CN105289601B - A kind of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane catalyst and preparation method thereof - Google Patents
A kind of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane catalyst, comprise the following steps：(1) activated carbon is chosen as drying at 100~200 DEG C of catalyst carrier；(2) dried activated carbon is added into the ammonium paramolybdate aqueous solution, dries, obtain the catalyst carrier presoma containing molybdenum；(3) the catalyst carrier presoma containing molybdenum is placed into Muffle furnace calcining, obtains the catalyst carrier containing molybdenum；(4) solution of ruthenium trichloride is added into catalyst carrier dipping, dries, obtain the catalyst carrier presoma containing ruthenium and molybdenum；(5) the catalyst carrier presoma containing ruthenium and molybdenum is calcined, obtains primary catalyst；(6) primary catalyst is carried out to hydrogen reducing at 250~400 DEG C 4~8 hours, obtains sorbierite aqueous phase hydrogenation catalyst.The present invention suppresses carbon-carbon bond fracture selectivity fracture carbon-oxygen bond, improves the selectivity and activation capacity of the reaction of sorbierite hydrogenation deoxidation by step impregnation method.
Description
Technical field
The invention belongs to the technical field of fuel and chemicals is prepared using biomass and its derivative, and in particular to a kind of
Sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane catalyst and preparation method thereof.
Background technology
Pentane and hexane (C5And C6) as important Organic Chemicals and solvent, it is widely used in medicine, chemical industry, height
The industries such as molecular material, rubber industry, electronics industry and food analysis, as foaming agent, solvent, extractant, cooling agent with
And cleaning agent etc..C5-C6Alkane has the characteristics that low cost, high heating value, easily storage transport as light-hydrocarbon fuel；Add as gasoline
Add agent, can mix in high proportion in motor petrol, suitable for any general-utility car or ethanol petrol automobile, and than traditional second
Alcohol gasoline efficiency is higher.
C5-C6The raw materials for production of alkane are mainly derived from oil plant, are split mostly from direct steaming gasoline, natural gas condensate, hydrogenation
Change and be fractionated into obtaining in tail oil, Reformed Gasoline, raw material depends on non-renewable petroleum resources.At present, seek independent of petrochemical industry
The chemicals substitution of resources of resource, the production line of non-fossil is developed, the dependence for breaking away from limited fossil resource, it has also become state
The inside and outside focus competitively researched and developed.Biomass prepares the regenerative resource of liquid alkane as uniquely a kind of, wherein containing
Abundant cellulose and hemicellulose, sorbierite can be obtained by hydrolyzing and being hydrogenated with means.In recent years, sorbierite turns into new one
For Energy Platform compound, hydrogen, liquid alkane and chemicals can be synthesized by catalytic hydrogenation, aqueous phase reforming technology.Huber
Et al. (Angew Chem Int Ed, 2004,43:1549) it is prepared for a kind of Pt/Al2O3-SiO2Catalyst, can be effectively
Control sorbitol aqueous phase reforming selectivity synthesis C1-C6Alkane, at 225 DEG C, under 3.96MPa, the combined selective of alkane can reach
To 58-89%, the selectivity of wherein pentane and n-hexane is respectively 21% and 40%.Patent CN101671571A discloses one
The method that kind prepares biogasoline using lignocellulose-like biomass as raw material hydrolysis reformation, by filled with catalyst n i/
SiO2-Al2O3Low-temperature reformate reactor and high temperature reformation catalyst converter filled with Ni/HZSM-5 in carry out aqueous catalysis reformation
Reaction, biogasoline and aqueous phase natural separation.Patent CN 101550350A and CN102389832A disclose two kinds with sorbierite
The catalyst and preparation technology of biogasoline are prepared for raw material, molecular sieve HZSM-5 supporting Pts and composite molecular screen is respectively adopted
(HZSM-5 and MCM-41) nickel-loaded is catalyst, can obtain biogasoline product more with high selectivity, and sorbierite highest turns
Rate is up to 73.3%, C5And C6Alkane combined selective is up to 98.6%.
Patent CN103962173A discloses a kind of catalyst and its work that C5-C6 light paraffins are prepared from carbohydrate
Skill, using with double activity center's catalyst：The acid centre of carrier containing Nb and Rh, Pd, Pt, Ir, Ru metal hydrogenation are lived
Property center, realize glucose prepare C5+C6 total recovery reach 60%.Due to molecular sieve HZSM-5, MCM-41 and amorphous
Al2O3-SiO2Deng carrier hydro-thermal unstability, carrier is corroded by hydro-thermal and structure destruction causes catalyst performance and life-span not
It is stable to be not easy to industrial amplification；Non-noble metal Ni easily causes catalyst inactivation to acid-sensitive in solution.
Catalyst needs design effectively to suppress carbon-carbon bond cleavage activity, improves carbon-oxygen bond and is selectively broken, selective obtains
Obtain C5-C6Alkane, acquisition hydrothermally stable, activated centre not easily run off, acidproof and long catalytic life catalyst, are particularly suitable for solid
The amplification application of fixed bed reactor, promote the efficient utilization of biomass resource.
The content of the invention
It is an object of the invention to provide a kind of preparation side of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane catalyst
Method, it is suppressed by step impregnation method, the acid site on regulation and control bimetallic catalyst surface and hydrogenation sites distribution and content
Carbon-carbon bond fracture selectivity fracture carbon-oxygen bond, improve the selectivity and activation capacity of the reaction of sorbierite hydrogenation deoxidation.
It is another object of the present invention to provide a kind of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane catalyst,
It has layer structure feature, and upper strata is Ru hydrogenation sites, and lower floor is the amorphous state MoO of high dispersivexIn/C deoxy activities
The heart；Ru activated centres, which are not easy to be wrapped, in layer structure covers so as to keep highly effective hydrogenation active；Ru and MoOx synergy tables
The characteristics of revealing catalytic activity height, hydrothermally stable, long acidproof and catalyst life, the conversion ratio of sorbierite can be made up to 100%, directly
Chain C5/C6For alkane combined selective up to 90%, the paraffin selectivity of straight chain C 6 reaches 80%, has good industrial applications prospect.
In order to realize foregoing invention purpose, technical scheme is as follows：
A kind of preparation method of the catalyst of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane, comprises the following steps：
(1) preparation of catalyst carrier：Activated carbon is chosen as catalyst carrier, 10~12 are dried at 100~200 DEG C
Hour；
(2) preparation of the catalyst carrier presoma containing molybdenum：Dried activated carbon described in step (1) is added into secondary molybdenum
In sour aqueous ammonium, and dried 10~12 hours at 100~120 DEG C, obtain the catalyst carrier presoma containing molybdenum；
(3) preparation of the catalyst carrier containing molybdenum：Catalyst carrier presoma containing molybdenum described in step (2) is placed
Muffle furnace, 4-8 hours are calcined at 200~600 DEG C under inert atmosphere protection, obtain the catalyst carrier containing molybdenum；
(4) preparation of the catalyst carrier presoma containing ruthenium and molybdenum：Solution of ruthenium trichloride is added described in step (3)
Catalyst carrier, impregnate 10~12 hours, 100~120 DEG C of dryings 10~12 hours, obtain the catalyst carrier containing ruthenium and molybdenum
Presoma；
(5) preparation of primary catalyst：By the catalyst carrier presoma containing ruthenium and molybdenum described in step (4) 200
It is calcined 4~8 hours at~600 DEG C, obtains primary catalyst；
(6) preparation of sorbierite aqueous phase hydrogenation catalyst：By primary catalyst described in step (5) at 250~400 DEG C
Carry out hydrogen reducing 4~8 hours, obtain sorbierite aqueous phase hydrogenation catalyst.
The present invention is by controlling molybdenum and the bimetallic dipping method of ruthenium, impregnation sequence, molybdenum and ruthenium in catalyst preparation process
Between quality composition and ratio, stratiform structure catalyst can be formed, the acid site on regulation and control bimetallic catalyst surface and hydrogenation
Active center distribution and content, suppress carbon-carbon bond fracture selectivity fracture carbon-oxygen bond, improve the choosing of sorbierite hydrogenation deoxidation reaction
Selecting property and activation capacity.
Preferably, molybdenum mass percent in activated carbon is 0.5~50.0% in the step (2).
Further, molybdenum mass percent in activated carbon is 10~30% in the step (2).
Preferably, sintering temperature is 200~600 DEG C under inert atmosphere protection in the step (3), and roasting time is 4~8
Hour.
Further, sintering temperature is 250~400 DEG C under inert atmosphere protection in the step (3).
Preferably, the mass percent of ruthenium load capacity is 0.5~10.0% in the step (4).
Further, the mass percent of ruthenium load capacity is 1~4% in the step (4).
The beneficial effects of the invention are as follows：
(1) present invention is by controlling in catalyst preparation process between bimetallic dipping method, impregnation sequence, molybdenum and ruthenium
Quality composition and ratio, can regulate and control bimetallic catalyst surface acid site and hydrogenation sites distribution and content, suppress
Carbon-carbon bond fracture selectivity fracture carbon-oxygen bond, improve the selectivity and activation capacity of the reaction of sorbierite hydrogenation deoxidation；
(2) in bimetallic layered catalyst of the present invention active component ruthenium in 1~4% catalyst activity,
For active component molybdenum content at 10~30%, the catalyst prepared has the characteristics of high activity and high selectivity, sorbierite
Conversion ratio is up to 100%, straight chain C5/C6For alkane combined selective up to 90%, the paraffin selectivity of straight chain C 6 reaches 80%.
Brief description of the drawings
Fig. 1：Catalyst Cat7 aqueous phase Hydrogenations, which negate, answers gas-phase product distribution map.
Embodiment
With reference to instantiation, the present invention is furture elucidated.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit protection scope of the present invention.The improvement and tune that technical staff makes according to the present invention in actual applications
It is whole, still fall within protection scope of the present invention.
The equipment and reagent used except special instruction, the present invention is the art routine commercial products.
The activity rating of catalyst of the present invention is carried out in continuous high pressure fixed bed reactors, loaded catalyst 5
Gram, so that mass concentration is 20% sorbitol solution as an example, reaction pressure 4.0MPa, reaction temperature is 240~320 DEG C.Production
Thing is detected using gas-chromatography flame ionization ditector (FID) and thermal conductivity detector (TCD) (TCD).
Embodiment 1
100 grams of mesh commercialization absorbent charcoal carriers of graininess 40~60 are weighed to dry 12 hours at 200 DEG C, it is standby.Take 30 grams
Dried activated carbon is put into 60ml degrees in 4.40% molybdenum ammonium solution, to impregnate 10 hours, 100 DEG C of dryings 12
Hour, sample is placed in Muffle furnace 400 DEG C and is calcined 4 hours after drying, and obtains molybdenum load capacity as 5%, i.e., containing single metal molybdenum
Catalyst carrier 5Mo/C；15g catalyst carrier 5Mo/C are then taken out, it is 1.32% ruthenium trichloride to be put into 30ml degrees
In solution, impregnate 12 hours, 120 DEG C of drying 10 hours, sample is placed in Muffle furnace 400 DEG C of roastings 4 hours after drying, and obtains
The 1Ru5Mo/C catalyst of 1% load ruthenium and 5% load molybdenum, gained catalyst are designated as Cat1.
Weigh 4 grams of Cat1 to be filled into continuous high pressure fixed bed reactors, 300 DEG C of hydrogen reduce 6 hours online, in hydrogen
Reacted at 280 DEG C of atmospheric pressure 4.0MPa and reaction temperature, hydrogen flow rate 150ml/min, sorbitol solution 20wt% is molten
Liquid sample introduction flow velocity 0.05ml/min.
Embodiment 2
100 grams of mesh commercialization absorbent charcoal carriers of graininess 40~60 are weighed to dry 12 hours at 200 DEG C, it is standby.Take 30 grams
It is co-impregnation in 4.40% ammonium paramolybdate and 1.32% solution of ruthenium trichloride that dried activated carbon, which is put into 60ml degrees,
10 hours, 100 DEG C of dryings 12 hours, sample was placed in Muffle furnace 400 DEG C and is calcined 4 hours after drying, obtain 1% load ruthenium and
The 1Ru5Mo/C catalyst of 5% load molybdenum, gained catalyst are designated as Cat2.
Weigh 4 grams of Cat2 to be filled into continuous high pressure fixed bed reactors, 300 DEG C of hydrogen reduce 6 hours online, in hydrogen
Reacted at 280 DEG C of atmospheric pressure 4.0MPa and reaction temperature, hydrogen flow rate 150ml/min, sorbitol solution 20wt%, solution
Sample introduction flow velocity 0.05ml/min.
Embodiment 3
100 grams of mesh commercialization absorbent charcoal carriers of graininess 40~60 are weighed to dry 12 hours at 200 DEG C, it is standby.Take 30 grams
Dried activated carbon is put into 60ml degrees in 1.32% solution of ruthenium trichloride, to impregnate 10 hours, 100 DEG C of dryings 12
Hour, sample is placed in Muffle furnace 400 DEG C and is calcined 4 hours after drying, and obtains ruthenium load capacity as 1%, i.e., containing single metal Ru
Catalyst carrier 1Ru/C；15g catalyst carrier 1Ru/C are then taken out, it is 4.40% ammonium paramolybdate to be put into 30ml degrees
In solution, impregnate 12 hours, 120 DEG C of drying 10 hours, sample is placed in Muffle furnace 400 DEG C of roastings 4 hours after drying, and obtains
The 1Ru5Mo/C catalyst of 1% load ruthenium and 5% load molybdenum, gained catalyst are designated as Cat3.
Weigh 4 grams of Cat3 to be filled into continuous high pressure fixed bed reactors, 300 DEG C of hydrogen reduce 6 hours online, in hydrogen
Reacted at 280 DEG C of atmospheric pressure 4.0MPa and reaction temperature, hydrogen flow rate 150ml/min, sorbitol solution 20wt% is molten
Liquid sample introduction flow velocity 0.05ml/min.
Table 1 is the catalyst reaction condition and reaction result that molybdenum is prepared with ruthenium metal difference impregnation sequence in embodiment 1-3,
Specific embodiment 1-3 reaction condition and reaction result is as shown in table 1.
Table 1
Drawn by table 1：The ruthenium molybdenum bimetallic catalyst that molybdenum is prepared with ruthenium metal difference impregnation sequence shows different urge
Agent activity, ruthenium molybdenum impregnates simultaneously and first dipping ruthenium impregnates molybdenum again, because ruthenium hydrogenation sites are wrapped and are covered and shows
Go out relatively low gas phase Auditory steady-state responses；And first impregnate molybdenum and impregnate ruthenium again and form layered catalyst design feature, utilize activated carbon also
Original work are used, and activated carbon and molybdenum salts form amorphous MoO of high dispersive under inert gas roasting effectx/ C is as urging
Agent lower floor carrier, upper strata load Ru hydrogenation sites；Ru activated centres are not easy to be wrapped and covered so as to protect in layer structure
Hold highly effective hydrogenation activity；Show Ru and MoOx synergies again simultaneously；So as to have higher catalytic activity, the production of gas phase alkane
Rate improves about 1 times.
Embodiment 4
100 grams of mesh commercialization absorbent charcoal carriers of graininess 40~60 are weighed to dry 10 hours at 200 DEG C, it is standby.Take 15 grams
Dried activated carbon is put into 30ml degrees in 1.32% solution of ruthenium trichloride, to impregnate 10 hours, 120 DEG C of dryings 10
Hour, sample is placed in Muffle furnace 600 DEG C and is calcined 4 hours after drying, and obtains 1% load 1Ru/C catalyst, gained catalyst
It is designated as Cat4.
Weigh 4 grams of Cat4 to be filled into continuous high pressure fixed bed reactors, 250 DEG C of hydrogen reduce 8 hours online, in hydrogen
Reacted at 280 DEG C of atmospheric pressure 4.0MPa and reaction temperature, hydrogen flow rate 150ml/min, sorbitol solution 20wt% is molten
Liquid sample introduction flow velocity 0.05ml/min.
Embodiment 5
100 grams of mesh commercialization absorbent charcoal carriers of graininess 40~60 are weighed to dry 12 hours at 100 DEG C, it is standby.Take 15 grams
Dried activated carbon is put into 30ml degrees in 0.45% molybdenum ammonium solution, to impregnate 12 hours, 100 DEG C of dryings 12
Hour, sample is placed in Muffle furnace 400 DEG C and is calcined 8 hours after drying, and obtains the catalyst of the 0.5% single metal molybdenum of molybdenum load capacity
Carrier 0.5Mo/C；15g catalyst carrier 0.5Mo/C are then taken out, it is molten for 1.32% ruthenium trichloride to be put into 30ml degrees
In liquid, impregnate 12 hours, 120 DEG C of drying 10 hours, sample is placed in Muffle furnace 400 DEG C of roastings 4 hours after drying, and obtains 1%
The 1Ru0.5Mo/C catalyst of ruthenium and 0.5% load molybdenum is loaded, gained catalyst is designated as Cat5.
Weigh 4 grams of Cat5 to be filled into continuous high pressure fixed bed reactors, 400 DEG C of hydrogen reduce 4 hours online, in hydrogen
Reacted at 280 DEG C of atmospheric pressure 4.0MPa and reaction temperature, hydrogen flow rate 150ml/min, sorbitol solution 20wt% is molten
Liquid sample introduction flow velocity 0.05ml/min.
Embodiment 6
100 grams of mesh commercialization absorbent charcoal carriers of graininess 40~60 are weighed to dry 11 hours at 180 DEG C, it is standby.Take 30 grams
Dried activated carbon is put into 60ml degrees in 0.91% molybdenum ammonium solution, to impregnate 11 hours, 110 DEG C of dryings
10 hours, sample was placed in Muffle furnace 200 DEG C and is calcined 8 hours after drying, and obtained molybdenum load capacity as 1%, i.e., containing single metal molybdenum
Catalyst carrier 1Mo/C；15g catalyst carrier 1Ru/C are then taken out, it is 1.32% tri-chlorination to be put into 30ml degrees
In ruthenium solution, impregnate 12 hours, 120 DEG C of drying 10 hours, sample is placed in Muffle furnace 400 DEG C of roastings 4 hours after drying, and obtains
The 1Ru1Mo/C catalyst of 1% load molybdenum and 1% load ruthenium, gained catalyst are designated as Cat6.
Weigh 4 grams of Cat6 to be filled into continuous high pressure fixed bed reactors, 350 DEG C of hydrogen reduce 5 hours online, in hydrogen
Reacted at 280 DEG C of atmospheric pressure 4.0MPa and reaction temperature, hydrogen flow rate 150ml/min, sorbitol solution 20wt% is molten
Liquid sample introduction flow velocity 0.05ml/min.
Embodiment 7
100 grams of mesh commercialization absorbent charcoal carriers of graininess 40~60 are weighed to dry 10 hours at 150 DEG C, it is standby.Take 30 grams
Dried activated carbon is put into 60ml degrees in 8.43% molybdenum ammonium solution, to impregnate 10 hours, 100 DEG C of dryings 12
Hour, sample is placed in Muffle furnace 200 DEG C and is calcined 8 hours after drying, and obtains molybdenum load capacity as 5%, i.e., containing single metal molybdenum
Catalyst carrier 10Mo/C；15g catalyst carrier 10Mo/C are then taken out, it is 1.32% tri-chlorination to be put into 30ml degrees
In ruthenium solution, impregnate 12 hours, 120 DEG C of drying 10 hours, sample is placed in Muffle furnace 200 DEG C of roastings 4 hours after drying, and obtains
The 1Ru10Mo/C catalyst of 1% load ruthenium and 5% load molybdenum, gained catalyst are designated as Cat7.
Weigh 4 grams of Cat7 to be filled into continuous high pressure fixed bed reactors, 320 DEG C of hydrogen reduce 6 hours online, in hydrogen
Reacted at 280 DEG C of atmospheric pressure 4.0MPa and reaction temperature, hydrogen flow rate 150ml/min, sorbitol solution 20wt% is molten
Liquid sample introduction flow velocity 0.05ml/min.
Fig. 1 shows that catalyst Cat7 aqueous phase Hydrogenations negate and answers gas-phase product distribution map, absolute product in gas-phase product
For linear paraffin, micro other isoparaffins and alkene are comprised only, n-hexane is that primary product accounts for 61.5%, straight chain C5/C6Alkane
Hydrocarbon combined selective is up to 80%.
Embodiment 8~12
Implementation steps and experiment condition with embodiment 1, by molybdenum ammonium solution degree be changed into 12.13%~
31.51%, finally give 1Ru15Mo/C~1Ru50Mo/C catalyst of 1% load ruthenium and 15-50% load molybdenums, gained catalysis
Agent is designated as Cat8-Cat12.
Table 2 be the different molybdenum load capacity of embodiment 4~12 catalyst reaction condition and reaction result, specific embodiment 4~
12 reaction condition and reaction result is as shown in table 2.
Table 2
Drawn by table 2：No matter first how much dipping molybdenum impregnates ruthenium molybdenum content again, ruthenium activated centre is equal in layered catalyst
It is not easy to be wrapped and cover, remains highly effective hydrogenation activity and sorb alcohol conversion；But the load capacity of metal molybdenum is to catalysis
The selectivity of agent has strong influence, when metal molybdenum is supported on more than 10%, straight chain C5/C6Alkane combined selective up to 80% with
On, the paraffin selectivity of straight chain C 6 reaches more than 60%；The metal molybdenum load capacity of optimization is 10~30%.
Embodiment 13
100 grams of mesh commercialization absorbent charcoal carriers of graininess 40~60 are weighed to dry 12 hours at 200 DEG C, it is standby.Take 15 grams
Dried activated carbon is put into 30ml degrees in 21.63% molybdenum ammonium solution, to impregnate 10 hours, 110 DEG C of dryings
11 hours, sample was placed in Muffle furnace 500 DEG C and is calcined 6 hours after drying, and it is 30%, 30Mo/C catalyst to obtain molybdenum load capacity,
Gained catalyst is designated as Cat13.
4 grams of Cat13 are weighed to be filled into continuous high pressure fixed bed reactors, 400 DEG C of hydrogen reduce 8 hours online,
Reacted at 280 DEG C of Hydrogen Vapor Pressure 4.0MPa and reaction temperature, hydrogen flow rate 150ml/min, sorbitol solution 20wt%,
Solution sample introduction flow velocity 0.05ml/min.
Embodiment 14~19
With embodiment 1, difference is that molybdenum ammonium solution degree is 21.63% for implementation steps and experiment condition,
Solution of ruthenium trichloride degree 0.66%~11.76%, finally give 0.5~10% load ruthenium and 30% and load molybdenum
0.5Ru30Mo/C~10Ru30Mo/C catalyst, gained catalyst are designated as Cat14~Cat19 respectively, and wherein Cat10 is
1Ru30Mo/C catalyst.
Table 3 is the reaction condition and reaction result that the different ruthenium content of metal of embodiment 13~19 prepare catalyst, specifically
The reaction condition and reaction result of embodiment 13~19 are as shown in table 3.
Table 3
Drawn by table 3：The load capacity of metal Ru is to straight chain C in molybdenum ruthenium bimetallic layered catalyst5/C6The selectivity of alkane
With significantly affecting；The metal Ru of load 0.5% can promote catalyst activity to improve 1 times；Metal Ru is supported on more than 5%
When, excessive metal Ru shows that short chain alkanes selectivity significantly rises, and shows strong C-C key cleavage activities, other alkane
Hydrocarbon (predominantly C1-C4 alkane) selectivity rises more than 1 times；The metal Ru load capacity of optimization is 1~4%.
Embodiment 20~21
Implementation steps and experiment condition with embodiment 10, distinguish in molybdenum ammonium solution degree be
21.63%, solution of ruthenium trichloride degree 1.32%, sample is placed in Muffle furnace respectively at 250 after step impregnation is dried
DEG C and 600 DEG C be calcined 4 hours, finally give 1% load ruthenium and 30% load molybdenum 1Ru30Mo/C catalyst, gained catalyst
Cat20~Cat21 is designated as respectively.
Table 4 is the reaction condition and reaction result that embodiment 10,20~21 different sintering temperatures of embodiment prepare catalyst,
Specific embodiment 8, the reaction condition of embodiment 20~21 and reaction result are as shown in table 4.
Table 4
Drawn by table 4：Too high sintering temperature can cause amorphous Ru-MoO of high dispersivex/ C catalyst molybdenum and ruthenium gold
Category occurs aggregation and forms obvious crystalline structure, so as to the catalytic activity reduced, causes the decline of gas phase alkane yield；Optimization
Sintering temperature be 250~400 DEG C.
Embodiment 22~25
With embodiment 6, catalyst takes 1% load ruthenium and 1% in embodiment 6 to load molybdenum for implementation steps and condition
1Ru1Mo/C catalyst Cat6.
Weigh 4 grams of Cat6 to be filled into continuous high pressure fixed bed reactors, 350 DEG C of hydrogen reduce 5 hours online, in hydrogen
Reacted at 240-320 DEG C of atmospheric pressure 4.0MPa and reaction temperature, hydrogen flow rate 150ml/min, sorbitol solution
20wt%, solution sample introduction flow velocity 0.05ml/min.
Table 5 is the reaction condition and reaction result at a temperature of the differential responses of embodiment 6, embodiment 22~25, specific real
It is as shown in table 5 to apply example 6, the reaction condition of embodiment 22~25 and reaction result.
Table 5
Drawn by table 5：With the raising of reaction temperature, catalyst activity gradually steps up；But too high reaction temperature can be led
The raising of cause cracking catalyst activity, other alkane yields (predominantly C1-C4 alkane) are selective close to 50%.
Above-listed detailed description is illustrating for possible embodiments of the present invention, and the embodiment simultaneously is not used to limit this hair
Bright the scope of the claims, all equivalence enforcements or change without departing from carried out by the present invention, it is intended to be limited solely by the scope of patent protection of this case
In.
Claims (7)
1. a kind of preparation method of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane catalyst, it is characterised in that including following
Step：
(1) preparation of catalyst carrier：Activated carbon is chosen as catalyst carrier, it is small that 10~12 are dried at 100~200 DEG C
When；
(2) preparation of the catalyst carrier presoma containing molybdenum：Dried activated carbon described in step (1) is added into quality containing molybdenum
Percentage be 0.5~50.0% the ammonium paramolybdate aqueous solution in, and at 100~120 DEG C dry 10~12 hours, obtain containing molybdenum
Catalyst carrier presoma；
(3) preparation of the catalyst carrier containing molybdenum：Catalyst carrier presoma containing molybdenum described in step (2) is placed into Muffle
Stove, it is calcined 4~8 hours at 200~600 DEG C under inert atmosphere protection, obtains the catalyst carrier containing molybdenum；
(4) preparation of the catalyst carrier presoma containing ruthenium and molybdenum：By the trichlorine that mass percent containing ruthenium is 0.5~10.0%
Change ruthenium solution and add the catalyst carrier containing molybdenum described in step (3), impregnate 10~12 hours, 100~120 DEG C of dryings 10~12
Hour, obtain the catalyst carrier presoma containing ruthenium and molybdenum；
(5) preparation of primary catalyst：By the catalyst carrier presoma containing ruthenium and molybdenum described in step (4) 200~600
It is calcined 4~8 hours at DEG C, obtains primary catalyst；
(6) preparation of sorbierite aqueous phase hydrogenation catalyst：Primary catalyst described in step (5) is carried out at 250~400 DEG C
Hydrogen reducing 4~8 hours, obtain sorbierite aqueous phase hydrogenation catalyst.
2. the preparation method of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane catalyst according to claim 1, it is special
Sign is that the mass percent of molybdenum load capacity is 10~30% in the step (2).
3. the preparation method of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane catalyst according to claim 1, it is special
Sign is that sintering temperature is 200~600 DEG C under inert atmosphere protection in the step (3), and calcination time is 4~8 hours.
4. the preparation method of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane catalyst according to claim 3, it is special
Sign is that sintering temperature is 250~400 DEG C under inert atmosphere protection in the step (3).
5. the preparation method of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane catalyst according to claim 1, it is special
Sign is that the mass percent of ruthenium load capacity is 1~4% in the step (4).
6. the catalysis of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane prepared by the preparation method described in a kind of claim 1
Agent, it is characterised in that the catalyst accounts for carrier matter using activated carbon as carrier, using molybdenum and ruthenium as double activated metal, the molybdenum
It is 0.5~50.0% to measure percentage, and the mass percent of the ruthenium load capacity is 0.5~10.0%.
7. the catalyst of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane according to claim 6, it is characterised in that
It is 10~30% that the molybdenum, which accounts for carrier quality percentage, and the mass percent of the ruthenium load capacity is 1~4%.
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| CN201510897305.1A CN105289601B (en) | 2015-12-07 | 2015-12-07 | A kind of sorbierite aqueous phase Hydrogenation cut-off chain C5/C6 alkane catalyst and preparation method thereof |
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| CN105597752B (en) * | 2015-12-22 | 2018-03-09 | 中国科学院广州能源研究所 | C5, the load type carbon material catalyst of C6 alkane and preparation method thereof are produced in a kind of sugar alcohol selective hydrogenation deoxidation |
| CN106987285B (en) * | 2017-03-20 | 2019-03-01 | 中国科学院广州能源研究所 | A kind of method that multi phase state prepares high alcohol bio-fuel |
| CN110229058B (en) * | 2019-07-18 | 2021-08-03 | 重庆理工大学 | Method for preparing propionic acid by catalytic conversion of lactic acid |
| CN110862342B (en) * | 2019-11-13 | 2021-10-29 | 天津利安隆新材料股份有限公司 | Preparation method of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate |
| CN112010726B (en) * | 2020-08-20 | 2023-02-24 | 中国科学院广州能源研究所 | Method for selectively preparing micromolecular alkane by catalyzing cellulose |
| CN113145146B (en) * | 2021-03-05 | 2023-03-07 | 广东工业大学 | Molybdenum carbide-molybdenum oxide catalyst and preparation method and application thereof |
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