CN110479369A - The method that Yolk-shell type catalyst and its synthetic method and its catalysis levulic acid prepare gamma-valerolactone - Google Patents
The method that Yolk-shell type catalyst and its synthetic method and its catalysis levulic acid prepare gamma-valerolactone Download PDFInfo
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- CN110479369A CN110479369A CN201910768645.2A CN201910768645A CN110479369A CN 110479369 A CN110479369 A CN 110479369A CN 201910768645 A CN201910768645 A CN 201910768645A CN 110479369 A CN110479369 A CN 110479369A
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- valerolactone
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 72
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000006555 catalytic reaction Methods 0.000 title claims description 17
- 238000010189 synthetic method Methods 0.000 title abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 14
- 229910000510 noble metal Inorganic materials 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005580 one pot reaction Methods 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 239000010970 precious metal Substances 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 2
- 229910020427 K2PtCl4 Inorganic materials 0.000 claims description 2
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004064 recycling Methods 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
- 238000010792 warming Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 229910052681 coesite Inorganic materials 0.000 abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 150000007513 acids Chemical class 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 35
- 239000000047 product Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 8
- 238000012805 post-processing Methods 0.000 description 7
- 230000009471 action Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 3
- -1 among these Chemical compound 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J23/44—Palladium
-
- 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
- B01J23/464—Rhodium
-
- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- B01J35/398—
-
- B01J35/60—
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to levulic acids plus hydrogen to prepare gamma-valerolactone technical field, discloses Yolk-shell type catalyst and its synthetic method and it is catalyzed the method that levulic acid prepares gamma-valerolactone.Yolk-shell type catalyst M@mHSiO prepared by the present invention2, be core it is hydrogenation metal, shell is organic-inorganic hybrid mesoporous SiO2" yolk-eggshell " nanostructure, which can be catalyzed levulic acid and add hydrogen that gamma-valerolactone is prepared.The Yolk-shell type catalyst M@mHSiO of method synthesis provided by the invention2Regular appearance, shell hydrothermal stability is preferable, and the catalyst levulic acid prepares gamma-valerolactone, catalyst stability, catalytic activity and reusability with higher.
Description
Technical field
The present invention relates to levulic acids plus hydrogen to prepare gamma-valerolactone, in particular to Yolk-shell type catalyst and its conjunction
The method for preparing gamma-valerolactone at method and its catalysis levulic acid.
Background technique
Currently, it is the sustainable of more Green Future that environmental protection and effective use natural resources, which are by our social transformation,
Selection.The utilization of biomass or biological products just becomes most important because it not to be only intended to development effectively and environmentally sound
Technology, and the Utilizing question of agricultural and forestry waste is solved simultaneously.Levulic acid is considered as that a kind of important biology base is flat
Platform chemical substance easily, can be produced inexpensively by the simple hydrolysis of lignocellulosic.A series of valuable chemicals
Hydrogen can be added to obtain by levulic acid, such as gamma-valerolactone, valeric acid and 2- methyltetrahydrofuran, among these, gamma-valerolactone
It is widely used as fuel additive, food composition and fine chemicals produce intermediate.
Currently, the catalyst of levulic acid hydrogenation synthesis gamma-valerolactone mainly includes noble metal Ru, Rh, Pt, Pd, Au base
Catalyst and non-noble metal Ni, Cu, Co base catalyst, United States Patent (USP) US20030055270 disclose carried noble metal catalysis
Agent is catalyzed heating levulinic acid preparation 5- methylbutyrolactone (also referred to as 5- valerolactone or gamma-valerolactone), metallic catalyst load
On a catalyst support, catalyst carrier is selected from carbon, SiO2Or Al2O3, most preferred catalyst carrier is oxidation-stabilized carbon；
Chinese patent CN109651304A uses Ag/ZrO2For catalyst, it is catalyzed levulic acid and hydrogen is added to prepare gamma-valerolactone, it is above-mentioned to urge
Agent is loaded catalyst, although improving the yield of gamma-valerolactone to a certain extent, catalyst itself
Stability is poor, and active material metal is easy to reunite and be lost in the reaction, and the repeat performance of catalyst is poor.
In recent years, yolk-shell structure catalyst makes great progress, and yolk-shell type catalyst is a kind of
" yolk-eggshell " nanostructure composite material, by cavity removable active core and outer layer porous shell form, due to this
Special construction can integrate the advantages of two or more materials, thus it can be used as functional material and is applied to different necks
Domain.Compared with above-mentioned load type metal catalyst in the prior art, because its chamber portion can be enriched with more reactant ginsengs
React with catalysis, is conducive to raising reaction rate, while shell serves as protective layer can prevent the reunion of kernel；But it is being catalyzed
In terms of adding hydrogen, which kind of component is chosen as kernel and shell, the yolk-shell type catalyst that could make is more advantageous to second
Acyl propionic acid catalytic hydrogenation synthesizes gamma-valerolactone also not it is found that different constituent is as shell and kernel, the material that could make
Material has the characteristics that the superior and new research hotspot in one, this field；In addition, yolk-shell type is urged in the prior art
The preparation step of agent is cumbersome, can not one kettle way complete, while needing the period long, pattern is not regular enough, consume it is bigger, finally
Obtained pure silicon shell hydrothermal stability is bad.Therefore, a kind of yolk- with new shell and kernel constituent is researched and developed
Shell type catalyst and preparation method thereof enables the catalyst favorable catalyst levulic acid catalytic hydrogenation, it has also become one urgently
Problem to be solved.
Summary of the invention
In view of this, the present invention provides Yolk-shell type catalyst and its synthetic method and its catalysis levulinics
The method that acid prepares gamma-valerolactone.The Yolk-shell type catalyst can effectively be catalyzed levulic acid catalytic hydrogenation, should
The preparation method of Yolk-shell type catalyst can be realized one kettle way complete, the period is short, consumption is small, obtained using the preparation method
The Yolk-shell type catalyst morphology arrived is regular, and shell hydrothermal stability is preferable.
In order to achieve the above-mentioned object of the invention, the invention adopts the following technical scheme:
There is provided the method for one pot process Yolk-shell type catalyst, the party for first goal of the invention of the invention
Method the following steps are included:
S1, CTAB mixed with water, after agitating and heating plus precious metal salt solution, continue to stir, it is water-soluble that ascorbic acid be added dropwise
Liquid stirs to get noble metal M colloidal solution；The water is preferably deionized water.
S2, be added NaOH solution in the M colloidal solution, adjust solution ph, TEOS solution be then added dropwise and causes silicon
Glue polymerization reaction is added dropwise BTME solution and is reacted, and centrifugation obtains the product M@HSiO with even mesoporous channel2, dried
Night；
S3, by the M@HSiO after described be dried overnight2It roasts and in H2The lower reduction of effect, obtains M@mHSiO2。
The CTAB is cetyl trimethylammonium bromide, and the TEOS is ethyl orthosilicate, and the BTME is that 1,2- is bis-
(trimethoxy silicon substrate) ethane, TEOS and BTME is used for the hybrid mesoporous SiO of synthesizing organic-inorganic as silicon source2Outer shell.
Above-mentioned one-pot synthesis method, more specifically steps are as follows:
S1, 0.10g CTAB and 45mL deionized water is mixed in flask, agitating and heating at a temperature of room temperature is to 95 DEG C,
And 30min is kept, 5mL 0.02mol/L precious metal salt solution is then added, continues after stirring 10min, solution is by colorless and transparent
Become orange red, aqueous ascorbic acid is added dropwise, continues to stir 30min, obtain noble metal M colloidal solution；
S2, 0.5mol/L NaOH solution is added in noble metal M colloidal solution, adjust solution ph to 10~11, then
0.42mL TEOS solution is added dropwise, causes silica gel polymerization reaction, 0.3mL BTME solution reaction 30min is added dropwise after 3h, centrifugation obtains
M@HSiO2Product, and be dried overnight at 60 DEG C；
S3, by the M@HSiO after the drying2In Muffle kiln roasting, roasting, temperature is warming up to the speed of 5 DEG C/min
350 DEG C, calcining time 3h, then use the H of 60mL/min flow2To the M@HSiO after roasting at a temperature of 500 DEG C2Powder
Reductase 12 h finally obtains Yolk-shell type catalyst M@mHSiO2。
One pot process Yolk-shell type catalyst M@mHSiO provided by the invention2, preparation process can be in one pot
It realizes, step is simple, short preparation period；Yolk-shell type catalyst M@mHSiO prepared by the present invention2, it is that core is plus hydrogen is golden
Belong to, shell is organic-inorganic hybrid mesoporous SiO2" yolk-eggshell " nanostructure, organic-inorganic hybrid mesoporous silica and
The hydrogenation metal is as shell and kernel constituent, the nano material M mHSiO that makes2Levulic acid can be catalyzed to add
Gamma-valerolactone is prepared in hydrogen.
Not plus when BTME, System forming is pure silicon shell, when organosilicon composition BTME is added, thus outside script pure silicon
Organic inorganic hybridization shell is formed on the basis of shell, hydridization shell has higher hydrothermal stability, the internal right pure silicon of low-shrinkage
It being dissolved and forms boring, internal biggish cavity can be used as the nanometer reaction chamber of hydrogenation reaction, in reaction chamber, reaction
Object and catalyst can be contacted preferably, are conducive to the progress of reaction, greatly improved reactivity, one kettle way provided by the invention
Reaction system carries out at 95 DEG C always, and high-temperature water at this time facilitates internal pure silicon dissolution, but because of the water of hydridization shell
Thermal stability thereby may be ensured that hybrid silicon shell dissolves.
The CTAB takes on the stabilizer of stable metal particle in metal recovery process, and in coated with silica
During take on shell made to generate mesoporous template, in organic-inorganic hybrid mesoporous SiO2Hole is uniform-distribution on shell
Road, and inventor can regulate and control the size in duct in shell by changing template chain length, and use is provided by the invention
The duct pore size for the catalyst that CTAB is obtained can make M@mHSiO2The catalytic effect of catalysis levulic acid reaches best.
If Yolk-shell type catalyst pattern is irregular, it will cause its shell thickness different, reactant molecule connects
Shell after touch will be obstructed, the catalyst M@mHSiO that synthetic method provided by the invention obtains2Pattern is more regular, miscellaneous
Outside the pale of civilization thickness of the shell is more uniform, is conducive to active metal of the reactant molecule inside shell contact.
Preferably, the precious metal salt is selected from K2PdCl4、RuCl3、Na2RhCl4、HAuCl4Or K2PtCl4One of.
One pot process Yolk-shell type catalyst M@mHSiO of the present invention2Synthesis mechanism it is as shown in Figure 1.
Another goal of the invention of the invention is prepared there is provided a kind of according to above-mentioned one-pot synthesis method
Yolk-shell type catalyst M@mHSiO2。
The last one goal of the invention of the invention, there is provided catalyst M@mHSiO2It is catalyzed levulic acid and prepares γ-penta
The method of lactone, yolk-shell type catalyst M@mHSiO2Catalysis levulic acid adds hydrogen that gamma-valerolactone is prepared.
Preferably, the catalyst M@mHSiO2Account for the 1~3% of the levulic acid quality, reaction temperature 160~
200 DEG C, 1.0~3.0MPa of Hydrogen Vapor Pressure, 2.0~4.0h of reaction time.
Preferably, catalytic hydrogenation reaction carries out in stainless steel autoclave, first using air in nitrogen displacement kettle
Charged pressure hydrogen after for several times, heating stirring carry out hydrogenation reaction.
After reaction, catalyst M@mHSiO is recycled in centrifugation to catalyst to catalyzing hydrogenating provided by the invention2With product γ-
Valerolactone, catalyst are mutually not necessarily to post-process direct reuse.
Yolk-shell type catalyst M@mHSiO provided by the invention2Hydrogen is added to prepare gamma-valerolactone in catalysis levulic acid
Catalytic activity and selectivity with higher when reaction；Gained by-product is few after reaction, and product postprocessing is simple；Levulinic
After sour hydrogenation reaction, what can be simple and efficient in the way of centrifugation separates catalyst with product, and catalyst is mutually not necessarily to
Post-processing, can directly reuse, and catalytic performance, which has no, after reusing 10 times is substantially reduced, and it is preferable that effect is recycled.
From the above technical scheme, catalyst M@mHSiO provided by the invention2One-pot preparation thereof, can be realized one kettle way
Completion, the period is short, consumption is small, and the Yolk-shell type catalyst morphology synthesized using method provided by the invention is regular, hydridization
Shell hydrothermal stability is preferable, and the catalyst levulic acid prepares gamma-valerolactone, catalyst stabilization with higher
Property, catalytic activity and reusability.
Detailed description of the invention
Fig. 1 is one pot process Yolk-shell type catalyst M@mHSiO provided by the present invention2Synthesis mechanism signal
Figure；
Fig. 2 is Yolk-shell type catalyst M@mHSiO provided by the present invention2The TEM of intermediate in the synthesis process
Figure；
Fig. 3 is that each Catalyst Conversion that provides of comparative example 1, selectivity change over time figure.
Specific embodiment
The invention discloses Yolk-shell type catalyst and its synthetic methods and its catalysis levulic acid to prepare γ-
The method of valerolactone.Those skilled in the art can use for reference present disclosure, be suitably modified realization of process parameters.In particular
, all similar substitutions and modifications are apparent to those skilled in the art, they are considered as being included in
In the present invention.Method and application of the invention is described by preferred embodiment, and related personnel obviously can be not
It is detached from the content of present invention, in spirit and scope to method described herein and application is modified or appropriate changes and combinations, comes
Implementation and application the technology of the present invention.
In order to enable those skilled in the art to better understand the present invention, With reference to embodiment to the present invention
It is described in further detail.
1 Yolk-shell type catalyst Pd@mHSiO of embodiment2Synthesis
S1, 0.10g CTAB and 45mL deionized water is mixed in flask, agitating and heating at a temperature of room temperature is to 95 DEG C,
And 30min is kept, 5mL 0.02mol/L K is then added2PdCl4Solution continues after stirring 10min, and solution is by colorless and transparent change
Be it is orange red, be added dropwise aqueous ascorbic acid, continue stir 30min, obtain precious metals pd colloidal solution；
S2, in precious metals pd colloidal solution be added 0.5mol/L NaOH solution, adjust solution ph to 10, then drip
Add 0.42mL TEOS solution, causes silica gel polymerization reaction, 0.3mL BTME solution reaction 30min is added dropwise after 3h, centrifugation obtains
Pd@HSiO2Product, and be dried overnight at 60 DEG C；
S3, by the Pd@HSiO after the drying2In Muffle kiln roasting, roasting, temperature heats up from the speed of 5 DEG C/min
To 350 DEG C, calcining time 3h, the H of 60mL/min flow is then used2To the Pd@HSiO after roasting at a temperature of 500 DEG C2Powder
Last reductase 12 h finally obtains Yolk-shell type catalyst Pd@mHSiO2。
S in the first stage1, vertical to synthesize Pd nanometers by restoring tetrachloro-palladium acid salt by ascorbic acid in the presence of CTAB
Cube, obtained Pd nanoparticle are uniform cubes, and average-size is 15 ± 1nm (Fig. 2 a), their polycrystalline structure can
To find out from HRTEM image clearly, (referring to the illustration in Fig. 1 a) consistent with the spacing of lattice of Pd (100) plane is abundant
Crystal face compared with the metallic particles of unformed or low crystallization with higher hydrogenation activity because crystal face has more excellent suction
The ability of attached hydrogen atom, to promote catalytic activity higher.
In second stage S2, firstly, the hydrolysis of the latter generates negatively charged oligomeric silicic acid after NaOH and TEOS is added
Salt, can interact strongly with the hydrophilic end of CTAB and successive sedimentation is in spherical micelle and matrix, ultimately form Pd@
SiO2Catalyst obtains Pd@SiO of uniform size as shown in Figure 2 a2Catalyst, average diameter are 72 ± 3nm；Finally, addition
BTME organosilane based precursor causes from Pd@SiO2It is changed into Pd@HSiO2, observe Pd@HSiO2Keep uniform after structure transformation
Spherical shape and smooth surface (Fig. 2 b), it is notable that after adding BTME, Pd@HSiO2The diameter of catalyst increases to
118±4nm。
In phase III S3, the Pd@HSiO that will obtain2It is calcined in air to remove CTAB, then in H2Lower reduction, obtains
To Pd@mHSiO2(Fig. 2 d), Pd@mHSiO2HRTEM image clearly demonstrate the vermiform hole in shell.
2 Yolk-shell type catalyst Rh@mHSiO of embodiment2Synthesis
S1, 0.10g CTAB and 45mL deionized water is mixed in flask, agitating and heating at a temperature of room temperature is to 95 DEG C,
And 30min is kept, 5mL 0.02mol/L Na is then added2RhCl4Solution continues after stirring 10min, and solution is by colorless and transparent
Become orange red, aqueous ascorbic acid is added dropwise, continues to stir 30min, obtain noble metal Rh colloidal solution；
S2, in noble metal Rh colloidal solution be added 0.5mol/L NaOH solution, adjust solution ph to 11, then drip
Add 0.42mL TEOS solution, causes silica gel polymerization reaction, 0.3mL BTME solution reaction 30min is added dropwise after 3h, centrifugation obtains
Rh@HSiO2Product, and be dried overnight at 60 DEG C；
S3, by the Rh@HSiO after the drying2In Muffle kiln roasting, roasting, temperature heats up from the speed of 5 DEG C/min
To 350 DEG C, calcining time 3h, the H of 60mL/min flow is then used2To the Rh@HSiO after roasting at a temperature of 500 DEG C2Powder
Last reductase 12 h finally obtains Yolk-shell type catalyst Rh@mHSiO2。
3 Yolk-shell type catalyst Au@mHSiO of embodiment2Synthesis
S1, 0.10g CTAB and 45mL deionized water is mixed in flask, agitating and heating at a temperature of room temperature is to 95 DEG C,
And 30min is kept, 5mL 0.02mol/L HAuCl is then added4Solution continues after stirring 10min, and solution is by colorless and transparent change
Be it is orange red, be added dropwise aqueous ascorbic acid, continue stir 30min, obtain noble metal Au colloidal solution；
S2, in noble metal Au colloidal solution be added 0.5mol/L NaOH solution, adjust solution ph to 10, then drip
Add 0.42mL TEOS solution, causes silica gel polymerization reaction, 0.3mL BTME solution reaction 30min is added dropwise after 3h, centrifugation obtains
Au@HSiO2Product, and be dried overnight at 60 DEG C；
S3, by the Au@HSiO after the drying2In Muffle kiln roasting, roasting, temperature heats up from the speed of 5 DEG C/min
To 350 DEG C, calcining time 3h, the H of 60mL/min flow is then used2To the Au@HSiO after roasting at a temperature of 500 DEG C2Powder
Last reductase 12 h finally obtains Yolk-shell type catalyst Au@mHSiO2。
4 catalyst Pd@mHSiO of embodiment2The method that catalysis levulic acid prepares gamma-valerolactone
Pd@mHSiO prepared by 5g levulic acid and 0.05g embodiment 12It is added in stainless steel autoclave, uses
It is filled with 2.0MPa hydrogen after air 5 times in nitrogen displacement kettle, heating stirring 3h, standing are cooled to room temperature at 160 DEG C.In high speed
Under the action of centrifugation, product phase is mutually separated with catalyst, the catalyst after separation can be with direct reuse without post-processing.
The conversion ratio of levulic acid is 56.1%, and the selectivity of gamma-valerolactone is 99.2%, the conversion ratio of levulic acid
(Conversion) and the calculation formula of the selectivity of gamma-valerolactone (Slelctivity) is as follows:
Wherein, the quality of levulic acid before M is reaction, m are the quality of levulic acid after reaction.
5 catalyst Au@mHSiO of embodiment2The method that catalysis levulic acid prepares gamma-valerolactone
The Au@mHSiO that 5g levulic acid and 0.15g embodiment 3 are synthesized2It is added in stainless steel autoclave, uses
It is filled with 2.0MPa hydrogen after air 5 times in nitrogen displacement kettle, heating stirring 2h, standing are cooled to room temperature at 180 DEG C.In high speed
Under the action of centrifugation, product phase is mutually separated with catalyst, the catalyst after separation can be with direct reuse without post-processing.
The conversion ratio of levulic acid is 99.7%, and the selectivity of gamma-valerolactone is 99.1%.
6 catalyst Rh@mHSiO of embodiment2The method that catalysis levulic acid prepares gamma-valerolactone
The Rh@mHSiO that 5g levulic acid and 0.1g embodiment 2 are synthesized2It is added in stainless steel autoclave, uses nitrogen
It is filled with 1.0MPa hydrogen after air 4 times in gas displacement kettle, heating stirring 3h, standing are cooled to room temperature at 180 DEG C.High speed from
Under the action of the heart, product phase is mutually separated with catalyst, the catalyst after separation can be with direct reuse without post-processing.Second
The conversion ratio of acyl propionic acid is 70.7%, and the selectivity of gamma-valerolactone is 99.0%.
7 catalyst Pd@mHSiO of embodiment2The method that catalysis levulic acid prepares gamma-valerolactone
The Pd@mHSiO that 5g levulic acid and 0.15g embodiment 1 are synthesized2It is added in stainless steel autoclave, uses
It is filled with 3.0MPa hydrogen after air 6 times in nitrogen displacement kettle, heating stirring 4h, standing are cooled to room temperature at 200 DEG C.In high speed
Under the action of centrifugation, product phase is mutually separated with catalyst, the catalyst after separation can be with direct reuse without post-processing.
The conversion ratio of levulic acid is 99.4%, and the selectivity of gamma-valerolactone is 99.1%.
8 catalyst M@mHSiO of embodiment2The method that catalysis levulic acid prepares gamma-valerolactone
The Pd@mHSiO that 5g levulic acid and 0.15g embodiment 1 are synthesized2It is added in stainless steel autoclave, uses
It is filled with 2.0MPa hydrogen after air 5 times in nitrogen displacement kettle, heating stirring 3h, standing are cooled to room temperature at 160 DEG C.In high speed
Under the action of centrifugation, product phase is mutually separated with catalyst, the catalyst after separation can be with direct reuse without post-processing.
The conversion ratio of levulic acid is 99.8%, and the selectivity of gamma-valerolactone is 99.5%.
Catalyst catalytic performance after embodiment 9 is reused detects
Catalyst is only changed to the catalyst recycled in embodiment 8 with embodiment 8 by experiment condition and step, carries out 10
Secondary recycling experiment, levulic acid conversion ratio is 98.3% after reusing 10 times, and the selectivity of gamma-valerolactone is
99.2%.
Comparative example 1
Yolk-shell type catalyst Pd@mHSiO2Synthetic method and embodiment 1 it is identical, only template CTAB is changed to
DTAB, TTAB and STAB, the Pd@mHSiO that template DTAB, TTAB and STAB are respectively prepared2Respectively it is labeled as Pd@
m12HSiO2、Pd@m14HSiO2And Pd@m18HSiO2, the catalyst that embodiment 1 synthesizes is labeled as Pd@m16HSiO2, to four kinds
Catalyst Pd@m12HSiO2、Pd@m14HSiO2、Pd@m16HSiO2With Pd@m18HSiO2Activity detected, detection method and reality
The detection method for applying example 4 is identical, and the catalytic activity testing result of four kinds of catalyst is as shown in Figure 3.
Fig. 3 data show, by shown in Fig. 3 (a), can clearly observe reaction conversion ratio as aperture size increases and
Increase, when template is DTAB, aperture is minimum, and reaction rate is most slow.When template is STAB, aperture is maximum, therefore anti-
Answer rate also maximum, but when reacted between be 4 hours when, Pd m16HSiO2With Pd@m18HSiO2Conversion ratio it is suitable；By Fig. 3
(b) it can be seen that the selectivity of pore size influences product, aperture is big, and selectivity of product is low, when the time is 4h, Pd m16HSiO2Both
There is high conversion also and have and is highly selective.Therefore synthetic method provided by the invention can just obtain high reaction rate using template CTAB
With highly selective Yolk-shell type catalyst Pd@mHSiO2。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. the method for one pot process Yolk-shell type catalyst, which comprises the following steps:
S1, CTAB mixed with water, precious metal salt solution is added after agitating and heating, continues to stir, aqueous ascorbic acid is added dropwise,
Stir to get corresponding noble metal M colloidal solution；
S2, be added NaOH solution in the noble metal M colloidal solution, adjust solution ph, TEOS solution be then added dropwise and causes silicon
Glue polymerization reaction is finally added dropwise BTME solution and is reacted, and centrifugation obtains the product M@HSiO with even mesoporous channel2, do
It is dry overnight；
S3, by the M@HSiO after described be dried overnight2It roasts and in H2The lower reduction of effect, obtains M@mHSiO2。
2. the method as described in claim 1, which is characterized in that specifically includes the following steps:
S1, 0.10g CTAB and 45mL deionized water is mixed in flask, agitating and heating at a temperature of room temperature is to 95 DEG C, and protect
30min is held, 5mL 0.02mol/L precious metal salt solution is then added, is continued after stirring 10min, solution is become from colorless and transparent
It is orange red, aqueous ascorbic acid is added dropwise, continues to stir 30min, obtains noble metal M colloidal solution；
S2, in noble metal M colloidal solution be added 0.5mol/L NaOH solution, adjust solution ph to 10~11, be then added dropwise
0.42mL TEOS solution causes silica gel polymerization reaction, 0.3mL BTME solution reaction 30min is added dropwise after 3h, and centrifugation obtains M@
HSiO2Product, and be dried overnight at 60 DEG C；
S3, by the M@HSiO after the drying2In Muffle kiln roasting, roasting, temperature is warming up to 350 with the speed of 5 DEG C/min
DEG C, then calcining time 3h uses the H of 60mL/min flow2To the M@HSiO after roasting at a temperature of 500 DEG C2Powder reduction
2h finally obtains Yolk-shell type catalyst M@mHSiO2。
3. method according to claim 1 or 2, which is characterized in that the precious metal salt is selected from K2PdCl4、RuCl3、
Na2RhCl4、HAuCl4Or K2PtCl4One of.
4. the Yolk-shell type catalyst M@mHSiO being prepared using any method of claim 1-32。
5. catalyst M@mHSiO as claimed in claim 42The method that catalysis levulic acid prepares gamma-valerolactone, feature exist
In yolk-shell type catalyst M@mHSiO2Catalysis levulic acid adds hydrogen that gamma-valerolactone is prepared.
6. method as claimed in claim 5, which is characterized in that the catalyst M@mHSiO2Account for the 1 of the levulic acid quality
~3%, 160~200 DEG C of reaction temperature, 1.0~3.0MPa of Hydrogen Vapor Pressure, 2.0~4.0h of reaction time.
7. such as method described in claim 5 or 6, which is characterized in that catalytic hydrogenation reaction in stainless steel autoclave into
Row, first using air in nitrogen displacement kettle, rear charged pressure hydrogen, heating stirring carry out hydrogenation reaction for several times.
8. such as method described in claim 5 or 6, which is characterized in that after catalytic hydrogenation reaction, centrifugation recycling catalyst M@
mHSiO2With product gamma-valerolactone, catalyst is mutually not necessarily to post-process direct reuse.
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