CN108311141A - A kind of preparation method and applications of ruthenium base plant graphitization multifunctional material - Google Patents
A kind of preparation method and applications of ruthenium base plant graphitization multifunctional material Download PDFInfo
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- CN108311141A CN108311141A CN201810139165.5A CN201810139165A CN108311141A CN 108311141 A CN108311141 A CN 108311141A CN 201810139165 A CN201810139165 A CN 201810139165A CN 108311141 A CN108311141 A CN 108311141A
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005087 graphitization Methods 0.000 title claims abstract description 14
- 239000007777 multifunctional material Substances 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 99
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 235000019441 ethanol Nutrition 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 27
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 230000006835 compression Effects 0.000 claims abstract description 14
- 238000007906 compression Methods 0.000 claims abstract description 14
- 239000007770 graphite material Substances 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000011943 nanocatalyst Substances 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 61
- 238000006555 catalytic reaction Methods 0.000 claims description 42
- 241000196324 Embryophyta Species 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000002131 composite material Substances 0.000 claims description 21
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 235000013339 cereals Nutrition 0.000 claims description 13
- 238000003306 harvesting Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910021603 Ruthenium iodide Inorganic materials 0.000 claims description 7
- 238000002474 experimental method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 241000878006 Miscanthus sinensis Species 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 4
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 244000003416 Asparagus officinalis Species 0.000 claims description 3
- 235000005340 Asparagus officinalis Nutrition 0.000 claims description 3
- 240000003173 Drymaria cordata Species 0.000 claims description 3
- 240000003826 Eichhornia crassipes Species 0.000 claims description 3
- 244000025670 Eleusine indica Species 0.000 claims description 3
- 235000014716 Eleusine indica Nutrition 0.000 claims description 3
- 240000006240 Linum usitatissimum Species 0.000 claims description 3
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 3
- 241000718543 Ormosia krugii Species 0.000 claims description 3
- 241001070186 Salsola collina Species 0.000 claims description 3
- 244000143590 Salvia chinensis Species 0.000 claims description 3
- 235000007154 Salvia chinensis Nutrition 0.000 claims description 3
- 235000005794 Salvia japonica Nutrition 0.000 claims description 3
- 235000010086 Setaria viridis var. viridis Nutrition 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical compound [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 235000009973 maize Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 241000735527 Eupatorium Species 0.000 claims description 2
- 235000011609 Pinus massoniana Nutrition 0.000 claims description 2
- 241000018650 Pinus massoniana Species 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000012847 fine chemical Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 244000230342 green foxtail Species 0.000 claims 1
- 239000013528 metallic particle Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical class CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 abstract description 45
- 239000007789 gas Substances 0.000 abstract description 37
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 39
- 239000002585 base Substances 0.000 description 38
- 239000002253 acid Substances 0.000 description 16
- 239000004809 Teflon Substances 0.000 description 12
- 229920006362 Teflon® Polymers 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 11
- 238000011056 performance test Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 244000304962 green bristle grass Species 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- -1 propyl alcohols Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation method and applications of a kind of plant graphitization multifunctional material and its loading ruthenium nanocatalyst, include the following steps：1) plant sequentially adds 0.2~4.2g urea, 0.5~3.5mL ammonium hydroxide after crushing, drying; 1.5~5.0mL ethyl alcohol is ultrasonically treated 2~12h, is then transferred into reaction kettle; 120~180 DEG C of 6~12h of hydro-thermal process; product is transferred to after 4000rpm centrifuges 10min in tube furnace, under Ar gas shieldeds, first 3~5h dry at 90~130 DEG C; 1 DEG C/min of heating rate; 2~3h of graphitization is carried out at 300~500 DEG C again, 2 DEG C/min of heating rate is then cooled to room temperature；2) in Ar compression rings border, porous graphite carbon material obtained by metal precursor and step 1) is added in 3~7mL ethyl alcohol by a certain percentage, it is allowed to be completely dispersed in 1000rpm stirrings 12h, it adds 2~10mL reducing agents (0.2~2.0M) and reacts 0.5~2h in 60~100 DEG C, product is dried in vacuo 6h after 5000rpm centrifuges 10min at 90 DEG C.Synthesized catalyst adds hydrogen levulic acid to prepare γ valerolactones for efficient catalytic.
Description
Technical field
The invention belongs to environmentally conscious materials technical fields and environmental friendly catalysis technological development clean fuel field, and in particular to
A kind of preparation method and applications of ruthenium base plant graphitization multifunctional material, this method is graphitized multi-functional using plant
Material passes through simple infusion process supported ruthenium catalyst conversion of biomass platform chemicals levulinic in a mild condition as carrier
Acid prepares gamma-valerolactone.
Background technology
Global environmental problem caused by the world energy sources structure based on oil, coal is mainly reflected in greenhouse effect at present
Answer, depletion of the ozone layer, acid rain etc..Energy resource structure of the China based on oil, coal also results in very serious air
Pollution, and the discharge capacity of carbon dioxide and sulfur dioxide all occupies countries in the world forefront.On the other hand, in the past few decades
In, since the factors such as the increasingly exhausted of fossil resource, the increase of crude oil price and the sustainable growth of energy demand cause
Seeking to develop renewable resources to synthesize, there is the chemical products of high value and clean fuel to attract attention.
As a kind of important greening platform compound, levulic acid has caused that many researchers' in the world is extensive emerging
Interest.Up to now, the compound of all kinds of high values and novel macromolecule material are prepared for using the good activity of levulic acid
Material, wherein levulic acid can form widely used fine chemicals gamma-valerolactone by adding hydrogen and closed loop lactone to convert.γ-
Valerolactone can not only be used for the gelling agent of plasticizer, lubricant, food odorant, nonionic surface active agent, it is also possible to close
At medicine, resin solvent and various related compound intermediates.Meanwhile gamma-valerolactone or a kind of ideal renewable green
Biomass fuel has suitable polarity and higher energy density, can be miscible with existing transport fuel arbitrary proportion, has
Good application potential is paid attention to by more and more researchers in recent years.
The technique noble metal multi-purpose greatly of existing synthesis gamma-valerolactone is as catalysis material, although transformation efficiency is higher, one
As need to realize under more exacting terms.Want reduction levulic acid under the conditions of comparatively gentle to usually require to add
Enter additional accelerant, such as alkali compounds, thus inevitably complicate reaction system, target product is caused to detach
Difficulty increases.In addition, another very important problem, which is the direct catalytic hydrogenation of levulic acid, easy tos produce 2- methyl tetrahydrochysene furans
It mutters, a kind of over reduction product, and peroxidating easily occurs in air environment for this substance, generates inflammable and explosive danger
Substance.Therefore, it is badly in need of seeking a kind of safer efficient, simple for process, environmentally protective gamma-valerolactone route of synthesis at present.
Invention content
It is prepared present in gamma-valerolactone technique for the above existing catalyzed conversion biomass platform chemicals levulic acid
Problem, the present invention is intended to provide a kind of novel plant body graphitization multifunctional C carried metal ruthenium catalyst is real in a mild condition
Existing levulic acid catalytic hydrogenation prepares gamma-valerolactone process, and the method is easy to operate, of low cost, has relatively strong industrialization
Application potential, and efficiently use non-consumption plant and prepare porous graphite carbon carrier；The catalysis material transformation efficiency
Height, selectivity is good, and stability is superior.
The main purpose of the present invention is to provide a kind of ruthenium base plant be graphitized multifunctional material preparation method and its
Using specifically including following steps：
(1) in the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by levulic acid and nanometer ruthenium base is compound urges
Change material to be added to by a certain percentage in 5~10mL aqueous solutions, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures reaction kettle
Interior air completely removes；
(2) it is filled with H in a kettle2Gas, and control its pressure in 20~80bar, when reaction system reaches 100~
5~10h is reacted after 220 DEG C, continuing magnetic force stirs in entire catalytic hydrogenation, and rotating speed is 800~1800rpm；
(3) after reaction, it waits for reaction kettle cooled to room temperature, is filtered separation, collect product liquid and divided
Analysis.Catalyst after use carries out cycle catalytic hydrogenation experiment after centrifugation, washing, drying.
The mass ratio of the levulic acid and nanometer ruthenium based composite catalysis material is 20: 1~40: 1.
After catalysis material after the use carries out cycle catalytic hydrogenation experiment as that will react after centrifugation, washing, drying
Catalysis material centrifugation 20min after wash 3 times with methanol, distillation water washing 3 times, then at 100 DEG C after vacuum drying 6h
Carry out next round Catalysis experiments.
The nanometer ruthenium based composite catalysis material is by the nanometer ruthenium metal of porous graphite carbon support material and its load
Particle forms, and is prepared by the following method to obtain, be as follows：
(1) by the plant of harvesting after physical crushing, the drying at 100 DEG C is until it is fully dry；
(2) the sample 2g after drying is taken, 0.2~4.2g urea, 0.5~3.5mL ammonium hydroxide, 1.5~5.0mL second are sequentially added
Alcohol carries out 2~12h of supersound process；
(3) said mixture is transferred in 100mL Teflon liner reaction kettles, 120~180 DEG C of hydro-thermal process 6~
12h；
(4) product is transferred to after 4000rpm centrifuges 10min in tube furnace, under Ar gas shieldeds, first at 90~130 DEG C
Dry 3~5h, 1 DEG C/min of heating rate, then 2~3h of graphitization is carried out at 300~500 DEG C, 2 DEG C/min of heating rate, with
Postcooling is to room temperature；
(5) in Ar compression rings border, porous graphite carbon material obtained by metal precursor and step 4) is added by a certain percentage
Enter into 3~7mL ethyl alcohol, is allowed to be completely dispersed in 1000rpm stirrings 12h；
(6) in said mixture solution be added 2~10mL reducing agents (0.2~2.0M) in 60~100 DEG C react 0.5~
2h, products therefrom at 90 DEG C after 5000rpm centrifugations 10min by being dried in vacuo 6h.
The plant is masson pine, green bristlegrass, Chinese silvergrass leaf, maize straw, fibre of flax for textile material, Salvia japonica, eleusine indica, aircraft
Grass, toad grass, ox chickweed, Canton love-pea vine, tongue of sparrow grass, Eichhornia crassipes, lady's-grass and salsola collina one or more.
The grain size of plant after the physical crushing drying is made of the particle that size is 0.5~20mm.
The metal precursor is RuI3、RuCl3、RuNO(NO3)3、Ru3(CO)12、Ru(acac)3One or more of.
The mass ratio of the ruthenium predecessor and porous graphite carbon material is 1: 5~1: 40.
The reducing agent is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, ethylene glycol or sodium borohydride.
Compared with prior art, the invention has the advantages that：
(1) the porous graphite carbon prepared using a variety of non-consumption plants has high-specific surface area, high conductivity thin
Interlayer electrostatic force prevents the multiple functions of accumulation of metal.
(2) nanometer ruthenium based composite catalysis material activity is high, and good reaction selectivity, gamma-valerolactone yield height is up to 99%.
(3) the ruthenium based composite catalysis material prepared by can be recycled with continuous several times, have higher commercial Application valence
Value.
(4) when ruthenium based composite catalysis material prepared by is used for levulic acid hydro-conversion gamma-valerolactone, raw material can compared with
Conversion completely is realized in short time, and reaction condition is mild, avoided in reaction process using a large amount of inorganic acid or alkali, no
But the adverse effect to environment avoided also improves the safety of transformation system.
Description of the drawings
Fig. 1 is the SEM spectrum for the novel porous graphitized carbon material that the present invention is prepared by raw material of Chinese silvergrass leaf plant；
Fig. 2 is the nanometer ruthenium based composite catalysis material SEM spectrum prepared by the present invention.
Specific implementation mode
The present invention is furtherd elucidate below by drawings and examples, but protection domain of the present invention is not limited to
Shown content.
Embodiment 1：
New Ruthenium base plant is graphitized the preparation of catalysis material：
By the Chinese silvergrass leaf of harvesting through physical crushing after, the drying at 100 DEG C is until it is fully dry.Take the grain after drying
Diameter is 0.5~20mm sample 2g, sequentially adds 0.2g urea, 0.5mL ammonium hydroxide, 1.5mL ethyl alcohol carries out supersound process 2h.It will be upper
It states mixture to be transferred in 25mL Teflon liner reaction kettles, 120 DEG C of hydro-thermal process 6h.Product centrifuges 10min in 4000rpm
After be transferred in tube furnace, under Ar gas shieldeds, first dry 3h, 1 DEG C/min of heating rate at 90 DEG C, then carried out at 300 DEG C
It is graphitized 2h, 2 DEG C/min of heating rate is then cooled to room temperature.In Ar compression rings border, by 10mg RuI3Much with 50mg institutes
Hole graphitized carbon material is added in 3mL ethyl alcohol, is allowed to be completely dispersed in 1000rpm stirrings 12h.In said mixture solution
2mL methanol (0.2M) is added and reacts 0.5h in 60 DEG C, products therefrom is by the way that vacuum is dry at 90 DEG C after 5000rpm centrifugations 10min
Dry 6h obtains New Ruthenium base plant and is graphitized multi-functional catalysis material.It is obtained to be prepared by raw material of Chinese silvergrass leaf plant
Novel porous graphitized carbon material SEM spectrum it is as shown in Figure 1；Obtained nanometer ruthenium based composite catalysis material SEM spectrum
As shown in Figure 2.
Catalytic performance test：
In the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by 2.0g levulic acids and 0.1g nanometers of ruthenium bases
Composite catalyzing material is added to by a certain percentage in 5mL aqueous solutions, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures reaction
Air completely removes in kettle.It is filled with H in a kettle2Gas, and its pressure is controlled in 20bar, when reaction system reaches 200 DEG C
After react 5h, in entire catalytic hydrogenation continuing magnetic force stir, rotating speed 800rpm.After reaction, wait for reaction kettle certainly
It is so cooled to room temperature, is filtered separation, product is analyzed with gas-chromatography after handling filtrate, calculates levulic acid
Conversion ratio be 99.7%, gamma-valerolactone selectively be 90.5%.
After 6 continuous circulation experiments, regenerated ruthenium base plant is graphitized catalysis material catalytic hydrogenation levulic acid
Conversion ratio still be up to 99.3%, gamma-valerolactone selectively be 87.4%.
Embodiment 2：
New Ruthenium base plant is graphitized the preparation of catalysis material：
By the horse hair loose warp physical crushing of harvesting at rear, the drying at 100 DEG C is until it is fully dry.Take the grain after drying
Diameter is 0.5~20mm sample 2g, sequentially adds 0.6g urea, 1.0mL ammonium hydroxide, 2.0mL ethyl alcohol carries out supersound process 4h.It will be upper
It states mixture to be transferred in 25mL Teflon liner reaction kettles, 130 DEG C of hydro-thermal process 8h.Product centrifuges 10min in 4000rpm
After be transferred in tube furnace, under Ar gas shieldeds, first dry 3h, 1 DEG C/min of heating rate at 100 DEG C, then carried out at 300 DEG C
It is graphitized 3h, 2 DEG C/min of heating rate is then cooled to room temperature.In Ar compression rings border, by 10mg RuCl3Obtained by 100mg
Porous graphite carbon material is added in 5mL ethyl alcohol, is allowed to be completely dispersed in 1000rpm stirrings 12h.In said mixture solution
Middle addition 2mL ethyl alcohol (1.0M) in 60 DEG C react 0.5h, products therefrom by 5000rpm centrifuge 10min after at 90 DEG C vacuum
Dry 6h obtains New Ruthenium base plant and is graphitized multi-functional catalysis material.
Catalytic performance test：
In the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by 2.5g levulic acids and 0.1g nanometers of ruthenium bases
Composite catalyzing material is added to by a certain percentage in 5mL aqueous solutions, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures reaction
Air completely removes in kettle.It is filled with H in a kettle2Gas, and its pressure is controlled in 20bar, when reaction system reaches 160 DEG C
After react 5h, in entire catalytic hydrogenation continuing magnetic force stir, rotating speed 1000rpm.After reaction, wait for reaction kettle certainly
It is so cooled to room temperature, is filtered separation, product is analyzed with gas-chromatography after handling filtrate, calculates levulic acid
Conversion ratio be 98.9%, gamma-valerolactone selectively be 91.3%.
Embodiment 3：
New Ruthenium base plant is graphitized the preparation of catalysis material：
By the green bristlegrass of harvesting through physical crushing after, the drying at 100 DEG C is until it is fully dry.Take the grain after drying
Diameter is 0.5~20mm sample 2g, sequentially adds 1.0g urea, 1.5mL ammonium hydroxide, 2.5mL ethyl alcohol carries out supersound process 6h.It will be upper
It states mixture to be transferred in 25mL Teflon liner reaction kettles, 140 DEG C of hydro-thermal process 10h.Product centrifuges 10min in 4000rpm
After be transferred in tube furnace, under Ar gas shieldeds, first dry 3h, 1 DEG C/min of heating rate at 110 DEG C, then carried out at 400 DEG C
It is graphitized 2h, 2 DEG C/min of heating rate is then cooled to room temperature.In Ar compression rings border, by 10mg RuNO (NO3)3And 150mg
Gained porous graphite carbon material is added in 7mL ethyl alcohol, is allowed to be completely dispersed in 1000rpm stirrings 12h.In said mixture
In solution be added 2mL normal propyl alcohols (1.5M) in 60 DEG C react 0.5h, products therefrom by 5000rpm centrifuge 10min after at 90 DEG C
Lower vacuum drying 6h obtains New Ruthenium base plant and is graphitized multi-functional catalysis material.
Catalytic performance test：
In the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by 3.0g levulic acids and 0.1g nanometers of ruthenium bases
Composite catalyzing material is added to by a certain percentage in 10mL water alkane solution, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures anti-
Air in kettle is answered to completely remove.It is filled with H in a kettle2Gas, and its pressure is controlled in 40bar, when reaction system reaches 180
8h is reacted after DEG C, continuing magnetic force stirs in entire catalytic hydrogenation, rotating speed 1200rpm.After reaction, reaction kettle is waited for
Cooled to room temperature is filtered separation, is analyzed product with gas-chromatography after handling filtrate, calculates levulinic
The conversion ratio of acid is 98.6%, and gamma-valerolactone is selectively 90.1%.
Embodiment 4：
New Ruthenium base plant is graphitized the preparation of catalysis material：
By the Salvia japonica of harvesting and lady's-grass through physical crushing after, the drying at 100 DEG C is until it is fully dry.Take drying
Grain size afterwards is 0.5~20mm sample 2g, sequentially adds 1.4g urea, 2.0mL ammonium hydroxide, 3.0mL ethyl alcohol is ultrasonically treated
8h.Said mixture is transferred in 25mL Teflon liner reaction kettles, 150 DEG C of hydro-thermal process 12h.Product in 4000rpm from
It is transferred in tube furnace after heart 10min, under Ar gas shieldeds, first dry at 120 DEG C 3h, 1 DEG C/min of heating rate, then 400
Graphitization 3h is carried out at DEG C, 2 DEG C/min of heating rate is then cooled to room temperature.In Ar compression rings border, by 10mg Ru3(CO)12
It is added in 3mL ethyl alcohol with porous graphite carbon material obtained by 200mg, is allowed to be completely dispersed in 1000rpm stirrings 12h.Upper
It states and 2mL isopropanols (2.0M) is added in mixture solution in 60 DEG C of reaction 0.5h, products therefrom centrifuges 10min by 5000rpm
It is dried in vacuo 6h at 90 DEG C afterwards, New Ruthenium base plant is obtained and is graphitized multi-functional catalysis material.
Catalytic performance test：
In the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by 3.5g levulic acids and 0.1g nanometers of ruthenium bases
Composite catalyzing material is added to by a certain percentage in 5mL aqueous solutions, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures reaction
Air completely removes in kettle.It is filled with H in a kettle2Gas, and its pressure is controlled in 60bar, when reaction system reaches 140 DEG C
After react 10h, in entire catalytic hydrogenation continuing magnetic force stir, rotating speed 1800rpm.After reaction, reaction kettle is waited for
Cooled to room temperature is filtered separation, is analyzed product with gas-chromatography after handling filtrate, calculates levulinic
The conversion ratio of acid is 98.9%, and gamma-valerolactone is selectively 91.7%.
Embodiment 5：
New Ruthenium base plant is graphitized the preparation of catalysis material：
By the fibre of flax for textile material of harvesting and ox chickweed through physical crushing after, the drying at 100 DEG C is until it is fully dry.It takes
Grain size after drying is 0.5~20mm sample 2g, sequentially adds 1.8g urea, 2.5mL ammonium hydroxide, and 3.5mL ethyl alcohol carries out at ultrasound
Manage 10h.Said mixture is transferred in 25mL Teflon liner reaction kettles, 160 DEG C of hydro-thermal process 8h.Product is in 4000rpm
It is transferred in tube furnace after centrifugation 10min, under Ar gas shieldeds, first dry at 130 DEG C 3h, 1 DEG C/min of heating rate, then
Graphitization 2h is carried out at 500 DEG C, 2 DEG C/min of heating rate is then cooled to room temperature.In Ar compression rings border, by 10mg Ru
(acac)3It is added in 3mL ethyl alcohol with porous graphite carbon material obtained by 250mg, is allowed to divide completely in 1000rpm stirrings 12h
It dissipates.10mL ethylene glycol (0.2M) is added in said mixture solution and reacts 1h in 80 DEG C, products therefrom is centrifuged by 5000rpm
It is dried in vacuo 6h at 90 DEG C after 10min, New Ruthenium base plant is obtained and is graphitized multi-functional catalysis material.
Catalytic performance test：
In the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by 4.0g levulic acids and 0.1g nanometers of ruthenium bases
Composite catalyzing material is added to by a certain percentage in 10mL aqueous solutions, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures reaction
Air completely removes in kettle.It is filled with H in a kettle2Gas, and its pressure is controlled in 80bar, when reaction system reaches 120 DEG C
After react 5h, in entire catalytic hydrogenation continuing magnetic force stir, rotating speed 1600rpm.After reaction, wait for reaction kettle certainly
It is so cooled to room temperature, is filtered separation, product is analyzed with gas-chromatography after handling filtrate, calculates levulic acid
Conversion ratio be 96.5%, gamma-valerolactone selectively be 93.7%.
Embodiment 6：
New Ruthenium base plant is graphitized the preparation of catalysis material：
By the eleusine indica of harvesting and tongue of sparrow grass through physical crushing after, the drying at 100 DEG C is until it is fully dry.Take baking
Grain size after dry is 0.5~20mm sample 2g, sequentially adds 2.2g urea, 3.0mL ammonium hydroxide, 4.0mL ethyl alcohol is ultrasonically treated
12h.Said mixture is transferred in 25mL Teflon liner reaction kettles, 170 DEG C of hydro-thermal process 8h.Product in 4000rpm from
It is transferred in tube furnace after heart 10min, under Ar gas shieldeds, first dry at 90 DEG C 4h, 1 DEG C/min of heating rate, then at 500 DEG C
Under carry out graphitization 3h, 2 DEG C/min of heating rate is then cooled to room temperature.In Ar compression rings border, by 10mg RuI3And 300mg
Gained porous graphite carbon material is added in 5mL ethyl alcohol, is allowed to be completely dispersed in 1000rpm stirrings 12h.In said mixture
In solution be added 10mL sodium borohydrides (0.5M) in 100 DEG C react 2h, products therefrom by 5000rpm centrifuge 10min after 90
It is dried in vacuo 6h at DEG C, obtains New Ruthenium base plant and is graphitized multi-functional catalysis material.
Catalytic performance test：
In the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by 3.0g levulic acids and 0.1g nanometers of ruthenium bases
Composite catalyzing material is added to by a certain percentage in 5mL aqueous solutions, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures reaction
Air completely removes in kettle.It is filled with H in a kettle2Gas, and its pressure is controlled in 80bar, when reaction system reaches 220 DEG C
After react 10h, in entire catalytic hydrogenation continuing magnetic force stir, rotating speed 1400rpm.After reaction, reaction kettle is waited for
Cooled to room temperature is filtered separation, is analyzed product with gas-chromatography after handling filtrate, calculates levulinic
The conversion ratio of acid is 99.8%, and gamma-valerolactone is selectively 94.2%.
Embodiment 7：
New Ruthenium base plant is graphitized the preparation of catalysis material：
By the fragrant eupatorium herb of harvesting and salsola collina through physical crushing after, the drying at 100 DEG C is until it is fully dry.Take baking
Grain size after dry is 0.5~20mm sample 2g, sequentially adds 2.6g urea, 3.5mL ammonium hydroxide, 4.5mL ethyl alcohol is ultrasonically treated
6h.Said mixture is transferred in 25mL Teflon liner reaction kettles, 180 DEG C of hydro-thermal process 8h.Product in 4000rpm from
It is transferred in tube furnace after heart 10min, under Ar gas shieldeds, first dry at 90 DEG C 5h, 1 DEG C/min of heating rate, then at 350 DEG C
Under carry out graphitization 2h, 2 DEG C/min of heating rate is then cooled to room temperature.In Ar compression rings border, by 10mg RuI3And 350mg
Gained porous graphite carbon material is added in 7mL ethyl alcohol, is allowed to be completely dispersed in 1000rpm stirrings 12h.In said mixture
In solution be added 10mL sodium borohydrides (1.0M) in 100 DEG C react 1.5h, products therefrom by 5000rpm centrifuge 10min after
It is dried in vacuo 6h at 90 DEG C, New Ruthenium base plant is obtained and is graphitized multi-functional catalysis material.
Catalytic performance test：
In the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by 4.0g levulic acids and 0.1g nanometers of ruthenium bases
Composite catalyzing material is added to by a certain percentage in 5mL aqueous solutions, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures reaction
Air completely removes in kettle.It is filled with H in a kettle2Gas, and its pressure is controlled in 80bar, when reaction system reaches 200 DEG C
After react 8h, in entire catalytic hydrogenation continuing magnetic force stir, rotating speed 1200rpm.After reaction, wait for reaction kettle certainly
It is so cooled to room temperature, is filtered separation, product is analyzed with gas-chromatography after handling filtrate, calculates levulic acid
Conversion ratio be 99.9%, gamma-valerolactone selectively be 93.5%.
Embodiment 8：
New Ruthenium base plant is graphitized the preparation of catalysis material：
By the toad grass of harvesting through physical crushing after, the drying at 100 DEG C is until it is fully dry.Take the grain after drying
Diameter is 0.5~20mm sample 2g, sequentially adds 3.0g urea, 3.0mL ammonium hydroxide, 5.0mL ethyl alcohol carries out supersound process 10h.It will be upper
It states mixture to be transferred in 25mL Teflon liner reaction kettles, 120 DEG C of hydro-thermal process 6h.Product centrifuges 10min in 4000rpm
After be transferred in tube furnace, under Ar gas shieldeds, first dry 4h, 1 DEG C/min of heating rate at 100 DEG C, then carried out at 450 DEG C
It is graphitized 2h, 2 DEG C/min of heating rate is then cooled to room temperature.In Ar compression rings border, by 10mg RuI3Much with 400mg institutes
Hole graphitized carbon material is added in 3mL ethyl alcohol, is allowed to be completely dispersed in 1000rpm stirrings 12h.In said mixture solution
5mL ethyl alcohol (0.5M) is added and reacts 2h in 80 DEG C, products therefrom after 5000rpm centrifugations 10min at 90 DEG C by being dried in vacuo
6h obtains New Ruthenium base plant and is graphitized multi-functional catalysis material.
Catalytic performance test：
In the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by 3.0g levulic acids and 0.1g nanometers of ruthenium bases
Composite catalyzing material is added to by a certain percentage in 10mL aqueous solutions, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures reaction
Air completely removes in kettle.It is filled with H in a kettle2Gas, and its pressure is controlled in 60bar, when reaction system reaches 100 DEG C
After react 5h, in entire catalytic hydrogenation continuing magnetic force stir, rotating speed 1000rpm.After reaction, wait for reaction kettle certainly
It is so cooled to room temperature, is filtered separation, product is analyzed with gas-chromatography after handling filtrate, calculates levulic acid
Conversion ratio be 99.2%, gamma-valerolactone selectively be 88.2%.
Embodiment 9：
New Ruthenium base plant is graphitized the preparation of catalysis material：
By the Canton love-pea vine of harvesting through physical crushing after, the drying at 100 DEG C is until it is fully dry.Take the grain after drying
Diameter is 0.5~20mm sample 2g, sequentially adds 3.4g urea, 3.5mL ammonium hydroxide, 3.5mL ethyl alcohol carries out supersound process 4h.It will be upper
It states mixture to be transferred in 25mL Teflon liner reaction kettles, 140 DEG C of hydro-thermal process 6h.Product centrifuges 10min in 4000rpm
After be transferred in tube furnace, under Ar gas shieldeds, first dry 4h, 1 DEG C/min of heating rate at 120 DEG C, then carried out at 300 DEG C
It is graphitized 2.5h, 2 DEG C/min of heating rate is then cooled to room temperature.In Ar compression rings border, by 10mg Ru (acac)3With
Porous graphite carbon material is added in 3mL ethyl alcohol obtained by 100mg, is allowed to be completely dispersed in 1000rpm stirrings 12h.Above-mentioned
In mixture solution be added 5mL ethyl alcohol (1.5M) in 60 DEG C react 2h, products therefrom by 5000rpm centrifuge 10min after 90
It is dried in vacuo 6h at DEG C, obtains New Ruthenium base plant and is graphitized multi-functional catalysis material.
Catalytic performance test：
In the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by 4.0g levulic acids and 0.1g nanometers of ruthenium bases
Composite catalyzing material is added to by a certain percentage in 5mL aqueous solutions, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures reaction
Air completely removes in kettle.It is filled with H in a kettle2Gas, and its pressure is controlled in 40bar, when reaction system reaches 220 DEG C
After react 10h, in entire catalytic hydrogenation continuing magnetic force stir, rotating speed 1800rpm.After reaction, reaction kettle is waited for
Cooled to room temperature is filtered separation, is analyzed product with gas-chromatography after handling filtrate, calculates levulinic
The conversion ratio of acid is 99.3%, and gamma-valerolactone is selectively 92.7%.
Embodiment 10：
New Ruthenium base plant is graphitized the preparation of catalysis material：
By the maize straw of harvesting through physical crushing after, the drying at 100 DEG C is until it is fully dry.After taking drying
Grain size is 0.5~20mm sample 2g, sequentially adds 3.8g urea, 3.5mL ammonium hydroxide, 3.5mL ethyl alcohol carries out supersound process 8h.It will
Said mixture is transferred in 25mL Teflon liner reaction kettles, 180 DEG C of hydro-thermal process 6h.Product is centrifuged in 4000rpm
It is transferred in tube furnace after 10min, under Ar gas shieldeds, first dry at 130 DEG C 5h, 1 DEG C/min of heating rate, then at 400 DEG C
Under carry out graphitization 2.5h, 2 DEG C/min of heating rate is then cooled to room temperature.In Ar compression rings border, by 10mg RuCl3With
Porous graphite carbon material is added in 3mL ethyl alcohol obtained by 50mg, is allowed to be completely dispersed in 1000rpm stirrings 12h.Above-mentioned mixed
In polymer solution be added 5mL ethyl alcohol (1.0M) in 60 DEG C react 2h, products therefrom by 5000rpm centrifuge 10min after at 90 DEG C
Lower vacuum drying 6h obtains New Ruthenium base plant and is graphitized multi-functional catalysis material.
Catalytic performance test：
In the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by 4.0g levulic acids and 0.1g nanometers of ruthenium bases
Composite catalyzing material is added to by a certain percentage in 10mL aqueous solutions, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures reaction
Air completely removes in kettle.It is filled with H in a kettle2Gas, and its pressure is controlled in 20bar, when reaction system reaches 100 DEG C
After react 5h, in entire catalytic hydrogenation continuing magnetic force stir, rotating speed 800rpm.After reaction, wait for reaction kettle certainly
It is so cooled to room temperature, is filtered separation, product is analyzed with gas-chromatography after handling filtrate, calculates levulic acid
Conversion ratio be 98.5%, gamma-valerolactone selectively be 94.1%.
Embodiment 11：
New Ruthenium base plant is graphitized the preparation of catalysis material：
By the Eichhornia crassipes of harvesting through physical crushing after, the drying at 100 DEG C is until it is fully dry.Take the grain after drying
Diameter is 0.5~20mm sample 2g, sequentially adds 4.2g urea, 3.5mL ammonium hydroxide, 4.5mL ethyl alcohol carries out supersound process 6h.It will be upper
It states mixture to be transferred in 25mL Teflon liner reaction kettles, 160 DEG C of hydro-thermal process 10h.Product centrifuges 10min in 4000rpm
After be transferred in tube furnace, under Ar gas shieldeds, first dry 3h, 1 DEG C/min of heating rate at 90 DEG C, then carried out at 500 DEG C
It is graphitized 2.5h, 2 DEG C/min of heating rate is then cooled to room temperature.In Ar compression rings border, by 10mg RuI3Obtained by 250mg
Porous graphite carbon material is added in 7mL ethyl alcohol, is allowed to be completely dispersed in 1000rpm stirrings 12h.In said mixture solution
Middle addition 10mL ethyl alcohol (2.0M) in 100 DEG C react 2h, products therefrom by 5000rpm centrifuge 10min after at 90 DEG C vacuum
Dry 6h obtains New Ruthenium base plant and is graphitized multi-functional catalysis material.
Catalytic performance test：
In the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by 2.0g levulic acids and 0.1g nanometers of ruthenium bases
Composite catalyzing material is added to by a certain percentage in 5~10mL aqueous solutions, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures
Air completely removes in reaction kettle.It is filled with H in a kettle2Gas, and its pressure is controlled in 80bar, when reaction system reaches
10h is reacted after 220 DEG C, continuing magnetic force stirs in entire catalytic hydrogenation, rotating speed 800rpm.After reaction, it waits for anti-
Kettle cooled to room temperature is answered, separation is filtered, product is analyzed with gas-chromatography after handling filtrate, calculates second
The conversion ratio of acyl propionic acid is 99.6%, and gamma-valerolactone is selectively 95.8%.
Claims (10)
1. a kind of plant graphitization multifunctional material and its loading ruthenium nanocatalyst are (hereinafter referred to as：Ruthenium base plant stone
Inkization multifunctional material) preparation method and applications, it is characterised in that include the following steps：
(1) in the 100mL glass-lineds for being built in high-temperature high-pressure reaction kettle, by levulic acid and nanometer ruthenium based composite catalysis material
Material is added to by a certain percentage in 5~10mL aqueous solutions, is then passed through N continuous 3 times2Gas simultaneously vacuumizes, and ensures empty in reaction kettle
Gas completely removes；
(2) it is filled with H in a kettle2Gas, and its pressure is controlled in 20~80bar, after reaction system reaches 100~220 DEG C
5~10h is reacted, continuing magnetic force stirs in entire catalytic hydrogenation, and rotating speed is 800~1800rpm；
(3) after reaction, it waits for reaction kettle cooled to room temperature, is filtered separation, collect product liquid and analyzed.Make
Catalyst after carries out cycle catalytic hydrogenation experiment after centrifugation, washing, drying.
2. according to the method described in claim 1, it is characterized in that, the levulic acid and nanometer ruthenium based composite catalysis material
Mass ratio is 20: 1~40: 1.
3. according to the method described in claim 1, it is characterized in that, the catalysis material after the use is through centrifugation, washing, drying
It is to be washed 3 times with methanol after the catalysis material after reacting centrifuges 20min to carry out cycle catalytic hydrogenation experiment afterwards, distills water washing
3 times, then can carry out next round Catalysis experiments after being dried in vacuo 6h at 100 DEG C.
4. according to the method described in claim 1, it is characterized in that, the nanometer ruthenium based composite catalysis material is by porous graphite
Change carbon support material and the nanometer ruthenium metallic particles composition of its load, is prepared by the following method to obtain, be as follows：
(1) by the plant of harvesting after physical crushing, the drying at 100 DEG C is until it is fully dry；
(2) the sample 2g after drying is taken, sequentially adds 0.2~4.2g urea, 0.5~3.5mL ammonium hydroxide, 1.5~5.0mL ethyl alcohol,
Carry out 2~12h of supersound process；
(3) said mixture is transferred in 25mLTeflon liner reaction kettles, 120~180 DEG C of 6~12h of hydro-thermal process；
(4) product is transferred to after 4000rpm centrifuges 10min in tube furnace, under Ar gas shieldeds, first dry 3 at 90~130 DEG C
~5h, 1 DEG C/min of heating rate, then 2~3h of graphitization is carried out at 300~500 DEG C, 2 DEG C/min of heating rate, with postcooling
To room temperature；
(5) in Ar compression rings border, porous graphite carbon material obtained by metal precursor and step 4) is added to 3 by a certain percentage
In~7mL ethyl alcohol, it is allowed to be completely dispersed in 1000rpm stirrings 12h；
(6) 2~10mL reducing agents (0.2~2.0M) are added in said mixture solution and react 0.5~2h in 60~100 DEG C,
Products therefrom at 90 DEG C after 5000rpm centrifugations 10min by being dried in vacuo 6h.
5. according to the method described in claim 4, it is characterized in that, the plant be masson pine, green bristlegrass, maize straw,
Fibre of flax for textile material, Chinese silvergrass leaf, Salvia japonica, eleusine indica, fragrant eupatorium herb, toad grass, ox chickweed, Canton love-pea vine, tongue of sparrow grass, Eichhornia crassipes, lady's-grass
With the one or more of salsola collina.
6. according to the method described in claim 4, it is characterized in that, the grain size of the plant after physical crushing drying is by ruler
The very little particle composition for being 0.5~20mm.
7. according to the method described in claim 4, it is characterized in that, the metal precursor is RuI3、RuCl3、RuNO(NO3)3、
Ru3(CO)12、Ru(acac)3One or more of.
8. according to the method described in claim 4, it is characterized in that, the quality of the ruthenium predecessor and porous graphite carbon material
Than being 1: 5~1: 40.
9. according to the method described in claim 4, it is characterized in that, the reducing agent be methanol, ethyl alcohol, normal propyl alcohol, isopropanol,
Ethylene glycol or sodium borohydride.
10. the ruthenium base plant according to claim 1-9 is graphitized the preparation of multifunctional material and its applies in biomass
Catalyzed conversion prepares the application in clean fuel and high added value fine chemical product.
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| CN102658131A (en) * | 2012-04-26 | 2012-09-12 | 大连理工大学 | Ruthenium-based catalyst for preparing gamma-valerolactone from acetylpropionic acid, and preparation method for ruthenium-based catalyst |
| CN104445138A (en) * | 2014-11-04 | 2015-03-25 | 东北林业大学 | Method for preparing high-conductivity carbon material by virtue of hydrothermal method |
| CN105289592A (en) * | 2015-11-19 | 2016-02-03 | 中科合成油技术有限公司 | Method for preparing gamma-valerolactone by acetylpropionic acid catalytic hydrogenation |
| CN105858636A (en) * | 2016-04-05 | 2016-08-17 | 陕西科技大学 | Method for preparing pine needle derived micro-nano structure hard carbon material |
| CN105883748A (en) * | 2016-04-12 | 2016-08-24 | 湘潭大学 | Highly-graphitized carbon nanowire ball material and preparation method thereof |
| CN107159214A (en) * | 2017-06-22 | 2017-09-15 | 桂林电子科技大学 | A kind of porous active carbon material load cobalt nanometer particle material and its preparation method and application |
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2018
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| CN102658131A (en) * | 2012-04-26 | 2012-09-12 | 大连理工大学 | Ruthenium-based catalyst for preparing gamma-valerolactone from acetylpropionic acid, and preparation method for ruthenium-based catalyst |
| CN104445138A (en) * | 2014-11-04 | 2015-03-25 | 东北林业大学 | Method for preparing high-conductivity carbon material by virtue of hydrothermal method |
| CN105289592A (en) * | 2015-11-19 | 2016-02-03 | 中科合成油技术有限公司 | Method for preparing gamma-valerolactone by acetylpropionic acid catalytic hydrogenation |
| CN105858636A (en) * | 2016-04-05 | 2016-08-17 | 陕西科技大学 | Method for preparing pine needle derived micro-nano structure hard carbon material |
| CN105883748A (en) * | 2016-04-12 | 2016-08-24 | 湘潭大学 | Highly-graphitized carbon nanowire ball material and preparation method thereof |
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