CN110479279A - For synthesizing the preparation method and application of the catalyst of gamma-valerolactone - Google Patents
For synthesizing the preparation method and application of the catalyst of gamma-valerolactone Download PDFInfo
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- CN110479279A CN110479279A CN201910596565.3A CN201910596565A CN110479279A CN 110479279 A CN110479279 A CN 110479279A CN 201910596565 A CN201910596565 A CN 201910596565A CN 110479279 A CN110479279 A CN 110479279A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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Abstract
The method for preparing catalyst and application that the present invention provides a kind of for synthesizing gamma-valerolactone, it is that 2-15wt% carries out weighing metallorganic precursors and carrier by the load capacity of cobalt, nickel, copper, mechanical mixture is in reaction tube, it vacuumizes, 100-300 DEG C at a temperature of keep 6-12h, so that metallorganic precursors is sufficiently distilled and be adsorbed on carrier；After absorption completely, it is drawn off being placed in tube furnace, Dynamic deposition is carried out under the gaseous mixture of hydrogen and inert gas, thermally decomposes metallorganic precursors in tube furnace, cobalt, nickel, copper-based catalysts can be obtained in the resolving time >=2h.The catalyst series are applied in the reaction of synthesis GVL, solve the problems such as tradition catalyst activity component load capacity prepared by infusion process can not be controlled effectively, active component dispersion is uneven.Target product GVL high income, has a good application prospect.
Description
Technical field
The invention belongs to a kind of new catalyst preparation method and application technical fields, relate in particular to a kind of monometallic
The preparation method of loaded catalyst and the catalyst prepared using this method are in levulic acid and its esters synthesis γ-
Application on valerolactone (GVL).
Background technique
Due to caused by the continuous exhaustion of the fossil energies such as petroleum, natural gas and the use of traditional fossil energy
The problems such as a series of environmental pollution, such as greenhouse effects and haze, therefore searching clean reproducible energy just seems especially heavy
It wants.Biomass energy is considered as unique carbon containing renewable resource, discharges CO after biomass utilization2, and can be by photosynthetic
Effect is stored in biomass, and the Nature is made to remain Carbon balance.Wherein GVL is extremely important in biomass plateform molecules
Organic intermediate compound.GVL acts not only as food additives, can also be directly as liquid fuel etc., using very
Extensively, there is wide commercial market and application prospect.
It is applied to levulic acid at present and its esters prepares the custom catalysts in GVL reaction and can be divided into noble metal catalyst
And non-precious metal catalyst.For noble metal catalyst, due to higher cost, and homogeneous noble metal catalyst and product are not
Easily separated, reusing is poor, greatly limits the application of noble metal catalyst.Therefore non-precious metal catalyst is more studied
The favor of person, but the problem that non-precious metal catalyst is harsher there is also reaction condition.The preparation of non-precious metal catalyst at present
Method mainly has infusion process, the precipitation method, ion-exchange etc..The preparation method of catalyst directly affects catalyst activity component
Dispersion degree, actual negative carrying capacity, particle diameter distribution etc., to affect the activity of catalyst.Wherein monometallic loaded catalyst
Preparation method based on infusion process, and infusion process there are dispersion degrees it is not high enough, loading is uneven the problems such as.
Therefore it the present invention provides a kind of catalyst using Metalorganic Chemical Vapor Deposition preparation and its is synthesizing
Application on GVL.Not only preparation process is simple for this method for preparing catalyst, and operating condition is mild, active component Load Balanced,
And effect of the catalyst prepared of this method in the reaction that levulic acid and its esters prepare GVL is no less than tradition preparation
The catalyst that method prepares, it is even better.
Summary of the invention
Of the existing technology in order to solve the problems, such as, the present invention provides a kind of Metalorganic Chemical Vapor Depositions to close
At a series of monometallic loaded catalysts and its application on levulic acid and its esters synthesis GVL, tradition dipping is solved
The problems such as catalyst activity component load capacity of method preparation can not be controlled effectively, active component dispersion is uneven.
To achieve the goals above, technical solutions according to the invention are as follows:
It is a kind of for synthesizing the method for preparing catalyst of gamma-valerolactone, catalyst is heavy using Metallo-Organic Chemical Vapor
Metallorganic precursors are supported on carrier by area method, active component for example cobalt, nickel, copper load capacity be 2-15wt%.
The carrier of the catalyst is γ-Al2O3、ZrO2、SiO2, on the carriers such as AC, Graphene or meso-porous carbon material
Deng.
The metal organic precursor object of the catalyst is acetylacetone cobalt (Co (acac)2), nickel acetylacetonate (Ni
(acac)2), acetylacetone copper (Cu (acac)2) etc. predecessors.
It is that 2-15wt% carries out weighing metallorganic precursors and carrier that specific method, which is by the load capacity of cobalt, nickel, copper, mechanical
Be mixed in reaction tube, vacuumize, 100-300 DEG C at a temperature of keep 6-12h, so that metallorganic precursors is sufficiently distilled and is inhaled
It invests on carrier；It after absorption completely, is drawn off being placed in tube furnace, dynamic is carried out under the gaseous mixture of hydrogen and inert gas
Deposition, thermally decomposes metallorganic precursors in tube furnace, cobalt, nickel, cupper-based catalyst can be obtained in the resolving time >=2h
Agent.
The thermal decomposition temperature that carries out in tube furnace is 200-600 DEG C.
The catalyst for synthesizing GVL reaction is carried out in batch type high pressure reactor, and reaction substrate is levulinic
Acid and its esters, are designated as heat-staple organic matter in reaction, and reaction medium can not only dissolve substrate and reaction product etc., but also can be with
Promote the progress of reaction as hydrogen donor, the mass ratio of reaction raw materials 100-1000mmol/L, reaction substrate and catalyst are
1:1-50:1, the initial pressure for filling hydrogen in batch reactor at room temperature is 1-6MPa, and reaction temperature is 150-300 DEG C,
Reaction time is 1-6h, and the agitation revolution of reaction kettle is 300-1500r/min.
The reaction substrate includes levulic acid, methyl ester levulinate, ethyl levulinate, Butyl acetylpropanoate etc.,
Its molar concentration is 100-500mmol/L.
The reaction medium is methanol, ethyl alcohol, isopropanol or sec-butyl alcohol.
The internal standard compound is dodecane or tridecane.
A series of single-metal reforming catalyst that the present invention is prepared with Metalorganic Chemical Vapor Deposition, active component can be high
Degree is dispersed in the surface of carrier.The catalyst series are applied in the reaction of synthesis GVL, solve tradition catalysis prepared by infusion process
The problems such as agent activity component load quantity can not be controlled effectively, active component dispersion is uneven.Target product GVL high income, has
Good application prospect.
Detailed description of the invention
Fig. 1 is the XRD spectra of the nickel-base catalyst of different loads amount of the present invention；
Fig. 2 is the XRD spectra of the cobalt-base catalyst of different loads amount of the present invention；
Fig. 3 is the XRD spectra of the copper-based catalysts of different loads amount of the present invention.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and detailed description, but protection scope of the present invention
It is not limited to the content.
Embodiment 1
The preparation of organonickel precursor:
(1) by Ni (NO3)2·6H2O is soluble in water, is made into the solution of 10-20wt%, and a certain amount of NaOH is taken to be made into water
The solution of 5-15wt%.
(2) nickel salt solution is added in the reactor with collet and stirring, NaOH to pH=8-9 is added dropwise.
(3) 15min is stirred, temperature is added a certain amount of acetylacetone,2,4-pentanedione, is heated to reflux when rising to 50-60 DEG C, temperature control
System is at 100 DEG C, isothermal reaction 2.5-3h, speed of agitator 600-2500r/min.
(4) after reaction, product is filtered with Buchner funnel, when suction filtration is washed with distilled water product.
(5) products obtained therefrom is dried in vacuo 2h at 60 DEG C, obtains acetylacetone,2,4-pentanedione nickel by powder.
Embodiment 2
The preparation of Ni/AC catalyst: being that 2-15wt% carries out weighing metal organonickel precursor by the load capacity of nickel, with activity
High-area carbon mechanical mixture vacuumizes in reaction tube, 200 DEG C at a temperature of keep 12h, rise metal organonickel precursor sufficiently
China is simultaneously adsorbed on carrier；Absorption completely after, be drawn off being placed in tube furnace, under the gaseous mixture of hydrogen and inert gas into
Mobile state deposition, thermally decomposes metal organonickel precursor in tube furnace, and decomposition temperature is 460 DEG C, resolving time 5h, i.e.,
The Ni/AC catalyst that loading is 2-15wt% can be obtained.
Embodiment 3
Ni/ZrO2The preparation of catalyst: being that 2-15wt% carries out weighing metal organonickel precursor by the load capacity of nickel, with work
Property high-area carbon mechanical mixture vacuumizes in reaction tube, 200 DEG C at a temperature of keep 12h, keep metal organonickel precursor abundant
It distils and is adsorbed on carrier；After absorption completely, it is drawn off being placed in tube furnace, under the gaseous mixture of hydrogen and inert gas
Dynamic deposition is carried out, thermally decomposes metal organonickel precursor in tube furnace, decomposition temperature is 460 DEG C, resolving time 5h,
The Ni/ZrO that loading is 2-15wt% can be obtained2Catalyst.
Embodiment 4
Ni/SiO2The preparation of catalyst: being that 2-15wt% carries out weighing metal organonickel precursor by the load capacity of nickel, with work
Property high-area carbon mechanical mixture vacuumizes in reaction tube, 200 DEG C at a temperature of keep 12h, keep metal organonickel precursor abundant
It distils and is adsorbed on carrier；After absorption completely, it is drawn off being placed in tube furnace, under the gaseous mixture of hydrogen and inert gas
Dynamic deposition is carried out, thermally decomposes metal organonickel precursor in tube furnace, decomposition temperature is 460 DEG C, resolving time 5h,
The Ni/SiO that loading is 2-15wt% can be obtained2Catalyst.
Embodiment 5
Ni/γ-Al2O3The preparation of catalyst: being that 2-15wt% carries out weighing metal organonickel precursor by the load capacity of nickel,
With absorbent charcoal carrier mechanical mixture in reaction tube, vacuumize, 200 DEG C at a temperature of keep 12h, make metal organonickel precursor
It sufficiently distils and is adsorbed on carrier；After absorption completely, it is drawn off being placed in tube furnace, in the mixing of hydrogen and inert gas
Dynamic deposition is carried out under gas, thermally decomposes metal organonickel precursor in tube furnace, and decomposition temperature is 460 DEG C, when decomposition
Between 5h, can be obtained loading be 2-15wt% Ni/ γ-Al2O3Catalyst.
Embodiment 6
The preparation of organic cobalt precursors:
(1) by Co (NO3)2·6H2O is soluble in water, is made into the solution of 10-20wt%, and a certain amount of NaOH is taken to be made into water
The solution of 5-15wt%.
(2) cobalt salt solution is added in the reactor with collet and stirring, NaOH to pH=8-9 is added dropwise.
(3) 15min is stirred, temperature is added a certain amount of acetylacetone,2,4-pentanedione, is heated to reflux when rising to 50-60 DEG C, temperature control
System is at 100 DEG C, isothermal reaction 2.5-3h, speed of agitator 600-2500r/min.
(4) after reaction, product is filtered with Buchner funnel, when suction filtration is washed with distilled water product.
(5) products obtained therefrom is dried in vacuo 2h at 60 DEG C, obtains acetylacetone,2,4-pentanedione cobalt dust.
Embodiment 7
The preparation of Co base catalyst: preparation process is similar to embodiment 2-5, the difference is that active component Ni is replaced
At Co, carrier and preparation condition are as embodiment 2-5.
Embodiment 8
The preparation of organic copper precursors:
(1) by Cu (NO3)2·6H2O is soluble in water, is made into the solution of 10-20wt%, and a certain amount of NaOH is taken to be made into water
The solution of 5-15wt%.
(2) copper salt solution is added in the reactor with collet and stirring, NaOH to pH=8-9 is added dropwise.
(3) 15min is stirred, temperature is added a certain amount of acetylacetone,2,4-pentanedione, is heated to reflux when rising to 50-60 DEG C, temperature control
System is at 100 DEG C, isothermal reaction 2.5-3h, speed of agitator 600-2500r/min.
(4) after reaction, product is filtered with Buchner funnel, when suction filtration is washed with distilled water product.
(5) products obtained therefrom is dried in vacuo 2h at 60 DEG C, obtains acetylacetone,2,4-pentanedione copper powders.
Embodiment 9
The preparation of Cu base catalyst: preparation process is similar to embodiment 2-5, the difference is that active component Ni is replaced
At Cu, carrier and preparation condition are as embodiment 2-5.
Embodiment 10
The application of Ni/AC catalyst: a certain amount of ethyl levulinate and dodecane are dissolved in isopropanol, together with
Ni/AC catalyst is added in batch reactor, after being passed through hydrogen five gases of displacement, the hydrogen of 1MPa is filled, with 1000r/
The speed of min is stirred, while being warming up to 250 DEG C of reaction 2h and being down to room temperature after reaction, is taken product liquid, is used gas phase
Chromatograph-mas spectrometer and gas chromatograph carry out qualitative and quantitative detection.The conversion ratio of ethyl levulinate is with (levulic acid
Ethyl ester initial number moles-ethyl levulinate residue molal quantity)/(ethyl levulinate initial number moles) x 100% calculating.It produces
The yield of object is calculated with (product molar number/Nc)/(ethyl levulinate initial number moles) x 100%, wherein Nc=
(molal quantity that 1mol substrate generates corresponding product)/mol.The Ni/AC catalyst prepared in embodiment 2 is closed in ethyl levulinate
At the result that GVL reacts be ethyl levulinate conversion ratio be 100%, GVL yield be 79.9%.
Embodiment 11
The application of Co/AC catalyst: a certain amount of ethyl levulinate and dodecane are dissolved in isopropanol, together with
Co/AC catalyst is added in batch reactor, after being passed through hydrogen five gases of displacement, the hydrogen of 1MPa is filled, with 1000r/
The speed of min is stirred, while being warming up to 250 DEG C of reaction 2h and being down to room temperature after reaction, is taken product liquid, is used gas phase
Chromatograph-mas spectrometer and gas chromatograph carry out qualitative and quantitative detection.The Co/AC catalyst prepared in embodiment 7 is in second
Acyl ethyl propionate synthesis GVL reaction on result be ethyl levulinate conversion ratio be 92.2%, GVL yield be 90.6%.
Embodiment 12
The application of Cu/AC catalyst: a certain amount of ethyl levulinate and dodecane are dissolved in isopropanol, together with
Cu/AC catalyst is added in batch reactor, after being passed through hydrogen five gases of displacement, the hydrogen of 1MPa is filled, with 1000r/
The speed of min is stirred, while being warming up to 250 DEG C of reaction 2h and being down to room temperature after reaction, is taken product liquid, is used gas phase
Chromatograph-mas spectrometer and gas chromatograph carry out qualitative and quantitative detection.The Cu/AC catalyst prepared in embodiment 9 is in second
Acyl ethyl propionate synthesis GVL reaction on result be ethyl levulinate conversion ratio be 100%, GVL yield be 91.5%.
The preparation method and application for the catalyst for synthesizing gamma-valerolactone that the present invention is disclosed and proposed, this field skill
Art personnel can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, although method of the invention and preparation skill
Art is described by preferred embodiment, and related technical personnel can obviously not depart from the content of present invention, spirit and model
Enclose it is interior methods and techniques described herein route is modified or is reconfigured, to realize final technology of preparing.Especially need
It is noted that all similar replacements and change are apparent to those skilled in the art, they are regarded
To be included in spirit of that invention, range and content.
Claims (10)
1. a kind of for synthesizing the method for preparing catalyst of gamma-valerolactone, it is characterised in that: the catalyst is using metal
Metal organic precursor object is supported on carrier by organic chemical vapor deposition method, and cobalt, nickel, copper load capacity are respectively 2-10wt%.
2. according to the method described in claim 1, it is characterized in that the carrier of the catalyst is γ-Al2O3、ZrO2、SiO2、
On AC, Graphene or meso-porous carbon material carrier.
3. according to the method described in claim 1, it is characterized by: the metal organic precursor object of the catalyst is acetylacetone,2,4-pentanedione
Cobalt (Co (acac)2), nickel acetylacetonate (Ni (acac)2) or acetylacetone copper (Cu (acac)2) predecessor.
4. according to the method described in claim 1, it is characterized by: being that 2-15wt% is weighed by the load capacity of cobalt, nickel, copper
Metallorganic precursors and carrier, mechanical mixture vacuumize in reaction tube, 100-300 DEG C at a temperature of keep 6-12h, make
Metallorganic precursors sufficiently distil and are adsorbed on carrier；It after absorption completely, is drawn off being placed in tube furnace, in hydrogen and lazy
Dynamic deposition is carried out under the gaseous mixture of property gas, thermally decomposes metallorganic precursors in tube furnace, the resolving time >=2h,
Obtain cobalt, nickel, copper-based catalysts.
5. according to the method described in claim 4, it is characterized in that carrying out thermal decomposition temperature in tube furnace is 200-600 DEG C.
6. application of the catalyst of preparation in synthesis gamma-valerolactone according to the method for claim 1, it is characterised in that:
The described synthesis gamma-valerolactone reaction is carried out in batch type high pressure reactor, and reaction substrate is levulic acid and its esters,
Heat-staple organic matter is designated as in reaction, reaction medium can not only dissolve substrate and reaction product, but also can be used as hydrogen donor rush
Into the progress of reaction, the mass ratio of reaction raw materials 100-1000mmol/L, reaction substrate and catalyst are 1:1-50:1, room temperature
The initial pressure that hydrogen is filled in lower batch reactor is 1-6MPa, and reaction temperature is 150-300 DEG C, reaction time 1-
6h, the agitation revolution of reaction kettle are 300-1500r/min.
7. application according to claim 6, it is characterised in that: the reaction substrate includes levulic acid, levulic acid
Methyl esters, ethyl levulinate or Butyl acetylpropanoate, molar concentration 100-500mmol/L.
8. application according to claim 6, it is characterised in that: the reaction medium is methanol, ethyl alcohol, isopropanol or secondary
Butanol.
9. application according to claim 6, it is characterised in that: the internal standard compound is dodecane or tridecane.
10. application according to claim 6, it is characterised in that: at room temperature in batch reactor hydrogen initial pressure
For 1-3MPa, reaction temperature >=150 DEG C, reaction time 1-6h, speed of agitator 800-1200r/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111036239A (en) * | 2019-12-03 | 2020-04-21 | 天津大学 | Supported sulfide catalyst, preparation method thereof and method for synthesizing gamma-valerolactone |
| CN111253347A (en) * | 2020-02-14 | 2020-06-09 | 大连大学 | Method for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid |
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| CN103193736A (en) * | 2013-03-30 | 2013-07-10 | 浙江工业大学 | Method for synthesizing gamma-valerolactone based on catalytic hydrogenation |
| CN106866589A (en) * | 2017-01-17 | 2017-06-20 | 浙江大学 | A kind of preparation method of γ valerolactones |
| CN107138164A (en) * | 2017-06-13 | 2017-09-08 | 天津大学 | Metalorganic Chemical Vapor Deposition synthesizes metallic catalyst and method |
| EP3359529A1 (en) * | 2015-10-06 | 2018-08-15 | Synvina C.V. | Process for the preparation of gamma-valerolactone |
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| CN102617519A (en) * | 2012-03-05 | 2012-08-01 | 中国石油大学(华东) | Method for using levulinic acid to prepare gamma-valerolactone by hydrogenation |
| CN103193736A (en) * | 2013-03-30 | 2013-07-10 | 浙江工业大学 | Method for synthesizing gamma-valerolactone based on catalytic hydrogenation |
| EP3359529A1 (en) * | 2015-10-06 | 2018-08-15 | Synvina C.V. | Process for the preparation of gamma-valerolactone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111036239A (en) * | 2019-12-03 | 2020-04-21 | 天津大学 | Supported sulfide catalyst, preparation method thereof and method for synthesizing gamma-valerolactone |
| CN111253347A (en) * | 2020-02-14 | 2020-06-09 | 大连大学 | Method for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid |
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