CN105597752A - Supported carbon material catalyst for preparing C5 and C6 alkane through sugar alcohol selective hydrodeoxygenation and preparation method for catalyst - Google Patents

Supported carbon material catalyst for preparing C5 and C6 alkane through sugar alcohol selective hydrodeoxygenation and preparation method for catalyst Download PDF

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Publication number
CN105597752A
CN105597752A CN201510979448.7A CN201510979448A CN105597752A CN 105597752 A CN105597752 A CN 105597752A CN 201510979448 A CN201510979448 A CN 201510979448A CN 105597752 A CN105597752 A CN 105597752A
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catalyst
sugar alcohol
carbon material
carrier
load type
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CN105597752B (en
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王铁军
翁育靖
马隆龙
仇松柏
陈伦刚
张琦
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/652—Chromium, molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
    • C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2527/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
    • C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2527/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
    • C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2527/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • C07C2527/19—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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    • C10G2400/02—Gasoline
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Abstract

The invention relates to a supported carbon material catalyst for preparing C5 and C6 alkane through sugar alcohol selective hydrodeoxygenation. One of active carbon, graphene and a carbon nanotube is taken as a catalyst carrier and Ru is taken as active metal; and a first additive or a second additive is added, wherein the first additive is selected from one or two of Mo, Re and W oxides, the second additive is phosphorus, Ru accounts for 1-5wt% of the carrier, and phosphorus accounts for 2-20wt% of the carrier. According to the catalyst, the active carbon, the graphene or the carbon nanotube is taken as the carrier and a metal active center and the additive are introduced by step with an impregnation method after acidification treatment. The catalyst is used for sugar alcohol aqueous phase hydrodeoxygenation and has very good reaction activity and stability; and the sugar alcohol conversion rate is 100% and the C5 and C6 alkane selectivity reaches up to 80%.

Description

A kind of sugar alcohol selective hydrogenation deoxidation is produced C5, load type carbon material catalyst of C6 alkane and preparation method thereof
Technical field
The invention belongs to catalytic field and chemical technology field, be specifically related to a kind of sugar alcohol selective hydrogenation deoxidationProduce C5, load type carbon material catalyst of C6 alkane and preparation method thereof.
Background technology
Although the fossil resources such as current oil, coal, natural gas are still the main source of liquid fuel, its toolThere is obvious dependent resource. The day by day sternness of fossil resource supply conditions and being on the rise of environmental problem,Force us to find the new type resource that can replace or supplement current energy general layout, at present biomass resourceBe considered to substitute the optimal selection of fossil resource. Saccharide compound is called again carbohydrate, is led to by plantCrossing photosynthesis natural synthetic, is the type organic that distributed in nature is the most extensive, quantity is maximum. Wherein haveVegeto-animal construction unit, such as cellulose, hemicellulose, chitin etc., also has energy unit, such asGlycogen, starch, chrysanthemum root powder etc. They by hydrolysis and oxygenation means can obtain sugar (be mainly glucose withWood sugar) or sugar alcohol (being mainly sorbierite and xylitol). These sugar/sugar alcohols are considered to biomass energy of new generationHardware and software platform compound, can synthesize hydrogen, alkane and chemicals by catalysis hydro-denitrification or aqueous phase reforming technology.
In the world, Dumesic and Huber (AngewChemIntEd, 2004,43:1549) first proposePrepare the new method of C5, C6 alkane by sugar alcohol hydrogenation deoxidation, prepared a kind of Pt/Si02-A1203Catalyst,Can effectively sugar alcohol be converted into C1～C6 alkane (C5, C6 paraffin selectivity reach 60%), thus emergingPlay a kind of development of living beings liquid alkane technology.
Domesticly prepare C5/C6 alkane technology at sugar alcohol and be also studied simultaneously and develop. Wherein, China speciallyProfit CN101550350A discloses a kind of preparation method and catalyst of biogasoline, and its feature is with mountainPears alcohol solution is raw material, adopts carried noble metal Pt/HZM-5 catalyst, at miniature paste state bed reactorIn carry out hydrogenation deoxidation reaction, obtain compared with the C5/C6 alkane of high selectivity. In addition, in order to substitute noble metalCatalyst, Chinese patent CN102389832 discloses a kind of common metal Ni catalyst, and carrier isThe complex form of HZSM-5 and MCM-41. Expensive and the reserves rareness of precious metals pt on the one hand,And in use loss of active component and carbon distribution, cause catalyst cost relatively high, make its industry shouldUse and be subject to certain restrictions. Although sieve and silica-sesquioxide or molecular sieve can provide as carrier on the one hand in additionAcidic site is to be conducive to the dehydration of hydroxyl. But under thermal and hydric environment, sieve and silica-sesquioxide or molecular sieve are wantedFace the problems such as hydrothermal stability deficiency and aluminium loss, thereby cause catalyst stability poor, for catalysisThe development and application of agent is a large obstacle.
Summary of the invention
The object of the present invention is to provide a kind of sugar alcohol selective hydrogenation deoxidation to produce C5, the support type of C6 alkaneMaterial with carbon element catalyst, has very good reactivity and stability, sugar for sugar alcohol water hydrogenation deoxidationAlcohol conversion is 100%, C5, and C6 paraffin selectivity, up to 80%, has solved carried catalyst hydro-thermal simultaneouslyThe technical barrier of poor stability.
Another object of the present invention is to provide a kind of sugar alcohol selective hydrogenation deoxidation to produce C5, C6 alkaneThe preparation method of load type carbon material catalyst, introduces metal active with infusion process substep after acidified processingCenter and auxiliary agent, energy consumption is low, technical process is simple, is easy to the popularization of suitability for industrialized production.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
C5 is produced in a kind of sugar alcohol selective hydrogenation deoxidation, the load type carbon material catalyst of C6 alkane, described in urgeThe structural formula of agent is A-Z1-Z2/C or A-Z1/C, and support C is with in active carbon, Graphene and CNTOne as catalyst carrier, component A is metal Ru, auxiliary agent Z1 is selected from one in Mo, Re and WKind, auxiliary agent Z2 is phosphorus, and the mass percent that described metal Ru accounts for carrier is 1～5%, and described auxiliary agent Z1 accounts forThe mass percent of carrier is 2～20%, and the mass percent that described phosphorus accounts for carrier is 2～20%.
Preferably, described metal Ru is 1:0.5～1:2 with the atomic molar ratio of described Mo or Re or W.
The present invention passes through with the good metal Ru of the catalyst carrier load resistance to acids and bases of the good modification of hydro-thermalBe main active sites, improve metal Ru's by the oxide that adds Mo, Re or W as auxiliary agent simultaneouslyElectronics, the methanation activity of inhibition metal Ru, improves the selective of liquid alkane.
A kind of sugar alcohol selective hydrogenation deoxidation is produced C5, the preparation side of the load type carbon material catalyst of C6 alkaneMethod, comprises the following steps:
(1) taking the one in active carbon, Graphene and CNT as carrier, by carrier mass percentBe that more than 30% phosphoric acid solution stirs 1～8h at 60～120 DEG C, washing, and dry at 80～150 DEG CDry;
(2) by the carbon carrier dipping ruthenium trichloride solution obtaining in step (1), keep metal Ru contentAt 1～5wt%, roasting, obtains Ru-P/C catalyst;
(3) add step (2) to make in Ru-P/C catalyst described the first auxiliary agent, mixture is dryProcess;
(4) by the drying sample obtaining in step (3) in 300～420 DEG C of hydrogen reducing 2～8h, obtain instituteState sugar alcohol hydrogenation deoxidation load type carbon material catalyst.
Preferably, described in step (2), the step of roasting is: by described catalyst carrier incipient impregnation threeRuthenic chloride solution, after ultrasonic processing or stir process 1～8h, 80～150 DEG C dry, at nitrogen or argon gasLower 300～420 DEG C of roastings.
Preferably, in step (3) by ultrasonic described mixture processing or stir process 1～8h, 80～150 DEG CDry.
Preferably, the first auxiliary agent described in step (3) is selected from the one in the oxide of Mo, Re and WOr two kinds.
Preferably, to account for the mass percent of carrier be 2～20% to described phosphorus.
The present invention also protects load type carbon material catalyst to produce C5 in sugar alcohol selective hydrogenation deoxidation, C6 alkaneApplication, utilize the load type carbon material catalyst catalysis sugar alcohol hydrogenation deoxygenation prepared in the present invention can beAt low pressure and lower temperature, carry out, energy consumption is low, technical process is simple and easy to control, has good industrial applicationsProspect.
A kind of load type carbon material catalyst is produced C5 in sugar alcohol selective hydrogenation deoxidation, the application of C6 alkane,Described load type carbon material catalyst is the reaction of catalysis sugar/sugar alcohol generation hydrogenation deoxidation in hydrothermal system, and sugar alcohol existsUnder the effect of load type carbon material catalyst, hydrogenolysis occurs and finally generate C5/C6 alkane, reaction is at batch (-type)In autoclave or continous way trickle bed reactor, carry out 250～360 DEG C of reaction temperatures, Hydrogen Vapor Pressure1～10MPa. Liquid volume air speed is at 0.1～5.0h-1Between, gas volume air speed is at 1000～5000h-1Between.The product that hydrogenolysis generates adopts gas-chromatography flame ionization ditector (FID) and thermal conductivity detector (TCD)(TCD) detect.
Preferably, described sugar alcohol be selected from glucose solution, xylose solution, sorbitol solution, xylitol solution,One or more in Ismotic, described sugar/sugar alcohol aqueous solution mass concentration is 10～60%. Sugar alcohol canBy high-content of starch plant, as potato, fermentation or hydrolysis make, and have broken away from existing liquid fuel and have producedDependence to oil in technique.
Preferably, described C5, C6 alkane are pentane and hexane and their isomers, are selected from 2-methylpentOne or more in alkane, 3-methylpentane, methyl cyclopentane, cyclohexane and pentamethylene.
The invention has the beneficial effects as follows:
(1) the present invention is taking active carbon, Graphene, CNT as carrier, and these carbon material surfaces have prosperityMicrocellular structure, hydrophobicity is strong, acidified and oxidation processes can have very strong selective absorption performance;
(2) catalyst that the present invention proposes has very good reactivity for sugar alcohol water hydrogenation deoxidationAnd stability, sugar alcohol conversion ratio is 100%, C5, C6 paraffin selectivity is up to 80%.
Detailed description of the invention
Below in conjunction with instantiation, further illustrate the present invention. Should be appreciated that, these embodiment are only for sayingBright the present invention, and be not intended to limit the scope of the invention. Technical staff is according to this in actual applicationsThe bright improvement of making and adjustment, still belong to protection scope of the present invention.
Except special instruction, the equipment that the present invention uses and reagent are the conventional commercial product of the art. ActiveCharcoal is purchased from Huaneng Group, Tangshan science and technology Tan Ye Co., Ltd, and Graphene and CNT are purchased from the organic institute in Chinese Academy of Sciences ChengduEpoch nanosecond science and technology Co., Ltd of middle section, the present invention's phosphoric acid solution used is that chemical analysis is pure.
Embodiment 1
A kind of sugar alcohol selective hydrogenation deoxidation is produced C5, the preparation side of the load type carbon material catalyst of C6 alkaneMethod, comprises the following steps:
Claim 5g active carbon (70-120 order) to add in round-bottomed flask, then slowly add 100mL phosphoric acid moltenLiquid (85wt%), 100mL deionized water and stirring magneton, then condensation reflux unit on round-bottomed flask,Place it in and in oil bath pan, heat and keep magneton to stir 450 revs/min, 90 DEG C of constant temperature of oil bath are processed 5h, coldBut normal temperature, filtration washing, filter cake, with after deionized water washing 3 times, is put into 120 DEG C of dried overnight of drying box,Can obtain phosphoric acid and process the absorbent charcoal carrier of activation.
Take 2 grams of phosphoric acid and process the absorbent charcoal carrier of activation, incipient impregnation ruthenium trichloride (Ru content 37%,RuCl3.xH2O:0.05g) solution, after ultrasonic processing 1h leave standstill 8h, then in baking oven 120 DEG C be driedNight, then put into 400 DEG C of roastings of nitrogen muffle furnace, be cooled to after room temperature, then incipient impregnation ammonium heptamolybdate (MoContent 54%, (NH4)6Mo7O24.4H2O:0.04g) solution, leaves standstill 8h after ultrasonic processing 1h, then dryingIn case, 120 DEG C are spent the night, and gained catalyst is designated as Cat1 (Ru load capacity is 1%, Ru:Mo=1:1).
Get dried catalyst 4mL and pack reaction tube into, before and after beds, add respectively silica wool and fill outMaterial (quartz sand), then connects device, passes into hydrogen intensification and prepares reduction, and 320 DEG C of reduction are spent the night. SugarThere is hydrogenolysis and finally generate C5/C6 alkane in alcoholic solution, reaction under the effect of load type carbon material catalystIn continous way trickle bed reactor, carry out 320 DEG C of reaction temperatures, Hydrogen Vapor Pressure 4MPa. Liquid volume skySpeed is at 0.1～5.0h-1Between, gas volume air speed is at 1000～5000h-1Between. The product that hydrogenolysis generatesThing adopts gas-chromatography flame ionization ditector (FID) and thermal conductivity detector (TCD) (TCD) to detect.
In the present embodiment, sugar alcohol solution is sorbitol solution, and its mass concentration is 20%. Activity in the present inventionCharcoal is purchased from Huaneng Group, Tangshan science and technology Tan Ye Co., Ltd, and model is HN-Y14,70-120 order.
Embodiment 2
Identical with embodiment 1, difference is:
The quality of the ammonium molybdate of incipient impregnation is 0.08g, and the mass concentration of sorbitol solution is 10%.
Embodiment 3
Identical with embodiment 1, difference is:
The mass concentration of sorbitol solution is 40%.
Embodiment 4
Identical with embodiment 1, difference is:
The mass concentration of sorbitol solution is 20%, 280 DEG C of reaction temperatures, and reaction pressure is 2MPa.
Embodiment 5
Identical with embodiment 1, difference is:
The mass concentration of sorbitol solution is 20%, 300 DEG C of reaction temperatures.
Embodiment 6
Identical with embodiment 1, difference is:
Sugar alcohol solution is glucose solution, and the mass concentration of glucose solution is 20%.
Embodiment 7
Identical with embodiment 1, difference is:
Sugar alcohol solution is xylose solution, and the mass concentration of xylose solution is 20%.
Embodiment 8
Identical with embodiment 1, difference is:
Sugar alcohol solution is xylitol solution, and the mass concentration of xylitol solution is 20%.
Embodiment 9
Identical with embodiment 1, difference is:
When Activated Carbon Pretreatment, be to add 50mL phosphoric acid solution (85wt%) and 100mL deionized water to mixStir condensing reflux. Sugar alcohol solution is sorbitol solution, and the mass concentration of sorbitol solution is 20%.
Embodiment 10
Claim that 2g Graphene adds in round-bottomed flask, then slowly add 100mL phosphoric acid solution (85wt%),100mL deionized water and stirring magneton, then condensation reflux unit on round-bottomed flask, places it in oil bathIn pot, heat and keep magneton to stir 450 revs/min, 90 DEG C of constant temperature of oil bath are processed 5h, and cooling normal temperature filtersWashing, filter cake, with after deionized water washing 3 times, is put into 120 DEG C of dried overnight of drying box, can obtain phosphoric acidProcess the absorbent charcoal carrier of activation.
Take 2 grams of phosphoric acid and process the absorbent charcoal carrier of activation, incipient impregnation ruthenium trichloride (Ru content 37%,RuCl3.xH2O:0.05g) solution, after ultrasonic processing 1h leave standstill 8h, then in baking oven 120 DEG C be driedNight, then put into 400 DEG C of roastings of nitrogen muffle furnace, be cooled to after room temperature, then the preparation of incipient impregnation ammonium molybdate(Ru-Mo/GC), after ultrasonic processing 1h leave standstill 8h, then in baking oven 120 DEG C spend the night, gained catalystBe designated as Cat10.
Course of reaction is identical with embodiment 1,320 DEG C of reaction temperatures, Hydrogen Vapor Pressure 4MPa, sorbitol solutionMass concentration be 20%.
Embodiment 11
Claim that 2g CNT adds in round-bottomed flask, then slowly add 100mL phosphoric acid solution (85wt%),100mL deionized water and stirring magneton, then condensation reflux unit on round-bottomed flask, places it in oil bathIn pot, heat and keep magneton to stir 450 revs/min, 90 DEG C of constant temperature of oil bath are processed 5h, and cooling normal temperature filtersWashing, filter cake, with after deionized water washing 3 times, is put into 120 DEG C of dried overnight of drying box, can obtain phosphoric acidProcess the absorbent charcoal carrier of activation.
Take 2 grams of phosphoric acid and process the absorbent charcoal carrier of activation, incipient impregnation ruthenium trichloride (Ru content 37%,RuCl3.xH2O:0.05g) solution, after ultrasonic processing 1h leave standstill 8h, then in baking oven 120 DEG C be driedNight, then put into 400 DEG C of roastings of nitrogen muffle furnace, be cooled to after room temperature, then the preparation of incipient impregnation ammonium molybdate(Ru-Mo/CNT), after ultrasonic processing 1h leave standstill 8h, then in baking oven 120 DEG C spend the night, gained catalysisAgent is designated as Cat11.
Course of reaction is identical with embodiment 1,320 DEG C of reaction temperatures, Hydrogen Vapor Pressure 4MPa, sorbitol solutionMass concentration be 20%.
Embodiment 12
Identical with embodiment 11, difference is:
The Ru-P/CNT preparing is incipient impregnation ammonium perrhenate (Ru-ReP/CNT) solution again. Sugar alcohol is moltenLiquid is sorbitol solution, and the mass concentration of sorbitol solution is 20%.
Embodiment 13
Identical with embodiment 1, difference is:
The Ru-P/C preparing is incipient impregnation ammonium metatungstate (Ru-WP/CNT) solution again. Sugar alcohol solution is mountainPears alcoholic solution, the mass concentration of sorbitol solution is 20%.
Comparative example 1
Identical with embodiment 1, difference is:
When Activated Carbon Pretreatment, be add 100mL salpeter solution (60wt%) and 50mL deionized water and stirMix, then condensing reflux. Sugar alcohol solution is sorbitol solution, and the mass concentration of sorbitol solution is 20%.
Embodiment reaction condition and reaction result are in table 1.
Can see from the experimental result of embodiment 1 and embodiment 10-13, this RuMoP/C catalyst not onlyThere is better alkane yield, under identical condition, its target product selective also more superior. From implementingThe contrast and experiment of example 1～3 and embodiment 6-8 can find out, this catalyst system and catalyzing is not for variable concentrations andSugar alcohol raw material of the same type has good catalytic effect. In addition, in conjunction with the embodiments 4, embodiment 5 is not forThe investigation of carrying out with reaction condition, different reaction pressures all have a certain impact, but best reaction condition(320 DEG C, 4MPa). Embodiment 1 and embodiment 9 and comparative example 1 are pretreated to catalyst carrierJourney phosphorus acid content and different liquids acid investigation can find out, the acid-treated reaction effect of phosphorus of high concentrationBetter. The contrast that embodiment 10 and 11 carries out can be found out, although CNT (CNT) and Graphene(GC) not high as the catalyst alkane overall yield of carrier, but target alkane is selectively fine. ImplementExample 12, embodiment 13 has investigated for different auxiliary agent Z1 compositions, finds that Re is the same with Mo with W,On the reaction effect of these catalyst, there is no too large difference with Ru-MoP/AC. In a word, the present invention is in low pressureAt lower temperature, carry out, energy consumption is low, technical process is simple and easy to control, has good industrial applications prospect.
Above-listed detailed description is for the illustrating of possible embodiments of the present invention, and this embodiment is not in order to limitMake the scope of the claims of the present invention, the equivalence that all the present invention of disengaging do is implemented or is changed, and all should be contained in thisIn the scope of patent protection of case.

Claims (10)

1. a C5 is produced in sugar alcohol selective hydrogenation deoxidation, the load type carbon material catalyst of C6 alkane, its featureBe, the structural formula of described catalyst is A-Z1-Z2/C or A-Z1/C, and support C is with active carbon, GrapheneAs catalyst carrier, component A is metal Ru with the one in CNT, auxiliary agent Z1 be selected from Mo,One in Re and W, auxiliary agent Z2 is phosphorus, the mass percent that described metal Ru accounts for carrier is 1～5%,The mass percent that described auxiliary agent Z1 accounts for carrier is 2～20%, and the mass percent that described phosphorus accounts for carrier is2～20％。
2. sugar alcohol selective hydrogenation deoxidation according to claim 1 is produced C5, the load type carbon material of C6 alkaneMaterial catalyst, is characterized in that, described metal Ru with the atomic molar ratio of described Mo or Re or W is1:0.5～1:2。
3. the sugar alcohol selective hydrogenation deoxidation described in claim 1 or 2 is produced a C5, the support type of C6 alkaneThe preparation method of material with carbon element catalyst, is characterized in that, comprises the following steps:
(1) taking the one in active carbon, Graphene and CNT as carrier, by carrier mass percentFor phosphoric acid solution more than 30wt% stirs 1～8h at 60～120 DEG C, washing, and dry at 80～150 DEG CDry oven dry;
(2) by the carbon carrier dipping ruthenium trichloride solution obtaining in step (1), keep metal Ru contentAt 1～5wt%, roasting, obtains Ru-P/C catalyst;
(3) add step (2) to make in Ru-P/C catalyst described the first auxiliary agent, mixture is dryProcess;
(4) by the drying sample obtaining in step (3) in 300～420 DEG C of hydrogen reducing 2～8h, obtain instituteState sugar alcohol hydrogenation deoxidation load type carbon material catalyst.
4. sugar alcohol selective hydrogenation deoxidation according to claim 3 is produced C5, the load type carbon material of C6 alkaneThe preparation method of material catalyst, is characterized in that, described in step (2), the step of roasting is: described in inciting somebody to action, urgeAgent carrier incipient impregnation ruthenium trichloride solution, after ultrasonic processing or stir process 1～8h, 80～150 DEG CDry, 300～420 DEG C of roastings under nitrogen or argon gas.
5. sugar alcohol selective hydrogenation deoxidation according to claim 3 is produced C5, the load type carbon material of C6 alkaneThe preparation method of material catalyst, is characterized in that, in step (3) by ultrasonic described mixture processing or stirMix and process 1～8h, 80～150 DEG C dry.
6. sugar alcohol selective hydrogenation deoxidation according to claim 3 is produced C5, the load type carbon material of C6 alkaneMaterial catalyst preparation method, it is characterized in that, the first auxiliary agent described in step (3) be selected from Mo, Re andOne or both in the oxide of W.
7. sugar alcohol selective hydrogenation deoxidation according to claim 3 is produced C5, the load type carbon material of C6 alkaneThe preparation method of material catalyst, is characterized in that, the mass percent that described phosphorus accounts for carrier is 2～20%.
8. load type carbon material catalyst claimed in claim 1 is produced a C5 in sugar alcohol selective hydrogenation deoxidation,The application of C6 alkane, is characterized in that, described load type carbon material catalyst in hydrothermal system catalysis sugar/The reaction of sugar alcohol generation hydrogenation deoxidation there is hydrogenolysis and generates in sugar alcohol under the effect of load type carbon material catalystC5/C6 alkane, reaction is carried out in intermittent high-pressure reactor or continous way trickle bed reactor, reaction temperature250～360 DEG C, Hydrogen Vapor Pressure 1～10MPa.
9. load type carbon material catalyst according to claim 8 is produced C5 in sugar alcohol selective hydrogenation deoxidation,The application of C6 alkane, is characterized in that, it is molten that described sugar alcohol is selected from glucose solution, xylose solution, sorbieriteOne or more in liquid, xylitol solution, Ismotic, described sugar/sugar alcohol aqueous solution mass concentrationBe 10～60%.
10. load type carbon material catalyst according to claim 8 is produced C5 in sugar alcohol selective hydrogenation deoxidation,The application of C6 alkane, is characterized in that, described C5, C6 alkane are pentane and hexane and their isomeryBody, is selected from a kind of or several in 2-methylpentane, 3-methylpentane, methyl cyclopentane, cyclohexane and pentamethyleneKind.
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