CN105478145A - Hydrogenation desulfurization and dearomatization catalyst, system and preparation method thereof, and diesel hydrogenation desulfurization and dearomatization method - Google Patents
Hydrogenation desulfurization and dearomatization catalyst, system and preparation method thereof, and diesel hydrogenation desulfurization and dearomatization method Download PDFInfo
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Abstract
The invention relates to a hydrogenation desulfurization and dearomatization catalyst, a preparation method thereof, a hydrogenation desulfurization and dearomatization catalyst system, and a diesel hydrogenation desulfurization and dearomatization method. The hydrogenation desulfurization and dearomatization catalyst comprises a carrier and sulfide-state metal active components and trace elements loaded on the carrier. The trace elements are one or more selected from P, F, Si, B and Mg. The metal active components comprise Group VIII and Group VIB metal elements. The catalyst is characterized in that, tested with XPS, the vulcanization degree of the Group VIII metal elements in the catalyst is no lower than 70%, and the vulcanization degree of the Group VIB metal elements in the catalyst is no lower than 70%; and counted with TEM, an active phase ratio of a three-layer stack of the catalyst is no lower than 30%. With the hydrogenation desulfurization and dearomatization catalyst provided by the invention, both the desulfurization effect and the dearomatization effect are taken into account.
Description
Technical field
The present invention relates to a kind of hydrodesulfurization dearomatization catalyst and hydrodesulfurization dearomatization catalyst system and application and this catalyst system of use thereof carry out hydrodesulfurization Porous deproteinized bone method to diesel oil.
Background technology
Along with the increasingly stringent of environmental regulation, more and more stricter to the quality requirement of diesel oil, gradually to ultra-low sulfur (sulfur content is not higher than 10ppm) future development.On the other hand, the ratio of crude oil with poor quality is more and more higher, and cause the source of diesel oil to be in poor quality and diversification, this causes huge pressure to current diesel hydrotreating unit.Different diesel oil hydrogenation raw materials, its character has very large difference, and such as sulfur content, sulfur compound, nitrogen content, arene content etc. all may be obviously different.And these sulfur-containing compounds, nitrogen-containing compound and aromatic compound all can be had an effect with catalyst active center, there is strong competition and mutual inhibitory action between reacting in hydrodesulfurization (HDS), hydrodenitrogeneration (HDN) and hydrogenation dearomatization (HAD).In addition, the H generated gradually in course of reaction
2s also can have an effect with catalyst active center thus suppress the activity of catalyst.Research display, dissimilar catalyst has bigger difference by the inhibitory action of sulfide, nitride and aromatic hydrocarbons.Along with the continuous intensification of reaction depth, also there is larger change in the content of logistics medium sulphide content, nitride and type, and the oil property for the differential responses stage selects suitable Hydrobon catalyst can reduce sulfur content in diesel oil better.
CN101092573A describes a kind of grading distribution scheme, and the agent of filling hydrogenation protecting, Hydrobon catalyst I, Hydrobon catalyst II contact with optional Hydrobon catalyst III in the reactor.The program gives full play to the advantage function of respective catalyst in different desulfurization stage, can be met the low-sulfur diesel-oil of EUROIII Emission Standard and IV standard.Due to the demand to more high-quality diesel, the activity of catalyst needs to improve further.
Reactor is divided into four reaction areas by CN101591566A, loads hydrogenation protecting agent, the mixture of Hydrobon catalyst I, Hydrobon catalyst I and Hydrobon catalyst II containing active metal cobalt-molybdenum, the Hydrobon catalyst II containing active metal nickel-tungsten successively.This system, by the synergy between each catalyst, improves integer catalyzer activity.But this system can not produce the diesel oil of more low sulfur content under lower reaction temperature.
CN102311759A arranges two or more mixed catalyst beds be made up of Mo-Co type catalyst and Mo-Ni type catalyst, and in mixing bed, the ratio of Mo-Ni catalyst improves gradually.
Reactor is divided into four reaction areas by CN102876374A, at the first reaction zone filling first kind catalyst, the mixture of first kind catalyst and Equations of The Second Kind catalyst is loaded in second reaction zone, Equations of The Second Kind catalyst is loaded in the 3rd reaction zone, first kind catalyst is loaded in the 4th reaction zone, wherein first kind catalyst is Mo-Co catalyst, and Equations of The Second Kind catalyst is W-Mo-Ni catalyst or W-Ni.This technique is processed high-sulfur, high nitrogen poor ignition quality fuel by the grating of different catalysts.
Above-mentioned type of feed is comparatively complicated in actual use, is unfavorable for the regeneration of catalyst.And along with the severization of environmental protection standard and the decline of diesel raw material quality, existing catalyst preparation technology can not meet the demands gradually.
Summary of the invention
The object of the present invention is to provide and a kind ofly can take into account the hydrodesulfurization dearomatization catalyst of desulfurized effect and Porous deproteinized bone effect and the hydrodesulfurization Porous deproteinized bone method of system and application and diesel oil.
The present inventor finds, the main cause that existing hydrodesulfurization dearomatization catalyst can not take into account desulfurization and Porous deproteinized bone effect is that the active Phase Proportion that the sulphidity of catalyst and multilayer are piled up is lower.General commercially available Hydrobon catalyst is oxidation state (for the purpose of difference, being called oxidation state presoma in the present invention), needs before use to carry out sulfuration to obtain the sulphided state with high active of hydrogenation catalysis.The method of existing sulfuration is divided into sulfuration and the outer vulcanization process of device in device, but no matter is sulfuration method or the outer sulfuration method of device in device, and it is all carry out sulfuration by making oxidation state presoma and sulfurized oil contact under conditions of vulcanization.The sulphidity of the hydrogenation catalyst of prior art sulphided state is on the low side, the sulphidity of group VIII metal is generally lower than 70%, the sulphidity of group vib metal M o is lower than 80%, the sulphidity of W is lower than 70%, and/or three layers of active Phase Proportion piled up are lower than 25%, be generally about 20%, the ratio of the active phase of four layers and above accumulation, lower than 8%, is generally about 7%.The present inventor is found further by research, carry out under specific alcohol compound exists by making sulfidation, greatly can improve sulphidity and three layers of active Phase Proportion of sulfuration rear catalyst, and greatly improve hydrodesulfurization and the Porous deproteinized bone effect of catalyst.
Thus, the invention provides a kind of hydrodesulfurization dearomatization catalyst, this hydrodesulfurization dearomatization catalyst contains the metal active constituent of carrier and load sulphided state on this carrier, described metal active constituent contains group VIII metallic element and group vib metallic element and trace element, described trace element is selected from P, F, Si, B, one or more in Mg, it is characterized in that, the sulphidity adopting XPS to record group VIII metallic element in this catalyst is not less than 70%, the sulphidity of group vib metallic element is not less than 70%, three layers of active Phase Proportion piled up of this catalyst of TEM statistics are adopted to be not less than 30%.
The present invention also provides a kind of preparation method of hydrodesulfurization dearomatization catalyst, the method comprises carries out sulfuration by the oxidation state presoma of described hydrodesulfurization dearomatization catalyst, this oxidation state presoma contains metal active constituent and the trace element of carrier and load oxidation state on this carrier, described trace element is selected from P, F, Si, B, one or more in Mg, described metal active constituent contains group VIII metallic element and group vib metallic element, it is characterized in that, described sulfuration is carried out under alcohol compound exists, described alcohol compound has at least one exothermic peak at 200-400 DEG C, reach the temperature required mode of described sulfuration and comprise the temperature being warming up to by described hydrodesulfurization dearomatization catalyst and being close with the temperature corresponding to the exothermic peak of described alcohol compound, then the temperature corresponding to exothermic peak of alcohol compound described in is warming up to the programming rate of 1-10 DEG C/h, and at the temperature corresponding to the exothermic peak of described alcohol compound constant temperature 1-15 hour, the temperature that the temperature corresponding to exothermic peak of described and described alcohol compound is close for the temperature of the temperature difference 20-70 corresponding to the exothermic peak of described alcohol compound DEG C.
The invention provides a kind of hydrodesulfurization dearomatization catalyst system, this hydrodesulfurization dearomatization catalyst system comprises the first beds and the second beds,
The catalyst forming described first beds contains carrier and load one or more first alcohol compounds on this carrier and respectively with the molybdenum that the oxide basis content cobalt that is 1-8 % by weight, content are 10-35 % by weight, and the mol ratio of the first alcohol compound and cobalt element is 0.3-3:1;
The catalyst forming described second beds contains carrier and load one or more second alcohol compounds on this carrier and respectively with the tungsten of the oxide basis content nickel that is 1-8 % by weight, molybdenum that content is 10-35 % by weight and/or 15-40 % by weight, and the mol ratio of the second alcohol compound and nickel element is 0.3-3:1
Described first alcohol compound and the second alcohol compound separately for have the hydroxy-containing compounds of at least one exothermic peak at 200-400 DEG C, and the first alcohol compound and the second alcohol compound identical or different.
Present invention also offers a kind of hydrodesulfurization Porous deproteinized bone method of diesel oil, the method comprises carries out sulfuration by above-mentioned hydrodesulfurization dearomatization catalyst system, then pass into and treat hydrogenation desulfurizing and dearomatizing diesel oil, this first beds until the hydrodesulfurization dearomatization catalyst system of hydrogenation desulfurizing and dearomatizing diesel oil under hydrodesulfurizationconditions conditions successively after above-mentioned sulfuration is contacted with the second beds.
The preparation method of hydrodesulfurization dearomatization catalyst provided by the invention and diesel hydrogenation for removal sulphur Porous deproteinized bone method, by adding certain alcohols compounds in the vulcanizing treatment of routine, sulfidation is carried out under alcohol compound exists, the hydrodesulfurization dearomatization catalyst of the sulphided state obtained has higher desulphurizing activated and aromatic saturation performance, thus makes the diesel oil after hydrogenation can possess the advantage of low-sulfur and low arene content simultaneously.Trace it to its cause, may be because owing to containing alcohol compound in catalyst, by specific heating mode, the heat that alcohol compound decomposes or burning produces in vulcanizing treatment contributes to the reaction of metal and sulphur, thus improves the sulphidity of metal.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
In the present invention, for convenience of and difference for the purpose of, the catalyst of uncured is called oxidized catalyst, the catalyst after sulfuration is called sulphided state catalyst.
In the present invention, the content of catalyst all with the butt weight of catalyst for benchmark.
According to an aspect of the present invention, the invention provides a kind of hydrodesulfurization dearomatization catalyst, this hydrodesulfurization dearomatization catalyst contains metal active constituent and the trace element of carrier and load sulphided state on this carrier, described trace element is selected from P, F, Si, B, one or more in Mg, described metal active constituent contains group VIII metallic element and group vib metallic element, it is characterized in that, the sulphidity adopting XPS to record group VIII metallic element in this catalyst is not less than 70%, the sulphidity of group vib metallic element is not less than 70%, three layers of active Phase Proportion piled up of this catalyst of TEM statistics are adopted to be not less than 30%.
In the present invention, sulphidity adopts x-ray photoelectron spectroscopy (XPS) to measure.Concrete mensuration process is as follows: be transferred under inert gas shielding in xps energy spectrum instrument by the hydrogenation catalyst samples after sulfuration, carry out scanning the spectrum curve obtaining each metallic element to sample again, then according to document (L.Qiu, G.Xu, PeakoverlapsandcorrespondingsolutionsintheX-rayphotoelec tronspectroscopicstudyofhydrodesulfurizationcatalysts.Ap pl.Surf.Sci.2010, method 256:3413-3417) carries out matching to spectrum curve, obtain the ratio of oxidation state and sulphided state metal respectively, the percentage that the content of sulphided state metal accounts for total metal content is sulphidity.The ratio of sulphided state metal is higher then illustrates that sulphidity is higher, and the cure efficiency of catalyst is also better.
According to hydrodesulfurization dearomatization catalyst of the present invention, preferably, the sulphidity adopting XPS to record group VIII metallic element in this catalyst is 71%-76%, and the sulphidity of group vib metallic element is 70%-88%.
Activity in sulphided state hydrogenation catalyst is piled up the number of plies mutually and is obtained by statistical method, detailed process is as follows: to be immersed by the hydrogenation catalyst samples after sulfuration in cyclohexane and to clay into power, being then transferred on carbon-coating copper grid and analyzing with high-resolution-ration transmission electric-lens (TEM).The detailed packed structures of active phase can be seen from electromicroscopic photograph, add up 700-800 active phase, obtain the distribution situation of piling up the number of plies, specifically can reference literature (ZuoDH, VrinatM, NieH, etal.TheformationoftheactivephasesinsulfidedNiW/Al
2o
3catalystsandtheirevolutionduringpost-reductiontreatment. Catal.Today, 2004,93-95:751-760) disclosed in method operate.Three layers of activity of piling up the number of plies may be conducive to hydrodesulfurization and aromatic saturation reaction mutually simultaneously.The activity of four layers and the above accumulation number of plies is highly beneficial relative to hydrodesulfurization.
Preferably, catalyst provided by the invention adopts three layers of active Phase Proportion piled up of this catalyst of TEM statistics to be 30%-40%.
Preferably, catalyst provided by the invention adopts four layers of this catalyst of TEM statistics and the ratio of the active phase of above accumulation to be 8-12%, is preferably 8.5-11.5%.
Preferably, three layers of active Phase Proportion piled up are not less than 20% with the difference of the ratio of the active phase of four layers and above accumulation, preferably 21-26%.
According to hydrodesulfurization dearomatization catalyst of the present invention, in described catalyst, the content of each metal component can be content disclosed in prior art.Under preferable case, with the total amount of catalyst for benchmark, respectively with oxide basis, the content of described group VIII metallic element is 1-8 % by weight, and the content of group vib metallic element is 10-34 % by weight, and the content of trace element is 2-4 % by weight.
Under further preferable case, when trace element is phosphorus, the content of phosphorus can reach with the amount of the total amount of catalyst for benchmark 0.5-8 % by weight.
Described group VIII metallic element is preferably cobalt and/or nickel, and group vib metallic element is preferably molybdenum and/or tungsten.
In the present invention, described carrier is gama-alumina.
According to a further aspect in the invention, the invention provides a kind of preparation method of hydrodesulfurization dearomatization catalyst, the method comprises carries out sulfuration by the oxidation state presoma of described hydrodesulfurization dearomatization catalyst, this oxidation state presoma contains metal active constituent and the trace element of carrier and load oxidation state on this carrier, described trace element is selected from P, F, Si, B, one or more in Mg, described metal active constituent contains group VIII metallic element and group vib metallic element, it is characterized in that, described sulfuration is carried out under alcohol compound exists, described alcohol compound has at least one exothermic peak at 200-400 DEG C, reach the temperature required mode of described sulfuration and comprise the temperature being warming up to by described hydrodesulfurization dearomatization catalyst and being close with the temperature corresponding to the exothermic peak of described alcohol compound, then the temperature corresponding to exothermic peak of alcohol compound described in is warming up to the programming rate of 1-20 DEG C/h, and at the temperature corresponding to the exothermic peak of described alcohol compound constant temperature 1-15 hour, the temperature that the temperature corresponding to exothermic peak of described and described alcohol compound is close for the temperature of the temperature difference 20-70 corresponding to the exothermic peak of described alcohol compound DEG C.
According to the present invention, the heating rate of the temperature-rise period be warming up to before the temperature be close with the temperature corresponding to the exothermic peak of described alcohol compound by described hydrodesulfurization dearomatization catalyst can be selected in relative broad range, if ensure close to described alcohol compound exothermic peak corresponding to temperature time heating rate be 1-20 DEG C of preferred 1-10 DEG C of more preferably 5-10 DEG C.The time of constant temperature is preferably 1-10 hour.Preferred programming rate can either make metal oxide be able to sulfuration more fully, can obtain rate of cure faster again.It should be noted that, in sulfidation, the heating rate in each stage can be identical, also can be different.
Because the active metal particles in catalyst is less, too much heat may cause the sintering of metallic particles, and reduce the decentralization of catalyst, this is unfavorable to the activity of catalyst.Therefore, in sulfidation, temperature should slowly near the temperature spot of each generation exothermic reaction and constant temperature certain hour, exothermic reaction is slowly occurred and by even for metal sulfuration, in case the sintering of metallic particles.
According to the present invention, in sulfidation, when described alcohol compound has multiple exothermic peak, above-mentioned intensification, constant temperature program are applicable to each exothermic peak.Concrete vulcanisation step is: under curing medium exists, the temperature of described oxidation state hydrogenation catalyst is risen to described alcohol compound constant temperature sulfuration 1-15h under the temperature corresponding to each exothermic peak peak value of 200-400 DEG C with the speed of 1-20 DEG C/h successively from room temperature, and then temperature is raised 20-150 DEG C with the speed of 1-20 DEG C/h from the temperature corresponding to the highest exothermic peak peak value of the temperature of described organic alcohol compound between 200-400 DEG C, preferred high 20-40 DEG C and constant temperature sulfuration 1-15h, preferred 1-10h.
Particularly, suppose that alcohol compound can successively at T when intensification decomposes
1, T
2t
n(T
n≤ 400 DEG C) there is exothermic reaction, the corresponding exothermic peak of each exothermic reaction, so in sulfidation, makes curing temperature slowly be warming up to T successively
1, T
2t
n(T
n≤ 400 DEG C) these temperature spots each self-constant temperature sulfuration certain hour, exothermic reaction is occurred completely.Usually can there is the certain heat of specific reaction releasing at 150 DEG C-300 DEG C and/or 300 DEG C of-600 DEG C of two temperature ranges in alcohol compound, the release of this heat can impel at least one metal in VIII and group vib metal to reach better cure efficiency, the state of cure (vulcanization) of metal is increased, promote the synergy between metal, increase the quantity of catalytic active center.Preferably, selected alcohols material is 200 DEG C-300 DEG C and/or 300 DEG C of-400 DEG C two temperature range generation exothermic reactions.That is, described alcohol compound has the first exothermic peak to being less than between 300 DEG C being more than or equal to 200 DEG C, has the second exothermic peak between 300-400 DEG C.In this case, reach the temperature required mode of described sulfuration to comprise described hydrodesulfurization dearomatization catalyst is warming up to the temperature close with the temperature corresponding to described first exothermic peak, then be warming up to and the temperature corresponding to described first exothermic peak with the programming rate of 1-20 DEG C/h, and with constant temperature 1-15 hour at the temperature corresponding to described first exothermic peak, be warming up to the temperature close with the temperature corresponding to described second exothermic peak afterwards, be warming up to and the temperature corresponding to described second exothermic peak with the programming rate of 1-20 DEG C/h again, and with constant temperature 1-15 hour at the temperature corresponding to described first exothermic peak, the close temperature of temperature corresponding to described and described first exothermic peak is the temperature with temperature difference 20-40 DEG C corresponding to described first exothermic peak, the close temperature of temperature corresponding to described and described second exothermic peak is the temperature with temperature difference 30-70 DEG C corresponding to described second exothermic peak.
The present invention has at least one exothermic peak by controlling alcohol compound at 200-400 DEG C, make in the sulfidation of catalyst, at least one exothermic reaction of alcohol compound must be there is, this reaction liberated heat contributes to the sulfidation of catalyst, makes the catalyst after sulfuration have higher desulfurization, Porous deproteinized bone is active.
In described oxidation state hydrogenation catalyst, the temperature corresponding to exothermic peak of alcohol compound can be determined by existing various method, such as, can be determined by differential thermal analysis, ascending order heating and oxidation method etc.Particularly, get the described oxidation state hydrogenation catalyst of certain mass, heat up gradually with the speed of 1-15 DEG C/min, and record thermal change feature or the air release process of catalyst, thus the temperature of alcohol compound generation exothermic reaction and the power of exothermic reaction in catalyst can be determined.When the heat discharged occurs that peak value appears in the burst size of peak value or gas, corresponding temperature is the temperature corresponding to exothermic peak.In the process, the atmosphere adopted can be air atmosphere, oxygen atmosphere or hydrogen atmosphere.When during very exothermic, slower heating rate being adopted in sulfidation close to this temperature spot at certain temperature.
The preparation method of catalyst according to the invention, under preferable case, the method also comprises and again temperature is raised 20-150 DEG C of preferred 1-10 DEG C of more preferably 5-10 DEG C and the preferred 1-10 hour of constant temperature 1-15h with the speed of 1-20 DEG C/h from the temperature corresponding to the exothermic peak the highest with described alcohol compound.
By adopting multistage vulcanization, improve the state of cure (vulcanization) of metal in catalyst, thus catalyst has high activated centre quantity.
In order to improve the activity of catalyst, in the present invention, take special vulcanisation step.The method can make more active metal in oxidized catalyst be converted into sulphided state, increases active component number, and improve the ratio of the active phase of three level stack, thus catalyst shows higher hydrodesulfurization and arene saturating activity.
When described oxidation state hydrogenation catalyst is in air atmosphere during decomposes, may there is self decomposition or combustion reaction and release CO in described alcohol compound on the surface of catalyst
2; And in hydrogen atmosphere during decomposes, the isolation of described alcohol compound may have certain change, its may with hydrogen generation hydrogenation reaction, also may have an effect with the oxygen of catalyst surface, the condensation reaction of self also may occur.These reactions all can produce exothermic effect, and liberated heat can promote the reaction between metal and sulphur, and then improve the sulphidity of metal and the active Phase Proportion of three layers of packed structures.
When catalyst is heated in air atmosphere, may there is self decomposition or combustion reaction and release heat in alcohol on the surface of catalyst.And catalyst when being heated in hydrogen atmosphere, the isolation of alcohols may have certain change, may occur and hydrogenation reaction between hydrogen, or has an effect with the oxygen of catalyst surface or self reaction.These reactions all can produce exothermic effect makes liberated heat promote the reaction of metal and sulphur, and then improves the sulphidity of metal.
The preparation method of catalyst according to the invention, as long as although ensure that sulfuration is under alcohol compound exists, described alcohol compound can exist as a mixture with catalyst, under preferable case, described alcohol compound is dispersed in the oxidation state presoma of described hydrodesulfurization dearomatization catalyst, under further preferable case, described alcohol compound is dispersed in the oxidation state presoma of described hydrodesulfurization dearomatization catalyst in a supported form.
According to the present invention, as long as although there is hydrodesulfurization and the Porous deproteinized bone performance that described alcohol compound can improve catalyst in sulfidation, but under preferable case, in order to obtain obviously higher hydrodesulfurization and Porous deproteinized bone performance, in order to control the thermal discharge reacted, the content of alcohols species suitably should be controlled.Preferably, the mol ratio of the group VIII metallic element in the oxidation state presoma of the carbon in described alcohol compound and described hydrodesulfurization dearomatization catalyst is 0.1-20:1, is preferably 0.3-5:1.
According to the present invention, described alcohol compound can be the various hydroxyl materials at 200-400 DEG C with at least one exothermic peak, under preferable case, one or more in the monohydric alcohol of described alcohol compound to be carbon number be 1-20, ethylene glycol, propane diols, BDO, glycerine, pentaerythrite, pentitol, polyethylene glycol and D-sorbite.
Method of the present invention is applicable to the sulfuration of various Hydrobon catalyst, under preferable case, with the total amount of oxidation state presoma for benchmark, respectively with oxide basis, the content of described group VIII metallic element is 1-8 % by weight, the content of group vib metallic element is 10-34 % by weight, and the content of trace element is 0.5-5 % by weight, preferred 2-4 % by weight.
Under further preferable case, when trace element is phosphorus, the content of phosphorus in this oxidation state presoma can reach with the amount of the total amount of oxidation state presoma for benchmark 0.5-8 % by weight.
Described group VIII metallic element is preferably cobalt and/or nickel, and group vib metallic element is preferably molybdenum and/or tungsten.
According to a further aspect in the invention, present invention also offers a kind of hydrodesulfurization dearomatization catalyst system, this hydrodesulfurization dearomatization catalyst system comprises the first beds and the second beds,
The catalyst forming described first beds contains carrier and load one or more first alcohol compounds on this carrier and is that the molybdenum of 10-35 % by weight is (by MoO in the oxide basis content cobalt (by CoO) that is 1-8 % by weight, content respectively
3meter), at least one exothermic reaction temperature 100-150 DEG C lower than the curing temperature of this hydrodesulfurization dearomatization catalyst of described first alcohol compound, and the mol ratio of the first alcohol compound and cobalt element is 0.1-6:1;
The catalyst forming described second beds contains carrier and load one or more second alcohol compounds on this carrier and is that the molybdenum of 10-35 % by weight is (by MoO in the oxide basis content nickel (by NiO) that is 1-8 % by weight, content respectively
3meter) and/or the tungsten of 15-40 % by weight (by WO
3meter),
Described first alcohol compound and the second alcohol compound separately for have the hydroxy-containing compounds of at least one exothermic peak at 200-400 DEG C, and the first alcohol compound and the second alcohol compound identical or different.
According to the present invention, under preferable case, the catalyst forming described first beds and the catalyst the forming described second beds trace element separately also containing the preferred 2-4 % by weight of 0.5-8 % by weight, described trace element be selected from P, F, Si, B, Mg one or more.
A preferred embodiment of the invention, the catalyst forming described first beds contains carrier and load one or more first alcohol compounds on this carrier and is that the molybdenum of 10-35 % by weight is (by MoO in the oxide basis content cobalt (by CoO) that is 1-8 % by weight, content respectively
3meter) and content be that the phosphorus of 0.5-8 % by weight is (by P
2o
5meter), at least one exothermic reaction temperature 100-150 DEG C lower than the curing temperature of this hydrodesulfurization dearomatization catalyst of described first alcohol compound, and the mol ratio of the first alcohol compound and cobalt element is 0.1-6:1;
The catalyst forming described second beds contains carrier and load one or more second alcohol compounds on this carrier and is that the molybdenum of 10-35 % by weight is (by MoO in the oxide basis content nickel (by NiO) that is 1-8 % by weight, content respectively
3meter) and/or the tungsten of 15-40 % by weight (by WO
3meter), content is that the phosphorus of 0.5-8 % by weight is (by P
2o
5meter).
The preparation method of the present invention to described oxidized catalyst is not particularly limited, can according to well known to a person skilled in the art that various mode is carried out.Such as, first conventionally can prepare and comprise carrier and the reactive metal oxides of load on carrier and the catalyst of trace element, then organic alcohols compound is passed through the load of the mode such as infusion process, spray process in said catalyst carrier, or first micro-source is introduced in carrier, then active metal presoma and organic alcohols compound are introduced in the carrier containing trace element, detailed process is known to the skilled person, and therefore not to repeat here.In addition, the mode of loading in described organic alcohols compound and micro-source should ensure that described organic alcohols compound can comparatively be evenly dispersed in catalyst carrier, does not substantially form agglomerated particle.After load organic alcohols compound, before sulfuration, described oxidation state hydrogenation catalyst cannot through higher than the drying of 200 DEG C or activation process.
Described micro-source can be such as ammonium fluoride, Ludox, boric acid, boron oxide, magnesium nitrate, magnesia etc.According to hydrodesulfurization dearomatization catalyst system provided by the invention, adopt the catalyst containing cobalt and molybdenum at the first beds of catalyst system, catalyst system can be made to have higher direct desulfurization active, remove the sulfur-containing compound of easily reaction.Nickeliferous and molybdenum and/or tungsten catalyst is adopted at the second beds of catalyst system, this catalyst has stronger hydrogenation capability, can comparatively be easy to carry out saturated to aromatic hydrocarbons, remove constitutionally stable sulfur-containing compound, as 4,6-dimethyl Dibenzothiophene class sulfide.Configure in this manner, catalyst system has higher desulfurization and aromatic saturation performance.
According to the preferred embodiment of the present invention, the mol ratio of the first alcohol compound and cobalt element is 0.3-3:1.
According to the preferred embodiment of the present invention, the mol ratio of the second alcohol compound and nickel element is 0.3-3:1.
Under further preferable case, in this hydrodesulfurization dearomatization catalyst system, the mol ratio of carbon and metallic element is 0.1-20:1, is preferably 0.3-5:1.
According to the present invention, described first alcohol compound and the second alcohol compound can be one or more in the monohydric alcohol of 1-20, ethylene glycol, propane diols, BDO, glycerine, pentaerythrite, pentitol, polyethylene glycol and D-sorbite for carbon number separately.
For catalyst system, first beds preferably contains identical alcohol compound with in the catalyst of the second beds, object is to make the first beds have similar exothermic reaction temperature with alcohol compound in the second beds catalyst, make thermostat temperature during sulfuration identical like this, control simple.If the exothermic reaction temperature of alcohol compound has difference in the first beds and the second beds, be preferably as the criterion with the decomposition temperature of alcohol compound in the first beds catalyst or all carry out constant temperature sulfuration in each decomposition temperature of two kinds of alcohol.
In the present invention, name the first beds and the second beds according to the sequencing contacted with material (sulfurized oil or treat hydrogenation aromatics-removing diesel oil), the beds contacted with material with elder generation is the first beds, the like.
According to the present invention, under preferable case, the volume ratio of described first beds and the second beds is 1:4-4:1.
Present invention also offers above-mentioned hydrogenation catalyst system in hydrodesulfurization and the application in reacting with aromatic saturation.
According to the hydrodesulfurization Porous deproteinized bone method of diesel oil provided by the invention, the method comprises carries out sulfuration by above-mentioned hydrodesulfurization dearomatization catalyst system, then pass into and treat hydrogenation desulfurizing and dearomatizing diesel oil, this first beds until the hydrodesulfurization dearomatization catalyst system of hydrogenation desulfurizing and dearomatizing diesel oil under hydrodesulfurizationconditions conditions successively after above-mentioned sulfuration is contacted with the second beds.
The mode that sulfuration heats up is with reference to description above.
In the present invention, except aforesaid way being adopted to temperature and controls, the condition of sulfuration and concrete operations all can refer to prior art and carry out, such as, conventional vulcanized gas can be adopted, the sulfurized oil of the gaseous mixture of such as hydrogen and hydrogen sulfide or organic solvent and organic compounds containing sulfur in sulfidation.When adopting sulfurized oil to carry out sulfuration, it can be 0.1-15MPa that the condition of described sulfuration comprises sulfide stress, and volume space velocity can be 0.5-20 hour
-1, hydrogen to oil volume ratio can be 100-2000:1.Sulfurized oil can adopt sulfur content to be the cyclohexane solution of 5 % by weight carbon disulfide.
According to the present invention, the mode of described sulfuration can be dry pre-sulfiding, also can be wet method sulfuration, can also adopt dry pre-sulfiding and wet method sulfuration simultaneously.Particularly, for dry pre-sulfiding, the curing medium of employing can be H
2and H
2the mixture of S, and H in described curing medium
2the volumetric concentration of S can be 0.5-5v%, is preferably 1-2v%.For wet method sulfuration, it usually adopts and faces hydrogen sulfuration, the curing medium adopted can be the mixture of at least one in n-hexane, cyclohexane, kerosene and diesel oil and disulphide and/or mercaptan, and the volumetric concentration of sulphur-containing substance can be 0.5-10v% in described curing medium, be preferably 0.8-3.5v%.Wherein, described disulphide can be CS
2, CH
3-S-S-CH
3, C
2h
5-S-S-C
2h
5, CH
3-S-S-C
2h
5, C
3h
7-S-S-C
3h
7in one or more.Described mercaptan can be C
4h
9sH, C
2h
4(SH)
2, C
3h
7sH and C
8h
17one or more in SH.
The concrete operations of hydrodesulfurization and condition also can be carried out with reference to prior art, and such as, it can be 260-410 DEG C that described hydrodesulfurizationconditions conditions comprises temperature, and hydrogen dividing potential drop can be 2-16MPa, and during liquid, volume space velocity can be 0.1-2h
-1, hydrogen to oil volume ratio can be 200-2000.
Under preferable case, the volume ratio of the first beds and the second beds is 1:4-4:1.
Hydrodesulfurization Porous deproteinized bone method provided by the invention goes for the hydrogenation of various high-sulfur, high aromatic hydrocarbons poor ignition quality fuel, such as, the described sulfur content treating hydrogenation desulfurizing and dearomatizing diesel oil can be 10000-30000 quality ppm, nitrogen content can be 50-500 quality ppm, and arene content can be 20-60 % by weight.Under preferable case, described in treat that hydrogenation desulfurizing and dearomatizing diesel oil 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 examples and comparative example:
(1) sulphidity adopts x-ray photoelectron spectroscopy (XPS) to measure, detailed process is as follows: be transferred under inert gas shielding in xps energy spectrum instrument by the hydrogenation catalyst samples after sulfuration, carry out scanning the spectrum curve obtaining each metallic element to sample again, then according to document (L.Qiu, G.Xu, PeakoverlapsandcorrespondingsolutionsintheX-rayphotoelec tronspectroscopicstudyofhydrodesulfurizationcatalysts.Ap pl.Surf.Sci.2010, method 256:3413-3417) carries out matching to spectrum curve, obtain the ratio of oxidation state and sulphided state metal respectively, the percentage that the content of sulphided state metal accounts for total metal content is sulphidity.The ratio of sulphided state metal is higher, and illustrate that the cure efficiency of catalyst is better, sulphidity is higher.
(2) activity in sulphided state hydrogenation catalyst is piled up the number of plies mutually and is obtained by statistical method, detailed process is as follows: to be immersed by the hydrogenation catalyst samples after sulfuration in cyclohexane and to clay into power, being then transferred on carbon-coating copper grid and analyzing with high-resolution-ration transmission electric-lens (TEM).The detailed packed structures of active phase can be seen from electromicroscopic photograph, add up 700-800 active phase, obtain the distribution situation of piling up the number of plies, specifically can reference literature (ZuoDH, VrinatM, NieH, etal.TheformationoftheactivephasesinsulfidedNiW/Al
2o
3catalystsandtheirevolutionduringpost-reductiontreatment. Catal.Today, 2004,93-95:751-760) disclosed in method operate.
In following examples, the saturated infusion process in following hole is adopted to prepare the oxidized catalyst of load alcohol compound:
First introduce in carrier by dipping or the just micro-source of kneading method, by carrier 600 DEG C of roastings 5 hours, obtain the carrier containing trace element.The presoma (as ammonium heptamolybdate or ammonium metatungstate) of group VIII metal precursor (as cobalt nitrate or nickel nitrate), group vib metal is dissolved in deionized water or ammoniacal liquor and obtains maceration extract.By maceration extract and carrier Homogeneous phase mixing, leave standstill after 2 hours, be then placed in baking oven 120 DEG C of dryings 10 hours.Dried sample is placed in Muffle furnace 450 DEG C of roastings 3 hours.Alcohol compound is mixed with solution, then adopts hole saturated infusion process to be immersed in above-mentioned solution by the product after above-mentioned roasting, and at 100-200 DEG C dry 3 hours, prepare oxidized catalyst.
Content in following examples is weight percentage, each content all with the total amount of oxidized catalyst for benchmark, and surplus is gamma-aluminium oxide carrier.
Embodiment 1
The alcohol compound contained in catalyst A 1 is ethylene glycol, and cobalt oxide content is 3%, and molybdenum oxide content is 17%, B
2o
3content is 1.5%, P
2o
5content is 6%, and ethylene glycol and cobalt mol ratio are 1:1.
Containing nickel oxide 3% in catalyst B 1, molybdenum oxide content is 17%, B
2o
3content is 1.5%, P
2o
5content is 6%, and the mol ratio of ethylene glycol and nickel is 1:1.
Above-mentioned catalyst, through temperature programmed oxidation measuring, can decompose and discharge CO between 230-300 DEG C and 300-400 DEG C
2, release temperature is respectively 260 DEG C and 350 DEG C.
Catalyst A 1 fills in upper bed layer, and catalyst B 1 fills in lower bed layer, and catalyst A 1 is 1:1 with the volume ratio of catalyst B 1.
The activity rating of catalyst system carries out on 20mL high-pressure hydrogenation HDS evaluation device.Before evaluation, adopt vulcanization sulfuration of the present invention to obtain sulphided state catalyst system to catalyst system.Sulfurized oil is the cyclohexane solution containing 5 % by weight carbon disulfide, step is for be warming up to 260 DEG C of then constant temperature 2h with the heating rate of 5 DEG C/h, and then be warming up to 350 DEG C and constant temperature 2h, finally again with same ramp to 400 DEG C sulfuration 4h with the heating rate of 5 DEG C/h.Sulfide stress is 6.4MPa, and air speed is 4h
-1, hydrogen-oil ratio is 300v/v.
Adopt XPS to test the sulphidity of metal in sulphided state catalyst A 1, the sulphidity of Co and Mo is respectively 75.5% and 84.5%.To adopt TEM to count three layers of active Phase Proportion piled up be the ratio of the active phase of 34.5%, four layers and above accumulation is 9.5%.The sulphidity adopting same method to obtain Ni and Mo in sulphided state catalyst B 1 is respectively 77.6% and 85.0%, and the ratio of three layers of active phase of piling up is the ratio of the active phase of 36.1%, four layers and above accumulation is 10.8%.
After sulfuration, incision diesel raw material (arene content is 31.2% for sulfur content: 11000ppm, nitrogen content: 265ppm), reaction pressure is 6.4MPa, and reaction temperature is 350 DEG C, and reaction velocity is 2.0h
-1, hydrogen-oil ratio is 300v/v.Stable reaction 7 days post analysis product sulfur levels are 10.5ppm, and arene content is 19.5% (following activity rating all adopts the method).
Comparative example 1
Oxidized catalyst system in embodiment 1 is adopted the vulcanization sulfuration directly heated up, cancel 260 DEG C and 350 DEG C of constant temperature stages, directly carry out the sulfuration of same time to 400 DEG C with the ramp of 5 DEG C/h, all the other conditions of vulcanizations are identical with embodiment 1, obtain sulphided state catalyst A 1-1 and catalyst B 1-1 respectively.
Carry out sulphidity and active phase test to sulphided state catalyst, in catalyst A 1-1, the sulphidity of Co and Mo is respectively 68.3% and 78.3%.Adopting TEM to count three layers, to pile up the ratio of active phases be the ratio of the active phase of 18.2%, four layers and above accumulation is 6.4%.In sulphided state catalyst B 1-1, the sulphidity of Ni and Mo is respectively 69.0% and 79.4%, and three layers are piled up the ratio of active phases be the ratio of the active phase of 19.5%, four layers and above accumulation is 7.2%.
The system of sulphided state catalyst A 1-1 and catalyst B 1-1 composition is carried out active testing, and test condition is with embodiment 1.The sulfur content obtaining product after identical reaction condition is 37.0ppm, and arene content is 22.3%.
Contrast known with embodiment 1, the vulcanisation step adopted in the present invention can increase substantially desulfurization and the aromatic saturation performance of catalyst system.
Comparative example 2
In this comparative example, catalyst system is made up of catalyst A 1 completely.This system obtains sulphided state catalyst system according to after vulcanization sulfuration in embodiment 1, and in the product obtained after activity rating, sulfur content is 85.0ppm, and arene content is 24.2%.Visible, be used alone catalyst A 1 system not composite sulfuration state system as described in the present invention.
Comparative example 3
In this comparative example, catalyst system is made up of catalyst B 1 completely.This system obtains sulphided state catalyst system according to after vulcanization sulfuration in embodiment 1, and in the product obtained after activity rating, sulfur content is 26.5ppm, and arene content is 22.0%.Visible, be used alone catalyst B 1 system not composite sulfuration state system as described in the present invention.
From embodiment 1 and comparative example 1,2 and 3, the catalyst system used in the present invention has higher hydrodesulfurization and hydrogenation aromatics-removing is active.
Embodiment 2
The alcohol matter contained in catalyst A 2 is glycerine, and cobalt oxide content is 6%, and molybdenum oxide content is 25%, and content of MgO is 1.9%, and glycerine and cobalt mol ratio are 1.5:1.
Containing nickel oxide 6% in catalyst B 2, molybdenum oxide content is 25%, and content of MgO is 1.9%, and the mol ratio of glycerine and nickel is 1.5:1.
Catalyst A 2 fills in upper bed layer, and catalyst B 2 fills in lower bed layer, and catalyst A 2 is 2:1 with the volume ratio of catalyst B 2.
Through temperature programmed oxidation measuring, catalyst is respectively 265 DEG C and 345 DEG C of decomposition discharge CO
2.Conditions of vulcanization is identical with embodiment 1 with active testing condition, sulfuration program more becomes: be warming up to 265 DEG C of then constant temperature 3h with the heating rate of 8 DEG C/h, and then be warming up to 345 DEG C and constant temperature 2.5h with the heating rate of 5 DEG C/h, final again with same ramp to 400 DEG C sulfuration 3.5h, obtain the catalyst system be made up of sulphided state catalyst A 2 and catalyst B 2.
Adopt XPS to test the sulphidity of metal in sulphided state catalyst A 2, the sulphidity of Co and Mo is respectively 73% and 82.6%.To adopt TEM to count three layers of active Phase Proportion piled up be the ratio of the active phase of 32.5%, four layers and above accumulation is 10.3%.The sulphidity adopting same method to obtain Ni and Mo in sulphided state catalyst B 2 is respectively 75.0% and 84.1%, and the ratio of three layers of active phase of piling up is the ratio of the active phase of 34.5%, four layers and above accumulation is 11.5%.
The system that sulphided state catalyst A 2 and catalyst B 2 form is carried out active testing, and the sulfur content of product is 8.6ppm, and arene content is 18.5%.
Comparative example 4
In embodiment 2 based on oxidized catalyst system, in sulfidation, cancel 265 DEG C and 345 DEG C of constant temperature stages, directly carry out the sulfuration of same time with the ramp of 5 DEG C/h to 400 DEG C, obtain sulphided state catalyst A 2-1 and catalyst B 2-1.Adopt XPS to test the sulphidity of metal in sulphided state catalyst A 2-1, the sulphidity of Co and Mo is respectively 67.5% and 77.0%.To adopt TEM to count three layers of active Phase Proportion piled up be the ratio of the active phase of 17.6%, four layers and above accumulation is 6.8%.The sulphidity adopting same method to obtain Ni and Mo in sulphided state catalyst B 2-1 is respectively 67.3% and 77.9%, and the ratio of three layers of active phase of piling up is the ratio of the active phase of 18.4%, four layers and above accumulation is 7.3%.
Carry out active testing to this catalyst system, obtaining product sulfur levels is 29.0ppm, and arene content is 21.5%.Contrast with embodiment 2, can find out that the effect of the present invention program is better.
Comparative example 5
In this comparative example, catalyst system is made up of catalyst A 2 completely.This system obtains sulphided state catalyst system according to after vulcanization sulfuration in embodiment 2, and in the product obtained after activity rating, sulfur content is 35.5ppm, and arene content is 23.2%.Visible, be used alone catalyst A 2 system not composite sulfuration state system as described in the present invention.
Comparative example 6
In this comparative example, catalyst system is made up of catalyst B 2 completely.This system obtains sulphided state catalyst system according to after vulcanization sulfuration in embodiment 2, and in the product obtained after activity rating, sulfur content is 18.2ppm, and arene content is 20.9%.Visible, be used alone catalyst B 2 system not composite sulfuration state system as described in the present invention.
From embodiment 2 and comparative example 4,5 and 6, use the catalyst system in the present invention can obtain higher desulphurizing activated and arene saturating activity.
Embodiment 3
The alcohol matter contained in catalyst A 3 is the tert-butyl alcohol, and cobalt oxide content is 5.5%, and molybdenum oxide content is 20%, F content is 2.5%, P
2o
5content is 6%, and the tert-butyl alcohol and cobalt mol ratio are 2:1.
Containing nickel oxide 5.5% in catalyst B 3, tungsten oxide content is 25%, F content is 2.5%, P
2o
5content is 6%, and the mol ratio of the tert-butyl alcohol and nickel is 1:1.
Catalyst A 3 fills in upper bed layer, and catalyst B 3 fills in lower bed layer, and catalyst A 3 is 1:3 with the volume ratio of catalyst B 3.
Through temperature programmed oxidation measuring, catalyst is respectively 270 DEG C and 320 DEG C of decomposition discharge CO
2.Conditions of vulcanization is identical with embodiment 1 with active testing condition, sulfuration program more becomes: be warming up to 270 DEG C of then constant temperature 2h with the heating rate of 10 DEG C/h, and then be warming up to 320 DEG C and constant temperature 4h, finally again with same ramp to 400 DEG C sulfuration 3h with the heating rate of 8 DEG C/h.Obtain the catalyst system be made up of sulphided state catalyst A 3 and catalyst B 3 thus.
Adopt XPS to test the sulphidity of metal in sulphided state catalyst A 3, the sulphidity of Co and Mo is respectively 71.8% and 80.0%.To adopt TEM to count three layers of active Phase Proportion piled up be the ratio of the active phase of 31.0%, four layers and above accumulation is 8.5%.The sulphidity adopting same method to obtain Ni and W in sulphided state catalyst B 3 is respectively 71.2% and 81.5%, and the ratio of three layers of active phase of piling up is the ratio of the active phase of 34.0%, four layers and above accumulation is 10.2%.
The sulfur content that active testing obtains product is 7.8ppm, and arene content is 18.6%.
Comparative example 7
Based on oxidized catalyst in embodiment 3, in the constant temperature stage in the middle of cancelling in sulfidation, directly carry out the sulfuration of same time with the ramp of 5 DEG C/h to 400 DEG C, obtain sulphided state catalyst A 3-1 and catalyst B 3-1.Adopt XPS to test the sulphidity of metal in sulphided state catalyst A 3-1, the sulphidity of Co and Mo is respectively 66.0% and 76.5%.To adopt TEM to count three layers of active Phase Proportion piled up be the ratio of the active phase of 18.6%, four layers and above accumulation is 6%.The sulphidity adopting same method to obtain Ni and W in sulphided state catalyst B 3-1 is respectively 68.5% and 69.6%, and the ratio of three layers of active phase of piling up is the ratio of the active phase of 22.7%, four layers and above accumulation is 7.4%.
Carry out active testing to this catalyst system, obtaining product sulfur levels is 19.0ppm, and arene content is 21.5%.Contrast with embodiment 3, can find out that the effect of employing the present invention program is better.
Comparative example 8
In this comparative example, catalyst system is made up of catalyst A 3 completely.This system obtains sulphided state catalyst system according to after vulcanization sulfuration in embodiment 3, and in the product obtained after activity rating, sulfur content is 32.5ppm, and arene content is 22.5%.Visible, be used alone catalyst A 3 system not composite sulfuration state system as described in the present invention.
Comparative example 9
In this comparative example, catalyst system is made up of catalyst B 3 completely.This system obtains sulphided state catalyst system according to after vulcanization sulfuration in embodiment 2, and in the product obtained after activity rating, sulfur content is 20.6ppm, and arene content is 20.8%.Visible, be used alone catalyst B 3 system not composite sulfuration state system as described in the present invention.
From embodiment 3 and comparative example 7,8 and 9, the catalyst system in the present invention has better desulfurization and arene saturating activity.
Comparative example 10
According to the catalyst system that the method sulfuration of embodiment 3 is identical with embodiment 3, unlike, each speed heated up is 50 DEG C/h, obtains sulphided state catalyst A 3-2 and catalyst B 3-2.Adopt XPS to test the sulphidity of metal in sulphided state catalyst A 3-2, the sulphidity of Co and Mo is respectively 68.0% and 77.5%.To adopt TEM to count three layers of active Phase Proportion piled up be the ratio of the active phase of 16.5%, four layers and above accumulation is 6.8%.The sulphidity adopting same method to obtain Ni and W in sulphided state catalyst B 3-2 is respectively 68.9% and 69.2%, and the ratio of three layers of active phase of piling up is the ratio of the active phase of 21.5%, four layers and above accumulation is 7.2%.
Carry out active testing to this catalyst system, obtaining product sulfur levels is 29.5ppm, and arene content is 22.5%.Contrast with embodiment 3, can find out that the effect of employing the present invention program is better.
Comparative example 11
Adopt the catalyst system identical with embodiment 3 and according to the method sulfuration of embodiment 3, unlike, only front twice intensification of experience and thermostatic process, be not exposed to intensification and the thermostatic process of 400 DEG C, obtain sulphided state catalyst A 3-3 and catalyst B 3-3.Adopt XPS to test the sulphidity of metal in sulphided state catalyst A 3-3, the sulphidity of Co and Mo is respectively 68.9% and 78.6%.To adopt TEM to count three layers of active Phase Proportion piled up be the ratio of the active phase of 22.5%, four layers and above accumulation is 5.5%.The sulphidity adopting same method to obtain Ni and W in sulphided state catalyst B 3-3 is respectively 69.0% and 68.5%, and the ratio of three layers of active phase of piling up is the ratio of the active phase of 24.5%, four layers and above accumulation is 6.0%.
Carry out active testing to this catalyst system, obtaining product sulfur levels is 24.0ppm, and arene content is 22.2%.Contrast with embodiment 3, can find out that the effect of the employing preferred embodiment for the present invention is better.
Embodiment 4
According to the catalyst system that the method sulfuration of embodiment 3 is identical with embodiment 3, unlike, in the oxidation state presoma of the carbon in described alcohol compound and described hydrodesulfurization dearomatization catalyst, the mol ratio of group VIII metal is 10:1, obtains sulphided state catalyst A 4 and catalyst B 4.Adopt XPS to test the sulphidity of metal in sulphided state catalyst A 4, the sulphidity of Co and Mo is respectively 70.9% and 80.0%.To adopt TEM to count three layers of active Phase Proportion piled up be the ratio of the active phase of 30.2%, four layers and above accumulation is 8.9%.The sulphidity adopting same method to obtain Ni and W in sulphided state catalyst B 5 is respectively 70.5% and 80.5%, and the ratio of three layers of active phase of piling up is the ratio of the active phase of 31.5%, four layers and above accumulation is 10.5%.
Carry out active testing to this catalyst system, obtaining product sulfur levels is 15.6ppm, and arene content is 19.9%.Contrast with embodiment 3, can find out that the effect of the employing preferred embodiment for the present invention is better.
Can be found out by above embodiment, the catalyst system described in the present invention has higher hydrodesulfurization activity and arene saturating activity, can produce higher-quality diesel oil.In addition, this system is also applicable to the oil product processing procedure needing more aromatic saturation.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (28)
1. a hydrodesulfurization dearomatization catalyst, this hydrodesulfurization dearomatization catalyst contains metal active constituent and the trace element of carrier and load sulphided state on this carrier, described trace element is selected from P, F, Si, B, one or more in Mg, described metal active constituent contains group VIII metallic element and group vib metallic element, it is characterized in that, the sulphidity adopting XPS to record group VIII metallic element in this catalyst is not less than 70%, the sulphidity of group vib metallic element is not less than 70%, three layers of active Phase Proportion piled up of this catalyst of TEM statistics are adopted to be not less than 30%.
2. hydrodesulfurization dearomatization catalyst according to claim 1, wherein, the sulphidity adopting XPS to record group VIII metallic element in this catalyst is 71-76%, the sulphidity of group vib metallic element is 80-88%, three layers of this catalyst active Phase Proportion piled up adopting TEM statistics are 30-40%, and the ratio of the active phase of four layers and above accumulation is 8-12%.
3. hydrodesulfurization dearomatization catalyst according to claim 1, wherein, with the butt total amount of catalyst for benchmark, respectively with oxide basis, the content of described group VIII metallic element is 1-8 % by weight, the content of group vib metallic element is 10-34 % by weight, and the content of trace element is 0.5-8 % by weight.
4. hydrodesulfurization dearomatization catalyst according to claim 1, wherein, described group VIII metallic element is cobalt and/or nickel, and group vib metallic element is molybdenum and/or tungsten.
5. hydrodesulfurization dearomatization catalyst according to claim 4, wherein, group vib metallic element is molybdenum, and the sulphidity of molybdenum is not less than 80%.
6. the preparation method of a hydrodesulfurization dearomatization catalyst, the method comprises carries out sulfuration by the oxidation state presoma of described hydrodesulfurization dearomatization catalyst, this oxidation state presoma contains metal active constituent and the trace element of carrier and load oxidation state on this carrier, described trace element is selected from P, F, Si, B, one or more in Mg, described metal active constituent contains group VIII metallic element and group vib metallic element, it is characterized in that, described sulfuration is carried out under alcohol compound exists, described alcohol compound has at least one exothermic peak at 200-400 DEG C, reach the temperature required mode of described sulfuration and comprise the temperature being warming up to by described hydrodesulfurization dearomatization catalyst and being close with the temperature corresponding to the exothermic peak of described alcohol compound, then the temperature corresponding to exothermic peak of described alcohol compound is warming up to the programming rate of 1-20 DEG C/h, and at the temperature corresponding to the exothermic peak of described alcohol compound constant temperature 1-15 hour, the temperature that the temperature corresponding to exothermic peak of described and described alcohol compound is close for the temperature of the temperature difference 20-70 corresponding to the exothermic peak of described alcohol compound DEG C.
7. method according to claim 6, wherein, described alcohol compound has the first exothermic peak to being less than between 300 DEG C being more than or equal to 200 DEG C, there is the second exothermic peak between 300-400 DEG C, reach the temperature required mode of described sulfuration to comprise described hydrodesulfurization dearomatization catalyst is warming up to the temperature close with the temperature corresponding to described first exothermic peak, then be warming up to and the temperature corresponding to described first exothermic peak with the programming rate of 1-10 DEG C/h, and with constant temperature 1-15 hour at the temperature corresponding to described first exothermic peak, be warming up to the temperature close with the temperature corresponding to described second exothermic peak afterwards, be warming up to and the temperature corresponding to described second exothermic peak with the programming rate of 1-10 DEG C/h again, and with constant temperature 1-15 hour at the temperature corresponding to described first exothermic peak, the close temperature of temperature corresponding to described and described first exothermic peak is the temperature with temperature difference 20-40 DEG C corresponding to described first exothermic peak, the close temperature of temperature corresponding to described and described second exothermic peak is the temperature with temperature difference 30-70 DEG C corresponding to described second exothermic peak.
8. the method according to claim 6 or 7, wherein, the method also comprises and again temperature is raised 20-150 DEG C and constant temperature 1-15h with the speed of 1-20 DEG C/h from the temperature corresponding to the exothermic peak the highest with described alcohol compound.
9. the method according to claim 6 or 7, wherein, described alcohol compound is dispersed in the oxidation state presoma of described hydrodesulfurization dearomatization catalyst.
10. the method according to claim 6 or 7, wherein, the mol ratio of the group VIII metallic element in the oxidation state presoma of the carbon in described alcohol compound and described hydrodesulfurization dearomatization catalyst is 0.1-20:1, is preferably 0.3-5:1.
11. according to the method in claim 6-10 described in any one, wherein, one or more in the monohydric alcohol of described alcohol compound to be carbon number be 1-20, ethylene glycol, propane diols, BDO, glycerine, pentaerythrite, pentitol, polyethylene glycol and D-sorbite.
12. methods according to claim 6, wherein, with the total amount of oxidation state presoma for benchmark, respectively with oxide basis, the content of described group VIII metallic element is 1-8 % by weight, and the content of group vib metallic element is 10-34 % by weight, and the content of trace element is 0.5-8 % by weight.
13. according to the method in claim 6-12 described in any one, and wherein, described group VIII metallic element is cobalt and/or nickel, and group vib metallic element is molybdenum and/or tungsten.
14. 1 kinds of hydrodesulfurization dearomatization catalyst systems, this hydrodesulfurization dearomatization catalyst system comprises the first beds and the second beds,
The catalyst forming described first beds contains carrier and load one or more first alcohol compounds on this carrier and respectively with the molybdenum that the oxide basis content cobalt that is 1-8 % by weight and content are 10-35 % by weight, and the mol ratio of the first alcohol compound and cobalt element is 0.1-6:1;
The catalyst forming described second beds contains carrier and load one or more second alcohol compounds on this carrier and respectively with the tungsten of the oxide basis content nickel that is 1-8 % by weight, molybdenum that content is 10-35 % by weight and/or 15-40 % by weight, and the mol ratio of the second alcohol compound and nickel element is 0.1-6:1
Described first alcohol compound and the second alcohol compound separately for have the hydroxy-containing compounds of at least one exothermic peak at 200-400 DEG C, and the first alcohol compound and the second alcohol compound identical or different.
15. hydrodesulfurization dearomatization catalyst systems according to claim 14, wherein, the mol ratio of the first alcohol compound and cobalt element is 0.3-3:1, and the mol ratio of the second alcohol compound and nickel element is 0.3-3:1.
16. hydrodesulfurization dearomatization catalyst systems according to claims 14 or 15, wherein, in this hydrodesulfurization dearomatization catalyst system, the mol ratio of carbon and group VIII metallic element is 0.1-20:1, is preferably 0.3-5:1.
17. according to the hydrodesulfurization dearomatization catalyst system in claim 14-16 described in any one, wherein, described first alcohol compound and the second alcohol compound are separately for carbon number is one or more in the monohydric alcohol of 1-20, ethylene glycol, propane diols, BDO, glycerine, pentaerythrite, pentitol, polyethylene glycol and D-sorbite.
18. according to the hydrodesulfurization dearomatization catalyst system in claim 14-17 described in any one, and wherein, the volume ratio of the first beds and the second beds is 1:4-4:1.
19. according to the hydrodesulfurization dearomatization catalyst system in claim 14-18 described in any one, wherein, the catalyst forming described first beds and the catalyst forming described second beds separately also containing the trace element of 0.5-8 % by weight, described trace element be selected from P, F, Si, B, Mg one or more.
The hydrodesulfurization Porous deproteinized bone method of 20. 1 kinds of diesel oil, the method comprises carries out sulfuration by the hydrodesulfurization dearomatization catalyst system in claim 14-19 described in any one, then pass into and treat hydrogenation desulfurizing and dearomatizing diesel oil, this first beds until the hydrodesulfurization dearomatization catalyst system of hydrogenation desulfurizing and dearomatizing diesel oil under hydrodesulfurizationconditions conditions successively after above-mentioned sulfuration is contacted with the second beds.
21. hydrodesulfurization Porous deproteinized bone methods according to claim 20, wherein, described first alcohol compound is identical with the second alcohol compound, reach the temperature required mode of described sulfuration and comprise the temperature being warming up to by described hydrodesulfurization dearomatization catalyst and being close with the temperature corresponding to the exothermic peak of described first alcohol compound, then the temperature corresponding to exothermic peak of the first alcohol compound described in is warming up to the programming rate of 1-10 DEG C/h, and at the temperature corresponding to the exothermic peak of described first alcohol compound constant temperature 1-15 hour, the temperature that the temperature corresponding to exothermic peak of described and described first alcohol compound is close is the temperature with temperature difference 20-70 DEG C corresponding to the exothermic peak of described first alcohol compound.
22. methods according to claim 21, wherein, described first alcohol compound has the first exothermic peak to being less than between 300 DEG C being more than or equal to 200 DEG C, there is the second exothermic peak between 300-400 DEG C, reach the temperature required mode of described sulfuration to comprise described hydrodesulfurization dearomatization catalyst system is warming up to the temperature close with the temperature corresponding to described first exothermic peak, then be warming up to and the temperature corresponding to described first exothermic peak with the programming rate of 1-10 DEG C/h, and with constant temperature 1-15 hour at the temperature corresponding to described first exothermic peak, be warming up to the temperature close with the temperature corresponding to described second exothermic peak afterwards, be warming up to and the temperature corresponding to described second exothermic peak with the programming rate of 1-10 DEG C/h again, and with constant temperature 1-15 hour at the temperature corresponding to described first exothermic peak, the close temperature of temperature corresponding to described and described first exothermic peak is the temperature with temperature difference 20-40 DEG C corresponding to described first exothermic peak, the close temperature of temperature corresponding to described and described second exothermic peak is the temperature with temperature difference 30-70 DEG C corresponding to described second exothermic peak.
23. according to the method in claim 20-22 described in any one, and wherein, the method also comprises and again temperature raised 20-150 DEG C and constant temperature 1-15h with the speed of 1-20 DEG C/h from the temperature corresponding to the exothermic peak the highest with described first alcohol compound.
24. hydrodesulfurization Porous deproteinized bone methods according to claim 23, wherein, the volume ratio of the first beds and the second beds is 1:4-4:1.
25. according to the hydrodesulfurization Porous deproteinized bone method in claim 20-24 described in any one, and wherein, it is 0.1-15MPa that the condition of described sulfuration comprises sulfide stress, and volume space velocity is 0.5-20 hour
-1, hydrogen to oil volume ratio is 100-2000:1.
26. according to the hydrodesulfurization Porous deproteinized bone method in claim 20-25 described in any one, and wherein, it is 0.1-8MPa that described hydrodesulfurizationconditions conditions comprises pressure, and temperature is 260-410 DEG C, and volume space velocity is 0.5-10 hour
-1, hydrogen to oil volume ratio is 200-1000:1.
27. hydrodesulfurization Porous deproteinized bone methods according to claim 20, wherein, described in treat that the sulfur content of hydrogenation desulfurizing and dearomatizing diesel oil is 10000-30000ppm, nitrogen content is 50-500ppm, and arene content is 20-60 % by weight.
28. according to the hydrodesulfurization Porous deproteinized bone method in claim 20-27 described in any one, wherein, described in treat that hydrogenation desulfurizing and dearomatizing diesel oil is one or more in straight-run diesel oil, catalytic diesel oil and coker gas oil.
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| CN1417301A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Method of desulfurizing and dearomatizing diesel oil deeply |
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| CN1417301A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Method of desulfurizing and dearomatizing diesel oil deeply |
| EP1702682A1 (en) * | 2004-01-09 | 2006-09-20 | Nippon Oil Corporation | Hydrogenation desulfurization catalyst for petroleum hydrocarbon and method of hydrogenation desulfurization using the same |
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