CN105478145B - The hydrodesulfurization Porous deproteinized bone method of hydrodesulfurization dearomatization catalyst and system and preparation method thereof and diesel oil - Google Patents

Abstract

The present invention relates to a kind of hydrodesulfurization dearomatization catalyst and preparation method thereof and hydrodesulfurization dearomatization catalyst system and the hydrodesulfurization Porous deproteinized bone methods of diesel oil, the hydrodesulfurization dearomatization catalyst contains the metal active constituent and trace element of the sulphided state of carrier and load on this carrier, the trace element is selected from P, F, Si, B, it is one or more in Mg, the metal active constituent contains group VIII metallic element and vib metals element, it is characterized in that, the sulphidity that group VIII metallic element in the catalyst is measured using XPS is not less than 70%, the sulphidity of vib metals element is not less than 70%, active Phase Proportion using the three layer heaps product of the catalyst of TEM statistics is not less than 30%.Hydrodesulfurization dearomatization catalyst provided by the invention can take into account desulfurization effect and Porous deproteinized bone effect.

Description

Hydrodesulfurization dearomatization catalyst and system and preparation method thereof add hydrogen de- with diesel oil Sulphur Porous deproteinized bone method

Technical field

The present invention relates to a kind of hydrodesulfurization dearomatization catalyst and hydrodesulfurization dearomatization catalyst system and its applications With the method for using the catalyst system to carry out hydrodesulfurization Porous deproteinized bone to diesel oil.

Background technology

It is increasingly strict with environmental regulation, the quality requirement of diesel oil is increasingly stringenter, gradually to ultra-low sulfur (sulphur Content is not higher than 10ppm) direction develops.On the other hand, the ratio of crude oil with poor quality is higher and higher, causes the source of diesel oil in poor quality Change and diversification, this causes huge pressure to current diesel hydrotreating unit.Different diesel oil hydrogenation raw materials, property have very Big difference, such as sulfur content, sulfur compound, nitrogen content, arene content etc. may be significantly different.And these Containing Sulfurs Closing object, nitrogenous compound and aromatic compound can have an effect with catalyst active center, hydrodesulfurization (HDS) plus hydrogen There are strong competitions and mutual inhibiting effect between denitrogenation (HDN) and hydrogenation dearomatization (HAD) reaction.In addition, in reaction process The H increasingly generated₂S can also have an effect to inhibit the activity of catalyst with catalyst active center.Studies have shown that is different Type catalyst is had bigger difference by the inhibiting effect of sulfide, nitride and aromatic hydrocarbons.With the continuous intensification of reaction depth, object Containing amount and type larger change also occurs for sulfide in stream, nitride, for the oil property in differential responses stage selects to close The sulfur content that suitable Hydrobon catalyst can will preferably reduce in diesel oil.

CN101092573A describes a kind of grading distribution scheme, loads hydrogenation protecting agent, hydrofinishing catalysis in the reactor Agent I, Hydrobon catalyst II and optional Hydrobon catalyst III contacts.The program gives full play to respective catalyst and exists The advantage function of different desulfurization stages can obtain the low-sulfur diesel-oil for meeting EUROIII Emission Standard and IV standards.Due to higher quality The demand of diesel oil, the activity of catalyst need to further increase.

Reactor is divided into four reaction areas by CN101591566A, is loaded hydrogenation protecting agent successively, is contained active metal cobalt- The Hydrobon catalyst I of molybdenum, the mixture of Hydrobon catalyst I and Hydrobon catalyst II, contain active metal nickel- The Hydrobon catalyst II of tungsten.The system improves monolithic catalyst activity by the synergistic effect between each catalyst. However, the system cannot produce the diesel oil of more low sulfur content under lower reaction temperature.

Two or more are arranged in CN102311759A is mixed by what Mo-Co types catalyst and Mo-Ni type catalyst formed Catalyst bed is closed, the ratio of Mo-Ni catalyst is gradually increased in mixing bed.

Reactor is divided into four reaction areas by CN102876374A, first kind catalyst is loaded in the first reaction zone, the The mixture of filling first kind catalyst and the second class catalyst in two reaction zones, loads the catalysis of the second class in third reaction zone First kind catalyst is loaded in agent in the 4th reaction zone, and wherein first kind catalyst is Mo-Co catalyst, the second class catalyst For W-Mo-Ni catalyst or W-Ni.The technique is by the grading of different catalysts come to high-sulfur, high nitrogen poor ignition quality fuel Reason.

Above-mentioned type of feed is complex in actual use, is unfavorable for the regeneration of catalyst.And as environmental protection is marked The decline of accurate severization and diesel raw material quality, existing catalyst preparation technology cannot gradually be met the requirements.

Invention content

The purpose of the present invention is to provide a kind of hydrodesulfurization Porous deproteinized bones that can take into account desulfurization effect and Porous deproteinized bone effect Catalyst and system and its hydrodesulfurization Porous deproteinized bone method of application and diesel oil.

It was found by the inventors of the present invention that existing hydrodesulfurization dearomatization catalyst cannot take into account desulfurization and Porous deproteinized bone effect Main cause be catalyst sulphidity and multilayer accumulation active Phase Proportion it is relatively low.General commercially available Hydrobon catalyst is oxygen Change state (for the sake of difference, is known as oxidation state presoma) in the present invention, vulcanized before use and add hydrogen to obtain to have The sulphided state of catalytic activity.The method of existing vulcanization is divided into the interior vulcanization of device and the outer vulcanization process of device, however either vulcanizes in device Method or the outer vulcanization of device, are vulcanized by making oxidation state presoma be contacted under conditions of vulcanization with sulfurized oil.It is existing There is the sulphidity of the hydrogenation catalyst of technology sulphided state relatively low, the sulphidity of group VIII metal is generally below 70%, group VIB The sulphidity of metal Mo less than 80%, W sulphidity less than 70% and/or three layer heap product active Phase Proportion be less than 25%, lead to It is often 20% or so, the ratios of four layers or more the active phases accumulated is less than 8%, and usually 7% or so.The present inventor By research it has furthermore been found that being carried out in the presence of specific alcohol compound by making sulfidation, sulphur can be greatly improved Change the sulphidity and three layers of active Phase Proportion of rear catalyst, and greatly improves hydrodesulfurization and the Porous deproteinized bone effect of catalyst.

The present invention provides a kind of hydrodesulfurization dearomatization catalyst as a result, which contains load The metal active constituent of the sulphided state of body and load on this carrier, the metal active constituent contain group VIII metallic element With vib metals element and trace element, the trace element is one or more in P, F, Si, B, Mg, feature It is, the sulphidity that group VIII metallic element in the catalyst is measured using XPS is not less than 70%, vib metals element Sulphidity be not less than 70%, using TEM statistics the catalyst three layer heaps product active Phase Proportion be not less than 30%.

The present invention also provides a kind of preparation method of hydrodesulfurization dearomatization catalyst, this method includes taking off described plus hydrogen The oxidation state presoma of sulphur dearomatization catalyst is vulcanized, which contains carrier and load on this carrier The metal active constituent and trace element of oxidation state, the trace element is one or more in P, F, Si, B, Mg, described Metal active constituent contains group VIII metallic element and vib metals element, which is characterized in that the vulcanization is in alcohols It is carried out in the presence of conjunction object, the alcohol compound has at least one exothermic peak at 200-400 DEG C, reaches warm needed for the vulcanization The mode of degree include by the hydrodesulfurization dearomatization catalyst be warming up to corresponding to the exothermic peak of the alcohol compound Then the temperature that temperature is close is warming up to the exothermic peak institute of the alcohol compound with 1-10 DEG C/h of heating rate Corresponding temperature, and constant temperature 1-15 hours at the temperature corresponding to the exothermic peak of the alcohol compound, the described and alcohol The temperature that temperature corresponding to the exothermic peak of class compound is close is the temperature corresponding to the exothermic peak with the alcohol compound Degree differs 20-70 DEG C of temperature.

The present invention provides a kind of hydrodesulfurization dearomatization catalyst system, the hydrodesulfurization dearomatization catalyst system packets The first catalyst bed and the second catalyst bed are included,

The catalyst for forming first catalyst bed contains one or more the of carrier and load on this carrier One alcohol compound and respectively in terms of oxide content is the cobalt of 1-8 weight %, the molybdenum that content is 10-35 weight %, and The molar ratio of one alcohol compound and cobalt element is 0.3-3：1；

The catalyst for forming second catalyst bed contains one or more the of carrier and load on this carrier Glycol compound and content is the nickel of 1-8 weight %, content is 10-35 weight % in terms of oxide respectively molybdenum and/or The tungsten of 15-40 weight %, and the molar ratio of the second alcohol compound and nickel element is 0.3-3：1,

First alcohol compound and the second alcohol compound, which are respectively, has at least one exothermic peak at 200-400 DEG C Hydroxy-containing compounds, and the first alcohol compound and the second alcohol compound are identical or different.

The present invention also provides a kind of hydrodesulfurization Porous deproteinized bone method of diesel oil, this method includes taking off above-mentioned hydrodesulfurization Arenes catalytic agent system is vulcanized, and hydrogen desulfurizing and dearomatizing diesel oil to be added is then passed to, and makes the hydrogen desulfurizing and dearomatizing diesel oil to be added Under hydrodesulfurizationconditions conditions successively with the first catalyst bed of the hydrodesulfurization dearomatization catalyst system after above-mentioned vulcanization and Second catalyst bed contacts.

The preparation method and diesel hydrogenation for removal sulphur Porous deproteinized bone method of hydrodesulfurization dearomatization catalyst provided by the invention are led to It crosses and specific alcohol compound is added in conventional vulcanizing treatment, sulfidation is made to be carried out in the presence of alcohol compound, obtain The hydrodesulfurization dearomatization catalyst of sulphided state there is higher desulphurizing activated and aromatic hydrocarbons to be saturated performance so that plus after hydrogen Diesel oil the advantages of capable of being provided simultaneously with low-sulfur and low arene content.It traces it to its cause, it may be possible to because due to containing in catalyst Alcohol compound, by specific heating mode, the heat that alcohol compound decomposes in vulcanizing treatment or burning generates helps In reacting for metal and sulphur, to improve the sulphidity of metal.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Specific implementation mode

The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

In the present invention, for convenience of with for the sake of difference, uncured catalyst is known as oxidized catalyst, after vulcanization Catalyst be known as sulphided state catalyst.

In the present invention, the content of catalyst is on the basis of the dry weight of catalyst.

According to an aspect of the present invention, the present invention provides a kind of hydrodesulfurization dearomatization catalyst, the hydrodesulfurization is de- Arenes catalytic agent contains the metal active constituent and trace element of the sulphided state of carrier and load on this carrier, the micro member Element is one or more in P, F, Si, B, Mg, and the metal active constituent contains group VIII metallic element and group VIB Metallic element, which is characterized in that the sulphidity that group VIII metallic element in the catalyst is measured using XPS is not less than 70%, The sulphidity of vib metals element is not less than 70%, using the active Phase Proportion of the three layer heaps product of the catalyst of TEM statistics Not less than 30%.

In the present invention, sulphidity is measured using x-ray photoelectron spectroscopy (XPS).Specific continuous mode is as follows：It will Hydrogenation catalyst samples after vulcanization are transferred under inert gas protection in xps energy spectrum instrument, then are scanned acquisition to sample The spectrum curve of each metallic element, then according to document (L.Qiu, G.Xu, Peak overlaps and corresponding solutions in the X-ray photoelectron spectroscopic study of hydrodesulfurization catalysts.Appl.Surf.Sci.2010,256:Method disclosed in 3413-3417) Spectrum curve is fitted, obtains the ratio of oxidation state and sulphided state metal respectively, it is total that the content of sulphided state metal accounts for metal The percentage of content is sulphidity.The the ratio of sulphided state metal the high, illustrates that sulphidity is higher, the vulcanization effect of catalyst Also better.

Hydrodesulfurization dearomatization catalyst according to the present invention, it is preferable that group VIII in the catalyst is measured using XPS The sulphidity of metallic element is 71%-76%, and the sulphidity of vib metals element is 70%-88%.

Mutually the accumulation number of plies is obtained activity in sulphided state hydrogenation catalyst by statistical method, and detailed process is as follows：It will vulcanization Hydrogenation catalyst samples afterwards are immersed in hexamethylene and are clayed into power, and are then transferred on carbon-coating copper grid and are transmitted electricity with high-resolution Mirror (TEM) is analyzed.It can be seen that the detailed packed structures of active phase, count 700-800 active phase from electromicroscopic photograph Structure obtains the distribution situation of the accumulation number of plies, is specifically referred to document (Zuo D H, Vrinat M, Nie H, et al.The formation of the active phases in sulfided NiW/Al₂O₃catalysts and their evolution during post-reduction treatment.Catal.Today,2004,93-95:It is public in 751-760) The method opened is operated.The activity of three layer heap lamination numbers mutually may be conducive to hydrodesulfurization and aromatic hydrocarbons saturated reaction simultaneously.Four Layer or more the accumulation number of plies the opposite hydrodesulfurization of activity it is highly beneficial.

Preferably, the active Phase Proportion that catalyst provided by the invention is accumulated using three layer heaps of the catalyst of TEM statistics For 30%-40%.

Preferably, catalyst provided by the invention uses four layers or more the activity accumulated of the catalyst of TEM statistics The ratio of phase is 8-12%, preferably 8.5-11.5%.

Preferably, the difference of the ratio of the active Phase Proportion and four layers or more the active phases accumulated of three layer heaps product is not less than 20%, preferably 21-26%.

Hydrodesulfurization dearomatization catalyst according to the present invention, the content of each metal component can be existing in the catalyst There is content disclosed in technology.Under preferable case, on the basis of the total amount of catalyst, respectively in terms of oxide, the group VIII The content of metallic element is 1-8 weight %, and the content of vib metals element is 10-34 weight %, and micro- content is 2-4 weight %.

In the case of further preferably, when trace element is phosphorus, the content of phosphorus can reach using the total amount of catalyst as base The amount of quasi- 0.5-8 weight %.

The group VIII metallic element is preferably cobalt and/or nickel, and vib metals element is preferably molybdenum and/or tungsten.

In the present invention, the carrier is gama-alumina.

According to another aspect of the present invention, the present invention provides a kind of preparation method of hydrodesulfurization dearomatization catalyst, This method includes vulcanizing the oxidation state presoma of the hydrodesulfurization dearomatization catalyst, which contains The metal active constituent and trace element of carrier and load oxidation state on this carrier, the trace element selected from P, F, Si, B, one or more in Mg, the metal active constituent contains group VIII metallic element and vib metals element, special Sign is that the vulcanization carries out in the presence of alcohol compound, and the alcohol compound has at least one put at 200-400 DEG C Thermal spike, the mode for reaching the vulcanization required temperature includes being warming up to the hydrodesulfurization dearomatization catalyst and the alcohols Then the temperature that temperature corresponding to the exothermic peak of compound is close is warming up to institute with 1-20 DEG C/h of heating rate State the temperature corresponding to the exothermic peak of alcohol compound, and constant temperature at the temperature corresponding to the exothermic peak of the alcohol compound 1-15 hours, the temperature that the temperature with corresponding to the exothermic peak of the alcohol compound is close be and the alcohols chemical combination The temperature of 20-70 DEG C of temperature difference corresponding to the exothermic peak of object.

According to the present invention, the hydrodesulfurization dearomatization catalyst is warming up to and the exothermic peak of alcohol compound institute The heating rate of temperature-rise period before the temperature that corresponding temperature is close can select in wider range, as long as ensureing to connect Heating rate when temperature corresponding to the exothermic peak of the nearly alcohol compound is 1-20 DEG C of preferred 1-10 DEG C of more preferable 5-10 DEG C.The time of constant temperature is preferably 1-10 hours.Preferred heating rate can either make metal oxide be able to more fully Ground vulcanizes, and can obtain faster rate of cure.It should be noted that in sulfidation, the heating rate in each stage It may be the same or different.

Since the active metal particles in catalyst are smaller, excessive heat may lead to the sintering of metallic particles, reduce The dispersion degree of catalyst, this is unfavorable to the activity of catalyst.Therefore, temperature should slowly occur close to each in sulfidation The temperature spot of exothermic reaction and constant temperature certain time, so that exothermic reaction is slowly occurred and uniformly vulcanize metal, to prevent metal The sintering of grain.

According to the present invention, in sulfidation, when the alcohol compound has multiple exothermic peaks, above-mentioned heating, constant temperature Program is suitable for each exothermic peak.Specifically vulcanisation step is：In the presence of curing medium, by the oxidation state hydrogenation catalyst Temperature rise to each heat release peak-to-peak value of the alcohol compound at 200-400 DEG C successively from room temperature with the rate of 1-20 DEG C/h Constant temperature vulcanizes 1-15h at corresponding temperature, and then temperature is existed with the rate of 1-20 DEG C/h from the organic alcohol compound again Temperature corresponding to the highest heat release peak-to-peak value of temperature between 200-400 DEG C increases 20-150 DEG C, preferably high 20-40 DEG C and perseverance Temperature vulcanization 1-15h, preferably 1-10h.

Specifically, it is assumed that alcohol compound can be successively in T when heating is thermally decomposed₁、T₂……T_n(T_n≤400℃) Exothermic reaction occurs, each exothermic reaction corresponds to an exothermic peak makes curing temperature slowly rise successively then in sulfidation Temperature is to T₁、T₂……T_n(T_n≤ 400 DEG C) these temperature spots and each self-constant temperature vulcanize certain time, and so that exothermic reaction is occurred complete. Usually in 150 DEG C -300 DEG C and/or 300 DEG C of -600 DEG C of two temperature ranges specific reaction releasing can occur for alcohol compound The release of certain heat, the heat can promote at least one of VIII group and group vib metal metal to reach better sulphur Change effect so that the state of cure (vulcanization) of metal increases, and promotes the synergistic effect between metal, increases the quantity of catalytic active center. Preferably, in 200 DEG C -300 DEG C and/or 300 DEG C of -400 DEG C of two temperature ranges exothermic reaction occurs for selected alcohols material.That is, The alcohol compound has more than or equal to having the first exothermic peak between 200 DEG C to less than 300 DEG C between 300-400 DEG C There is the second exothermic peak.In this case, the mode for reaching the vulcanization required temperature includes by the hydrodesulfurization Porous deproteinized bone Catalyzer temperature-elevating is to the temperature close with the temperature corresponding to first exothermic peak, then with 1-20 DEG C/h of heating speed Degree be warming up to the temperature corresponding to first exothermic peak, and with constant temperature 1- at the temperature corresponding to first exothermic peak 15 hours, it is warming up to the temperature close with the temperature corresponding to second exothermic peak later, then with 1-20 DEG C/h of heating Speed be warming up to the temperature corresponding to second exothermic peak, and with constant temperature at the temperature corresponding to first exothermic peak 1-15 hours, it is described with first exothermic peak corresponding to the close temperature of temperature be with corresponding to first exothermic peak The temperature of 20-40 DEG C of temperature difference, the temperature close with temperature corresponding to second exothermic peak are and described second The temperature of 30-70 DEG C of temperature difference corresponding to exothermic peak.

The present invention has at least one exothermic peak at 200-400 DEG C by controlling alcohol compound so that in catalyst In sulfidation, at least one exothermic reaction of alcohol compound necessarily occurs, the heat which releases contributes to catalyst Sulfidation so that catalyst after vulcanization has higher desulfurization, Porous deproteinized bone activity.

Temperature in the oxidation state hydrogenation catalyst corresponding to the exothermic peak of alcohol compound can be by existing each Kind method determines, for example, can be determined by differential thermal analysis, ascending order heating and oxidation method etc..Specifically, certain mass is taken The oxidation state hydrogenation catalyst, gradually heated up with the rate of 1-15 DEG C/min, and record the thermal change feature of catalyst Or gas discharges process, may thereby determine that the temperature of alcohol compound generation exothermic reaction and exothermic reaction in catalyst Power.When peak value occurs in the burst size that peak value or gas occurs in the heat of release, corresponding temperature is exothermic peak institute Corresponding temperature.In the process, used atmosphere can be air atmosphere, oxygen atmosphere or hydrogen atmosphere.When at certain At a temperature when very exothermic, slower heating rate should be used close to the temperature spot in sulfidation.

The preparation method of catalyst according to the invention, under preferable case, this method further include again by temperature with 1-20 DEG C/ The rate of h increases 20-150 DEG C preferably 1-10 DEG C more preferably from the temperature corresponding to the highest exothermic peak of the alcohol compound 5-10 DEG C and constant temperature 1-15h 1-10 hours preferred.

By using multistage vulcanization, the state of cure (vulcanization) of metal in catalyst is improved, thus catalyst is with high Activated centre quantity.

In order to improve the activity of catalyst, special vulcanisation step is taken in the present invention.This method can make oxidation state More active metals are converted into sulphided state in catalyst, increase active component number, improve the ratio of three level stack activity phase, Catalyst thus shows higher hydrodesulfurization and arene saturating activity.

When the oxidation state hydrogenation catalyst is thermally decomposed in air atmosphere, the alcohol compound is in catalyst Surface may occur itself decomposition or combustion reaction and release CO₂；And when being thermally decomposed in hydrogen atmosphere, the alcohols The isolation of compound may have certain variation, hydrogenation reaction may occur with hydrogen, it is also possible to catalyst surface Oxygen have an effect, it is also possible to the condensation reaction of itself occurs.These reactions can generate exothermic effect, and the heat released Amount can promote reacting between metal and sulphur, and then the sulphidity of raising metal and the activity of three layers of packed structures are compared Example.

When catalyst is heated in air atmosphere, alcohol may occur the decomposition of itself on the surface of catalyst or burn anti- It answers and releases heat.And catalyst in hydrogen atmosphere be heated when, the isolation of alcohols may have certain variation, it may occur however that Hydrogenation reaction between hydrogen, either has an effect with the oxygen of catalyst surface or itself is reacted.These reactions can be with Generating exothermic effect makes the heat promotion metal of releasing and reacting for sulphur, and then improves the sulphidity of metal.

The preparation method of catalyst according to the invention, although as long as ensureing vulcanization in the presence of alcohol compound, The alcohol compound can as a mixture exist with catalyst, and under preferable case, the alcohol compound is dispersed in In the oxidation state presoma of the hydrodesulfurization dearomatization catalyst, in the case of further preferred, the alcohol compound is with negative Load form is dispersed in the oxidation state presoma of the hydrodesulfurization dearomatization catalyst.

According to the present invention, although as long as in sulfidation there are the alcohol compound be can be improved catalyst plus hydrogen Desulfurization and Porous deproteinized bone performance, but under preferable case, in order to obtain considerably higher hydrodesulfurization and Porous deproteinized bone performance, in order to control The thermal discharge to react answers the content of suitable control alcohols species.Preferably, the carbon in the alcohol compound and institute The molar ratio for stating the group VIII metallic element in the oxidation state presoma of hydrodesulfurization dearomatization catalyst is 0.1-20：1, it is excellent It is selected as 0.3-5：1.

According to the present invention, the alcohol compound can be various the containing at least one exothermic peak at 200-400 DEG C Hydroxylated material, under preferable case, the alcohol compound be carbon atom number be 1-20 monohydric alcohol, ethylene glycol, propylene glycol, Isosorbide-5-Nitrae- It is one or more in butanediol, glycerine, pentaerythrite, pentitol, polyethylene glycol and D-sorbite.

The method of the present invention is suitable for the vulcanization of various Hydrobon catalysts, under preferable case, with oxidation state presoma Total amount on the basis of, respectively in terms of oxide, the content of the group VIII metallic element is 1-8 weight %, vib metals The content of element is 10-34 weight %, and micro- content is 0.5-5 weight %, preferably 2-4 weight %.

In the case of further preferably, when trace element is phosphorus, content of the phosphorus in the oxidation state presoma can reach The amount of the 0.5-8 weight % on the basis of the total amount of oxidation state presoma.

The group VIII metallic element is preferably cobalt and/or nickel, and vib metals element is preferably molybdenum and/or tungsten.

According to another aspect of the present invention, the present invention also provides a kind of hydrodesulfurization dearomatization catalyst systems, should add Hydrogen desulfurizing and dearomatizing catalyst system includes the first catalyst bed and the second catalyst bed,

The catalyst for forming first catalyst bed contains one or more the of carrier and load on this carrier One alcohol compound and content is 1-8 weight % in terms of oxide respectively cobalt (based on CoO), content are 10-35 weight % Molybdenum (press MoO₃Meter), at least one exothermic reaction temperature of first alcohol compound is catalyzed than the hydrodesulfurization Porous deproteinized bone The curing temperature of agent is 100-150 DEG C low, and the molar ratio of the first alcohol compound and cobalt element is 0.1-6：1；

The catalyst for forming second catalyst bed contains one or more the of carrier and load on this carrier Glycol compound and content is 1-8 weight % in terms of oxide respectively nickel (based on NiO), content are 10-35 weight % Molybdenum (press MoO₃Meter) and/or 15-40 weight % tungsten (press WO₃Meter),

First alcohol compound and the second alcohol compound, which are respectively, has at least one exothermic peak at 200-400 DEG C Hydroxy-containing compounds, and the first alcohol compound and the second alcohol compound are identical or different.

In the case of, according to the invention it is preferred to, forms the catalyst of first catalyst bed and form described second and urge Respectively the trace element also containing the preferred 2-4 weight % of 0.5-8 weight %, the trace element are selected from the catalyst of agent bed P, one or more in F, Si, B, Mg.

A preferred embodiment of the invention, formed first catalyst bed catalyst contain carrier and Load one or more first alcohol compounds on this carrier and the cobalt that content is 1-8 weight % in terms of oxide respectively The molybdenum that (based on CoO), content are 10-35 weight % (presses MoO₃Meter) and phosphorus that content is 0.5-8 weight % (by P₂O₅Meter), institute At least one exothermic reaction temperature for stating the first alcohol compound is lower than the curing temperature of the hydrodesulfurization dearomatization catalyst 100-150 DEG C, and the molar ratio of the first alcohol compound and cobalt element is 0.1-6：1；

The catalyst for forming second catalyst bed contains one or more the of carrier and load on this carrier Glycol compound and content is 1-8 weight % in terms of oxide respectively nickel (based on NiO), content are 10-35 weight % Molybdenum (press MoO₃Meter) and/or 15-40 weight % tungsten (press WO₃Meter), content be 0.5-8 weight % phosphorus (press P₂O₅Meter).

The present invention is not particularly limited the preparation method of the oxidized catalyst, can be according to people in the art Various modes carry out well known to member.For example, can include carrier and be supported on carrier first, in accordance with conventional method preparation Then organic alcohols compound is passed through the side such as infusion process, spray process by the catalyst of reactive metal oxides and trace element Formula is supported in said catalyst carrier, or micro- source is introduced into carrier first, then by active metal presoma It is introduced into the carrier containing trace element with organic alcohols compound, detailed process is known to the skilled person, herein not It repeats.In addition, the mode of loading in the organic alcohols compound and micro- source should be ensured that the organic alcohols chemical combination Object can be more evenly dispersed in catalyst carrier, be not substantially formed agglomerated particle.Load organic alcohols compound it Afterwards, before vulcanizing, the oxidation state hydrogenation catalyst cannot pass through drying or the activation process higher than 200 DEG C.

The trace element source is such as can be ammonium fluoride, Ludox, boric acid, boron oxide, magnesium nitrate, magnesia.Root According to hydrodesulfurization dearomatization catalyst system provided by the invention, is used in the first catalyst bed of catalyst system and contain cobalt With the catalyst of molybdenum, it can make catalyst system that there is higher direct desulfurization activity, remove the sulfur-bearing chemical combination for being easy reaction Object.The catalyst of nickeliferous and molybdenum and/or tungsten, the catalyst is used to have stronger in the second catalyst bed of catalyst system Hydrogenation capability can be relatively easy to be saturated aromatic hydrocarbons, remove the sulfur-containing compound of stable structure, such as 4,6- dimethyl two Benzothiophene kind sulfide.It configures in this manner, there is catalyst system higher desulfurization and aromatic hydrocarbons to be saturated performance.

According to the preferred embodiment of the present invention, the molar ratio of the first alcohol compound and cobalt element is 0.3-3：1.

According to the preferred embodiment of the present invention, the molar ratio of the second alcohol compound and nickel element is 0.3-3：1.

In the case of further preferably, the molar ratio of carbon and metallic element in the hydrodesulfurization dearomatization catalyst system For 0.1-20：1, preferably 0.3-5：1.

According to the present invention, it is 1-20 that first alcohol compound and the second alcohol compound, which can be respectively carbon atom number, Monohydric alcohol, ethylene glycol, propylene glycol, 1,4- butanediols, glycerine, pentaerythrite, pentitol, in polyethylene glycol and D-sorbite It is one or more.

Preferably contain for catalyst system, in the catalyst of the first catalyst bed and the second catalyst bed identical Alcohol compound, in order to make alcohol compound in the first catalyst bed and the second catalyst bed catalyst that there is phase As exothermic reaction temperature, so that thermostat temperature when vulcanization is identical, and control is simple.If the first catalyst bed and The exothermic reaction temperature of alcohol compound has difference in two catalyst beds, preferably with alcohols in the first catalyst bed catalyst Constant temperature vulcanization is carried out subject to the decomposition temperature of compound or in each decomposition temperature of two kinds of alcohol.

In the present invention, first is named according to the sequencing contacted with material (sulfurized oil waits for hydrogenation aromatics-removing diesel oil) Catalyst bed and the second catalyst bed, the catalyst bed contacted with material with elder generation are the first catalyst bed, successively class It pushes away.

In the case of, according to the invention it is preferred to, the volume ratio of first catalyst bed and the second catalyst bed is 1: 4-4:1。

The present invention also provides above-mentioned hydrogenation catalyst system hydrodesulfurization and with the application in aromatic hydrocarbons saturated reaction.

According to the hydrodesulfurization Porous deproteinized bone method of diesel oil provided by the invention, this method includes by the de- virtue of above-mentioned hydrodesulfurization Hydrocarbon catalyst system is vulcanized, and hydrogen desulfurizing and dearomatizing diesel oil to be added is then passed to, and the hydrogen desulfurizing and dearomatizing diesel oil to be added is made to exist Under hydrodesulfurizationconditions conditions successively with the first catalyst bed of the hydrodesulfurization dearomatization catalyst system after above-mentioned vulcanization and Two catalyst beds contact.

Vulcanize the mode of heating with reference to described above.

In the present invention, other than being controlled using aforesaid way temperature, the condition of vulcanization and concrete operations can be joined Carried out according to the prior art, for example, common vulcanized gas may be used in sulfidation, such as hydrogen and hydrogen sulfide gaseous mixture Or the sulfurized oil of organic solvent and organic compounds containing sulfur.When being vulcanized using sulfurized oil, the condition packet of the vulcanization It can be 0.1-15MPa to include sulfide stress, and volume space velocity can be 0.5-20 hours^-1, hydrogen to oil volume ratio can be 100-2000： 1.The cyclohexane solution that sulfur content is 5 weight % carbon disulfide may be used in sulfurized oil.

According to the present invention, the mode of the vulcanization can be dry pre-sulfiding, or wet method vulcanizes, and can also adopt simultaneously With the vulcanization of dry pre-sulfiding and wet method.Specifically, for dry pre-sulfiding, the curing medium used can be H₂And H₂The mixing of S Object, and H in the curing medium₂The volumetric concentration of S can be 0.5-5v%, preferably 1-2v%.For wet method vulcanization, Its generally use face hydrogen vulcanization, the curing medium used can at least one of n-hexane, hexamethylene, kerosene and diesel oil with The mixture of disulphide and/or mercaptan, and the volumetric concentration of sulphur-containing substance can be 0.5-10v% in the curing medium, Preferably 0.8-3.5v%.Wherein, the disulphide can be CS₂、CH₃-S-S-CH₃、C₂H₅-S-S-C₂H₅、CH₃-S-S- C₂H₅、C₃H₇-S-S-C₃H₇In it is one or more.The mercaptan can be C₄H₉SH、C₂H₄(SH)₂、C₃H₇SH and C₈H₁₇In SH It is one or more.

The concrete operations of hydrodesulfurization and condition can also be carried out with reference to the prior art, for example, the hydrodesulfurizationconditions conditions It can be 260-410 DEG C including temperature, hydrogen partial pressure can be 2-16MPa, and volume space velocity can be 0.1-2h when liquid^-1, hydrogen oil body Product ratio can be 200-2000.

Under preferable case, the volume ratio of the first catalyst bed and the second catalyst bed is 1:4-4:1.

Hydrodesulfurization Porous deproteinized bone method provided by the invention can be adapted for various high-sulfurs, high aromatic hydrocarbons poor ignition quality fuel plus Hydrogen, for example, the sulfur content of the hydrogen desulfurizing and dearomatizing diesel oil to be added can be 10000-30000 mass ppm, nitrogen content can be 50-500 mass ppm, arene content can be 20-60 weight %.Under preferable case, the hydrogen desulfurizing and dearomatizing diesel oil to be added is It is one or more in straight-run diesel oil, catalytic diesel oil and coker gas oil.

The present invention is described further for the following examples, but these embodiments can not limit the present invention.

In following embodiment and comparative example：

(1) sulphidity is measured using x-ray photoelectron spectroscopy (XPS), and detailed process is as follows：By adding after vulcanization Hydrogen catalyst sample is transferred under inert gas protection in xps energy spectrum instrument, then is scanned to sample and is obtained each metallic element Spectrum curve, then according to document (L.Qiu, G.Xu, Peak overlaps and corresponding solutions in the X-ray photoelectron spectroscopic study of hydrodesulfurization catalysts.Appl.Surf.Sci.2010,256:Method disclosed in 3413-3417) is fitted spectrum curve, point Not Huo get oxidation state and sulphided state metal ratio, the percentage that the content of sulphided state metal accounts for total metal content is to vulcanize Degree.The the ratio of sulphided state metal the high, illustrates that the vulcanization effect of catalyst is better, sulphidity is higher.

(2) mutually the accumulation number of plies is obtained the activity in sulphided state hydrogenation catalyst by statistical method, and detailed process is as follows：By sulphur Hydrogenation catalyst samples after change are immersed in hexamethylene and are clayed into power, and are then transferred on carbon-coating copper grid and are transmitted with high-resolution Electronic Speculum (TEM) is analyzed.It can be seen that the detailed packed structures of active phase, count 700-800 activity from electromicroscopic photograph Phase structure obtains the distribution situation of the accumulation number of plies, is specifically referred to document (Zuo D H, Vrinat M, Nie H, et al.The formation of the active phases in sulfided NiW/Al₂O₃catalysts and their evolution during post-reduction treatment.Catal.Today,2004,93-95:It is public in 751-760) The method opened is operated.

In following embodiment, the oxidized catalyst of load alcohol compound is prepared using following holes saturation infusion process：

Micro- source will be introduced into carrier by dipping or kneading method first, it is small that carrier is roasted at 600 DEG C to 5 When, obtain the carrier containing trace element.It will be group VIII metal precursor (such as cobalt nitrate or nickel nitrate), vib metals Presoma (such as ammonium heptamolybdate or ammonium metatungstate), which is dissolved in deionized water or ammonium hydroxide, obtains maceration extract.Maceration extract is uniform with carrier Mixing after standing 2 hours, is subsequently placed in baking oven 120 DEG C of dryings 10 hours.Sample after drying is placed in Muffle furnace 450 DEG C Roasting 3 hours.Alcohol compound is configured to solution, hole saturation infusion process is then used to immerse the product after above-mentioned roasting It states in solution, and 3 hours dry at 100-200 DEG C, oxidized catalyst is prepared.

Content in following embodiment is weight percentage, and each content is using the total amount of oxidized catalyst as base Standard, and surplus is gamma-aluminium oxide carrier.

Embodiment 1

The alcohol compound contained in catalyst A1 is ethylene glycol, and cobalt oxide content 3%, oxidation molybdenum content is 17%, B₂O₃Content is 1.5%, P₂O₅Content is 6%, and ethylene glycol is 1 with cobalt molar ratio：1.

Contain nickel oxide 3% in catalyst B1, oxidation molybdenum content is 17%, B₂O₃Content is 1.5%, P₂O₅Content is 6%, the molar ratio of ethylene glycol and nickel is 1：1.

Above-mentioned catalyst can be decomposed between 230-300 DEG C and 300-400 DEG C and be released through temperature programmed oxidation measuring Release CO₂, release temperature is respectively 260 DEG C and 350 DEG C.

Catalyst A1 is loaded on upper bed layer, and catalyst B1 is loaded on lower bed layer, the volume ratio of catalyst A1 and catalyst B1 Example is 1:1.

The activity rating of catalyst system carries out on 20mL high-pressure hydrogenation HDS evaluation devices.To catalyst before evaluation System obtains sulphided state catalyst system using vulcanization of the present invention vulcanization.Sulfurized oil is the ring containing 5 weight % carbon disulfide Hexane solution, step is to be warming up to 260 DEG C of then constant temperature 2h with the heating rate of 5 DEG C/h, then again with the heating rate of 5 DEG C/h 350 DEG C and constant temperature 2h are warming up to, is finally warming up to 400 DEG C of vulcanization 4h at the same rate again.Sulfide stress is 6.4MPa, air speed For 4h^-1, hydrogen-oil ratio 300v/v.

The sulphidity of metal in sulphided state catalyst A1 is tested using XPS, the sulphidity of Co and Mo are respectively 75.5% and 84.5%.TEM is used to count the active Phase Proportion of three layer heaps product as 34.5%, four layers or more the activity accumulated The ratio of phase is 9.5%.The sulphidity that Ni and Mo in sulphided state catalyst B1 is obtained using same method is respectively 77.6% He 85.0%, the ratio of the active phase of three layer heaps product is 36.1%, and the ratio of four layers or more the active phases accumulated is 10.8%.

After vulcanization, diesel raw material (sulfur content is cut：11000ppm, nitrogen content：265ppm, arene content 31.2%), Reaction pressure is 6.4MPa, and reaction temperature is 350 DEG C, reaction velocity 2.0h^-1, hydrogen-oil ratio 300v/v.After stable reaction 7 days Analysis product sulfur levels are 10.5ppm, and arene content is 19.5% (following activity rating is all made of the method).

Comparative example 1

By oxidized catalyst system in embodiment 1 using the vulcanization vulcanization directly to heat up, cancel 260 DEG C and 350 DEG C constant temperature stage, be directly warming up to the vulcanizations of 400 DEG C of progress same times with the rate of 5 DEG C/h, remaining conditions of vulcanization with implement Example 1 is identical, obtains sulphided state catalyst A1-1 and catalyst B1-1 respectively.

Sulphidity is carried out to sulphided state catalyst and active phase is tested, the sulphidity point of Co and Mo in catalyst A1-1 It Wei 68.3% and 78.3%.The TEM is used to count the ratio of the active phase of three layer heaps product as 18.2%, four layers or more are accumulated The ratio of active phase is 6.4%.The sulphidity of Ni and Mo is respectively 69.0% and 79.4% in sulphided state catalyst B1-1, three layers The ratio of the active phase of accumulation is 19.5%, and the ratio of four layers or more the active phases accumulated is 7.2%.

The system of sulphided state catalyst A1-1 and catalyst B1-1 compositions are subjected to active testing, the same embodiment of test condition 1.The sulfur content that product is obtained after identical reaction condition is 37.0ppm, arene content 22.3%.

With the comparison of embodiment 1 it is found that the vulcanisation step used in the present invention can increase substantially the de- of catalyst system Sulphur and aromatic hydrocarbons are saturated performance.

Comparative example 2

In this comparative example, catalyst system is made of catalyst A1 completely.The system is according to vulcanization in embodiment 1 Sulphided state catalyst system is obtained after vulcanization, sulfur content is 85.0ppm in the product obtained after activity rating, and arene content is 24.2%.As it can be seen that catalyst A1 systems not composite sulfuration state system as described in the present invention is used alone.

Comparative example 3

In this comparative example, catalyst system is made of catalyst B1 completely.The system is according to vulcanization in embodiment 1 Sulphided state catalyst system is obtained after vulcanization, sulfur content is 26.5ppm in the product obtained after activity rating, and arene content is 22.0%.As it can be seen that catalyst B1 systems not composite sulfuration state system as described in the present invention is used alone.

By embodiment 1 and comparative example 1,2 and 3 as it can be seen that there is the catalyst system used in the present invention higher plus hydrogen to take off Sulphur and hydrogenation aromatics-removing activity.

Embodiment 2

The alcohol matter contained in catalyst A2 is glycerine, and cobalt oxide content 6%, oxidation molybdenum content is that 25%, MgO contains Amount is 1.9%, and glycerine is 1.5 with cobalt molar ratio：1.

Contain nickel oxide 6% in catalyst B2, oxidation molybdenum content is 25%, content of MgO 1.9%, glycerine and nickel Molar ratio is 1.5：1.

Catalyst A2 is loaded on upper bed layer, and catalyst B2 is loaded on lower bed layer, the volume ratio of catalyst A2 and catalyst B2 Example is 2:1.

Through temperature programmed oxidation measuring, catalyst is respectively that 265 DEG C and 345 DEG C decomposition release CO₂.Conditions of vulcanization Same as Example 1 with active testing condition, vulcanization program more becomes：It is warming up to 265 DEG C of then perseverances with the heating rate of 8 DEG C/h Then warm 3h is warming up to 345 DEG C and constant temperature 2.5h with the heating rate of 5 DEG C/h again, is finally warming up to 400 at the same rate again DEG C vulcanization 3.5h, obtain the catalyst system being made of sulphided state catalyst A2 and catalyst B2.

The sulphidity of metal in sulphided state catalyst A2 is tested using XPS, the sulphidity of Co and Mo are respectively 73% and 82.6%.TEM is used to count the active Phase Proportion of three layer heaps product as 32.5%, four layers or more the active phases accumulated Ratio be 10.3%.The sulphidity that Ni and Mo in sulphided state catalyst B2 is obtained using same method is respectively 75.0% He 84.1%, the ratio of the active phase of three layer heaps product is 34.5%, and the ratio of four layers or more the active phases accumulated is 11.5%.

The system of sulphided state catalyst A2 and catalyst B2 compositions are subjected to active testing, the sulfur content of product is 8.6ppm, arene content 18.5%.

Comparative example 4

Based on oxidized catalyst system in embodiment 2, cancel 265 DEG C and 345 DEG C of constant temperature ranks in sulfidation Section is directly warming up to the vulcanization of 400 DEG C of progress same times with the rate of 5 DEG C/h, obtains sulphided state catalyst A2-1 and catalysis Agent B2-1.The sulphidity of metal in sulphided state catalyst A2-1 is tested using XPS, the sulphidity of Co and Mo are respectively 67.5% and 77.0%.TEM is used to count the active Phase Proportion of three layer heaps product as 17.6%, four layers or more the activity accumulated The ratio of phase is 6.8%.The sulphidity that Ni and Mo in sulphided state catalyst B2-1 is obtained using same method is respectively 67.3% With 77.9%, the ratio of the active phase of three layer heaps product is 18.4%, and the ratio of four layers or more the active phases accumulated is 7.3%.

Active testing is carried out to this catalyst system, it is 29.0ppm, arene content 21.5% to obtain product sulfur levels. It is compared with embodiment 2, it can be seen that the effect of the present invention program is preferable.

Comparative example 5

In this comparative example, catalyst system is made of catalyst A2 completely.The system is according to vulcanization in embodiment 2 Sulphided state catalyst system is obtained after vulcanization, sulfur content is 35.5ppm in the product obtained after activity rating, and arene content is 23.2%.As it can be seen that catalyst A2 systems not composite sulfuration state system as described in the present invention is used alone.

Comparative example 6

In this comparative example, catalyst system is made of catalyst B2 completely.The system is according to vulcanization in embodiment 2 Sulphided state catalyst system is obtained after vulcanization, sulfur content is 18.2ppm in the product obtained after activity rating, and arene content is 20.9%.As it can be seen that catalyst B2 systems not composite sulfuration state system as described in the present invention is used alone.

By embodiment 2 and comparative example 4,5 and 6 as it can be seen that can be obtained using the catalyst system in the present invention higher de- Sulphur activity and arene saturating activity.

Embodiment 3

The alcohol matter contained in catalyst A3 is the tert-butyl alcohol, and cobalt oxide content 5.5%, oxidation molybdenum content is that 20%, F contains Amount is 2.5%, P₂O₅Content is 6%, and the tert-butyl alcohol is 2 with cobalt molar ratio：1.

Contain nickel oxide 5.5%, tungsten oxide content 25% in catalyst B3, F contents are 2.5%, P₂O₅Content is 6%, The molar ratio of the tert-butyl alcohol and nickel is 1：1.

Catalyst A3 is loaded on upper bed layer, and catalyst B3 is loaded on lower bed layer, the volume ratio of catalyst A3 and catalyst B3 Example is 1:3.

Through temperature programmed oxidation measuring, catalyst is respectively that 270 DEG C and 320 DEG C decomposition release CO₂.Conditions of vulcanization Same as Example 1 with active testing condition, vulcanization program more becomes：It is warming up to 270 DEG C then with the heating rate of 10 DEG C/h Then constant temperature 2h is warming up to 320 DEG C and constant temperature 4h with the heating rate of 8 DEG C/h again, is finally warming up to 400 at the same rate again DEG C vulcanization 3h.Thus the catalyst system being made of sulphided state catalyst A3 and catalyst B3 is obtained.

The sulphidity of metal in sulphided state catalyst A3 is tested using XPS, the sulphidity of Co and Mo are respectively 71.8% and 80.0%.TEM is used to count the active Phase Proportion of three layer heaps product as 31.0%, four layers or more the activity accumulated The ratio of phase is 8.5%.The sulphidity that Ni and W in sulphided state catalyst B3 is obtained using same method is respectively 71.2% He 81.5%, the ratio of the active phase of three layer heaps product is 34.0%, and the ratio of four layers or more the active phases accumulated is 10.2%.

The sulfur content that active testing obtains product is 7.8ppm, arene content 18.6%.

Comparative example 7

Based on the oxidized catalyst in embodiment 3, cancel the intermediate constant temperature stage in sulfidation, directly with 5 DEG C/rate of h is warming up to the vulcanizations of 400 DEG C of progress same times, obtain sulphided state catalyst A3-1 and catalyst B3-1.Using XPS tests the sulphidity of metal in sulphided state catalyst A3-1, and the sulphidity of Co and Mo are respectively 66.0% He 76.5%.TEM is used to count the active Phase Proportion of three layer heaps product as 18.6%, the ratio of four layers or more the active phases accumulated It is 6%.The sulphidity that Ni and W in sulphided state catalyst B3-1 is obtained using same method is respectively 68.5% and 69.6%, and three The ratio of the active phase of layer heap product is 22.7%, and the ratio of four layers or more the active phases accumulated is 7.4%.

Active testing is carried out to this catalyst system, it is 19.0ppm, arene content 21.5% to obtain product sulfur levels. It is compared with embodiment 3, it can be seen that preferable using the effect of the present invention program.

Comparative example 8

In this comparative example, catalyst system is made of catalyst A3 completely.The system is according to vulcanization in embodiment 3 Sulphided state catalyst system is obtained after vulcanization, sulfur content is 32.5ppm in the product obtained after activity rating, and arene content is 22.5%.As it can be seen that catalyst A3 systems not composite sulfuration state system as described in the present invention is used alone.

Comparative example 9

In this comparative example, catalyst system is made of catalyst B3 completely.The system is according to vulcanization in embodiment 2 Sulphided state catalyst system is obtained after vulcanization, sulfur content is 20.6ppm in the product obtained after activity rating, and arene content is 20.8%.As it can be seen that catalyst B3 systems not composite sulfuration state system as described in the present invention is used alone.

By embodiment 3 and comparative example 7,8 and 9 as it can be seen that the catalyst system in the present invention has more preferably desulfurization and aromatic hydrocarbons Saturated activity.

Comparative example 10

Vulcanize catalyst system same as Example 3 according to the method for embodiment 3, unlike, the speed to heat up every time Rate is 50 DEG C/h, obtains sulphided state catalyst A3-2 and catalyst B3-2.Using XPS to metal in sulphided state catalyst A3-2 Sulphidity is tested, and the sulphidity of Co and Mo are respectively 68.0% and 77.5%.The activity of three layer heaps product is counted using TEM Phase Proportion is 16.5%, and the ratio of four layers or more the active phases accumulated is 6.8%.Sulphided state catalysis is obtained using same method The sulphidity of Ni and W is respectively 68.9% and 69.2% in agent B3-2, and the ratio of the active phase of three layer heaps product is 21.5%, four layers The ratio for the active phase accumulated above is 7.2%.

Active testing is carried out to this catalyst system, it is 29.5ppm, arene content 22.5% to obtain product sulfur levels. It is compared with embodiment 3, it can be seen that preferable using the effect of the present invention program.

Comparative example 11

Vulcanize using catalyst system same as Example 3 and according to the method for embodiment 3, unlike, only undergo Preceding heating and thermostatic process twice, do not suffer from the heating to 400 DEG C and thermostatic process, obtain sulphided state catalyst A3-3 and catalysis Agent B3-3.The sulphidity of metal in sulphided state catalyst A3-3 is tested using XPS, the sulphidity of Co and Mo are respectively 68.9% and 78.6%.TEM is used to count the active Phase Proportion of three layer heaps product as 22.5%, four layers or more the activity accumulated The ratio of phase is 5.5%.The sulphidity that Ni and W in sulphided state catalyst B3-3 is obtained using same method is respectively 69.0% He 68.5%, the ratio of the active phase of three layer heaps product is 24.5%, and the ratio of four layers or more the active phases accumulated is 6.0%.

Active testing is carried out to this catalyst system, it is 24.0ppm, arene content 22.2% to obtain product sulfur levels. It is compared with embodiment 3, it can be seen that preferable using the effect of the preferred embodiment for the present invention.

Embodiment 4

Vulcanize catalyst system same as Example 3 according to the method for embodiment 3, unlike, the alcohols chemical combination The molar ratio of carbon in object and group VIII metal in the oxidation state presoma of the hydrodesulfurization dearomatization catalyst is 10： 1, obtain sulphided state catalyst A4 and catalyst B4.The sulphidity of metal in sulphided state catalyst A4 is tested using XPS, The sulphidity of Co and Mo is respectively 70.9% and 80.0%.TEM is used to count the active Phase Proportion of three layer heaps product as 30.2%, The ratio of four layers or more the active phases accumulated is 8.9%.The sulphur of Ni and W in sulphided state catalyst B5 is obtained using same method Change degree is respectively 70.5% and 80.5%, and the ratio of the active phase of three layer heaps product is 31.5%, four layers or more the activity accumulated The ratio of phase is 10.5%.

Active testing is carried out to this catalyst system, it is 15.6ppm, arene content 19.9% to obtain product sulfur levels. It is compared with embodiment 3, it can be seen that preferable using the effect of the preferred embodiment for the present invention.

It can be seen from the above embodiments that, catalyst system described in the present invention has higher hydrodesulfurization activity And arene saturating activity, higher-quality diesel oil can be produced.In addition, the system is also applicable to compared with polyaromatic fat oil Product processing procedure.

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (28)

1. a kind of hydrodesulfurization dearomatization catalyst, which contains carrier and load on this carrier Sulphided state metal active constituent and trace element, the trace element is one or more in P, F, Si, B, Mg, institute It states metal active constituent and contains group VIII metallic element and vib metals element, which is characterized in that this is measured using XPS The sulphidity of group VIII metallic element is not less than 70% in catalyst, and the sulphidity of vib metals element is not less than 70%, Active Phase Proportion using the three layer heaps product of the catalyst of TEM statistics is not less than 30%.

2. hydrodesulfurization dearomatization catalyst according to claim 1, wherein measured in the catalyst using XPS The sulphidity of group VIII metal element is 71-76%, and the sulphidity of vib metals element is 80-88%, is counted using TEM The active Phase Proportion of three layer heaps product of the catalyst be 30-40%, the ratios of four layers or more the active phases accumulated is 8- 12%.

3. hydrodesulfurization dearomatization catalyst according to claim 1, wherein on the basis of the butt total amount of catalyst, Respectively in terms of oxide, the content of the group VIII metallic element is 1-8 weight %, and the content of vib metals element is 10-34 weight %, micro- content are 0.5-8 weight %.

4. hydrodesulfurization dearomatization catalyst according to claim 1, wherein the group VIII metallic element is cobalt And/or nickel, vib metals element are molybdenum and/or tungsten.

5. hydrodesulfurization dearomatization catalyst according to claim 4, wherein vib metals element is molybdenum, and molybdenum Sulphidity is not less than 80%.

6. a kind of preparation method of hydrodesulfurization dearomatization catalyst, this method includes by the hydrodesulfurization dearomatization catalyst Oxidation state presoma vulcanized, which contains carrier and the metal of load oxidation state on this carrier is lived Property component and trace element, the trace element are one or more in P, F, Si, B, Mg, and the metal active constituent contains Have group VIII metallic element and vib metals element, which is characterized in that it is described vulcanization in the presence of alcohol compound into Row, the alcohol compound have at least one exothermic peak at 200-400 DEG C, and the mode for reaching the vulcanization required temperature includes The hydrodesulfurization dearomatization catalyst is warming up to and is close with the temperature corresponding to the exothermic peak of the alcohol compound Temperature, is then warming up to the temperature corresponding to the exothermic peak of the alcohol compound with 1-20 DEG C/h of heating rate, and Constant temperature 1-15 hours at temperature corresponding to the exothermic peak of the alcohol compound, the exothermic peak with the alcohol compound The temperature that corresponding temperature is close is the temperature of 20-70 DEG C of temperature difference corresponding to the exothermic peak with the alcohol compound Degree, the alcohol compound be carbon atom number be 1-20 monohydric alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerine, season It is one or more in penta tetrol, pentitol, polyethylene glycol and D-sorbite.

7. according to the method described in claim 6, wherein, the alcohol compound more than or equal to 200 DEG C to less than 300 DEG C it Between have the first exothermic peak, between 300-400 DEG C have the second exothermic peak, reach it is described vulcanization required temperature mode include The hydrodesulfurization dearomatization catalyst is warming up to the temperature close with the temperature corresponding to first exothermic peak, then with 1-10 DEG C/h of heating rate be warming up to the temperature corresponding to first exothermic peak, and with first exothermic peak Constant temperature 1-15 hours at corresponding temperature, it is warming up to the temperature close with the temperature corresponding to second exothermic peak later, Again with 1-10 DEG C/h of heating rate be warming up to the temperature corresponding to second exothermic peak, and put with described first Constant temperature 1-15 hours at temperature corresponding to thermal spike, it is described with first exothermic peak corresponding to the close temperature of temperature be with The temperature of 20-40 DEG C of temperature difference corresponding to first exothermic peak, the temperature with corresponding to second exothermic peak Close temperature is the temperature with 30-70 DEG C of temperature difference corresponding to second exothermic peak.

8. the method described according to claim 6 or 7, wherein this method further include again by temperature with the rate of 1-20 DEG C/h from 20-150 DEG C and constant temperature 1-15h is increased with the temperature corresponding to the highest exothermic peak of the alcohol compound.

9. the method described according to claim 6 or 7, wherein the alcohol compound is dispersed in the hydrodesulfurization Porous deproteinized bone In the oxidation state presoma of catalyst.

10. the method described according to claim 6 or 7, wherein the carbon in the alcohol compound and the hydrodesulfurization The molar ratio of group VIII metallic element in the oxidation state presoma of dearomatization catalyst is 0.1-20：1.

11. according to the method described in claim 10, wherein, the carbon and the hydrodesulfurization in the alcohol compound are de- The molar ratio of group VIII metallic element in the oxidation state presoma of arenes catalytic agent is 0.3-5：1.

12. according to the method described in claim 6, wherein, on the basis of the total amount of oxidation state presoma, respectively with oxide The content of meter, the group VIII metallic element is 1-8 weight %, and the content of vib metals element is 10-34 weight %, The content of trace element is 0.5-8 weight %.

13. the method described according to claim 6 or 7, wherein the group VIII metallic element is cobalt and/or nickel, Section VI B Race's metallic element is molybdenum and/or tungsten.

14. a kind of hydrodesulfurization dearomatization catalyst system, which includes the first catalyst Bed and the second catalyst bed,

The catalyst for forming first catalyst bed contains one or more first alcohol of carrier and load on this carrier Class compound and respectively in terms of oxide content is the cobalt of 1-8 weight % and the molybdenum that content is 10-35 weight %, and the first alcohol Class compound and the molar ratio of cobalt element are 0.1-6：1；

The catalyst for forming second catalyst bed contains one or more second alcohol of carrier and load on this carrier Class compound and content is the nickel of 1-8 weight %, content is 10-35 weight % in terms of oxide respectively molybdenum and/or 15-40 The tungsten of weight %, and the molar ratio of the second alcohol compound and nickel element is 0.1-6：1,

First alcohol compound and the second alcohol compound are respectively the containing at least one exothermic peak at 200-400 DEG C Hydroxy compounds, and the first alcohol compound and the second alcohol compound are identical or different, first alcohol compound and Glycol compound is respectively the monohydric alcohol that carbon atom number is 1-20, ethylene glycol, propylene glycol, 1,4- butanediols, glycerine, season penta It is one or more in tetrol, pentitol, polyethylene glycol and D-sorbite.

15. hydrodesulfurization dearomatization catalyst system according to claim 14, wherein the first alcohol compound and cobalt member The molar ratio of element is 0.3-3：1, the molar ratio of the second alcohol compound and nickel element is 0.3-3：1.

16. the hydrodesulfurization dearomatization catalyst system according to claims 14 or 15, wherein the hydrodesulfurization Porous deproteinized bone Carbon and the molar ratio of cobalt element and nickel element are 0.1-20 in catalyst system：1.

17. hydrodesulfurization dearomatization catalyst system according to claim 16, wherein the hydrodesulfurization Porous deproteinized bone is catalyzed Carbon and the molar ratio of cobalt element and nickel element are 0.3-5 in agent system：1.

18. the hydrodesulfurization dearomatization catalyst system according to claims 14 or 15, wherein the first catalyst bed and The volume ratio of second catalyst bed is 1:4-4:1.

19. the hydrodesulfurization dearomatization catalyst system according to claims 14 or 15, wherein form first catalysis The catalyst of agent bed and form the catalyst of the second catalyst bed respectively micro member also containing 0.5-8 weight % Element, the trace element are one or more in P, F, Si, B, Mg.

20. a kind of hydrodesulfurization Porous deproteinized bone method of diesel oil, this method includes will be described in any one of claim 14-19 Hydrodesulfurization dearomatization catalyst system is vulcanized, and then passes to hydrogen desulfurizing and dearomatizing diesel oil to be added, this is made to wait for hydrodesulfurization Porous deproteinized bone diesel oil is urged with first of the hydrodesulfurization dearomatization catalyst system after above-mentioned vulcanization successively under hydrodesulfurizationconditions conditions Agent bed and the contact of the second catalyst bed.

21. hydrodesulfurization Porous deproteinized bone method according to claim 20, wherein first alcohol compound and the second alcohol Class compound is identical, reach it is described vulcanization required temperature mode include by the hydrodesulfurization dearomatization catalyst be warming up to The temperature that temperature corresponding to the exothermic peak of first alcohol compound is close, then with 1-10 DEG C/h of heating speed Degree is warming up to the temperature corresponding to the exothermic peak of first alcohol compound, and in the heat release of first alcohol compound Constant temperature 1-15 hours at temperature corresponding to peak, the temperature with corresponding to the exothermic peak of first alcohol compound connects Close temperature is the temperature of 20-70 DEG C of temperature difference corresponding to the exothermic peak with first alcohol compound.

22. according to the method for claim 21, wherein first alcohol compound more than or equal to 200 DEG C to less than There is the first exothermic peak between 300 DEG C, there is the second exothermic peak between 300-400 DEG C, reach the vulcanization required temperature Mode includes being warming up to the hydrodesulfurization dearomatization catalyst system to approach with the temperature corresponding to first exothermic peak Temperature, then with 1-10 DEG C/h of heating rate be warming up to the temperature corresponding to first exothermic peak, and with institute It states at the temperature corresponding to the first exothermic peak constant temperature 1-15 hours, is warming up to later and the temperature corresponding to second exothermic peak Close temperature, then with 1-10 DEG C/h of heating rate be warming up to the temperature corresponding to second exothermic peak, and with Constant temperature 1-15 hours at temperature corresponding to first exothermic peak, it is described close with temperature corresponding to first exothermic peak Temperature be temperature with 20-40 DEG C of temperature difference corresponding to first exothermic peak, it is described with the second exothermic peak institute The close temperature of corresponding temperature is the temperature with 30-70 DEG C of temperature difference corresponding to second exothermic peak.

23. according to the method described in any one of claim 20-22, wherein this method further includes again by temperature with 1-20 DEG C/rate of h increases 20-150 DEG C and constant temperature 1- from the temperature corresponding to the highest exothermic peak of the first alcohol compound 15h。

24. hydrodesulfurization Porous deproteinized bone method according to claim 23, wherein the first catalyst bed and the second catalyst The volume ratio of bed is 1:4-4:1.

25. the hydrodesulfurization Porous deproteinized bone method according to any one of claim 20-22, wherein the item of the vulcanization Part includes that sulfide stress is 0.1-15MPa, and volume space velocity is 0.5-20 hours^-1, hydrogen to oil volume ratio 100-2000：1.

26. the hydrodesulfurization Porous deproteinized bone method according to any one of claim 20-22, wherein the hydrodesulfurization Condition includes that pressure is 0.1-8MPa, and temperature is 260-410 DEG C, and volume space velocity is 0.5-10 hours^-1, hydrogen to oil volume ratio 200- 1000：1.

27. hydrodesulfurization Porous deproteinized bone method according to claim 20, wherein the hydrogen desulfurizing and dearomatizing diesel oil to be added Sulfur content is 10000-30000ppm, and nitrogen content 50-500ppm, arene content is 20-60 weight %.

28. the hydrodesulfurization Porous deproteinized bone method according to any one of claim 20-22, wherein the hydrogen to be added is de- Sulphur Porous deproteinized bone diesel oil is one or more in straight-run diesel oil, catalytic diesel oil and coker gas oil.