CN105080554A - Sulfurized hydrogenation catalyst, preparation method therefor and applications thereof - Google Patents
Sulfurized hydrogenation catalyst, preparation method therefor and applications thereof Download PDFInfo
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Abstract
The present invention provides a sulfided hydrogenation catalyst, a preparation method therefor and applications thereof. The preparation method for the sulfided hydrogenation catalyst comprises the following steps: (1) preparing an oxidized hydrogenation catalyst, wherein the oxidized hydrogenation catalyst comprises a carrier, and a carboxylic acid compound and an active metal oxide that are loaded on the carrier, and the carboxylic acid compound has at least one exothermic peak within a temperature range of 200-400 DEG C; and (2) in the presence of a vulcanization medium, sequentially raising the temperature of the oxidized hydrogenation catalyst from room temperature to the temperature corresponding to each exothermic peak of the carboxylic acid compound within the temperature range of 200-400 DEG C at a rate of 1-20 DEG C/h to carry out vulcanization for 1-5 hours at the constant temperature, and then raising the temperature corresponding to the exothermic peak of the the carboxylic acid compound at the highest temperature between 200 DEG C and 400 DEG C by 20-150 DEG C at a rate of 1-20 DEG C/h, to carry out vulcanization for 1-5 hours at the constant temperature. The method provided by the present invention is capable of improving metal sulfidity in the catalyst and the ratio of packed structure with four or more layers, thereby increasing the hydrodesulfurization activity of the catalyst.
Description
Technical field
The preparation method that the present invention relates to a kind of sulphided state hydrogenation catalyst, the sulphided state hydrogenation catalyst obtained by the method and the application of described sulphided state hydrogenation catalyst in hydrodesulfurization reaction.
Background technology
Hydrotreatment is the mainstay in modern petroleum refining industry, its at production clean fuel, improve the quality of products, make full use of in petroleum resources and pretreatment of raw material etc. and play an important role.Along with the development of economy, environmental protection and society, make oil refining enterprise constantly propose higher requirement to the activity of hydrotreating catalyst and stability, activity of hydrocatalyst and option demand improve constantly.Wherein, hydrodesulfurization activity is the important indicator weighing hydrogenation catalyst performance.
As a rule, the active metal component of hydrogenation catalyst only just has higher catalytic activity when changing into sulphided state.Sulphided state hydrogenation catalyst usually using the sulfide of group vib metal (Mo and/or W) as main active component, and using the sulfide of group VIII metal (Co and/or Ni) as helping active component.Described sulphided state hydrogenation catalyst is normally by reacting oxidation state hydrogenation catalyst and curing medium, and then be that sulphided state prepares by the metal component in hydrogenation catalyst by oxidation state, wherein, sulphided state metal is the activated centre of corresponding hydrogenation catalyst.Research shows, is that sulphided state can produce more activated centre number to greatest extent, thus improves the hydrotreatment ability of catalyst by metal component from oxidation state.But in actual production process, the active metal in hydrogenation catalyst can not be converted into sulfided state completely, metal component greatly is therefore still had not to be fully used.
The cure efficiency changing hydrogenation catalyst mainly can be considered from the character and change conditions of vulcanization two aspects changing hydrogenation catalyst itself.For the character of hydrogenation catalyst itself, the interaction that bibliographical information can be reduced between active metal and carrier by interpolation Si element and/or Mg element reaches the object promoting sulfuration.For conditions of vulcanization, cure efficiency can be promoted by the kind and concentration controlling curing temperature, cure time, hydrogen dividing potential drop and change vulcanizing agent.
CN1256171A discloses the method for hydrocarbons hydrogenation reforming catalyst presulfurization under hydrogen and at least one sulfur-containing compound exist, and wherein, after the method is also included in catalyst preparing, before presulfurization, is contacted by catalyst with at least one hydrocarbon compound.Described hydrocarbon compound is selected from liquid hydrocarbon, oil base material, diesel oil, petroleum solvent, vegetable oil, nitrogenous and sulfur-containing compound, polythiaether and is selected from the oxygenatedchemicals of alcohol, acid, ketone and aldehyde.Described sulfurating stage can carry out in the rotary system of 200-500 DEG C under normal pressure.
CN1422179A discloses the method for the carbon monoxide-olefin polymeric sulfuration of the hydrogenation metal component containing at least one VI race and/or VIII and organic additive, the method comprises and first being contacted with organic liquid by carbon monoxide-olefin polymeric, then contact with sulfur-containing compound with hydrogen in the gas phase, be wherein present in sulphurized catalyst lower than 40% sulphur organic liquid add.Step catalyst and hydrogen contacted with sulfur-containing compound can be carried out with a step at 150-450 DEG C, also can carry out with two steps, the first step is carried out at the temperature lower than second step, and wherein the first step is carried out at 100-250 DEG C, and second step carries out at 150-450 DEG C.Described organic liquid to be boiling point the be hydrocarbon of 150-500 DEG C, is preferably gasoline, petroleum solvent, diesel oil, gas oil, mineral lubricating oil or white oil.
CN102019209A discloses a kind of method for hydrocarbon processing catalysts being carried out sulfuration, and it is HOOCR that the method comprises one or more formulas
1=CR
2the vulcanization aid of COOH deposits on catalyst surface, and then catalyst is contacted with the gaseous mixture of sulfur-bearing, the process that described catalyst contacts with the gaseous mixture of sulfur-bearing lower than 300 DEG C, preferably lower than 275 DEG C, more preferably less than the temperature of 250 DEG C under carry out.
CN102641749A discloses a kind of method for pre-sulphuration of hydrogenation catalyst, the method comprises vulcanizing agent and deposits the injection of segmentation in case reaction system at sulfurized oil I and hydrogen, carry out presulfurization reaction with oxidation state fixed bed hydrogenation catalyst exposure, reaction bed temperature controls at 150-300 DEG C; Stop noting sulfurized oil, switching sulfurized oil I is sulfurized oil II, and sulfurized oil II carries out presulfurization reaction with oxidation state fixed bed hydrogenation catalyst exposure in presence of hydrogen, and reaction bed temperature controls at 250-380 DEG C.Wherein, described sulfurized oil I is the petroleum distillate of boiling range 180-400 DEG C, and described sulfurized oil II is the petroleum distillate of boiling range 350-530 DEG C, and the sulfur content of described sulfurized oil II is 1-4 % by weight.
CN102465008A discloses a kind of catalyst vulcanization method of hydrocracking process, constant temperature sulfuration 5-16 hour, H at the method is included in 200-230 DEG C
2the concentration of S controls as 500-8000 μ L/L; Constant temperature sulfuration 5-16h hour, H at 260-300 DEG C
2the concentration of S controls as 5000-18000 μ L/L; Constant temperature sulfuration 6-20h, H at 350-380 DEG C
2the concentration of S controls as 8000-20000 μ L/L, and sulfuration terminates.
CN1769377A discloses a kind of method for pre-sulphuration of hydrogenation catalyst, and the method is included in the atmosphere of hydrogen, is contacted by the sulfurized oil containing additive and vulcanizing agent carry out presulfurization with oxidation state hydrogenation catalyst.Wherein, described additive is polar organic compound, comprises one or more in n-butanol, isobutanol, propyl alcohol, ethylene glycol, diethylene glycol (DEG), acetic acid, ethyl acetate and divinyl ether.It is 100-400 DEG C that the presulfurization condition adopted comprises temperature, and the time is 0.1-24 hour, and hydrogen dividing potential drop is 0.1-15MPa, and liquid hourly space velocity (LHSV) is 0.1-10h
-1, hydrogen to oil volume ratio is 50-2000:1.
CN1611577A discloses a kind of method for pre-sulphuration of hydrogenation catalyst, the method comprises a kind of component containing alkene, organic polysulfide and auxiliary agent mixing, and with the hydrogenation catalyst of the impregnation mixture oxidation state of Containing Sulfur alkene obtained after heating, then with hydrocarbon ils dipping, then evaporate to dryness hydrocarbon ils obtains the hydrogenation catalyst after sulfuration.
CN1417299A discloses a kind of method for pre-sulphuration of hydrogenation catalyst, the method comprises the solution impregnation hydrogenation catalyst with Containing Sulfur alkene, then heat this catalyst under an inert atmosphere, the solution of described Containing Sulfur alkene to be temperature be room temperature to 220 DEG C, be dissolved with the solution of the Containing Sulfur alkene of element sulphur.
Adopt said method can obtain the hydrogenation catalyst with certain cure efficiency, but in the catalyst after sulfuration, state of cure (vulcanization) is not high, sulphidity is generally only 55-70%.In order to improve the catalytic activity of hydrogenation catalyst, need a kind of method that can improve the sulphidity of hydrogenation catalyst of exploitation at present badly.
Summary of the invention
The object of the invention is to adopt existing method to carry out the lower defect of sulphidity that vulcanizing treatment obtains to hydrogenation catalyst to overcome, and provide a kind of can improve the sulphided state hydrogenation catalyst of sulphidity preparation method, the sulphided state hydrogenation catalyst obtained by the method and the application of described sulphided state hydrogenation catalyst in hydrodesulfurization reaction.
To achieve these goals, the invention provides a kind of preparation method of sulphided state hydrogenation catalyst, the method comprises the following steps:
(1) prepare oxidation state hydrogenation catalyst, described oxidation state hydrogenation catalyst comprises carrier and load carboxylic acid compound on the carrier and reactive metal oxides, and described carboxylic acid compound exists at least one exothermic peak in 200-400 DEG C;
(2) under curing medium exists, the temperature of described oxidation state hydrogenation catalyst is risen to described carboxylic acid compound constant temperature sulfuration 1-5 hour 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 and constant temperature sulfuration 1-5 hour 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 carboxylic acid compound between 200-400 DEG C.
Present invention also offers the sulphided state hydrogenation catalyst prepared by said method.
Present invention also offers the application of above-mentioned sulphided state hydrogenation catalyst in hydrodesulfurization reaction.
The present inventor finds after further investigation, adopts method provided by the invention can change the state of cure (vulcanization) of metal in hydrogenation catalyst, improves the quantity being in the metal of sulphided state in hydrogenation catalyst.Infer its reason, may be due to: on the one hand, the exothermic reaction of described carboxylic acid compound can assist the sulfuration of reactive metal oxides, on the other hand, because the particle of reactive metal oxides in hydrogenation catalyst is usually less, too much heat may cause the sintering of active metal oxide particles, and the too high sintering that also may cause metallic particles of curing temperature, thus the decentralization be reduced on carrier, be unfavorable for the raising of activity of hydrocatalyst, and final curing temperature is limited in a little more than at the temperature corresponding to the exothermic peak peak value of carboxylic acid compound before 400 DEG C by the present invention in sulfidation, and temperature is slowly risen to the temperature spot of each generation exothermic reaction and constant temperature sulfuration certain hour with the speed of 1-20 DEG C/h, exothermic reaction is slowly occurred and by even for metal sulfuration, thus avoid the sintering of metallic particles.In addition, method provided by the invention is adopted can also to improve the ratio of more than four layers packed structures in catalyst.As a rule, more than four layers packed structures have specifically selective to hydrodesulfurization reaction, therefore be conducive to the hydrogenation reaction of sulfide, therefore, adopt method provided by the invention that the hydrodesulfurization activity tool of the hydrogenation catalyst obtained can also be made to be greatly improved.
A preferred embodiment of the invention, when described carboxylic acid compound at least exists an exothermic peak in 200-299 DEG C, and in 300-400 DEG C, at least there is an exothermic peak, and when described reactive metal oxides is the mixture of at least one group VIII metal oxide and at least one group vib metal oxide, the sulphided state hydrogenation catalyst obtained can be made to have higher sulphidity.
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.
The preparation method of sulphided state hydrogenation catalyst provided by the invention comprises the following steps:
(1) prepare oxidation state hydrogenation catalyst, described oxidation state hydrogenation catalyst comprises carrier and load carboxylic acid compound on the carrier and reactive metal oxides, and described carboxylic acid compound exists at least one exothermic peak in 200-400 DEG C;
(2) under curing medium exists, the temperature of described oxidation state hydrogenation catalyst is risen to described carboxylic acid compound constant temperature sulfuration 1-5 hour 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 and constant temperature sulfuration 1-5 hour 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 carboxylic acid compound between 200-400 DEG C.
In the present invention, described room temperature is generally 0-40 DEG C.
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 carboxylic acid compound on the surface of catalyst
2; And in hydrogen atmosphere during decomposes, the isolation of described carboxylic acid 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.In concrete sulfidation, suppose that the carboxylic acid compound of load on carrier 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.
In described oxidation state hydrogenation catalyst, the temperature corresponding to exothermic peak of carboxylic acid 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 carboxylic acid 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.
According to the preparation method of sulphided state hydrogenation catalyst provided by the invention, as long as there is at least one exothermic peak in described carboxylic acid compound in 200-400 DEG C.But from the angle that raw material is ready availability, preferably, at least there is an exothermic peak in described carboxylic acid compound in 200-299 DEG C, and at least there is an exothermic peak in 300-400 DEG C.Particularly, the example of described carboxylic acid compound includes but not limited to: one or more in formic acid, acetic acid, propionic acid, butyric acid, citric acid, succinic acid, ethanedioic acid, tartaric acid and glutaric acid.
According to the preparation method of sulphided state hydrogenation catalyst provided by the invention, preferably, in step (2), heating rate is 5-10 DEG C/h, metal oxide can either be made like this to 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, and be 1-20 DEG C/h independently of one another, is preferably 5-10 DEG C/h.In addition, the temperature height 20-150 DEG C corresponding to exothermic peak peak value that the constant temperature curing temperature of the last stage is higher than the temperature of described carboxylic acid compound between 200-400 DEG C, preferred high 20-40 DEG C.
In addition, 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 present invention is not particularly limited the content of reactive metal oxides in described oxidation state hydrogenation catalyst, it can be the routine selection of this area, such as, with the gross weight of described oxidation state hydrogenation catalyst for benchmark, the content of described reactive metal oxides can be 10-45 % by weight, is preferably 15-30 % by weight.
The present invention is not particularly limited the kind of reactive metal oxides in described oxidation state hydrogenation catalyst, such as, can be group VIII metal oxide and/or group vib metal oxide, be preferably the mixture of at least one group VIII metal oxide and at least one group vib metal oxide.The present inventor also finds through further investigation, because the curing temperature of group VIII metal oxide is lower, the exothermic reaction that described carboxylic acid compound occurs in lower temperature (200-299 DEG C) scope just can assist the sulfuration of group VIII metal oxide; And curing temperature needed for group vib metal oxide is higher, the exothermic reaction that described carboxylic acid compound occurs in higher temperature (300-400 DEG C) scope can assist the sulfuration of group vib metal oxide.Therefore, when described oxidation state hydrogenation catalyst is the mixture of at least one group VIII metal oxide and at least one group vib metal oxide, adopts and in 200-299 DEG C, at least there is an exothermic peak and the carboxylic acid compound that at least there is an exothermic peak in 300-400 DEG C is very beneficial for the sulfuration of these oxidation state hydrogenation catalysts.Particularly, the example of described group VIII metal oxide includes but not limited to: one or more in iron oxide, cobalt oxide, nickel oxide, ruthenium-oxide, rhodium oxide and palladium oxide.The example of described group vib metal oxide includes but not limited to: one or more in chromium oxide, molybdenum oxide and tungsten oxide.In addition, the weight ratio of described group VIII metal oxide and group vib metal oxide can be 1:1-15, is preferably 1:3-10.
According to the preparation method of sulphided state hydrogenation catalyst provided by the invention, as long as although introduce the sulphidity that carboxylic acid compound just can improve catalyst in oxidation state hydrogenation catalyst, but as a rule, described carboxylic acid compound consumption then can make to release too many reaction heat in sulfidation too greatly, the even sulfuration of metal will be unfavorable for like this, likely cause the sintering of active metal particles, described carboxylic acid compound consumption is too little, and the reaction heat of releasing can be made to be not enough to fully assist the sulfuration of metal oxide, the amplitude that sulphidity improves is also not obvious, therefore, combined factors is from every side considered, preferably, the consumption of described carboxylic acid compound makes the mol ratio of the carbon atom in described oxidation state hydrogenation catalyst and the metallic atom in group VIII metal oxide be less than 20:1, be more preferably 2-10:1.
The kind of the present invention to described carrier is not particularly limited, such as, can be selected from aluminium oxide, silica, titanium oxide, zirconia, activated carbon and molecular sieve one or more.Wherein, described aluminas is as being one or more in gama-alumina, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide.Above-mentioned carrier can be commercially available, also can according to well known to a person skilled in the art that various method prepares.
The preparation method of the present invention to described oxidation state hydrogenation 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 the catalyst comprising carrier and the reactive metal oxides of load on carrier can conventionally be prepared, then carboxylic acid compound is passed through the load of the mode such as infusion process, spray process in said catalyst carrier, detailed process is known to the skilled person, and therefore not to repeat here.In addition, the mode of loading of described carboxylic acid compound should ensure that described carboxylic acid compound can comparatively be evenly dispersed in catalyst carrier, does not substantially form agglomerated particle.After load carboxylic acid compound, before sulfuration, described oxidation state hydrogenation catalyst cannot through higher than the drying of 200 DEG C or activation process.
Present invention also offers the sulphided state hydrogenation catalyst prepared by said method.
Present invention also offers the application of described sulphided state hydrogenation catalyst in hydrodesulfurization reaction.
Below will be described the present invention by embodiment.
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.
Embodiment 1
This embodiment is for illustration of sulphided state hydrogenation catalyst provided by the invention and preparation method thereof.
Conventionally prepare oxidation state hydrogenation catalyst A1, it comprises alumina support and load NiO and MoO on the alumina support
3active metal component and acetic acid, wherein, in oxidation state hydrogenation catalyst A1, the mol ratio of carbon atom and Ni metallic atom is 2:1, with the gross weight of oxidation state hydrogenation catalyst for benchmark, NiO and MoO
3mass content be respectively 3% and 15%.Oxidation state hydrogenation catalyst A1 records all can to decompose between 230 DEG C-295 DEG C and 300 DEG C-400 DEG C through temperature programmed oxidation method (heating rate is 10 DEG C/min, lower with) and discharges CO
2, CO
2burst size occurs that the temperature corresponding to peak value is respectively 290 DEG C and 370 DEG C.Adopt dry pre-sulfiding method to carry out sulfuration oxidation state hydrogenation catalyst A1, curing medium used is H
2and H
2gaseous mixture (the wherein H of S
2the volumetric concentration of S can be 1v%, lower same), in sulfidation, first oxidation state hydrogenation catalyst A1 is warming up to 290 DEG C of constant temperature sulfuration 2h with the heating rate of 5 DEG C/h, then 370 DEG C of constant temperature sulfuration 2h are warming up to the heating rate of 5 DEG C/h again, final again with the ramp to 400 of 5 DEG C/h DEG C constant temperature sulfuration 4h, obtain sulphided state hydrogenation catalyst SA1.The sulphidity recording Ni and Mo in sulphided state hydrogenation catalyst SA1 through xps energy spectrum instrument is respectively 71% and 82.5%.In addition, utilize TEM electron microscopic observation and add up the packed structures of active phase in sulphided state hydrogenation catalyst SA1, result is as shown in table 1.
Comparative example 1
This comparative example is for illustration of the sulphided state hydrogenation catalyst and preparation method thereof of reference.
The preparation of sulphided state hydrogenation catalyst is carried out according to the method for embodiment 1, unlike, described oxidation state hydrogenation catalyst A1 is alternative with the oxidation state hydrogenation catalyst A2 (kind of carrier in oxidation state hydrogenation catalyst A2 and the kind of metal oxide all identical with oxidation state hydrogenation catalyst A1 with content) containing acetic acid, obtains sulphided state hydrogenation catalyst SA2.The sulphidity recording Ni and Mo in sulphided state hydrogenation catalyst SA2 through xps energy spectrum instrument is respectively 65.5% and 78.0%.In addition, utilize TEM electron microscopic observation and add up the packed structures of active phase in sulphided state hydrogenation catalyst SA2, result is as shown in table 1.
Comparative example 2
This comparative example is for illustration of the sulphided state hydrogenation catalyst and preparation method thereof of reference.
Carry out the preparation of sulphided state hydrogenation catalyst according to the method for embodiment 1, unlike, in sulfidation, directly by oxidation state hydrogenation catalyst A1 with the ramp to 400 of 5 DEG C/h DEG C constant temperature sulfuration 8h, obtain sulphided state hydrogenation catalyst SA3.The sulphidity recording Ni and Mo in sulphided state hydrogenation catalyst SA3 through xps energy spectrum instrument is respectively 68.0% and 80.5%.In addition, utilize TEM electron microscopic observation and add up the packed structures of active phase in sulphided state hydrogenation catalyst SA3, result is as shown in table 1.
Embodiment 2
This embodiment is for illustration of sulphided state hydrogenation catalyst provided by the invention and preparation method thereof.
Conventionally prepare oxidation state hydrogenation catalyst B1, it comprises alumina support and load NiO and WO on the alumina support
3active metal component and citric acid, wherein, in oxidation state hydrogenation catalyst B1, the mol ratio of carbon atom and Ni metallic atom is 6:1, with the gross weight of oxidation state hydrogenation catalyst for benchmark, NiO and WO
3mass content be respectively 2.5% and 20.5%.Oxidation state hydrogenation catalyst B1 records all can to decompose between 200 DEG C-295 DEG C and 300 DEG C-400 DEG C through temperature programmed oxidation method and discharges CO
2, CO
2burst size occurs that the temperature corresponding to peak value is respectively 250 DEG C, 300 DEG C and 385 DEG C.Adopt dry pre-sulfiding method to carry out sulfuration oxidation state hydrogenation catalyst B1, curing medium used is H
2and H
2the gaseous mixture of S, in sulfidation, first oxidation state hydrogenation catalyst B1 is warming up to 250 DEG C of constant temperature sulfuration 2h with the heating rate of 5 DEG C/h, and then be warming up to 300 DEG C of constant temperature sulfuration 2h with the heating rate of 5 DEG C/h, then 385 DEG C of constant temperature sulfuration 2h are warming up to the heating rate of 5 DEG C/h again, final again with the ramp to 420 of 5 DEG C/h DEG C constant temperature sulfuration 4h, obtain sulphided state hydrogenation catalyst SB1.The sulphidity recording Ni and W in sulphided state hydrogenation catalyst SB1 through xps energy spectrum instrument is respectively 54.2% and 69.0%.In addition, utilize TEM electron microscopic observation and add up the packed structures of active phase in sulphided state hydrogenation catalyst SB1, result is as shown in table 1.
Comparative example 3
This comparative example is for illustration of the sulphided state hydrogenation catalyst and preparation method thereof of reference.
The preparation of sulphided state hydrogenation catalyst is carried out according to the method for embodiment 2, unlike, described oxidation state hydrogenation catalyst B1 is alternative with the oxidation state hydrogenation catalyst B2 (kind of carrier in oxidation state hydrogenation catalyst B2 and the kind of metal oxide all identical with oxidation state hydrogenation catalyst B1 with content) containing citric acid, obtains sulphided state hydrogenation catalyst SB2.The sulphidity recording Ni and W in sulphided state hydrogenation catalyst SB2 through xps energy spectrum instrument is respectively 50.5% and 64.6%.In addition, utilize TEM electron microscopic observation and add up the packed structures of active phase in sulphided state hydrogenation catalyst SB2, result is as shown in table 1.
Embodiment 3
This embodiment is for illustration of sulphided state hydrogenation catalyst provided by the invention and preparation method thereof.
Conventionally prepare oxidation state hydrogenation catalyst C1, it comprises alumina support and load CoO and MoO on the alumina support
3active metal component and succinic acid, wherein, in oxidation state hydrogenation catalyst C1, the mol ratio of carbon atom and Co metallic atom is 6:1, with the gross weight of oxidation state hydrogenation catalyst for benchmark, CoO and MoO
3mass content be respectively 4.0% and 14.5%.Oxidation state hydrogenation catalyst C1 records all can to decompose between 200 DEG C-280 DEG C and 300 DEG C-400 DEG C through temperature programmed oxidation method and discharges CO
2, CO
2burst size occurs that the temperature corresponding to peak value is respectively 240 DEG C, 290 DEG C and 370 DEG C.Wet method sulfuration method is adopted to carry out sulfuration oxidation state hydrogenation catalyst C1, curing medium used is the mixture of the cyclohexane of 95 % by weight and the carbon disulfide of 5 % by weight, in sulfidation, first oxidation state hydrogenation catalyst C1 is warming up to 240 DEG C of constant temperature sulfuration 2h with the heating rate of 8 DEG C/h, and then be warming up to 290 DEG C of constant temperature sulfuration 2h with the heating rate of 8 DEG C/h, then 370 DEG C of constant temperature sulfuration 2h are warming up to the heating rate of 8 DEG C/h again, final again with the ramp to 400 of 8 DEG C/h DEG C constant temperature sulfuration 4h, obtain sulphided state hydrogenation catalyst SC1.The sulphidity recording Co and Mo in sulphided state hydrogenation catalyst SC1 through xps energy spectrum instrument is respectively 67.5% and 80.0%.In addition, utilize TEM electron microscopic observation and add up the packed structures of active phase in sulphided state hydrogenation catalyst SC1, result is as shown in table 1.
Comparative example 4
This comparative example is for illustration of the sulphided state hydrogenation catalyst and preparation method thereof of reference.
The preparation of sulphided state hydrogenation catalyst is carried out according to the method for embodiment 3, unlike, described oxidation state hydrogenation catalyst C1 is alternative with the oxidation state hydrogenation catalyst C2 (kind of carrier in oxidation state hydrogenation catalyst C2 and the kind of metal oxide all identical with oxidation state hydrogenation catalyst C1 with content) containing succinic acid, obtains sulphided state hydrogenation catalyst SC2.The sulphidity recording Co and Mo in sulphided state hydrogenation catalyst SC2 through xps energy spectrum instrument is respectively 60.0% and 75.0%.In addition, utilize TEM electron microscopic observation and add up the packed structures of active phase in sulphided state hydrogenation catalyst SC2, result is as shown in table 1.
Embodiment 4
This embodiment is for illustration of sulphided state hydrogenation catalyst provided by the invention and preparation method thereof.
The preparation of sulphided state hydrogenation catalyst is carried out according to the method for embodiment 1, unlike, described oxidation state hydrogenation catalyst A1 is that the oxidation state hydrogenation catalyst D1 (carrier in oxidation state hydrogenation catalyst D1 and the kind of acetic acid and the kind of metal oxide all identical with oxidation state hydrogenation catalyst A1 with content) of 15:1 is alternative by wherein carbon atom and the mol ratio of Ni metallic atom, obtains sulphided state hydrogenation catalyst SD1.The sulphidity recording Ni and Mo in sulphided state hydrogenation catalyst SD1 through xps energy spectrum instrument is respectively 67.0% and 79.5%.In addition, utilize TEM electron microscopic observation and add up the packed structures of active phase in sulphided state hydrogenation catalyst SD1, result is as shown in table 1.
Comparative example 5
This comparative example is for illustration of the sulphided state hydrogenation catalyst and preparation method thereof of reference.
The preparation of sulphided state hydrogenation catalyst is carried out according to the method for embodiment 4, unlike, described oxidation state hydrogenation catalyst D1 is alternative with the oxidation state hydrogenation catalyst D2 (kind of carrier in oxidation state hydrogenation catalyst D2 and the kind of metal oxide all identical with oxidation state hydrogenation catalyst D1 with content) containing acetic acid, obtains sulphided state hydrogenation catalyst SD2.The sulphidity recording Ni and Mo in sulphided state hydrogenation catalyst SD2 through xps energy spectrum instrument is respectively 65.5% and 78.0%.In addition, utilize TEM electron microscopic observation and add up the packed structures of active phase in sulphided state hydrogenation catalyst SD2, result is as shown in table 1.
Embodiment 5
This embodiment is for illustration of sulphided state hydrogenation catalyst provided by the invention and preparation method thereof.
Conventionally prepare oxidation state hydrogenation catalyst E1, it comprises alumina support and load NiO and MoO on the alumina support
3active metal component and formic acid, wherein, in oxidation state hydrogenation catalyst E1, the mol ratio of carbon atom and Ni metallic atom is 2:1, with the gross weight of oxidation state hydrogenation catalyst for benchmark, NiO and MoO
3mass content be respectively 3% and 15%.Oxidation state hydrogenation catalyst E1 records can to decompose between 200-400 DEG C through temperature programmed oxidation method and discharges CO
2, CO
2burst size occurs that the temperature corresponding to peak value is 265 DEG C.Adopt dry pre-sulfiding method to carry out sulfuration oxidation state hydrogenation catalyst E1, curing medium used is H
2and H
2the gaseous mixture of S, in sulfidation, is first warming up to 265 DEG C of constant temperature sulfuration 4h by oxidation state hydrogenation catalyst E1 with the heating rate of 5 DEG C/h, finally again with the ramp to 400 of 5 DEG C/h DEG C constant temperature sulfuration 4h, obtains sulphided state hydrogenation catalyst SE1.The sulphidity recording Ni and Mo in sulphided state hydrogenation catalyst SE1 through xps energy spectrum instrument is respectively 67.5% and 79.5%.In addition, utilize TEM electron microscopic observation and add up the packed structures of active phase in sulphided state hydrogenation catalyst SE1, result is as shown in table 1.
Comparative example 6
This comparative example is for illustration of the sulphided state hydrogenation catalyst and preparation method thereof of reference.
The preparation of sulphided state hydrogenation catalyst is carried out according to the method for embodiment 5, unlike, described oxidation state hydrogenation catalyst E1 is alternative with the oxidation state hydrogenation catalyst E2 (kind of carrier in oxidation state hydrogenation catalyst E2 and the kind of metal oxide all identical with oxidation state hydrogenation catalyst E1 with content) containing formic acid, obtains sulphided state hydrogenation catalyst SE2.The sulphidity recording Ni and Mo in sulphided state hydrogenation catalyst SE2 through xps energy spectrum instrument is respectively 65.5% and 78.0%.In addition, utilize TEM electron microscopic observation and add up the packed structures of active phase in sulphided state hydrogenation catalyst SE2, result is as shown in table 1.
Table 1
From the results shown in Table 1, in the sulphided state hydrogenation catalyst adopting method provided by the invention to obtain, the ratio of more than four layers packed structures is enhanced.
Test case
Test case is for illustration of the test of sulphided state hydrogenation catalyst hydrodesulfurization performance.
The hydrodesulfurization performance of sulphided state hydrogenation catalyst measures on high-pressure micro-device.Particularly, respectively 0.15g sulphided state hydrogenation catalyst SA1, SA2, SA3, SB1, SB2, SC1, SC2, SD1, SD2, SE1 and SE2 are filled on high-pressure micro-device, introduce the n-heptane solution that thiophene mass fraction is 25% again, the air speed of raw material is 80mL/ (gh), reaction temperature is 300 DEG C, product takes on-line chromatograph analysis, and utilizes normalization method to calculate the conversion ratio of thiophene.
Result shows, the ratio of the thiophene conversion ratio of sulphided state hydrogenation catalyst SA1 and SA2 is 1.06; The ratio of the thiophene conversion ratio of sulphided state hydrogenation catalyst SA1 and SA3 is 1.04; The ratio of the thiophene conversion ratio of sulphided state hydrogenation catalyst SB1 and SB2 is 1.07; The ratio of the thiophene conversion ratio of sulphided state hydrogenation catalyst SC1 and SC2 is 1.07; The ratio of the thiophene conversion ratio of sulphided state hydrogenation catalyst SD1 and SD2 is 1.04; The ratio of the thiophene conversion ratio of sulphided state hydrogenation catalyst SE1 and SE2 is 1.03.As can be seen here, the sulphided state hydrogenation catalyst adopting method of the present invention to obtain has higher hydrodesulfurization activity.
To sum up, adopt method provided by the invention can the effectively sulfuration of reactive metal oxides in accelerating oxidation state hydrogenation catalyst, and improve the ratio of more than four layers packed structures in sulphided state catalyst, thus effectively improve the hydrodesulfurization activity of catalyst, have prospects for commercial application.
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 (11)
1. a preparation method for sulphided state hydrogenation catalyst, the method comprises the following steps:
(1) prepare oxidation state hydrogenation catalyst, described oxidation state hydrogenation catalyst comprises carrier and load carboxylic acid compound on the carrier and reactive metal oxides, and described carboxylic acid compound exists at least one exothermic peak in 200-400 DEG C;
(2) under curing medium exists, the temperature of described oxidation state hydrogenation catalyst is risen to described carboxylic acid compound constant temperature sulfuration 1-5 hour 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 and constant temperature sulfuration 1-5 hour 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 carboxylic acid compound between 200-400 DEG C.
2. method according to claim 1, wherein, at least there is an exothermic peak in described carboxylic acid compound in 200-299 DEG C, and in 300-400 DEG C, at least there is an exothermic peak.
3. method according to claim 1 and 2, wherein, described carboxylic acid compound be selected from formic acid, acetic acid, propionic acid, butyric acid, citric acid, succinic acid, ethanedioic acid, tartaric acid and glutaric acid one or more.
4. method according to claim 1 and 2, wherein, in step (2), heating rate is 5-10 DEG C/h.
5. method according to claim 1 and 2, wherein, with the gross weight of described oxidation state hydrogenation catalyst for benchmark, the content of described reactive metal oxides is 10-45 % by weight.
6. method according to claim 5, wherein, described reactive metal oxides is group VIII metal oxide and/or group vib metal oxide.
7. method according to claim 6, wherein, described reactive metal oxides is the mixture of at least one group VIII metal oxide and at least one group vib metal oxide.
8. method according to claim 7, wherein, the consumption of described carboxylic acid compound makes the mol ratio of the carbon atom in described oxidation state hydrogenation catalyst and the metallic atom in group VIII metal oxide be less than 20:1, is preferably 2-10:1.
9. method according to claim 1, wherein, one or more in described support selected from alumina, silica, titanium oxide, zirconia, activated carbon and molecular sieve.
10. the sulphided state hydrogenation catalyst prepared by the method in claim 1-9 described in any one.
11. application of sulphided state hydrogenation catalyst according to claim 10 in hydrodesulfurization reaction.
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