CN106268976B - A kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparation and application - Google Patents
A kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparations and application, are the S of Mo, 35-40wt% of VIII race's metal, 45-58wt% in catalyst containing 3-15wt% in terms of 100% by catalyst gross mass；The catalyst the preparation method is as follows: a) preparing the molybdenum disulfide nano sheet precursor of the non-stoichiometric of rich defect；B) a kind of VIII race's metal is introduced into molybdenum disulfide nano sheet precursor with ultrasonic assistant soakage method；The molar ratio of VIII race's metal and Mo are (0.1-0.5): 1；The specific surface area of the molybdenum disulfide nano sheet precursor is 40-90m2/ g, Kong Rongwei 0.1-0.25ml/g, sulphur and molybdenum molar ratio are (1.92-2.10): 1.The present invention is prepared for the molybdenum disulfide of rich defect by the stoichiometric ratio of control molybdenum disulfide, while more exposing active site；Compared with existing catalyst, catalyst provided by the invention is applied in gasoline selective hydrodesulfurizationmodification reaction, and alkene adds hydrogen saturation factor low, and the hydrodesulfurization rate of sulfur-containing compound is high.
Description
Technical field
The invention belongs to petrochemical industry, it is related to a kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparation and answers
With particularly relating to a kind of selective hydrodesulfurization bulk phase catalyst and preparation method thereof and in gasoline selective hydrodesulfurizationmodification
Application in reaction.
Background technique
Motor-vehicle tail-gas bring urban atmospheric pollution problem is on the rise, wherein the sulfur-containing compound burning in gasoline
The oxysulfide (SOx) generated afterwards can not only make the three-way catalyst of engine tail gas purification system generate irreversible poisoning, row
It is put into atmosphere and also will cause acid rain, and lead to the particles float object in atmosphere, cause 2.5 numerical value of PM raising etc. a series of
Problem.With the improvement of people's environmental awareness, various countries have worked out the sulfur content in stringent environmental legislation limitation fuel.Europe in
Start within 2009 to execute V standard requirements sulfur content of Europe lower than 10ppmw.Equally, motor petrol standard in China's wants sulfur content
Ask also higher and higher.It is required according to national standard body, China is on December 31st, 2009 in national III phase of state of enforcement
When in the discharge standard in Europe III.Beijing rate in 2012 first carries out V standard of capital that sulfur content is lower than 10ppmw.V motor petrol of state
Standard (being equivalent to V standard of Europe) will be issued in the end of the year 2013, transit to the completion of the end of the year 2016.This is de- to oil refining enterprise of China gasoline
More stringent requirements are proposed for sulphur technology.
In general, sulfide contained in gasoline fraction is easy to remove by hydrofinishing, still, contain in gasoline
A large amount of alkene easily add hydrogen saturation in the process, this not only causes declining to a great extent for octane number, while also resulting in a large amount of
Meaningless hydrogen consumption.Therefore, the main problem of gasoline hydrodesulfurizationmethod is how while guaranteeing desulfurization to reduce olefins hydrogenation,
Improve the selectivity of hydrodesulfurization reaction.
Supported hydrodesulphurizatiocatalyst catalyst is industrially the most frequently used, because carrier has biggish specific surface area and higher hole
The diameter degree of order, can be realized deep hydrodesulfurizationof.Michele Breysse et al. is in document (Catalysis Today 86
(2003) 5-16) in review the effect of various carriers, including oxide, mixed oxide, acid carrier, basic supports, point
Sub- sieve, mesoporous material, carbon material and concrete etc..Alumina support is widely used well because of large specific surface area, stability.
Chinese patent CN101089129A disclose it is a kind of with one of amorphous alumina, silicon-containing alumina and titanium-contained aluminum oxide or
A variety of is carrier, for the method for selectively hydrogenating and desulfurizing inferior gasoline.CN102091652A discloses one kind with little crystal grain TS-
The catalyst of 1 molecular sieve, inorganic oxide, molybdenum or tungsten and cobalt or nickel oxide composition is selected for catalytic gasoline of whole fraction
Property hydrodesulfurization reaction, when the sulfur content in FCC gasoline is close to 50ppmw, deolefination rate is 19.2%, is selectively reached
52.8%.United States Patent (USP) USP5358633 discloses a kind of method of the hydrodesulfurization of the pressure naphtha of reduction alkene saturation,
Used catalyst contains α, δ, γ, θ-alumina support of transitional face.The carrier that above-mentioned patent is related to has acidic site, acid
Site can usually promote skeletal isomerization, be unfavorable for the reduction of alkene saturation.For this purpose, a large amount of research work is concentrated mainly on carrier
Selection and modification.
Sylvette Brunet et al. is in document (278 (2005) 143- of Applied Catalysis A:General
172) hydrodesulfurization of FCC gasoline is reviewed in, and auxiliary agent, support, carrier modification, additive and poisoning effect are mainly discussed
Influence to the selectivity that hydrodesulfurization is saturated relative to alkene.The property of carrier has very big shadow to the selectivity of catalyst
It rings, and explains the hydrogenation activity for reducing the sour reduced performance catalyst of carrier in terms of electronic effect.Basic anhydride and water
Steatite support helps to improve selectivity of the catalyst hydrodesulfurization active relative to olefins hydrogenation；In addition, adsorbing alkali in advance
Property compound such as pyridine or Carbon deposition also contribute to improve selectivity.USP5441630 discloses one kind with houghite as load
Body, the houghite being fired have big specific surface area and alkalinity, and the catalyst after impregnating Co-Mo shows high desulfurization rate
It is saturated with low alkene.USP5340466 discloses one kind using hydrotalcite and aluminium oxide as carrier, and wherein hydrotalcite accounts for carrier quality
The 70% of score, desulfurization degree reach 90%, and alkene saturation factor is 30-40%, shows good desulfuration selectivity, but stablize
Property is poor.USP4140626 disclose one kind using magnesia and aluminium oxide as the catalyst of carrier, desulfurization degree be 96% when, alkene
Saturation reaches 64%, but the presence of a large amount of magnesia, so that catalytic mechanical intensity difference.CN1335361A discloses one kind and is used for
The catalyst of selective hydrogenation desulfurization of cracked gasoline, main component are the K of CoO+MoO, 0-5% of 6-20%2O, 0-5%
The MgAlO composite oxides of CuO, 30-95% and the A1 of 0-80%2O3, the catalyst is when hydrodesulfurization rate is 70%, alkene
Saturation factor is about 16%, and loss of octane number is 2.9 units.
Carrier modification is also the approach for improving selectivity.Chinese patent CN101439291A discloses a kind of multiple-addition agent and repairs
Catalyst for selectively hydrodesulfurizing of decorations and preparation method thereof, carrier select aluminium oxide and boron oxide, multiple-addition agent be magnesium, potassium and
Phosphorus.It is carrier that USP5525211, which discloses one kind through potassium carbonate modified magnesium aluminate spinel, and active component cobalt and molybdenum are born in two times
It is loaded on carrier, is 93% in desulfurization degree, alkene saturation factor is 31%, loss of octane number 3.5.In addition, organic additive also can
Improve selectivity.CN104250563A, which is disclosed, a kind of to be impregnated in the aqueous solution containing cobalt, molybdenum and at least one organic additive
Silica supports do not need to roast after dry lower than 200 DEG C, are used for naphtha selective hydrogenation desulfurization after directly vulcanizing
Reaction, catalyst of the discovery containing organic ligand have higher selectivity.EP0755995 disclose a kind of FCC gasoline selectively plus
Hydrogen desulphurization catalyst, the catalyst have carried out two o'clock improvement to conventional catalyst, and one of improvement is repaired with the potassium of 0.2-3.0wt%
Decorations reduce alkene saturation, inhibit carbon distribution；The two of improvement use area carbon method, and carbon distribution content is in 3-10wt%.The catalyst
Hydrodesulfurization selectivity it is opposite be improved, but be disadvantageous in that, complicated, harsh carbon distribution process increases industrial behaviour
Make difficulty, limits its industrial application.
United States Patent (USP) US6783663, US6712955, US6758963 etc. report the conjunction of novel NiMoW body catalyst
At and application, hydrodesulfurization activity be the three times or so of other industrial reference catalysts.Chinese patent CN1339985A,
CN101544904A, CN101153228A, CN101733120A and CN103657672A also disclose a kind of tri- metal sheet of NiMoW
The preparation method of body catalyst and the application in Ultra-deep Desulfurization of Diesel Fuels, although the catalyst prepared is in the ultra-deep of diesel oil
When showing higher activity in degree hydrodesulfurization reaction, but being used for the hydrodesulfurization of gasoline, since such catalyst adds
Hydrogen activity is too high, causes the saturation of a large amount of alkene, limits its application in gasoline selective hydrodesulfurizationmodification.
Nano molybdenum disulfide (MoS2) because of reference area with higher and excellent light, electricity, catalysis, greasy property,
The fields such as electron probe, photoelectrocatalysis, solar battery, petrochemical industry catalysis, hydrogen storage material and friction, lubrication, which have, widely answers
Use prospect.
Currently, occur a variety of methods for preparing nano molybdenum disulfide material both at home and abroad, it can according to the difference of preparing processes
It is divided into solid phase method, liquid phase method, vapor phase method.As long as solid phase method includes solid phase decomposition method, mechanical disruption method, self-propagating combustion etc..
Vapor phase method mainly includes gas-phase reaction method, vapour deposition process, magnetron sputtering method, template etc..Liquid phase method mainly includes that chemistry is heavy
Shallow lake method, hydrothermal synthesis method, sol-gel method, electrochemical process, microemulsion method, molybdenum disulfide restacking method and phonochemistry method etc..Benefit
It has been synthesized the molybdenum disulfide of various patterns with the above various methods, for example nanotube, nano flower, nanometer polyhedral are received
Rice noodles, nano-complex, nanometer rods and nanosphere etc..
Many patents also disclose the preparation method of the molybdenum disulfide of different-shape.Chinese patent CN101712492A is disclosed
A kind of preparation method of monodisperse molybdenum disulfide nano sheet, with the mixture of molybdenum oxide and sulphur, ball milling is living under protective atmosphere
Change, vulcanizes in 400-700 DEG C of cycle annealing.CN1752023A discloses a kind of preparation side of inorganic fullerene molybdenum disulfide
Four thio ammonium molybdate aqueous solution is spray-dried by method, obtains ultra-fine molybdenum trisulfide presoma, and then reduction obtains richness at high temperature
Strangle alkene molybdenum disulfide.These solid phase methods would generally be related to high temperature vulcanized or high temperature reduction process.Patent CN1994895A is disclosed
A kind of ionic liquid assisted hydrothermal synthesis MoS2Ionic liquid is added in the solution of molybdate and thiocarbamide in the preparation method of microballoon
Body 1- butyl -3- methyl imidazolium tetrafluoroborate carries out hydro-thermal reaction.CN101851006A discloses a kind of using solvent-thermal method
Prepare MoS2The method of micron ball is reacted in alcohols solvent using molybdenum source and sulphur source and molybdenum sulfide micron ball is made.
CN101857273A discloses the preparation method of nanoscale flaky molybdenum disulfide, is molybdenum source and sulphur source with four thio ammonium molybdate, with
Oxalic acid is reducing agent, and heated in water solution stirring obtains amorphous molybdenum disulfide through chemical precipitation method.CN102701281A is disclosed
A kind of preparation method of flower-shaped hollow molybdenum disulfide microspheres is dissolved in water with ammonium molybdate, thiocarbamide, hydroxylamine hydrochloride and surfactant
In, hydro-thermal reaction is carried out after adjusting PH.CN102992405A discloses a kind of preparation of molybdenum disulfide nanometer nuclear shell nano-structure
Sodium molybdate, vulcanized sodium, ascorbic acid are dissolved in the mixed solvent by method, are added surfactant and are carried out hydro-thermal reaction.
CN103086436A discloses a kind of preparation method of nano molybdenum disulfide, and using hydrothermal method, inorganic additives are added
K2CrO4Or H4O40SiW12Obtain flower-shaped and rod-like nano molybdenum disulfide.The method of these hydro-thermals or solvent heat passes through addition
Different reducing agent, surfactant or other inorganic salts control the pattern of molybdenum disulfide.
From work has been reported it is not difficult to find that existing catalyst for selectively hydrodesulfurizing has following deficiency:
(1) traditional Hydrobon catalyst causes a large amount of alkene in gasoline while removing Removal of Sulfur Compounds from Gasoline
Hydrocarbon adds hydrogen saturation, causes declining to a great extent for octane number, while also resulting in a large amount of meaningless hydrogen consumptions；
(2) raising of traditional loaded catalyst selectivity is limited by carrier；
(3) most of existing bulk phase catalyst is directed to diesel component, and hydrogenation activity with higher easily causes alkene
A large amount of saturations, thus it is not directly applicable the selective hydrodesulfurization reaction of gasoline；
(4) existing most of hydro-thermals or the method for solvent hot preparation molybdenum disulfide have used reducing agent, surfactant
Or inorganic salts, increase the complexity of preparation；
(5) existing selective hydrogenation desulfurization process causes a large amount of energy in such a way that pre-distillation separates weight component
Source waste.
Currently, catalyst for the highly selective and high desulfurization rate of gasoline selective hydrodesulfurizationmodification reaction and few.And
Molybdenum disulfide is as catalyst, and chief active position is the margin location (rims and edges) around lamella, and basal plane
(basal plane) basic catalytically inactive, prepares two-dimensional sheet nanostructure, can expose more sites edges, when drawing
After entering auxiliary agent Co, Ni, forms more active sites and be conducive to desulphurizing activated and selective raising.Therefore, it is highly desirable
Develop a kind of with high activity and highly selective catalyst based on rich defect molybdenum disulfide.
Summary of the invention
The object of the present invention is to provide a kind of catalyst for gasoline selective hydrodesulfurizationmodification.
Another object of the present invention is to provide a kind of method for preparing above-mentioned catalyst.
To achieve the above object, the technical solution of the present invention is as follows:
A kind of catalyst for selective hydrodesulfurizationof of gasoline is provided, the catalyst includes a kind of VIII race's metallic element, Mo
And S, by catalyst gross mass be 100% in terms of, Mo, 35-40wt%'s of VIII race's metal, 45-58wt% containing 3-15wt%
S；
The catalyst the preparation method is as follows: a) preparing the molybdenum disulfide nano sheet of the non-stoichiometric of rich defect before
Body；B) a kind of VIII race's metal is introduced into molybdenum disulfide nano sheet precursor with ultrasonic assistant soakage method.
The molar ratio of VIII race's metal and Mo are (0.1-0.5): 1；
The specific surface area of the molybdenum disulfide nano sheet precursor is 40-90m2/ g, Kong Rongwei 0.1-0.25ml/g, sulphur and molybdenum rub
Your ratio is (1.92-2.10): 1；
In a preferred aspect of the invention, wherein VIII race's metal is selected from Ni, Co.
In another aspect of the invention, a kind of preparation method of catalyst as described above is provided, this method includes following
Step:
A) it is added to the water after mixing the soluble-salt of molybdenum, vulcanizing agent and is configured to solution, is transferred in reaction kettle and carries out water
Thermal response；The mixed solvent supersound washing that water and dehydrated alcohol are used after cooling, is dried to obtain the non-stoichiometric of rich defect
Molybdenum disulfide nano sheet precursor.
B) solution is configured to by a kind of soluble-salt of VIII race's metal is soluble in water, be carried on dipping method a certain amount of
On the molybdenum disulfide nano sheet precursor of rich defect non-stoichiometric, 12-24h is dried in vacuo at 50-80 DEG C and obtains catalyst.
In the preparation method, wherein the concentration of the molybdenum solution is 0.03-0.06mol/L, the sulfur agent solution
Concentration be 0.06-0.20mol/L, the soluble salt solutions concentration of VIII race metal is 0.5~1.5mol/L.
In the preparation method, the reaction temperature of hydro-thermal reaction described in step a) is 160 DEG C~220 DEG C, reaction
Time is 9h~for 24 hours；The volume ratio of the mixed solvent of the water and dehydrated alcohol is 10:1-1:10；Leaching described in step b)
Stain method is excessive dipping, while being assisted with ultrasound and agitating mode.
In another preferred aspect of the invention, the molybdenum disulfide of the non-stoichiometric of rich defect described in step a)
The preparation method of nanometer sheet, wherein the stoichiometric ratio of the molybdenum disulfide of the rich defect is by changing the molybdenum in reactant
Soluble-salt and the mass ratio of vulcanizing agent control；Wherein the vulcanizing agent is also used as reducing agent and surfactant simultaneously；
Wherein the soluble-salt of the molybdenum is one of ammonium heptamolybdate, sodium molybdate；The vulcanizing agent is thiocarbamide, in thioacetamide
It is a kind of.
The soluble-salt of VIII race's metal described in step b) is one of cobalt nitrate, cobalt acetate, nickel acetate.
In another aspect of the invention, the selective hydrodesulfurization for providing catalyst as described above in gasoline is reacted
In application.
In a preferred aspect of the invention, the gasoline selective hydrodesulfurizationmodification reaction condition are as follows: reaction temperature
200-320 DEG C, Hydrogen Vapor Pressure 0.5-10.0MPa, the volume ratio 20:1-300:1 of hydrogen and material, and the volume space velocity of material
0.5-10.0h-1。
In another aspect of the invention, the catalyst makees following place before the selective hydrodesulfurization for carrying out gasoline
Reason,
A) grinding, kneading, molding；
B) on fixed bed reactors, original position is carried out with the mixed gas of sulfur-containing compound and hydrogen at 280-350 DEG C
Presulfurization；Wherein the sulfur-containing compound is hydrogen sulfide, carbon disulfide or dimethyl disulfide, and volume contains in mixed gas
Amount is 1-15%.
Catalyst for selective hydrodesulfurizationof of gasoline of the invention is compared with well-known technique, is had the advantages that
1. vulcanizing agent used in the present invention is also used as reducing agent and surfactant, other reducing agents and surface are avoided
The use of activating agent.
2. the present invention controls the curing of rich defect by changing the molar ratio of molybdenum source and vulcanizing agent in reactant
The stoichiometric ratio of molybdenum.
3. molybdenum disulfide exposure more edge and defect sites that the present invention synthesizes, as shown in Figure 3.
4. the method that the present invention uses the molybdenum disulfide nano sheet of the non-chemical amount ratio of rich defect to prepare catalyst as precursor,
Simple and easy to control, production cost is low, and yield height is suitble to industrialization large-scale production.
5. using contain 130ppmw thiophene, 25vol.% cyclohexene, 25vol.% toluene, 50vol.% normal heptane mould
Type compound carries out activity rating to catalyst, and evaluation result shows to urge with what is prepared according to control methods provided by the invention
Agent is compared, and under close desulfurization degree, the hydrogenation of olefins activity of the catalyst prepared according to the method provided by the invention is reduced
60%, show that catalyst has very high selectivity.For catalyst provided by the invention in desulfurization degree 88%, alkene saturation factor is not
To 8%, and reference catalyst is when desulfurization degree is 70%, and alkene saturation factor reaches 25%.
Detailed description of the invention
Fig. 1 is that the embodiment of the present invention 1 (Sample A), embodiment 2 (Sample B) and embodiment 6 (Sample F) are made
The XRD diagram of the molybdenum disulfide nano sheet precursor of the non-stoichiometric of standby rich defect.
Fig. 2 is the non-chemical of rich defect prepared by the embodiment of the present invention 1 (Sample A) and embodiment 2 (Sample B)
Measure the Raman spectrum of the molybdenum disulfide nano sheet precursor of ratio.
Fig. 3 is the molybdenum disulfide nano sheet precursor of the non-stoichiometric of rich defect prepared by the embodiment of the present invention 1
TEM ((a) Sample A) and HRTEM ((b) Sample A) figure.
Specific embodiment
In order to further illustrate the present invention, following embodiment is enumerated, but it is not intended to limit each accessory claim and is defined
Invention scope.
Embodiment 1
140ml deionized water dissolving is added after 4.94g ammonium heptamolybdate and 9.13g thiocarbamide are mixed, being transferred to volume is
In the water heating kettle of 200ml, be put into baking oven, hydro-thermal 18h carried out at 220 DEG C, then natural cooling, filter, with water and anhydrous
Ethyl alcohol volume ratio is mixed solvent supersound washing 2-4 time of 1, and vacuum drying obtains molybdenum disulfide nano sheet precursor；By 0.428g
Cobalt acetate is dissolved in 6ml water, takes 2.5g molybdenum disulfide nano sheet precursor that the cobalt-carrying solution that front is prepared is added, and ultrasound simultaneously stirs extremely
Sticky shape is then transferred to vacuum oven in 50 DEG C of dryings and obtains catalyst for 24 hours.The catalyst Cat- of this embodiment synthesis
A is indicated.The ICP elemental analysis of molybdenum disulfide nano sheet precursor shows that the molar ratio of sulphur and molybdenum is 2.03 in the embodiment, and nitrogen is inhaled
Attached measurement the specific area is 88m2/ g, XRD characterization is as shown in Figure 1, Raman is composed as shown in Fig. 2, HRTEM figure is as shown in Figure 3.
Embodiment 2
In addition to use 6.39g thiocarbamide replace thiocarbamide used in embodiment 1 other than, with phase Tongfang described in embodiment 1
Formula prepares catalyst.The catalyst of this embodiment synthesis is indicated with Cat-B.Molybdenum disulfide nano sheet precursor in the embodiment
ICP elemental analysis shows that the molar ratio of sulphur and molybdenum is 1.98, and N2 adsorption measurement the specific area is 60m2/ g, XRD characterization such as Fig. 1
Shown, Raman spectrum is as shown in Figure 2.
Embodiment 3
In addition to use 4.26g thiocarbamide replace thiocarbamide used in embodiment 1 other than, with phase Tongfang described in embodiment 1
Formula prepares catalyst.The catalyst of this embodiment synthesis is indicated with Cat-C.Molybdenum disulfide nano sheet precursor in the embodiment
ICP elemental analysis shows that the molar ratio of sulphur and molybdenum is 1.94, and N2 adsorption measurement the specific area is 41m2/g。
Embodiment 4
In addition to use 10.65g thiocarbamide replace thiocarbamide used in embodiment 1 other than, with phase Tongfang described in embodiment 1
Formula prepares catalyst.The catalyst of this embodiment synthesis is indicated with Cat-D.Molybdenum disulfide nano sheet precursor in the embodiment
ICP elemental analysis shows that the molar ratio of sulphur and molybdenum is 2.06, and N2 adsorption measurement the specific area is 84m2/g。
Embodiment 5
In addition to use 11.72g thiocarbamide replace thiocarbamide used in embodiment 1 other than, with phase Tongfang described in embodiment 1
Formula prepares catalyst.The catalyst of this embodiment synthesis is indicated with Cat-E.Molybdenum disulfide nano sheet precursor in the embodiment
ICP elemental analysis shows that the molar ratio of sulphur and molybdenum is 2.10, and N2 adsorption measurement the specific area is 73m2/g。
Embodiment 6
In addition to use 160 DEG C replace 220 DEG C used in embodiment 1 other than, with same way system described in embodiment 1
Standby catalyst.The catalyst of this embodiment synthesis is indicated with Cat-F.The ICP member of molybdenum disulfide nano sheet precursor in the embodiment
For element analysis shows the molar ratio of sulphur and molybdenum is 1.96, N2 adsorption measurement the specific area is 77m2/ g, XRD are as shown in Figure 1.
Embodiment 7
Other than using 9.88g ammonium heptamolybdate and 18.26g thiocarbamide to replace ammonium heptamolybdate used in embodiment 1 and thiocarbamide,
To prepare catalyst with same way described in embodiment 1.The catalyst of this embodiment synthesis is indicated with Cat-G.The implementation
The ICP elemental analysis of molybdenum disulfide nano sheet precursor shows that the molar ratio of sulphur and molybdenum is 2.01 in example, and N2 adsorption measures specific surface
Product is 68m2/g。
Embodiment 8
In addition to use 9.01g thioacetamide replace 9.13g thiocarbamide used in embodiment 1 other than, with in embodiment 1
The same way prepares catalyst.The catalyst of this embodiment synthesis is indicated with Cat-H.Molybdenum disulfide is received in the embodiment
The ICP elemental analysis of rice piece precursor shows that the molar ratio of sulphur and molybdenum is 2.02, and N2 adsorption measurement the specific area is 75m2/g。
Embodiment 9
In addition to use 6.28g thioacetamide replace 9.13g thiocarbamide used in embodiment 1 other than, with institute in embodiment 1
The same way stated prepares catalyst.The catalyst of this embodiment synthesis is indicated with Cat-I.Molybdenum disulfide nano in the embodiment
The ICP elemental analysis of piece precursor shows that the molar ratio of sulphur and molybdenum is 1.99, and N2 adsorption measurement the specific area is 65m2/g。
Embodiment 10
In addition to use 6.77g sodium molybdate replace 4.94g ammonium heptamolybdate used in embodiment 1 other than, with institute in embodiment 1
The same way stated prepares catalyst.The catalyst of this embodiment synthesis is indicated with Cat-J.Molybdenum disulfide nano in the embodiment
The ICP elemental analysis of piece precursor shows that the molar ratio of sulphur and molybdenum is 2.01, and N2 adsorption measurement the specific area is 62m2/g。
Embodiment 11
In addition to using 9.01g thioacetamide, 6.77g sodium molybdate to replace 9.13g thiocarbamide used in embodiment 1,4.94g
Outside ammonium heptamolybdate, to prepare catalyst with same way described in embodiment 1.The catalyst Cat-K of this embodiment synthesis
It indicates.The ICP elemental analysis of molybdenum disulfide nano sheet precursor shows that the molar ratio of sulphur and molybdenum is 2.02 in the embodiment, N2 adsorption
Measurement the specific area is 72m2/g。
Embodiment 12
In addition to use 8.65g sodium molybdate replace 4.94g ammonium heptamolybdate used in embodiment 1 other than, with institute in embodiment 1
The same way stated prepares catalyst.The catalyst of this embodiment synthesis is indicated with Cat-L.Molybdenum disulfide nano in the embodiment
The ICP elemental analysis of piece precursor shows that the molar ratio of sulphur and molybdenum is 1.98, and N2 adsorption measurement the specific area is 42m2/g。
Embodiment 13
In addition to use 0.214g cobalt acetate replace 0.428g cobalt acetate used in embodiment 1 other than, with institute in embodiment 1
The same way stated prepares catalyst.The catalyst of this embodiment synthesis is indicated with Cat-M.Molybdenum disulfide nano in the embodiment
The ICP elemental analysis of piece precursor shows that the molar ratio of sulphur and molybdenum is 2.03, and N2 adsorption measurement the specific area is 88m2/g。
Embodiment 14
In addition to use 0.856g cobalt acetate replace 0.428g cobalt acetate used in embodiment 1 other than, with institute in embodiment 1
The same way stated prepares catalyst.The catalyst of this embodiment synthesis indicates molybdenum disulfide nano in the embodiment with Cat-N
The ICP elemental analysis of piece precursor shows that the molar ratio of sulphur and molybdenum is 2.02, and N2 adsorption measurement the specific area is 83m2/g。
Embodiment 15
In addition to use 1.284g cobalt acetate replace 0.428g cobalt acetate used in embodiment 1 other than, with institute in embodiment 1
The same way stated prepares catalyst.The catalyst of this embodiment synthesis is indicated with Cat-O.Molybdenum disulfide nano in the embodiment
The ICP elemental analysis of piece precursor shows that the molar ratio of sulphur and molybdenum is 2.04, and N2 adsorption measurement the specific area is 87m2/g。
Embodiment 16
In addition to use 0.500g cabaltous nitrate hexahydrate replace 0.428g cobalt acetate used in embodiment 1 other than, with implementation
Same way described in example 1 prepares catalyst.The catalyst of this embodiment synthesis is indicated with Cat-P.Two sulphur in the embodiment
The ICP elemental analysis for changing molybdenum nanometer sheet precursor shows that the molar ratio of sulphur and molybdenum is 2.03, and N2 adsorption measurement the specific area is 85m2/
g。
Embodiment 17
In addition to use 0.428g nickel acetate tetrahydrate replace 0.428g cobalt acetate used in embodiment 1 other than, with implementation
Same way described in example 1 prepares catalyst.The catalyst of this embodiment synthesis is indicated with Cat-Q.Two sulphur in the embodiment
The ICP elemental analysis for changing molybdenum nanometer sheet precursor shows that the molar ratio of sulphur and molybdenum is 2.02, and N2 adsorption measurement the specific area is
81m2/。
Comparative example 1
Catalyst is prepared by the identical method of United States Patent (USP) USP5851382 embodiment 1, catalyst obtained is indicated with R1.
Through X- light fluorescence (XRF) elemental analysis, the group of the catalyst becomes 3.1%CoO, 11.9%MoO3, 59.3%MgO, 25.7%
Al2O3。
Comparative example 2
Catalyst is prepared by 1 same procedure of United States Patent (USP) USP5441630 embodiment, catalyst obtained is indicated with R2.Through
The group of X- light fluorescence (XRF) elemental analysis, the catalyst becomes 3.0%CoO, 15.0%MoO3, 22.2%MgO, 59.7%
Al2O3。
Embodiment 18
The performance evaluation of catalyst hydrodesulfurization and hydrogenation of olefins in gasoline selective hydrodesulfurizationmodification reaction:
With the mould formed containing 130ppmw thiophene, 25vol.% cyclohexene, 25vol.% toluene and 50vol.% normal heptane
Type compound investigates the hydrodesulfurization and olefins hydrogenation reactivity worth of catalyst.It is specific evaluation method is as follows: will be catalyzed
Agent is sieved into the particle of 20-40 mesh, and 0.70g catalyst is packed into the fixed bed reactors of 0.7cm diameter.It is right before charging
Catalyst carries out in-situ presulfurization.Specific conditions of vulcanization is using H2The H that S volume content is 10%2S/H2Mixed gas normal
Pressure, temperature are 320 DEG C and carry out vulcanization 2 hours.Rear feeding, which is completed, in vulcanization carries out selective hydrodesulfurization reaction, it is specific to react
Condition is 270 DEG C of reaction temperature, hydrogen partial pressure 1.0MPa, hydrogen to oil volume ratio 100NL/L, volume space velocity 6.0h-1.Urging in comparative example
For agent in addition to carrying out vulcanization with 400 DEG C and having reached optimum response state in 2 hours, other reaction conditions are identical.Sample after reaction
ANTEK constant sulphur appliance and Agilent GC 6890N chromatograph (50m HP-PONA is respectively adopted in sulfur content and cyclohexene content in product
Chromatographic column and fid detector) analysis.
In the above-mentioned selective hydrodesulfurization reaction to mould oil, it is catalyzed using catalyst of the present invention and comparison
Hds conversion (HDS%) and the alkene saturation conversion ratio (HYD%) of agent are listed in Table 1 below.
Table 1, the hds conversion of catalyst and hydrogenation of olefins conversion ratio
| Catalyst | HDS% | HYD% | HDS/HYD |
| Cat-A | 87.4 | 5.0 | 17.5 |
| Cat-B | 81.0 | 2.5 | 32.4 |
| Cat-C | 87.9 | 5.9 | 14.9 |
| Cat-D | 74.2 | 2.0 | 37.1 |
| Cat-E | 88.3 | 6.3 | 14.0 |
| Cat-F | 78.9 | 2.9 | 27.2 |
| Cat-G | 88.8 | 5.8 | 15.3 |
| Cat-H | 86.7 | 4.8 | 18.1 |
| Cat-I | 80.6 | 2.8 | 28.8 |
| Cat-J | 86.4 | 6.0 | 14.4 |
| Cat-K | 80.3 | 5.8 | 13.8 |
| Cat-L | 70.9 | 2.7 | 26.3 |
| Cat-M | 84.5 | 4.9 | 17.2 |
| Cat-N | 81.7 | 3.7 | 22.1 |
| Cat-O | 86.2 | 4.6 | 18.7 |
| Cat-P | 88.4 | 7.2 | 12.3 |
| Cat-Q | 92.9 | 67.8 | 1.4 |
| R1 | 70.5 | 25.8 | 2.7 |
| R2 | 62.8 | 20.9 | 3.0 |
It can be seen that catalyst prepared by the present invention compared with comparative catalyst from 1 test result of table, in addition to containing Ni's
Except Cat-Q (NiMoS) catalyst, the selectivity of other catalyst is above comparative catalyst, and such case and Ni auxiliary agent have
There is higher hydrogenation activity consistent.The hydrodesulfurization activity of wherein Cat-A, Cat-C, Cat-E, Cat-G, Cat-P catalyst
It is preferable with selective effect.For especially Cat-G catalyst in higher hydrodesulfurization rate, cyclohexene adds hydrogen saturation factor
Significantly lower than comparative catalyst, the selectivity of such catalyst is best.
In conclusion the catalyst that the present invention synthesizes is made using the molybdenum disulfide nano sheet of the non-stoichiometric of rich defect
For precursor, more active sites can be formed by introducing Co, Ni, facilitate the raising of activity and selectivity.In short, prepared by the present invention
Catalyst has higher selectivity compared with comparative catalyst, shows its industrial application value.
Claims (9)
1. a kind of catalyst for selective hydrodesulfurizationof of gasoline, it is characterised in that: the catalyst includes VIII race's metal member of one kind
Element, Mo and S are in terms of 100% by catalyst gross mass, wherein Mo, 35- of VIII race's metal, 45-58wt% containing 3-15wt%
The S of 40wt%；
The catalyst the preparation method is as follows: a) passing through the molybdenum disulfide that hydro-thermal reaction prepares the non-stoichiometric of rich defect
Nanometer sheet precursor；B) a kind of VIII race's metal is introduced into molybdenum disulfide nano sheet precursor with ultrasonic assistant soakage method, described VIII
Race's metal is selected from Ni, Co, the preparation method of the molybdenum disulfide nano sheet of the non-stoichiometric of the rich defect, wherein described
Rich defect molybdenum disulfide stoichiometric ratio be by change reactant in molybdenum soluble-salt and vulcanizing agent quality
Than controlling, and the molar ratio of sulphur and molybdenum is (1.92-2.1): 1.
2. catalyst for selective hydrodesulfurizationof of gasoline according to claim 1, it is characterised in that: VIII race's metal and Mo's rubs
Your ratio is (0.1-0.5): 1；The specific surface area of the molybdenum disulfide nano sheet precursor is 40-90 m2/ g, Kong Rongwei 0.1-0.25
ml/g。
3. the preparation method of catalyst according to claim 1 or claim 2, it is characterised in that:
Method includes the following steps:
A) it is added to the water after mixing the soluble-salt of molybdenum, vulcanizing agent and is configured to solution, it is anti-is transferred to progress hydro-thermal in reaction kettle
It answers；The mixed solvent supersound washing that water and dehydrated alcohol are used after cooling, is dried to obtain two sulphur of the non-stoichiometric of rich defect
Change molybdenum nanometer sheet precursor；
B) solution is configured to by a kind of soluble-salt of VIII race's metal is soluble in water, be carried on a certain amount of richness with dipping method
On the molybdenum disulfide nano sheet precursor of defect non-stoichiometric, 12-24h is dried in vacuo at 50-80 DEG C and obtains catalyst.
4. preparation method according to claim 3, it is characterised in that: wherein the concentration of the molybdenum solution is 0.03-0.06
The concentration of mol/L, the sulfur agent solution are 0.06-0.20 mol/L, and the soluble salt solutions concentration of VIII race metal is
0.5~1.5 mol/L。
5. preparation method according to claim 3, it is characterised in that:
Reaction temperature in hydro-thermal reaction described in step a) is 160oC~220oC, reaction time are 9h ~ for 24 hours；The water
Volume ratio with the mixed solvent of dehydrated alcohol is 10:1-1:10；
Dipping method described in step b) is excessive dipping, while being assisted with ultrasound and agitating mode.
6. preparation method according to claim 3, it is characterised in that: wherein the vulcanizing agent simultaneously also as reducing agent and
Surfactant；Wherein the soluble-salt of the molybdenum is one of ammonium heptamolybdate, sodium molybdate；The vulcanizing agent is thiocarbamide, sulphur
For one of acetamide；
The soluble-salt of VIII race's metal described in step b) is one of cobalt nitrate, cobalt acetate, nickel acetate.
7. a kind of application of catalyst as claimed in claim 1 or 2 in gasoline selective hydrodesulfurizationmodification reaction.
8. application according to claim 7, wherein the reaction condition in the gasoline selective hydrodesulfurizationmodification reaction
Are as follows: 200-320 DEG C of reaction temperature, Hydrogen Vapor Pressure 0.5-10.0 MPa, the volume ratio 20:1-300:1 of hydrogen and material, and object
The volume space velocity 0.5-10.0 h of material-1。
9. application according to claim 7, it is characterised in that: catalyst is before carrying out gasoline selective hydrodesulfurizationmodification reaction
It is handled as follows,
A) grinding, kneading, molding；
B) on fixed bed reactors, pre- sulphur in situ is carried out with the mixed gas of sulfur-containing compound and hydrogen at 280-350 DEG C
Change；Wherein the sulfur-containing compound is one of hydrogen sulfide, carbon disulfide, dimethyl disulfide, the volume in mixed gas
Content is 1-15%.
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| CN107638882A (en) * | 2017-05-08 | 2018-01-30 | 中国科学院大连化学物理研究所 | A kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparation and application |
| CN109174131A (en) * | 2018-08-29 | 2019-01-11 | 厦门大学 | The molybdenum disulfide nano floral material and its synthetic method of nickel cobalt modification and application |
| US11377601B2 (en) | 2018-09-18 | 2022-07-05 | King Fahd University Of Petroleum And Minerals | Boron and/or carbon nanofiber modified alumina-supported molybdenum-cobalt catalysts useful in hydrodesulfurization |
| RU2677285C1 (en) * | 2018-09-20 | 2019-01-16 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Method for preparing catalyst for hydraulic cleaning of oil fractions in sulfide form (options) |
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| CN112934244A (en) * | 2019-12-11 | 2021-06-11 | 中国科学院大连化学物理研究所 | Non-supported suspension bed hydrodesulfurization catalyst, preparation and application |
| CN112371141B (en) * | 2020-12-10 | 2022-05-13 | 福州大学 | Catalytic gasoline hydrodesulfurization catalyst and preparation method thereof |
| CN113522319B (en) * | 2021-07-05 | 2023-07-11 | 北京建筑大学 | Preparation method and application of catalytic material |
| CN113499787A (en) * | 2021-08-13 | 2021-10-15 | 中国科学院大连化学物理研究所 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof |
| CN115069275A (en) * | 2022-07-27 | 2022-09-20 | 广西民族大学 | Composite desulfurizer and preparation method and application thereof |
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