21.84 gram nickel nitrates (content of nickel nitrate is 98 % by weight), add ammoniacal liquor and 70 ml waters of 30 milliliter of 25 % by weight again, dissolving evenly;
Preparation aqueous solution B: take by weighing 33.76 gram ammonium heptamolybdates (with MoO
3Meter, 80.7 % by weight) add 60 ml waters, the ammonia solvent of 40 milliliter of 25 % by weight is even;
Water solution A is mixed with aqueous solution B, and the Hou Jiashui that stirs is settled to 257 milliliters, with the aforementioned S1 carrier of this solution impregnation 200 grams 2 hours, then 160 ℃ of dryings 4 hours, obtains catalyst D8.
Embodiment 10-18
Embodiment 10-18 is used for illustrating the hydrodesulfurization performance of hydrogenation catalyst of the present invention.
To contain 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) mixed solution of the n-decane of 0.59 % by weight is raw material, in high-pressure micro-device (manufacturer: Beijing petrochemical industry information automation company, model: the DADI) hydrodesulfurization activity of upper evaluate catalysts C1-C9, it is 40-60 purpose particle that catalyst C1-C9 is broken into diameter, and the loadings of catalyst is 0.15 gram.
Before formal charging, first respectively catalyst C1-C9 is carried out presulfurization take the cyclohexane that contains 6 % by weight carbon disulfide as sulfurized oil, the condition of presulfurization comprises: pressure is 4.14MPa, and temperature is 362 ℃, time is 3.5 hours, and the sulfurized oil feed rate is 0.2 ml/min.
After sulfuration finished, being cooled to reaction temperature was 280 ℃, the incision raw material.Reaction condition comprises: the raw material feed rate is 0.2 ml/min, and the hydrogen dividing potential drop is 4.14MPa, and hydrogen to oil volume ratio is 900.React and take a sample in the high-pressure separator exit after 3 hours.The gained sample is analyzed with the Agilent6890N gas chromatograph, the results are shown in Table 1.Wherein, the hydrodesulfurization activity A of 4,6-DMDBT is calculated as follows:
A＝ln[100/(100-X)]，
In the formula, X is that (wherein, the circular of desulfurization degree is referring to " catalysis journal ", 2002,23 (3): 271-275) for the desulfurization degree of 4,6-DMDBT.
Get 4 of comparative catalyst D3, the hydrodesulfurization activity of 6-DMDBT is 100, and then other catalyst is relative 4, and the hydrodesulfurization activity of 6-DMDBT can be represented by the formula, and the results are shown in Table 1.
Relative activity=(A
QT/ A
D3) * 100%,
A in the formula
QTBe the activity of other catalyst, A
D3Activity for reference catalyst.
Comparative Examples 9-16
Adopt the method evaluation Comparative Examples catalyst D1-D8 identical with embodiment 10-18, the results are shown in Table 1.
Table 1
| Numbering | Carrier | Catalyst | Relative hydrodesulfurization activity (%) |
| Embodiment 1 and 10 | S1 | C1 | 116 |
| Embodiment 2 and 11 | S1 | C2 | 114 |
| Embodiment 3 and 12 | S1 | C3 | 112 |
| Embodiment 4 and 13 | S2-1 | C4 | 117 |
| Embodiment 5 and 14 | S3-1 | C5 | 118 |
| Embodiment 6 and 15 | S3-2 | C6 | 120 |
| Embodiment 7 and 16 | S3-1 | C7 | 112 |
| Embodiment 8 and 17 | S3-1 | C8 | 117 |
| Embodiment 9 and 18 | S1 | C9 | 113 |
| Comparative Examples 1 and 9 | S1 | D1 | 104 |
| Comparative Examples 2 and 10 | S1 | D2 | 103 |
| Comparative Examples 3 and 11 | S1 | D3 | 100 |
| Comparative Examples 4 and 12 | S1 | D4 | 104 |
| Comparative Examples 5 and 13 | S1 | D5 | 103 |
| Comparative Examples 6 and 14 | S1 | D6 | 103 |
| Comparative Examples 7 and 15 | S1 | D7 | 102 |
| Comparative Examples 8 and 16 | S1 | D8 | 97 |
Result by table 1 obviously shows, all shows higher activity according to hydrogenation catalyst of the present invention.
Claims (19)
1. the preparation method of the maceration extract of a hydrogenation catalyst, the method comprises, group VIII metallic compound and the first organic complexing agent are mixed with water solution A; The group vib metallic compound is mixed with aqueous solution B; Described water solution A and aqueous solution B are mixed; Wherein, contain at least coordination atom N in the ligand of described the first organic complexing agent.
2. preparation method according to claim 1, wherein, the mol ratio of described the first organic complexing agent and group VIII metallic compound is 0.1-2: 1.
3. preparation method according to claim 1, wherein, described the first organic complexing agent is one or more in ammonia carboxylic acid, ammonia carboxylate and the hydramine.
4. preparation method according to claim 3, wherein, described the first organic complexing agent is trans 1,2-1,2-diaminocyclohexane tetraacetic acid, ethylenediamine tetra-acetic acid, aminotriacetic acid and ammonium salt thereof, and monoethanolamine, diethanol amine, triethanolamine, 3-Propanolamine, monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, N, N-dimethylethanolamine and N, one or more in the N-diethyl ethylene diamine.
5. preparation method according to claim 3, wherein, when described the first organic complexing agent is the ammonia carboxylic acid, in the process that group VIII metallic compound and the first organic complexing agent is mixed with water solution A, add ammoniacal liquor, and in ammonia, the mol ratio of ammoniacal liquor and the first organic complexing agent is 1-50: 1.
6. the described preparation method of any one according to claim 1-5, wherein, in the process that the group vib metallic compound is mixed with aqueous solution B, add the second organic complexing agent and/or the 3rd organic complexing agent, wherein, the second organic complexing agent is that coordination atom only is the organic carboxyl acid of O in the ligand, and the 3rd organic complexing agent is that coordination atom only is the alkylol of O in the ligand.
7. preparation method according to claim 6, wherein, add the second organic complexing agent and the 3rd organic complexing agent in the process that the group vib metallic compound is mixed with aqueous solution B, the mol ratio of described the 3rd organic complexing agent and the second organic complexing agent is 0.05-2: 1.
8. preparation method according to claim 6, wherein, the mol ratio of described the second organic complexing agent and/or the 3rd organic complexing agent and group vib metallic compound is 0.1-5: 1.
9. preparation method according to claim 6, wherein, described the second organic complexing agent is alkyl carboxylic acid, alkyl carboxylate, contain in the carboxylate of the carboxylic acid of the carboxylic acid of aldehyde radical, the carboxylate that contains aldehyde radical, hydroxyl and hydroxyl one or more, and described the 3rd organic complexing agent is the above alkylol of binary.
10. preparation method according to claim 9, wherein, described the second organic complexing agent is one or more in citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, glycolic acid, tartaric acid and malic acid and the ammonium salt thereof; Described the 3rd organic complexing agent is one or more in glycerine, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythrite, xylitol and the sorbierite.
11. the described preparation method of any one according to claim 1-5, wherein, described group VIII metallic compound is nickel compound containing and/or cobalt compound.
12. the described preparation method of any one according to claim 1-5, wherein, described group vib metallic compound is molybdate compound and/or Tungstenic compound.
13. the maceration extract of a hydrogenation catalyst that is prepared by the described preparation method of any one among the claim 1-12.
14. the preparation method of a hydrogenation catalyst, the method comprise, maceration extract is contacted with shaping carrier; It is characterized in that described maceration extract is the maceration extract of the described hydrogenation catalyst of claim 13.
15. the preparation method of a hydrogenation catalyst, the method comprises: prepare a kind of maceration extract, and this maceration extract is contacted with shaping carrier; It is characterized in that the preparation method of described maceration extract is the described preparation method of any one among the claim 1-12.
16. preparation method according to claim 15, wherein, described shaping carrier is obtained by one or more moulding in heat-resistant inorganic oxide, inorganic silicate and the molecular sieve.
17. preparation method according to claim 15, wherein, the condition of described contact comprises that the temperature of contact is room temperature to 80 ℃, and the time is 0.01-6 hour.
18. preparation method according to claim 15, wherein, the method is filtered or is not filtered after also comprising contact, then carries out the step of drying or dry and roasting.
19. hydrogenation catalyst that is prepared by the described preparation method of any one among the claim 14-18.
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