CN104772141A - Preparation method and use of catalyst for glucose hydrogenolysis preparation of low carbon dihydric alcohol - Google Patents
Preparation method and use of catalyst for glucose hydrogenolysis preparation of low carbon dihydric alcohol Download PDFInfo
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- CN104772141A CN104772141A CN201410018520.5A CN201410018520A CN104772141A CN 104772141 A CN104772141 A CN 104772141A CN 201410018520 A CN201410018520 A CN 201410018520A CN 104772141 A CN104772141 A CN 104772141A
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Abstract
The invention discloses a preparation method and use of a catalyst for glucose hydrogenolysis preparation of low carbon dihydric alcohol. The preparation method comprises the following steps of pre-treating a catalyst carrier, dipping the pre-treated catalyst carrier in an assistant metal solution, dipping the assistant metal-loaded catalyst carrier in an active metal solution, and feeding hydrogen into the catalyst carrier for reduction so that the catalyst for glucose hydrogenolysis preparation of low carbon dihydric alcohol is obtained. The preparation method has simple processes, low cost and high efficiency. In glucose catalytic hydrogenolysis, the catalyst can control and adjust glucose carbon chain breaking position and degree and has high activity and high low-carbon dihydric alcohol selectivity. The invention also discloses a use of the catalyst in glucose catalytic hydrogenolysis. The catalyst can be used for glucose hydrogenolysis catalysis and especially in glucose catalytic hydrogenolysis in a high pressure continuous fixed bed, an intermittent tank reactor and a hypergravity revolving bed.
Description
Technical field
The invention belongs to field of catalyst preparation, particularly a kind of preparation method and application thereof that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols.
Background technology
Along with day by day exhausted, environmental pollution increasingly severe of fossil resources, the exploitation of biomass energy and use impact on energy resource consumption, environmental protection and economic benefit own profound.The current catalyst for biomass conversion all adopts conventional impregnation to prepare usually, although this preparation method is easy and simple to handle, but exist obtained particle size differ, disperse uneven, metal surface utilization rate is low, cause conversion ratio and selective not high, catalytic effect is undesirable.In addition, for improving catalytic effect, the overwhelming majority needs to add acid/alkali as promoter, and this can cause corrosion to equipment, and increases production cost.These drawbacks of catalyst greatly limit its application.Especially prepare in low-carbon (LC) dihydroxylic alcohols field in glucose hydrogenolysis, these drawbacks of catalyst make to utilize glucose hydrogenolysis to prepare low-carbon (LC) dihydroxylic alcohols cannot realize scale.
The patent of the published catalyst for biomass conversion mainly contains at present:
1, a kind of structured ruthenium catalyst and preparation method thereof, CN101850249A; By being flooded or excessive dipping with containing ruthenium compound solution even by ordered structure nano-carbon fibre carrier, at room temperature aging, then dry, finally reduction obtains the ruthenium catalyst be carried on ordered structure carbon nano-fiber; This catalyst can be used for carrying out hydrogenolysis on sorbierite and prepares ethylene glycol and propane diols; The conversion ratio about about 50% of sorbierite, conversion ratio is not high.
2, plate-type carbon fiber supported ruthenium catalyst and its preparation method and application, CN101347731; By by the process of carbon nanofibers vector purification, flood carbon nanofibers, at room temperature age overnight with containing ruthenium compound solution even, and then 80 ~ 120 DEG C dry 6 ~ 12 hours, finally reduction obtains the catalyst of carried metal material; This catalyst also can be used for hydrogenolysis of sorbitol reaction and prepares ethylene glycol and propane diols; The conversion ratio about about 50% of sorbierite, conversion ratio is not high.
3, a kind of nickel/copper catalyst and preparation method thereof and use this catalyst directly to prepare the method for 1,2-hexylene glycol by cellulosan, CN103055870A; First prepare carrier active carbon and ethylenediamine nickel, ethylenediamine conjunction copper respectively, then fully mixing by ethylenediamine being closed copper solution, ethylenediamine nickel solution and active carbon, adding NaBH afterwards
4solution ice bath reacts, and obtains catalyst; Or close copper through incipient impregnation on the activated carbon by ethylenediamine nickel, ethylenediamine, reduce after roasting, obtain catalyst; This catalyst can carry out catalysis and directly prepare 1,2-hexylene glycol by cellulosan; Yield is 30 ~ 50%, and conversion ratio is not high.
4, ruthenium catalyst, its preparation method and the application in tetrahydrobiopterin synthesis furfuryl alcohol thereof, CN102489315A; First add carrier TiO to containing ruthenium saline solution or in the aqueous solution containing ruthenium salt and metal promoter salt
2, backward mixed liquor in add potassium borohydride or hydrazine hydrate solution, obtain catalyst; This catalyst application is at furfural one step hydrogenation synthesis tetrahydrofurfuryl alcohol; Yield can be greater than 99%; But need to add sodium sulphate and carry out hydrothermal treatment consists as solvent in preparation process, the introducing of sodium ion can affect catalyst performance.
6, a preparation method for activated carbon supported noble metal catalyst, CN102658133A; By active carbon is processed in the disodium EDTA aqueous solution, stir in the nitrate solution containing noble metal or the chlorate aqueous solution more afterwards, add alkaline aqueous solution adjust pH and continue to stir, finally with hydrazine hydrate or hydrogen reducing, obtain catalyst; This catalyst can be used on catalytic hydrogenation synthesis DSD acid; But in preparation process, processed by active carbon in the disodium EDTA aqueous solution, and adopt the alkaline solution such as NaOH, potassium hydroxide to regulate pH value in reaction, the metal ion of introducing can affect the performance of catalyst.
7, nickel/ruthenium catalyst and the method for aqueous phase reactions, CN1246077; This catalyst be the particle formed by porous carrier on this porous carrier, deposit some provide the reduced nickel metal catalytic of catalyst activity as the first decentralized photo, this particle is added in addition a kind of ruthenium metal on this porous carrier as the second decentralized photo, its quantity can make nickel-metal catalyst phase anti-agglomeration or sintering effectively, extends the life-span of catalyst in hydrogenation reaction; But the reaction condition adopted is 350 DEG C, 340atm, reaction temperature is slightly high and pressure is comparatively large, causes energy consumption and potential safety hazard.
8、Tungsten carbide catalyst supported on mesoporous carbon,preparation andapplication thereof,EP2495042A1。
The patent that published carbohydrate prepares dihydroxylic alcohols at present mainly contains:
1, the preparation method of dihydroxylic alcohols, CN101781166; Be in the basic conditions, carry out hydrogenolysis glucose with Raney's nickel, ruthenium/carbon, nickel/ruthenium or copper oxide-zinc oxide as hydrogenolysis catalyst; Corrosive equipment under alkali condition, under 10MPa ~ 13MPa, carry out reaction can produce potential safety hazard.
2, the preparation method of dihydroxylic alcohols, CN101781171; Be in the basic conditions, carry out hydrogenolysis glucose with the nickel-molybdenum-copper of chromium-doped or iron, tin, zinc as hydrogenolysis catalyst; Corrosive equipment under alkali condition, under 10MPa ~ 13MPa, carry out reaction can produce potential safety hazard.
3, a preparation method for low-carbon polyol, CN102020531; With non-noble metal Ni-W
2c/CNFs carrys out hydrogenolysis carbohydrate as hydrogenolysis catalyst; Low-carbon (LC) dihydroxylic alcohols total recovery is no more than 30%, selective not high.
4, stalk hydrolysis sugar liquid prepares a method for small molecule polyol, CN102898278; First as catalyst, solubility liquid glucose is hydrogenated into sugar alcohol solution with Raney's nickel, then the hydrocracking that heats up is to generating small molecule polyol; Low-carbon (LC) dihydroxylic alcohols total recovery is no more than 32%, selective not high.
5, the preparation method of dihydroxylic alcohols, CN101781170; With the mixture of sorbierite and sweet mellow wine as raw material, the nickel-molybdenum-copper of chromium-doped or iron, tin, zinc carrys out hydrogenolysis mixing sugar alcohol as hydrogenolysis catalyst; Catalytic amount is 3% ~ 10% of total combined aqueous phase, and use amount is excessive, easily causes the wasting of resources and water pollution.
6, the synthetic method of dihydroxylic alcohols and polyalcohol, CN101781168; With sucrose as raw material, the nickel-molybdenum-copper of chromium-doped or iron, tin, zinc takes hydrogenolysis sucrose as hydrogenolysis catalyst; Catalytic amount is 15% ~ 30% of sucrose quality, and use amount is excessive, easily causes the wasting of resources and water pollution.
7, the synthetic method of dihydroxylic alcohols and polyalcohol, CN101781167; With sucrose as raw material, Raney's nickel, ruthenium/carbon, nickel/ruthenium or copper oxide-zinc oxide take hydrogenolysis sucrose as hydrogenolysis catalyst; Catalytic amount is 15% ~ 30% of sucrose quality, and use amount is excessive, easily causes the wasting of resources.
Therefore, the preparation method exploring the new catalyst being used for glucose hydrogenolysis low-carbon (LC) dihydroxylic alcohols is significant.
Summary of the invention
First technical problem that the present invention will solve is to provide a kind of preparation method that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols; By first carrying out pretreatment to catalyst carrier, afterwards by pretreated catalyst carrier used additives metallic solution dipping; Again by the catalyst carrier of load promoter metal active metal solution impregnation; Finally logical hydrogen reducing, obtains can be used for the catalyst that glucose hydrogenolysis prepares low-carbon (LC) dihydroxylic alcohols; This preparation method is simple to operate, and cost is low, and efficiency is high, the catalyst position that controllable glucose carbochain disconnects when catalysis glucose and degree and active high, to the selective height of low-carbon (LC) dihydroxylic alcohols.
Second technical problem that the present invention will solve is to provide the application that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols, catalytic hydrogenolysis glucose response should be can be used to containing the catalyst of various metals component, be particularly useful for the continuous fixed bed of high pressure, batch tank reactor and high-gravity rotating bed middle catalytic hydrogenolysis glucose response.
The invention provides a kind of preparation method that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
1) pretreatment is carried out to catalyst carrier;
2) by pretreated catalyst carrier used additives metallic solution dipping;
3) by the catalyst carrier of load promoter metal active metal solution impregnation;
4) logical hydrogen reducing, obtains can be used for the catalyst that glucose hydrogenolysis prepares low-carbon (LC) dihydroxylic alcohols;
Wherein, described pretreatment is one or more mixture process catalyst carriers in ammonia spirit with the neat solvent of the neat solvent of the neat solvent of the neat solvent of PEG-200 or the aqueous solution, PEG-400 or the aqueous solution, PEG-600 or the aqueous solution, triton x-100 or the aqueous solution, EDTA, lemon aqueous acid.
Preferably, described promoter metal solution is one or more the aqueous solution in W, Mo, Zr, Al, Co; Described active metal solution is the aqueous solution of Ru and/or Ni.Pretreated catalyst carrier used additives metallic solution equal-volume or excessive dipping, the catalyst carrier active metal solution equal-volume of load promoter metal or excessive dipping.
Preferably, the mass ratio of described catalyst carrier and promoter metal is 1:0.05 ~ 0.5.The very few object that cannot reach regulation activity catalytic performance of promoter metal; Cross and easily cover active sites at most, reduce catalytic performance.The mass ratio of described catalyst carrier and active metal is 1:0.005 ~ 0.2.Active metal crosses that I haven't seen you for ages makes active sites not enough, reduces catalytic performance; Cross and easily reunite at most, reduce catalytic performance equally.
Preferably, described catalyst carrier is silica, active carbon or carbon fiber.
More preferably, described catalyst carrier is 20 ~ 40 order silica, 20 ~ 40 order active carbons or 50nm ~ 15 μm carbon fiber.Select 20 ~ 40 object silica and active carbon as carrier, the adverse effect of bed pressure drop and interior diffusion can be avoided; Adopt the carbon fiber of 50nm ~ 15 μm as carrier, can form larger specific area, conventional carbon fiber of comparing makes carrier, and it has significant structural advantage in commercial Application.
Preferably, in step 1), to the pretreatment of catalyst carrier be:
I is by catalyst carrier purifying;
Catalyst carrier after purifying is placed in preprocessing solution by II, and heating, obtains mixed liquor;
III, by mixed liquor suction filtration, vacuumizes, and dry, roasting, obtains pretreated catalyst carrier.
Can understand, the consumption, concentration etc. of preprocessing solution are without the need to limiting.
Preferably, described I catalyst carrier purifying is:
The purifying of silica: air atmosphere, 150 ~ 250 DEG C of calcined silica 2 ~ 3h;
The purifying of active carbon: nitrogen atmosphere, 150 ~ 250 DEG C of calcining active carbon 2 ~ 3h;
The purifying of carbon fiber: carbon fiber is placed in 50 ~ 120mL nitric acid, 60 ~ 90 DEG C are heated 2 ~ 3h and condensing reflux, then that phegma is dry.
Preferably, in the purifying of carbon fiber, phegma drying be by phegma at 100 ~ 150 DEG C in air or nitrogen atmosphere dry 6 ~ 12h.Temperature is too low, the time too shortly all cannot reach drying effect; Temperature is too high, overlong time then can make the speed except desolventizing too fast, has a negative impact to catalyst structure, stability.
Preferably, in described II, be heated to be: at 80 ~ 120 DEG C of heating 1 ~ 10h.Temperature is too low, the time too shortly all cannot reach pretreating effect; Temperature is too high, overlong time all then can make preprocessing solution at place's Formed class materials such as catalyst ducts, has a negative impact to metal impregnation, dispersion.
Preferably, in described III:
Suction filtration, vacuumize into:
By mixed liquor at room temperature suction filtration 1 ~ 3h, take out filter residue, vacuumize 1 ~ 2h; The suction filtration time is too short cannot reach suction filtration effect, and the suction filtration overlong time then easy pre-treatment solvents that will enter carrier duct is extracted out, affects pretreating effect; Vacuumize 1 ~ 2h and can drive gas in carrier hole most possibly out of, ensure content of metal;
Drying is:
At 100 ~ 150 DEG C of vacuum drying 6 ~ 15h; Temperature is too low, the time too shortly all cannot reach drying effect; Temperature is too high, overlong time then can make the speed except desolventizing too fast, has a negative impact to catalyst structure, stability;
Roasting is:
Silica: air atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h;
Active carbon: nitrogen atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h;
Carbon fiber: nitrogen atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h; Temperature is too low, the time too shortly all cannot reach roasting effect (that is, make the catalyst finally obtained have stable catalytic performance and obtain certain crystal formation, grain size, gap structure and specific surface, improving the mechanical strength of catalyst); Temperature is too high, overlong time then easy-sintering, makes carrier surface area not increase counter subtracting.
Preferably, step 2) in, after catalyst carrier used additives metallic solution is flooded, vacuumize, dry, roasting; Wherein,
Drying is: at 100 ~ 150 DEG C of drying 6 ~ 15h; Temperature is too low, the time too shortly all cannot reach drying effect; Temperature is too high, overlong time then can make the speed except desolventizing too fast, has a negative impact to catalyst structure, stability; Drying is carried out in atmosphere.
Roasting is:
Silica: air atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h;
Active carbon: nitrogen atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h;
Carbon fiber: nitrogen atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h; Temperature is too low, the time too shortly all cannot reach roasting effect (that is, make finally to obtain catalyst have stable catalytic performance and obtain certain crystal formation, grain size, gap structure and specific surface, improve the mechanical strength of catalyst); Temperature is too high, overlong time catalyst then easy-sintering, makes its surface area not increase counter subtracting.
Preferably, in step 3), by the catalyst carrier of load promoter metal with after active metal solution impregnation, vacuumize, dry, roasting; Wherein,
Drying is: at 100 ~ 150 DEG C of drying 6 ~ 15h; Temperature is too low, the time too shortly all cannot reach drying effect; Temperature is too high, overlong time then can make the speed except desolventizing too fast, has a negative impact to catalyst structure, stability; Drying is carried out in atmosphere.
Roasting is:
Silica: air atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h;
Active carbon: nitrogen atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h;
Carbon fiber: nitrogen atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h; Temperature is too low, the time too shortly all cannot reach roasting effect (that is, make the catalyst finally obtained have stable catalytic performance and obtain certain crystal formation, grain size, gap structure and specific surface, improving the mechanical strength of catalyst); Temperature is too high, overlong time catalyst then easy-sintering, makes its surface area not increase counter subtracting.
Further, in step 4), in hydrogen atmosphere, 300 ~ 500 DEG C of reduction 6 ~ 12h.Temperature is too low, the time too shortly all cannot reach activation effect; The Structure and stability that temperature is too high, overlong time then easily affects catalyst.
The invention provides a kind of application that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols, described catalyst can be used to catalytic hydrogenolysis glucose response.
Preferably, during catalytic hydrogenolysis glucose response, the concentration of D/W is 2 ~ 50wt%.
Preferably, it can be used for the continuous fixed bed of high pressure, batch tank reactor and high-gravity rotating bed middle catalytic hydrogenolysis glucose response; More preferably, it can be used for the continuous fixed bed of high pressure, high-gravity rotating bed middle catalytic hydrogenolysis glucose response.
Preferably, when described catalyst is used for high pressure continuous fixed-bed catalytic hydrogenolysis glucose response, process conditions are: temperature 175 ~ 215 DEG C, pressure 3 ~ 5MPa, and liquid air speed is 1 ~ 300h
-1;
When described catalyst is used for batch tank reactor catalysis hydrogenolysis glucose response, process conditions are: temperature 195 ~ 215 DEG C, pressure 3 ~ 5MPa, and liquid air speed is 1 ~ 300h
-1, rotating speed 1400 ~ 1800r/min;
When described catalyst is used for high-gravity rotating bed catalytic hydrogenolysis glucose response, process conditions are: temperature 195 ~ 215 DEG C, pressure 3 ~ 5MPa, and liquid air speed is 1 ~ 500h
-1, rotating speed 200 ~ 1500r/min.
Traditional living beings hydrogenation carries out in intermittent kettle reactor, reaction is slurry bed system pattern, by in disposable to hydrogen, glucose solution and catalyst input reactor, due to the impact of catalyst performance, most catalyst needs to add acid/alkaline accelerator to promote the carrying out of hydrogenation reaction.
In fixed bed reaction, react for trickle bed pattern, make material liquid pass slowly beds by the effect of gravity, product also departs from beds by gravity.Solid catalyst then adopts silica wool to be fixed.Because the time of staying is controlled, therefore by the degree of regulation and control raw material hydrogenolysis chain rupture, finally reach the object of regulation and control product distribution.The method has better continuity and operability compared to batch still reaction.
In high-gravity rotating bed reaction, become more tiny drop by rotating after raw material enters reactor, thus increase with the contact effect of beds, and departed from catalyst by centrifugal force, considerably increase mass-transfer efficiency.Supergravity reactor makes the time of staying of reacting have the minimizing of the order of magnitude in running, but the ratio that hydrogen is dissolved in the liquid phase of reaction simultaneously considerably increases, thus promotes the carrying out of hydrogenation chain-breaking reaction.And by adjustment rotating speed, the selection of one section of best results can be there is between the time of staying and mass transfer rate.Supergravity reactor can select vertical and horizontal two kinds.
Beneficial effect of the present invention is as follows:
1, by controlling specific operation condition, the preprocessing solutions such as polyethylene glycol, triton x-100, EDTA, citric acid are adopted to carry out pretreatment to carrier surface, change kind and the quantity (mainly creating the oxy radicals such as carboxyl, acid anhydrides, carbonyl) of carrier surface functional group, thus improve the decentralization of metallic particles, improve the utilization rate of metallic, finally reach the object of regulation and control distribution of reaction products (i.e. hydrogenation chain rupture degree);
2, in catalyst preparation process, add promoter metal, can regulate the Acidity of catalyst, regulation and control acid site quantity, finally reaches the object for regulating and controlling glucose hydrogenation chain rupture degree during catalysis glucose;
3, simple to operate, cost is low, and efficiency is high, is applicable to large-scale production, adopts environmental protection class preprocessing solution to avoid environmental pollution;
When 4, using catalyst glucose of the present invention, only raw materials of glucose need be dissolved in the water, relative to glucose being dissolved in dimethyl sulfoxide (DMSO), valerolactone equal solvent, can be cost-saving and there is high-dissolvability; Mass concentration is selected within 50%, can avoid glucose feed problem such as coking in reactor; And active high, to the selective height of low-carbon (LC) dihydroxylic alcohols;
5, during catalysis glucose hydrogenolysis, without the need to adding any alkaline accelerator, also drop to minimum to the damage of equipment in fixed bed, batch still and revolving bed three kinds of reactors;
When 6, using catalyst glucose of the present invention, can take not only cerelose as raw material, fermentation industry can also be used, as the industry etc. that brews alcoholic beverages, the polyalcohol be rich in, aldehyde, acid accessory substance even waste material as raw material, prepare with traditional polyalcohol compared with the fossil resources such as the multiplex oil and natural gas of Raw, effectively can utilize living beings, and can greatly increase economic efficiency.
Detailed description of the invention
For understanding the present invention better, will further illustrate the solution of the present invention below by specific embodiment, protection scope of the present invention should comprise the full content of claim, but is not limited thereto.
Inversion rate of glucose (%)=(in 1-product glucose carbon molal quantity/raw material in carbon molal quantity) × 100
Glycol selectivity (the %)=carbon molal quantity of the glucose of the carbon molal quantity/participation reaction of ethylene glycol (in the product) × 100
Propane diols selective (the %)=carbon molal quantity of the glucose of the carbon molal quantity/participation reaction of propane diols (in the product) × 100
Butanediol selective (the %)=carbon molal quantity of the glucose of the carbon molal quantity/participation reaction of butanediol (in the product) × 100
Ethylene glycol yield (%)=(in product ethylene glycol carbon molal quantity/raw material in carbon molal quantity) × 100
Propane diols yield (%)=(in product propane diols carbon molal quantity/raw material in carbon molal quantity) × 100
Butanediol yield (%)=(in product butanediol carbon molal quantity/raw material in carbon molal quantity) × 100
Embodiment 1
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
1, the pretreatment of silica supports
I takes 5g silica, at 200 DEG C, is placed on roasting 2h in air atmosphere, takes out after being cooled to room temperature, be transferred in there-necked flask;
II adds the pure solution of 80mL PEG-200 in flask, uses electric heating cover to be warming up to 120 DEG C, is cooled to room temperature after heating 2h;
III at room temperature uses Buchner funnel suction filtration 1h, and take out filter residue, vacuumize 1h, be then placed in vacuum drying chamber, vacuum drying 10h at 120 DEG C, finally at 500 DEG C, roasting 2h in air atmosphere, encapsulates stand-by after being cooled to room temperature.
2, load promoter metal on silica
1. get a certain amount of ammonium metatungstate precursor to be dissolved in deionized water and to be mixed with ammonium metatungstate aqueous solution, with the load factor of 10wt%W SiO after treatment
2equivalent impregnation on carrier;
2. after dipping, vacuumize 1h, then dry 10h in air atmosphere at 120 DEG C, afterwards at 500 DEG C in air atmosphere roasting 2h, successfully load to the pretreated SiO of PEG-200 by promoter metal W
2on carrier.
3, supported active metals on silica
1) by a certain amount of RuCl
3nH2O precursor is dissolved in deionized water prepares RuCl
3the aqueous solution, at the SiO of the above-mentioned W of load
2with the load factor equivalent impregnation of 1wt%Ru on carrier;
2) with 2 2., Ru-W/SiO is obtained
2(PEG-200) catalyst (1wt%Ru-10wt%W).
4, activating catalyst
This catalyst is reduced at 500 DEG C in hydrogen atmosphere 10h, obtain the catalyst after activation (1wt%Ru-10wt%W).
Carry out phenetic analysis to the catalyst after activation, average grain diameter is 2nm, is uniformly dispersed, soilless sticking.
Comparative example 1
With embodiment 1, change is:
Without any pre-treatment step.
Finally, the catalyst (1wt%Ru-10wt%W) after activating is obtained.
Carry out phenetic analysis to the catalyst after activation, average grain diameter is 10nm, there is agglomeration.
Embodiment 2
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
1, the pretreatment of active carbon AC
I takes 5g active carbon, at 200 DEG C, is placed on roasting 2h in nitrogen atmosphere, takes out after being cooled to room temperature, be transferred in there-necked flask;
II adds the pure solution of 80mL PEG-400 in flask, uses electric heating cover to be warming up to 120 DEG C, is cooled to room temperature after heating 2h;
III at room temperature uses Buchner funnel suction filtration 1h, and take out filter residue, vacuumize 1h, be then placed in vacuum drying chamber, vacuum drying 10h at 120 DEG C, finally at 500 DEG C, roasting 2h in nitrogen atmosphere, encapsulates stand-by after being cooled to room temperature.
2, load promoter metal on the activated carbon
1. get a certain amount of ammonium molybdate precursor to be dissolved in deionized water and to be mixed with ammonium molybdate aqueous solution, with equivalent impregnation on the load factor of 10wt%Mo AC carrier after treatment;
2., after dipping, 1h is vacuumized; Then, dry 10h in air atmosphere at 120 DEG C; After drying, at 500 DEG C in nitrogen atmosphere roasting 2h, successfully load on the pretreated AC carrier of PEG-400 by promoter metal Mo.
3, supported active metals on the activated carbon
1) a certain amount of Nickelous nitrate hexahydrate precursor is dissolved in deionized water prepares nickel nitrate aqueous solution, with the load factor equivalent impregnation of 10wt%Ni on the AC carrier of the above-mentioned W of load;
2) with 2 2., Ni-Mo/AC (PEG-400) catalyst (10wt%Ni-10wt%Mo) is obtained.
4, activating catalyst
With embodiment 1, obtain the catalyst (10wt%Ni-10wt%Mo) after activating.
Comparative example 2
With embodiment 2, change is:
Without any pre-treatment step.
Finally, the catalyst (10wt%Ni-10wt%Mo) after activating is obtained.
Embodiment 3
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
1, the pretreatment of carbon fiber CNFs
I takes 5g carbon fibre carrier and is placed in there-necked flask, adds 80mL salpeter solution in flask, uses electric heating cover to be warming up to 80 DEG C, and heating 2h is also cooled to room temperature after condensing reflux; And then, at 120 DEG C in air atmosphere dry 10h;
II adds the pure solution of 80mL PEG-600 in flask, uses electric heating cover to be warming up to 120 DEG C, is cooled to room temperature after heating 2h;
III is with embodiment 1.
2, load promoter metal on carbon fiber
1. get a certain amount of zirconyl nitrate precursor to be dissolved in deionized water and to be mixed with the zirconium nitrate aqueous solution, with equivalent impregnation on the load factor of 15wt%Zr CNFs carrier after treatment;
2., after dipping, 1h is vacuumized; Then, dry 10h in air atmosphere at 120 DEG C; After drying, at 500 DEG C in nitrogen atmosphere roasting 2h, successfully load on the pretreated CNFs carrier of PEG-600 by auxiliary agent zirconia.
3, supported active metals on carbon fiber
1) by a certain amount of RuCl
3nH
2o precursor is dissolved in deionized water prepares RuCl
3the aqueous solution, at the SiO of the above-mentioned Zr of load
2with the load factor equivalent impregnation of 2wt%Ru on carrier;
2) with 2 2., Ru-Zr/CNFs (PEG-600) catalyst is obtained.
4, activating catalyst
With embodiment 1, obtain the catalyst (2wt%Ru-15wt%Zr) after activating.
Embodiment 4
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
With embodiment 1, change is:
1, add the pure solution of 80mL TX-100 and carry out pretreatment.
2, get a certain amount of ANN aluminium nitrate nonahydrate precursor to be dissolved in deionized water and to be mixed with aluminum nitrate aqueous solution, with the load factor of 20wt%Al SiO after treatment
2equivalent impregnation on carrier; Obtain the SiO of load Al
2carrier.
3, a certain amount of Nickelous nitrate hexahydrate precursor is dissolved in deionized water prepares nickel nitrate aqueous solution, at the SiO of load Al
2with the load factor equivalent impregnation of 15wt%Ni on carrier; Obtain Ni-Al/SiO
2(TX-100) catalyst.
Finally, the catalyst (15wt%Ni-20wt%Al) after activating is obtained.
Embodiment 5
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
With embodiment 2, change is:
1, in flask, add the ammonia spirit (10wt%EDTA) of 80mL EDTA, use electric heating cover to be warming up to 90 DEG C, heating 2h.
2, get a certain amount of cobalt nitrate precursor to be dissolved in deionized water and to be mixed with cobalt nitrate aqueous solution, with equivalent impregnation on the load factor of 20wt%Co AC carrier after treatment; Obtain the AC carrier of load C o.
3, by RuCl
3nH
2o precursor is dissolved in deionized water prepares RuCl
3the aqueous solution, with the load factor equivalent impregnation of 1wt%Ru on the AC carrier of above-mentioned load C o; Obtain Ru-Co/AC (10wt%EDTA) catalyst.
Finally, the catalyst (1wt%Ru-20wt%Co) after activating is obtained.
Embodiment 6
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
With embodiment 3, change is:
1, in flask, add 80mL lemon aqueous acid (10wt% citric acid), use electric heating cover to be warming up to 90 DEG C, heating 2h.
2, get a certain amount of ammonium metatungstate precursor to be dissolved in deionized water and to be mixed with ammonium metatungstate aqueous solution, with equivalent impregnation on the load factor of 15wt%W CNFs carrier after treatment; Obtain the CNFs carrier of load W.
3, a certain amount of Nickelous nitrate hexahydrate precursor is dissolved in deionized water prepares nickel nitrate aqueous solution, with the load factor equivalent impregnation of 15wt%Ni on the CNFs carrier of the above-mentioned W of load;
Ni-W/CNFs (10wt% citric acid) catalyst.
Finally, the catalyst (15wt%Ni-15wt%W) after activating is obtained.
Embodiment 7
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
With embodiment 1, change is:
1, in flask, add the PEG-200 aqueous solution of 80mL80V%.
2, get a certain amount of ammonium molybdate precursor to be dissolved in deionized water and to be mixed with ammonium molybdate aqueous solution, with the load factor of 15wt%Mo SiO after treatment
2equivalent impregnation on carrier.
Finally, the catalyst (1wt%Ru-15wt%Mo) after activating is obtained.
Embodiment 8
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
With embodiment 2, change is:
1, in flask, add the PEG-200 aqueous solution of 80mL60V%.
2, get a certain amount of zirconyl nitrate precursor to be dissolved in deionized water and to be mixed with the zirconium nitrate aqueous solution, with equivalent impregnation on the load factor of 20wt%Zr AC carrier after treatment.
Finally, the catalyst (10wt%Ni-20wt%Zr) after activating is obtained.
Embodiment 9
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
With embodiment 3, change is:
1, in flask, add the PEG-200 aqueous solution of 80mL40V%.
2, get a certain amount of ANN aluminium nitrate nonahydrate precursor to be dissolved in deionized water and to be mixed with aluminum nitrate aqueous solution, with equivalent impregnation on the load factor of 10wt%Al CNFs carrier after treatment.
Finally, the catalyst (2wt%Ru-10wt%Al) after activating is obtained.
Embodiment 10
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
With embodiment 5, change is:
1, in flask, add ammonia spirit (20wt%EDTA) solution of 80mL EDTA.
2, with equivalent impregnation on the load factor of 10wt%Co AC carrier after treatment.
3, a certain amount of Nickelous nitrate hexahydrate precursor is dissolved in deionized water prepares nickel nitrate aqueous solution, with the load factor equivalent impregnation of 15wt%Ni on the AC carrier of above-mentioned load C o.
Finally, the catalyst (15wt%Ni-10wt%Co) after activating is obtained.
Embodiment 11
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
With embodiment 6, change is:
1, in flask, add 80mL lemon aqueous acid (20wt% citric acid).
3, by RuCl
3nH
2o precursor is dissolved in deionized water prepares RuCl
3the aqueous solution, with the load factor equivalent impregnation of 2wt%Ru on the CNFs carrier of load W.
Finally, the catalyst (2wt%Ru-15wt%W) after activating is obtained.
Embodiment 12
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
With embodiment 2, change is: first, gets a certain amount of ammonium metatungstate precursor and is dissolved in deionized water and is mixed with ammonium metatungstate aqueous solution, with equivalent impregnation on the load factor of 10wt%W AC carrier after treatment; Then according to operating process dipping 10wt%Mo and 10wt%Ni of embodiment 2; Finally obtain the catalyst (10wt%Ni-10wt%Mo-10wt%W) after activating.
Embodiment 13
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
With embodiment 7, change is: first, gets a certain amount of ammonium metatungstate precursor and is dissolved in deionized water and is mixed with ammonium metatungstate aqueous solution, with the load factor of 10wt%W SiO after treatment
2equivalent impregnation on carrier.Then according to operating process dipping 15wt%Mo and 1wt%Ru of embodiment 7; Finally obtain the catalyst (1wt%Ru-15wt%Mo-10wt%W) after activating.
Embodiment 14
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
With embodiment 11, change is: first, according to the operating process dipping 15wt%W of embodiment 11; Get a certain amount of Nickelous nitrate hexahydrate precursor to be afterwards dissolved in deionized water and to be mixed with nickel nitrate aqueous solution, with the load factor equivalent impregnation of 10wt%Ni on CNFs carrier after treatment; Finally according to the operating process dipping 2wt%Ru of embodiment 11; Finally obtain the catalyst (2wt%Ru-10wt%Ni-15wt%W) after activating.
Embodiment 15
Can be used for the application that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols:
Raw materials of glucose be dissolved in the water, add catalyst of the present invention, and carry out catalytic reaction according to the experiment condition in table 1,3,5, catalytic result is in table 2,4,6.
1, the continuous fixed bed reactors of high pressure
The reaction condition of table 1 fixed bed reactors
| Numbering | Temperature (DEG C) | Pressure (MPa) | Catalyst quality (g) | Concentration of glucose (wt%) | Liquid phase air speed (h -1） |
| Embodiment 1 | 205 | 4 | 0.5 | 50 | 4 |
| Embodiment 2 | 195 | 5 | 0.5 | 5 | 300 |
| Comparative example 2 | 205 | 4 | 0.5 | 5 | 300 |
| Embodiment 3 | 215 | 3 | 1 | 2 | 40 |
| Embodiment 4 | 205 | 4 | 1 | 10 | 40 |
| Embodiment 5 | 215 | 5 | 1 | 2 | 5 |
| Embodiment 6 | 195 | 3 | 0.5 | 10 | 30 |
| Embodiment 7 | 205 | 5 | 0.5 | 2 | 40 |
| Embodiment 8 | 215 | 4 | 1 | 5 | 40 |
| Embodiment 9 | 205 | 3 | 1 | 5 | 50 |
| Embodiment 10 | 215 | 5 | 1 | 2 | 40 |
| Embodiment 11 | 195 | 4 | 0.5 | 5 | 30 |
| Embodiment 12 | 205 | 5 | 0.5 | 10 | 40 |
| Embodiment 13 | 205 | 5 | 0.5 | 5 | 40 |
| Embodiment 14 | 215 | 4 | 1 | 10 | 40 |
The catalytic result evaluation table of table 2 fixed bed reactors
2, batch tank reactor
The reaction condition of table 3 intermittent kettle reactor
| Numbering | Temperature (DEG C) | Pressure (MPa) | Catalyst quality (g) | Concentration of glucose (wt%) | Rotating speed (r/min) |
| Embodiment 1 | 205 | 4 | 0.5 | 10 | 1400 |
| Embodiment 2 | 215 | 5 | 1 | 5 | 1600 |
| Comparative example 2 | 195 | 5 | 1 | 5 | 1800 |
| Embodiment 3 | 215 | 3 | 0.5 | 2 | 1400 |
| Embodiment 4 | 195 | 4 | 1 | 50 | 1600 |
| Embodiment 5 | 205 | 5 | 1 | 5 | 1800 |
| Embodiment 6 | 195 | 3 | 0.5 | 5 | 1400 |
| Embodiment 7 | 205 | 5 | 0.5 | 2 | 1400 |
| Embodiment 8 | 215 | 4 | 1 | 10 | 1600 |
| Embodiment 9 | 205 | 3 | 0.5 | 5 | 1800 |
| Embodiment 10 | 195 | 5 | 1 | 2 | 1400 |
| Embodiment 11 | 195 | 4 | 0.5 | 5 | 1600 |
| Embodiment 12 | 205 | 5 | 1 | 2 | 1400 |
| Embodiment 13 | 205 | 3 | 0.5 | 5 | 1800 |
| Embodiment 14 | 215 | 4 | 1 | 10 | 1400 |
The catalytic result evaluation table of table 4 intermittent kettle reactor
3, rotating packed bed reactor
The reaction condition of table 5 rotating packed bed reactor
The catalytic result evaluation table of table 6 rotating packed bed reactor
" low-carbon (LC) dihydroxylic alcohols " comprises ethylene glycol, propane diols and butanediol.It is wherein, selective in propane diols and butanediol that what have comparative advantage is 1,2-PD and 1,2-butanediol respectively.As can be seen from table 2,4,6, in product except low-carbon (LC) dihydroxylic alcohols, also comprise sorbierite, xylitol, antierythrite, other polyols such as (sweet mellow wine, 5 hydroxymethyl furfural, BT) and glycerine.Wherein, xylitol and antierythrite selective far below low-carbon (LC) dihydroxylic alcohols, the productive rate of glycerine is between xylitol and antierythrite, and the content of 5 hydroxymethyl furfural, BT is extremely low.
As can be seen from table 2,4, the catalytic result of 6, Ni-based, ruthenium-based catalyst all embodies different conversion ratio and selective in three kinds of different reactors.Therefore, for different operating conditions and object product, fixed bed reactors, intermittent kettle reactor and rotary drill reactor respectively have superiority.
Embodiment 16
Can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, comprise the following steps:
1) pretreatment is carried out to catalyst carrier:
I is by catalyst carrier purifying;
Catalyst carrier after purifying is placed in preprocessing solution by II, and heating, obtains mixed liquor;
III, by mixed liquor suction filtration, vacuumizes, and dry, roasting, obtains pretreated catalyst carrier.
2) by pretreated catalyst carrier used additives metallic solution dipping;
3) by the catalyst carrier of load promoter metal active metal solution impregnation;
4) logical hydrogen reducing, obtains can be used for the catalyst that glucose hydrogenolysis prepares low-carbon (LC) dihydroxylic alcohols;
Described catalyst carrier is silica.Described preprocessing solution is the mixture (volume ratio 1:1) of the neat solvent of PEG-200 and the neat solvent of PEG-400.Described promoter metal solution is the aqueous solution of W, Mo; Described active metal solution is the aqueous solution of Ru.The mass ratio of described catalyst carrier and promoter metal is 1:0.05; The mass ratio of described catalyst carrier and active metal is 1:0.005.
Embodiment 17
With embodiment 16, difference is:
Described catalyst carrier is 20 order silica.Described preprocessing solution is the mixture (volume ratio 1:3) of the neat solvent of PEG-600 and the neat solvent of triton x-100.Described promoter metal solution is the aqueous solution of Zr, Co; Described active metal solution is the aqueous solution of Ni.The mass ratio of described catalyst carrier and promoter metal is 1:0.5; The mass ratio of described catalyst carrier and active metal is 1:0.2.
Embodiment 18
With embodiment 16, difference is:
Described catalyst carrier is 40 order silica.Described preprocessing solution is the aqueous solution of PEG-600 and the mixture (volume ratio 2:3) of lemon aqueous acid.Described promoter metal solution is the aqueous solution of Co; Described active metal solution is the aqueous solution of Ni.The mass ratio of described catalyst carrier and promoter metal is 1:0.25; The mass ratio of described catalyst carrier and active metal is 1:0.1.
Catalyst is used for high-gravity rotating bed catalytic hydrogenolysis glucose response, and process conditions are: temperature 215 DEG C, pressure 3MPa, and liquid air speed is 500h
-1, rotating speed 200r/min.
Embodiment 19
With embodiment 16, difference is:
Described catalyst carrier is 20 order active carbons.
In I: purifying: nitrogen atmosphere, 150 DEG C of calcining active carbon 2h.
In II: be heated to be: at 80 DEG C of heating 1h;
In III: by mixed liquor at room temperature suction filtration 1h, take out filter residue, vacuumize 1h; Drying is: at 100 DEG C of vacuum drying 6h; Roasting is: nitrogen atmosphere, 300 DEG C of roasting 2h.
2), in, after catalyst carrier used additives metallic solution is flooded, vacuumize, dry, roasting; Wherein, drying is: at 100 DEG C of dry 6h; Roasting is: nitrogen atmosphere, 300 DEG C of roasting 2h.
3), in, by the catalyst carrier of load promoter metal with after active metal solution impregnation, vacuumize, dry, roasting; Wherein, drying is: at 100 DEG C of dry 6h; Roasting is: nitrogen atmosphere, 300 DEG C of roasting 2h.
4) in, in hydrogen atmosphere, 300 DEG C of reduction 6h.
Catalyst is used for high-gravity rotating bed catalytic hydrogenolysis glucose response, and process conditions are: temperature 195 DEG C, pressure 5MPa, and liquid air speed is 1h
-1, rotating speed 1500r/min.
Embodiment 20
With embodiment 16, difference is:
Described catalyst carrier is 30 order active carbons.
In I: purifying: nitrogen atmosphere, 250 DEG C of calcining active carbon 3h.
In II: be heated to be: at 120 DEG C of heating 10h;
In III: by mixed liquor at room temperature suction filtration 3h, take out filter residue, vacuumize 2h; Drying is: at 150 DEG C of vacuum drying 15h; Roasting is: nitrogen atmosphere, 500 DEG C of roasting 6h.
2), in, after catalyst carrier used additives metallic solution is flooded, vacuumize, dry, roasting; Wherein, drying is: at 150 DEG C of dry 15h; Roasting is: nitrogen atmosphere, 500 DEG C of roasting 6h.
3), in, by the catalyst carrier of load promoter metal with after active metal solution impregnation, vacuumize, dry, roasting; Wherein, drying is: at 150 DEG C of dry 15h; Roasting is: nitrogen atmosphere, 500 DEG C of roasting 6h.
4) in, in hydrogen atmosphere, 500 DEG C of reduction 12h.
Catalyst is used for batch tank reactor catalysis hydrogenolysis glucose response, and process conditions are: temperature 215 DEG C, pressure 5MPa, and liquid air speed is 300h
-1, rotating speed 1800r/min.
Embodiment 21
With embodiment 16, difference is:
Described catalyst carrier is 50nm carbon fiber.
In I: purifying: carbon fiber is placed in 50mL nitric acid, 60 DEG C of heating 2h condensing reflux, then by phegma at 100 DEG C of dry 6h in air atmosphere.
In II: be heated to be: at 80 DEG C of heating 1h;
In III: by mixed liquor at room temperature suction filtration 1h, take out filter residue, vacuumize 1h; Drying is: at 100 DEG C of vacuum drying 6h; Roasting is: nitrogen atmosphere, 300 DEG C of roasting 2h.
2), in, after catalyst carrier used additives metallic solution is flooded, vacuumize, dry, roasting; Wherein, drying is: at 120 DEG C of drying 6 ~ 15h; Roasting is: nitrogen atmosphere, 400 DEG C of roasting 4h.
3), in, by the catalyst carrier of load promoter metal with after active metal solution impregnation, vacuumize, dry, roasting; Wherein, drying is: at 150 DEG C of dry 15h; Roasting is: carbon fiber: nitrogen atmosphere, 400 DEG C of roasting 4h.
4) in, in hydrogen atmosphere, 400 DEG C of reduction 8h.
Catalyst is used for catalytic hydrogenolysis glucose response; The concentration of D/W is 2wt%.Catalyst is used for batch tank reactor catalysis hydrogenolysis glucose response, and process conditions are: temperature 195 DEG C, pressure 3MPa, and liquid air speed is 1h
-1, rotating speed 1400r/min.
Embodiment 22
With embodiment 16, difference is:
Described catalyst carrier is 15 μm of carbon fibers.
In I: purifying: carbon fiber is placed in 120mL nitric acid, 90 DEG C of heating 3h condensing reflux, then by phegma at 150 DEG C of dry 12h in nitrogen atmosphere.
In II: be heated to be: at 120 DEG C of heating 10h;
In III: by mixed liquor at room temperature suction filtration 3h, take out filter residue, vacuumize 2h; Drying is: at 150 DEG C of vacuum drying 15h; Roasting is: nitrogen atmosphere, 500 DEG C of roasting 6h.
2), in, after catalyst carrier used additives metallic solution is flooded, vacuumize, dry, roasting; Wherein, drying is: at 100 DEG C of dry 6h; Roasting is: nitrogen atmosphere, 500 DEG C of roasting 2h.
3), in, by the catalyst carrier of load promoter metal with after active metal solution impregnation, vacuumize, dry, roasting; Wherein, drying is: at 100 DEG C of dry 15h; Roasting is: nitrogen atmosphere, 300 DEG C of roasting 2h.
4) in, in hydrogen atmosphere, 300 DEG C of reduction 12h.
Catalyst is used for catalytic hydrogenolysis glucose response; The concentration of D/W is 50wt%.Catalytic hydrogenolysis glucose response in the continuous fixed bed of high pressure, process conditions are: temperature 175 DEG C, pressure 3MPa, and liquid air speed is 1h
-1.
Embodiment 23
With embodiment 16, difference is:
Described catalyst carrier is 30 order silica.
In I: purifying: air atmosphere, 150 DEG C of calcined silica 2h.
In II: be heated to be: at 80 DEG C of heating 1h;
In III: by mixed liquor at room temperature suction filtration 1h, take out filter residue, vacuumize 1h; Drying is: at 100 DEG C of vacuum drying 6h; Roasting is: air atmosphere, 300 DEG C of roasting 2h.
2), in, after catalyst carrier used additives metallic solution is flooded, vacuumize, dry, roasting; Wherein, drying is: at 100 DEG C of dry 6h; Roasting is: air atmosphere, 300 DEG C of roasting 2h.
3), in, by the catalyst carrier of load promoter metal with after active metal solution impregnation, vacuumize, dry, roasting; Wherein, drying is: at 100 DEG C of dry 6h; Roasting is air atmosphere, 300 DEG C of roasting 2h.
4) in, in hydrogen atmosphere, 300 DEG C of reduction 6h.
Described catalyst is used for catalytic hydrogenolysis glucose response; The concentration of D/W is 25wt%.Catalytic hydrogenolysis glucose response in the continuous fixed bed of high pressure, process conditions are: temperature 215 DEG C, pressure 5MPa, and liquid air speed is 300h
-1.
Embodiment 24
With embodiment 16, difference is:
Described catalyst carrier is 20 order silica.
In I: purifying: air atmosphere, 250 DEG C of calcined silica 3h.
In II: be heated to be: at 120 DEG C of heating 10h;
In III: by mixed liquor at room temperature suction filtration 3h, take out filter residue, vacuumize 2h; Drying is: at 150 DEG C of vacuum drying 15h; Roasting is: air atmosphere, 500 DEG C of roasting 6h.
2), in, after catalyst carrier used additives metallic solution is flooded, vacuumize, dry, roasting; Wherein, drying is: at 150 DEG C of dry 15h; Roasting is: air atmosphere, 500 DEG C of roasting 6h.
3), in, by the catalyst carrier of load promoter metal with after active metal solution impregnation, vacuumize, dry, roasting; Wherein, drying is: at 150 DEG C of dry 15h; Roasting is: air atmosphere, 500 DEG C of roasting 6h.
4) in, in hydrogen atmosphere, 500 DEG C of reduction 12h.
Catalyst is used for batch tank reactor catalysis hydrogenolysis glucose response, and process conditions are: temperature 195 ~ 215 DEG C, pressure 3 ~ 5MPa, and liquid air speed is 1 ~ 300h
-1, rotating speed 1400 ~ 1800r/min.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (15)
1. can be used for the preparation method that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, it is characterized in that, comprise the following steps:
1) pretreatment is carried out to catalyst carrier;
2) by pretreated catalyst carrier used additives metallic solution dipping;
3) by the catalyst carrier of load promoter metal active metal solution impregnation;
4) logical hydrogen reducing, obtains can be used for the catalyst that glucose hydrogenolysis prepares low-carbon (LC) dihydroxylic alcohols;
Wherein, preferably, described pretreatment is one or more mixture process catalyst carriers in ammonia spirit with the neat solvent of the neat solvent of the neat solvent of the neat solvent of PEG-200 or the aqueous solution, PEG-400 or the aqueous solution, PEG-600 or the aqueous solution, triton x-100 or the aqueous solution, EDTA, lemon aqueous acid.
2. the preparation method that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols according to claim 1, is characterized in that, described promoter metal solution is one or more the aqueous solution in W, Mo, Zr, Al, Co; Described active metal solution is the aqueous solution of Ru and/or Ni.
3. the preparation method that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols according to claim 1 and 2, is characterized in that, the mass ratio of described catalyst carrier and promoter metal is 1:0.05 ~ 0.5; The mass ratio of described catalyst carrier and active metal is 1:0.005 ~ 0.2.
4. the preparation method that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols according to claim 1, is characterized in that, described catalyst carrier is silica, active carbon or carbon fiber.
5. the preparation method that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols according to claim 4, is characterized in that, described catalyst carrier is 20 ~ 40 order silica, 20 ~ 40 order active carbons or 50nm ~ 15 μm carbon fiber.
6. the preparation method that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols according to claim 1, is characterized in that, in step 1), to the pretreatment of catalyst carrier is:
I is by catalyst carrier purifying;
Catalyst carrier after purifying is placed in preprocessing solution by II, and heating, obtains mixed liquor;
III, by mixed liquor suction filtration, vacuumizes, and dry, roasting, obtains pretreated catalyst carrier.
7. the preparation method that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols according to claim 6, is characterized in that,
In described I:
The purifying of silica: air atmosphere, 150 ~ 250 DEG C of calcined silica 2 ~ 3h; The purifying of active carbon: nitrogen atmosphere, 150 ~ 250 DEG C of calcining active carbon 2 ~ 3h; The purifying of carbon fiber: carbon fiber is placed in 50 ~ 120mL nitric acid, 60 ~ 90 DEG C are heated 2 ~ 3h and condensing reflux, then that phegma is dry;
In described II:
Be heated to be: at 80 ~ 120 DEG C of heating 1 ~ 10h;
In described III:
Suction filtration, vacuumize into: by mixed liquor at room temperature suction filtration 1 ~ 3h, take out filter residue, vacuumize 1 ~ 2h;
Drying is: at 100 ~ 150 DEG C of vacuum drying 6 ~ 15h;
Roasting is: silica: air atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h; Active carbon: nitrogen atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h; Carbon fiber: nitrogen atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h.
8. the preparation method that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols according to claim 7, is characterized in that, in the purifying of carbon fiber, phegma drying is at 100 ~ 150 DEG C of dry 6 ~ 12h in air or nitrogen atmosphere by phegma.
9. the preparation method that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols according to claim 1, is characterized in that, step 2) in, after catalyst carrier used additives metallic solution is flooded, vacuumize, dry, roasting; Wherein,
Drying is: at 100 ~ 150 DEG C of drying 6 ~ 15h;
Roasting is: silica: air atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h; Active carbon: nitrogen atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h; Carbon fiber: nitrogen atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h.
10. the preparation method that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols according to claim 1, is characterized in that, in step 3), by the catalyst carrier of load promoter metal with after active metal solution impregnation, vacuumizes, dry, roasting; Wherein,
Drying is: at 100 ~ 150 DEG C of drying 6 ~ 15h;
Roasting is: silica: air atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h; Active carbon: nitrogen atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h; Carbon fiber: nitrogen atmosphere, 300 ~ 500 DEG C of roasting 2 ~ 6h.
11. preparation methods that can be used for glucose hydrogenolysis and prepare the catalyst of low-carbon (LC) dihydroxylic alcohols according to claim 1, is characterized in that, in step 4), in hydrogen atmosphere, and 300 ~ 500 DEG C of reduction 6 ~ 12h.
12. as arbitrary in claim 1 ~ 11 as described in can be used for the application that glucose hydrogenolysis prepares the catalyst of low-carbon (LC) dihydroxylic alcohols, described catalyst can be used to catalytic hydrogenolysis glucose response.
13. application according to claim 12, is characterized in that, when described catalyst hydrogenolysis glucose response, the concentration of D/W is 2 ~ 50wt%.
14. application according to claim 12, is characterized in that, described catalyst can be used for the continuous fixed bed of high pressure, batch tank reactor and high-gravity rotating bed middle catalytic hydrogenolysis glucose response; More preferably, for the continuous fixed bed of high pressure, high-gravity rotating bed in.
15. application according to claim 14, is characterized in that, when described catalyst is used for high pressure continuous fixed-bed catalytic hydrogenolysis glucose response, process conditions are: temperature 175 ~ 215 DEG C, pressure 3 ~ 5MPa, and liquid air speed is 1 ~ 300h
-1;
When described catalyst is used for batch tank reactor catalysis hydrogenolysis glucose response, process conditions are: temperature 195 ~ 215 DEG C, pressure 3 ~ 5MPa, and liquid air speed is 1 ~ 300h
-1, rotating speed 1400 ~ 1800r/min;
When described catalyst is used for high-gravity rotating bed catalytic hydrogenolysis glucose response, process conditions are: temperature 195 ~ 215 DEG C, pressure 3 ~ 5MPa, and liquid air speed is 1 ~ 500h
-1, rotating speed 200 ~ 1500r/min.
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| CN105478133A (en) * | 2015-12-11 | 2016-04-13 | 福建工程学院 | Low-cost SCR denitration catalyst and preparation method thereof |
| CN109364948A (en) * | 2018-12-06 | 2019-02-22 | 浙江工业大学 | A kind of ruthenium nickel/active carbon is total to loaded catalyst and its preparation and application |
| CN111375421A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon dihydric alcohol by hydrogenolysis of saccharides and preparation method thereof |
| CN111686747A (en) * | 2019-03-15 | 2020-09-22 | 北京化工大学 | Preparation method of catalyst with target product of glucose hydrogenolysis reaction being dihydric alcohol |
| CN116328762A (en) * | 2023-04-12 | 2023-06-27 | 北京化工大学 | Carbon-based metal catalyst and supergravity macro preparation method thereof |
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| CN102658133A (en) * | 2012-05-09 | 2012-09-12 | 杭州凯大催化金属材料有限公司 | Method for preparing active carbon carrying precious metal catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105478133A (en) * | 2015-12-11 | 2016-04-13 | 福建工程学院 | Low-cost SCR denitration catalyst and preparation method thereof |
| CN109364948A (en) * | 2018-12-06 | 2019-02-22 | 浙江工业大学 | A kind of ruthenium nickel/active carbon is total to loaded catalyst and its preparation and application |
| CN111375421A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon dihydric alcohol by hydrogenolysis of saccharides and preparation method thereof |
| CN111686747A (en) * | 2019-03-15 | 2020-09-22 | 北京化工大学 | Preparation method of catalyst with target product of glucose hydrogenolysis reaction being dihydric alcohol |
| CN111686747B (en) * | 2019-03-15 | 2023-03-21 | 北京化工大学 | Preparation method of catalyst with target product of glucose hydrogenolysis reaction being dihydric alcohol |
| CN116328762A (en) * | 2023-04-12 | 2023-06-27 | 北京化工大学 | Carbon-based metal catalyst and supergravity macro preparation method thereof |
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