CN105013509A - Catalyst for water phase hydrogenation preparation of cyclopentanone from furfural or furfural alcohol and preparation method and application method thereof - Google Patents
Catalyst for water phase hydrogenation preparation of cyclopentanone from furfural or furfural alcohol and preparation method and application method thereof Download PDFInfo
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Abstract
The present invention provides a catalyst for water phase hydrogenation preparation of cyclopentanone from furfural or furfural alcohol and a preparation method thereof, the catalyst is a supported catalyst comprising an active ingredient and a carrier; the active component is one or two substance selected from Cu, Ni, Ru, Pd or Pt; the carrier is a magnetic iron oxide with the formula of FeyOx, wherein the ratio y / x is greater than 2/3 and less than 1; and the mass of the active ingredient 2. 0 to 10.0% of the carrier mass. The present invention also discloses a method for water phase hydrogenation preparation of cyclopentanone from furfural or furfural alcohol by use of the catalyst. The method has the advantages of simple operating steps and easy controlled operating conditions. The synthesized catalyst has good catalytic effect, high cyclopentanone product selectivity, and magnetic property, a magnet is used to attract the catalyst, separation and recovery of the catalyst are facilitated, and the catalyst has good prospects.
Description
Technical field
The present invention relates to catalyst preparation field, be specifically related to a kind of for catalysis furfural or the furfuryl alcohol aqueous phase Hydrogenation Catalysts and its preparation method and methods for using them for cyclopentanone.
Background technology
Cyclopentanone is a kind of important fine-chemical intermediate, is the raw material of medicine and perfume industry.Be that serial spices (alkyl cyclopentanone, jasmone, MDJ and white orchid ketone etc.), 2 prepared by raw material with cyclopentanone, 3-cyclopenta pyridine (medicine intermediate), buspirone (anxiolytic), multiple anti-inflammatory, cancer therapy drug and pesticide and herbicide, also for rubber synthesis and Biochemical Research.In addition, cyclopentanone has good solubility property to various resin, have also been obtained extensive use in electron trade as solvent.
At present, the industrial process of the cyclopentanone mainly adipic acid decarboxylation cyclisation method of petroleum path and cyclopentene oxidizing.Take adipic acid as the technology path that cyclopentanone prepared by raw material, raw material relies on the production of adipic acid, and relate to multiple loaded down with trivial details reactions steps, and relate to decarboxylation procedure in production process, Theoretical Mass yield is 57.5%, and Atom economy is not high.The subject matter preparing cyclopentanone method with cyclopentene is the limited source of cyclopentene raw material, and expensive, catalyst exists very side effect, and these all limit the practicality of time method.
Along with the exhaustion day by day of fossil resource, the catalyzed conversion of renewable resource is utilized to utilize the extensive attention day by day causing people.Furfural is a kind of bulk chemical deriving from agricultural wastes, is industrially for raw material is produced with agriculture and forestry organic waste materials such as the corncob of cheapness, bagasse, cotton seed hulls.China is furfural production big country and big export country, and Chinese furfural annual production in 2013 reaches more than 30 ten thousand tons, accounts for more than 80% of worldwide production total amount.Therefore, the exploitation of furfural downstream product and added value promote has appreciable prospect, and its effective utilization simultaneously not only can reduce the dependence of important chemical to petroleum resources, and can increase the added value of agricultural product.At present, furfural can prepare the chemicals such as furfuryl alcohol, tetrahydrofurfuryl alcohol, 2-methylfuran, 2-methyltetrahydrofuran, pentadiene, pentanediol by selective hydrogenation.Wherein preparing furfuryl alcohol with furfural is main utilization ways, accounts for about 80%.Because furfural or furfuryl alcohol and cyclopentanone all have five carbon atoms, therefore furfural or furfuryl alcohol are converted into the concern that everybody is introduced by cyclopentanone.
Summary of the invention
The object of the present invention is to provide a kind of high to furfural/furfuryl alcohol aqueous phase high active of hydrogenation catalysis, cyclopentanone selectivity of product is high, with magnetic iron oxide Fe
yo
xas the catalyst of carrier, and this catalyst furfural or furfuryl alcohol prepare the method for cyclopentanone, described catalyst not only has good catalytic activity and reaction selectivity, and catalyst self has good magnetic simultaneously, be convenient to separation and the recovery of catalyst, improve the utilization rate of catalyst.
In order to realize the object of foregoing invention, the present invention by the following technical solutions:
For catalysis furfural or the furfuryl alcohol aqueous phase Hydrogenation catalyst for cyclopentanone, described catalyst is loaded catalyst, comprises active component and carrier; Described active component be selected from Cu, Ni, Ru, Pd or Pt one or both; Described carrier is general formula is Fe
yo
xmagnetic iron oxide, wherein 2/3<y/x<1; The quality of active component is 2.0 ~ 10.0% of carrier quality.
Further, preferred active component is Ru, RuCu or RuPd; The quality of preferred active component is 3.0 ~ 5.0wt% of carrier quality.
The present invention also provides the preparation method of above-mentioned catalyst, comprises the following steps:
(1) be made into mixed solvent by alcohol-water quality than for 1:1 ~ 1:5, molysite added in mixed solvent and dissolve formation iron salt solutions, wherein Fe
3+the concentration of ion is 0.4 ~ 1.0mol/L;
(2) prepare aqueous slkali, described aqueous slkali is selected from aqueous sodium carbonate, sodium bicarbonate aqueous solution, sodium hydrate aqueous solution or ammoniacal liquor; Wherein, the concentration of aqueous slkali is 0.6 ~ 1.5mol/L; When aqueous slkali be aqueous sodium carbonate or sodium bicarbonate aqueous solution time, CO
3 2-the molar concentration of ion is at least Fe in step (1) iron salt solutions
3+1.5 times of the molar concentration of ion; When aqueous slkali be sodium hydrate aqueous solution or ammoniacal liquor time, OH
-ion molar concentration is at least Fe in step (1) iron salt solutions
3+3 times of the molar concentration of ion;
(3) single droplet method or two methods are adopted, the aqueous slkali of the iron salt solutions of step (1) and step (2) is carried out co-precipitation, dropping limit, limit is stirred, along with the precipitation in mixed solution increases gradually, until the pH value in mixed solution reaches 8 ~ 10; Then, the mixed solution after co-precipitation carries out aging, finally by suction filtration, washing, dry at 90 ~ 120 DEG C, then calcines 12 ~ 48h at 400-600 DEG C in Muffle furnace, obtains Fe
yo
x;
(4) with the Fe that step (3) is obtained
yo
xfor carrier, adopt equi-volume impregnating, active constituent loading in carrier, after drying, roasting, namely obtain described catalyst.Load adopts conventional method, with 4.0Ru/Fe
yo
xfor example, other catalyst preparation process is similar: the Fe getting more than 25 grams preparations
yo
xcarrier (20-40 order) floods the ruthenic chloride solution 40mL of 0.25mol/L, stirs after 2 hours and leaves standstill 12h, then 120 DEG C of dried overnight in baking oven, then put into muffle furnace 500 DEG C of roasting 6h, can obtain 4.0Ru/Fe after being cooled to room temperature
yo
x.
Further, in step (1), described alcohol is selected from methyl alcohol, ethanol, ethylene glycol, glycerine or sorbierite.Be preferably ethylene glycol or glycerine, preferred alcohol-water quality is than being 1:2 ~ 1:4.
Further, in step (1), described molysite is selected from ferric nitrate, ferric sulfate or iron chloride.
Further, in step (1), Fe in the iron salt solutions of preparation
3+the concentration of ion is preferably 0.6 ~ 1.0mol/L.In step (2), the concentration of the aqueous slkali of preparation is preferably 1.0 ~ 1.2mol/L.
Further, in step (3), after pH value reaches 8 ~ 10, also need to stir a period of time (preferred 0.5h).
Further, in step (3), the described aging time is 12 ~ 48h (being preferably 24 ~ 36h), the temperature of described drying is 90 ~ 120 DEG C (being preferably 100 ~ 120 DEG C), drying time is 12 ~ 48h (preferably 24 ~ 36h), the temperature of described calcining is 400 ~ 600 DEG C (being preferably 450 ~ 550 DEG C), and calcination time is 12 ~ 48h (being preferably 12 ~ 24h).
The present invention also provides a kind of above-mentioned catalyst furfural or furfuryl alcohol aqueous phase Hydrogenation of using for the method for cyclopentanone, comprise the following steps: first, described catalyst is added in autoclave after hydrogen reducing, add furfural or furfuryl alcohol, add deionized water, mix, sealed high pressure reactor; Wherein, the quality of furfural is 2 ~ 20% (preferably 5 ~ 10%) of deionized water quality, and the quality of catalyst is 1 ~ 20% (preferably 5 ~ 10%) of furfural quality; Then, (repeatedly replaceable with the air in nitrogen displacement autoclave, to reach better effect), use the nitrogen in hydrogen exchange autoclave (repeatedly replaceable again, to reach better effect), under the hydrogen-pressure of 2 ~ 6MPa, (be preferably 3 ~ 5MPa) afterwards, at 100 ~ 200 DEG C, react 2 ~ 10h (preferable temperature is 120 ~ 160 DEG C, and the preferred reaction time is 4 ~ 8h).
Characteristic of the present invention is: provide a kind of for catalysis furfural or the furfuryl alcohol aqueous phase Hydrogenation catalyst for cyclopentanone, high conversion, highly selective catalysis can prepare cyclopentanone.Catalyst of the present invention is applicable to pure water phase hydrogenation reaction, and organic solvent-free uses, and reaction process is simple, and mild condition, whole course of reaction is substantially without coking carbon distribution.Further, the preferred Ru of the present invention is catalyst based.Catalyst based compared to Cu, Ru is catalyst based has better acid-fast alkali-proof performance, has better stability of catalytic activity at thermal and hydric environment, has larger potentiality at catalysis furfural or furfuryl alcohol aqueous phase Hydrogenation in the application of cyclopentanone.Preparation method's technique of catalyst of the present invention is simple in addition, easy to operate, and catalyst has magnetic is beneficial to separation and recovery and recycling, and catalyst can repeatedly use and active not obvious reduction.In addition, with Fe
yo
xas carrier loaded above-mentioned active material, not obvious for the catalytic action of cyclopentanone to furfuryl alcohol or furfural aqueous phase Hydrogenation within the scope of general load capacity, inventor finds, in the loading range that the present invention limits through research, there is the catalytic efficiency significantly improved, achieve with Fe
yo
xas above-mentioned active ingredient carriers at catalysis furfuryl alcohol or furfural aqueous phase Hydrogenation for the application in cyclopentanone.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from the following description of the accompanying drawings of embodiments, wherein:
Fig. 1 is the GC-MS spectrogram of the embodiment of the present invention 2 by the product of furfural aqueous phase Hydrogenation cyclopentanone.
Fig. 2 is the GC spectrogram of the embodiment of the present invention 13 by the product of furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Fig. 3 is the ferriferous oxide (Fe that the embodiment of the present invention 6 obtains
xo
y) XRD figure.
Detailed description of the invention
Illustrate in greater detail the present invention below by instantiation, the embodiment provided is only for example the present invention, but the protection domain do not limited the present invention in any way.
Embodiment 1
Catalyst preparing: (1) is that 1:1 is made into mixed solvent by methanol-water mass ratio, added by ferric nitrate in mixed solvent and dissolve formation iron nitrate solution (being referred to as solution A), the molar concentration of ferric nitrate is 0.4mol/L; (2) join aqueous sodium carbonate (being referred to as solution B), molar concentration is 0.6mol/L; (3) solution B slowly joined gradually in solution A, limit edged stirs, and along with the precipitation in solution increases gradually, until when the pH value in mixed solution reaches 8 ~ 10, can stop.Then, the solution containing precipitation after co-precipitation is carried out aging 12h, finally by suction filtration, washing, 90 DEG C of dry 48h, then in Muffle furnace after 400 DEG C of calcining 48h, obtain the magnetic ferriferous oxide (Fe of a kind of tool
yo
x, 2/3<y/x<1); (4) with obtained ferriferous oxide (Fe
yo
x) be carrier, equi-volume impregnating prepares load Ru catalyst, and the quality of Ru is 4.0% of carrier quality, the 4.0Ru/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: 4.0Ru/Fe prepared by said method
yo
xcatalyst adds in autoclave after hydrogen reducing, adds furfural, deionized water mixes, sealed high pressure reactor; Wherein, the quality of furfural is 2% of deionized water quality; The quality of catalyst is 5% of furfural quality; Then, with nitrogen displacement autoclave in air repeatedly, use nitrogen in hydrogen exchange autoclave repeatedly again, afterwards under the hydrogen-pressure of 2.0MPa, at 100 DEG C, react 2h, reacted and be cooled to room temperature, with gas-chromatography and GC-MS analytic liquid phase component, furfural conversion ratio is close to 100%, and cyclopentanone is selective reaches 43%.Reaction evaluating condition and the results are shown in Table 1.
Embodiment 2
Catalyst preparing: (1) is that 1:2 is made into mixed solvent by alcohol-water mass ratio, added by iron chloride in mixed solvent and dissolve formation ferric chloride solution (being referred to as solution A), the molar concentration of iron chloride is 0.8mol/L; (2) join aqueous sodium carbonate (being referred to as solution B), molar concentration is 1.2mol/L; (3) solution B slowly joined gradually in solution A, limit edged stirs, and along with the precipitation in solution increases gradually, until when the pH value in mixed solution reaches 8 ~ 10, can stop.Then, the solution containing precipitation after co-precipitation is carried out aging 24h, finally by suction filtration, washing, 120 DEG C of dry 24h, then in Muffle furnace after 500 DEG C of calcining 24h, obtain the magnetic ferriferous oxide (Fe of a kind of tool
yo
x, 2/3<y/x<1); (4) with obtained ferriferous oxide (Fe
yo
x) be carrier, equi-volume impregnating prepares load Ru catalyst, and the quality of Ru is 4.0% of carrier quality, the 4.0Ru/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 2.
Embodiment 3
Catalyst preparing: (1) is made into mixed solvent by ethylene glycol-water quality than for 1:2, added by ferric nitrate in mixed solvent and dissolve formation iron nitrate solution (being referred to as solution A), the molar concentration of ferric nitrate is 1.0mol/L; (2) join sodium bicarbonate aqueous solution (being referred to as solution B), molar concentration is 1.5mol/L; (3) solution B slowly joined gradually in solution A, limit edged stirs, and along with the precipitation in solution increases gradually, until when the pH value in mixed solution reaches 8 ~ 10, can stop.Then, the solution containing precipitation after co-precipitation is carried out aging 48h, finally by suction filtration, washing, 100 DEG C of dry 24h, then in Muffle furnace after 600 DEG C of calcining 12h, obtain the magnetic ferriferous oxide (Fe of a kind of tool
yo
x, 2/3<y/x<1); (4) with obtained ferriferous oxide (Fe
yo
x) be carrier, equi-volume impregnating prepares load Ru catalyst, and the quality of Ru is 4.0% of carrier quality, the 4.0Ru/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 3.
Embodiment 4
Catalyst preparing: (1) is that 1:2 is made into mixed solvent by glycerol-water mass ratio, added by ferric sulfate in mixed solvent and dissolve formation ferrum sulfuricum oxydatum solutum (being referred to as solution A), the molar concentration of ferric sulfate is 0.2mol/L; (2) join sodium hydrate aqueous solution (being referred to as solution B), molar concentration is 1.2mol/L; (3) solution B and solution A are joined in container simultaneously and carry out co-precipitation, limit edged stirs, and along with the precipitation in solution increases gradually, until when the pH value in mixed solution reaches 8 ~ 10, can stop.Then, the solution containing precipitation after co-precipitation is carried out aging 24h, finally by suction filtration, washing, 120 DEG C of dry 12h, then in Muffle furnace after 500 DEG C of calcining 24h, obtain the magnetic ferriferous oxide (Fe of a kind of tool
yo
x, 2/3<y/x<1); (4) with obtained ferriferous oxide (Fe
yo
x) be carrier, equi-volume impregnating prepares load Ru catalyst, and the quality of Ru is 2.0% of carrier quality, the 2.0Ru/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 4.
Embodiment 5
Catalyst preparing: (1) is made into mixed solvent by sorbierite-water quality than for 1:5, added by ferric nitrate in mixed solvent and dissolve formation iron nitrate solution (being referred to as solution A), the molar concentration of ferric nitrate is 0.4mol/L; (2) join ammonia spirit (being referred to as solution B), molar concentration is 1.2mol/L; (3) solution B and solution A are joined in container simultaneously and carry out co-precipitation, limit edged stirs, and along with the precipitation in solution increases gradually, until when the pH value in mixed solution reaches 8 ~ 10, can stop.Then, the solution containing precipitation after co-precipitation is carried out aging 24h, finally by suction filtration, washing, 120 DEG C of dry 24h, then in Muffle furnace after 500 DEG C of calcining 24h, obtain the magnetic ferriferous oxide (Fe of a kind of tool
yo
x, 2/3<y/x<1); (4) with obtained ferriferous oxide (Fe
yo
x) be carrier, equi-volume impregnating prepares load Ru catalyst, and the quality of Ru is 4.0% of carrier quality, the 4.0Ru/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 5.
Embodiment 6
Catalyst preparing: (1) is made into mixed solvent by ethylene glycol-water quality than for 1:2, added by ferric nitrate in mixed solvent and dissolve formation iron nitrate solution (being referred to as solution A), the molar concentration of ferric nitrate is 0.8mol/L; (2) join aqueous sodium carbonate (being referred to as solution B), molar concentration is 1.2mol/L; (3) solution B slowly joined gradually in solution A, limit edged stirs, and along with the precipitation in solution increases gradually, until when the pH value in mixed solution reaches 8 ~ 10, can stop.Then, the solution containing precipitation is carried out aging 24h, finally by suction filtration, washing, 120 DEG C of dry 24h, then in Muffle furnace after 500 DEG C of calcining 24h, obtain the magnetic ferriferous oxide (Fe of a kind of tool
yo
x, 2/3<y/x<1); (4) with obtained ferriferous oxide (Fe
yo
x) be carrier, equi-volume impregnating prepares load Ru catalyst, and the quality of Ru is 6.0% of carrier quality, the 6.0Ru/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 6.
Embodiment 7
Catalyst preparing: with the ferriferous oxide (Fe that embodiment 6 is obtained
yo
x) be carrier, equi-volume impregnating prepares load Ru catalyst, and the quality of Ru is 4.0% of carrier quality, the 4.0Ru/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 7.
Embodiment 8
Catalyst preparing: with the ferriferous oxide (Fe that embodiment 6 is obtained
yo
x) be carrier, equi-volume impregnating prepares loaded Cu catalyst, and the quality of Cu is 10.0% of carrier quality, the 10.0Cu/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 8.
Embodiment 9
Catalyst preparing: with the ferriferous oxide (Fe that embodiment 6 is obtained
yo
x) be carrier, equi-volume impregnating prepares supported ni catalyst, and the quality of Ni is 10.0% of carrier quality, the 10.0Ni/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 9.
Embodiment 10
Catalyst preparing: with the ferriferous oxide (Fe that embodiment 6 is obtained
yo
x) be carrier, equi-volume impregnating prepares Pt-supported catalyst, and the quality of Pd is 4.0% of carrier quality, the 4.0Pd/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 10.
Embodiment 11
Catalyst preparing: with the ferriferous oxide (Fe that embodiment 6 is obtained
yo
x) be carrier, equi-volume impregnating prepares loaded Pt catalyst, and the quality of Pt is 4.0% of carrier quality, the 4.0Pt/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 11.
Embodiment 12
Catalyst preparing: with the ferriferous oxide (Fe that embodiment 6 is obtained
yo
x) be carrier, equi-volume impregnating prepares load RuNi catalyst, and the quality of Ru, Ni is respectively 2.0%, 4.0% of carrier quality, the 2Ru4Ni/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 12.
Embodiment 13
Catalyst preparing: with the ferriferous oxide (Fe that embodiment 6 is obtained
yo
x) be carrier, equi-volume impregnating prepares load RuCu catalyst, and the quality of Ru, Cu is respectively carrier quality 2.0%, 4.0%, the 2Ru4Cu/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 13.
Embodiment 14
Catalyst preparing: with the ferriferous oxide (Fe that embodiment 6 is obtained
yo
x) be carrier, equi-volume impregnating prepares load RuPd catalyst, and the quality of Ru, Pd is respectively 2.0%, 2.0% of carrier quality, the 2Ru2Pd/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfural/furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1 shown in enforcement 14.
Comparative example 15
Catalyst preparing: with the ferriferous oxide (Fe that embodiment 6 is obtained
yo
x) be carrier, equi-volume impregnating prepares load Ru catalyst, and the quality of Ru is 1.0% of carrier quality, the 1.0Ru/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table shown in 15 in 1.
Comparative example 16
Catalyst preparing: with the ferriferous oxide (Fe that embodiment 6 is obtained
yo
x) be carrier, equi-volume impregnating prepares load Ru catalyst, and the quality of Ru is 12.0% of carrier quality, the 12.0Ru/Fe obtained after drying, roasting
yo
xloaded catalyst is used for the reaction of furfuryl alcohol aqueous phase Hydrogenation cyclopentanone.
Reaction evaluating: the operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table shown in 16 in 1.
Comparative example 15,16 and embodiment 5 contrast known, work as Fe in comparative example 15
yo
xthe content of carrier to load metal Ru is too low, and during load capacity as 1.0%, conversion ratio is lower is 53%, and is selectively reduced to 56% on the contrary; Fe is worked as in comparative example 16
yo
xthe too high levels of carrier to load metal Ru, during load capacity as 12.0%, although conversion ratio is 100%, is selectively significantly reduced to 36%; Fe is worked as in embodiment 5
yo
xwhen the content of carrier to load metal Ru is 4.0%, conversion ratio and selectivity of product arrive optimum efficiency, are respectively 94%, 73%.
The condition of the catalyst reaction evaluation of each embodiment of table 1 and reaction result
Claims (8)
1. furfural or furfuryl alcohol aqueous phase Hydrogenation are for a catalyst for cyclopentanone, and it is characterized in that, described catalyst is loaded catalyst, comprises active component and carrier; Described active component be selected from Cu, Ni, Ru, Pd or Pt one or both; Described carrier is general formula is Fe
yo
xmagnetic iron oxide, wherein 2/3<y/x<1; The quality of described active component is 2.0 ~ 10.0% of carrier quality.
2. furfural as claimed in claim 1 or furfuryl alcohol aqueous phase Hydrogenation are for the catalyst of cyclopentanone, it is characterized in that, described active component preferred Ru, RuCu or RuPd; The quality of described active component is 3.0 ~ 5.0% of carrier quality.
3. furfural as claimed in claim 1 or 2 or furfuryl alcohol Hydrogenation are for a preparation method for the catalyst of cyclopentanone, it is characterized in that, comprise the following steps:
(1) be made into mixed solvent by alcohol-water quality than for 1:1 ~ 1:5, molysite added in mixed solvent and dissolve formation iron salt solutions, Fe
3+the concentration of ion is 0.4 ~ 1.0mol/L;
(2) prepare aqueous slkali, described aqueous slkali is selected from aqueous sodium carbonate, sodium bicarbonate aqueous solution, sodium hydrate aqueous solution or ammoniacal liquor; Wherein, the concentration of aqueous slkali is 0.6 ~ 1.5mol/L, and meet: when aqueous slkali be aqueous sodium carbonate or sodium bicarbonate aqueous solution time, CO
3 2-the molar concentration of ion is at least Fe in step (1) iron salt solutions
3+1.5 times of the molar concentration of ion; When aqueous slkali be sodium hydrate aqueous solution or ammoniacal liquor time, OH
-ion molar concentration is at least Fe in step (1) iron salt solutions
3+3 times of the molar concentration of ion;
(3) adopt single droplet method or two methods, the aqueous slkali of the iron salt solutions of step (1) and step (2) is carried out co-precipitation, until the pH value in mixed solution reaches 8 ~ 10; Mixed solution after co-precipitation carries out aging, finally by suction filtration, washing, dry at 90 ~ 120 DEG C, then calcines 12 ~ 48h at 400-600 DEG C in Muffle furnace, obtains Fe
yo
x;
(4) with the Fe that step (3) is obtained
yo
xfor carrier, employing equi-volume impregnating in carrier, namely obtains described catalyst after drying, roasting active constituent loading.
4. preparation method as claimed in claim 3, it is characterized in that, in step (1), described alcohol is selected from methyl alcohol, ethanol, ethylene glycol, glycerine or sorbierite, and alcohol-water quality is than being 1:2 ~ 1:4; Described molysite is selected from ferric nitrate, ferric sulfate or iron chloride, Fe
3+the concentration of ion is 0.6 ~ 1.0mol/L.
5. preparation method as claimed in claim 3, it is characterized in that, in step (2), the concentration of aqueous slkali is 1.0 ~ 1.2mol/L.
6. preparation method as claimed in claim 3, it is characterized in that, in step (3), the described aging time is 12 ~ 48h, and the time of described drying is 12 ~ 48h.
7. catalyst as claimed in claim 1 or 2 at catalysis furfural or furfuryl alcohol aqueous phase Hydrogenation for the application process in cyclopentanone, it is characterized in that, comprise the following steps: first, described catalyst is added in autoclave after hydrogen reducing, add furfural or furfuryl alcohol, add deionized water, mix, sealed high pressure reactor; Wherein, the quality of furfural is 2 ~ 20% of deionized water quality, and the quality of catalyst is 1 ~ 20% of furfural quality; Then, with the air in nitrogen displacement autoclave, then use the nitrogen in hydrogen exchange autoclave, afterwards under the hydrogen-pressure of 2 ~ 6MPa, at 100 ~ 200 DEG C, react 2 ~ 10h.
8. application process as claimed in claim 7, it is characterized in that, the quality of furfural is 5 ~ 10% of deionized water quality, and the quality of catalyst is 5 ~ 10% of furfural quality; The hydrogen-pressure of reaction is 3 ~ 5MPa, and reaction temperature is 120 ~ 160 DEG C, and the reaction time is 4 ~ 8h.
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