CN110227450A - A kind of metal cooperates with efficient catalytic glycerol to prepare the catalyst and preparation method thereof of DHA with carrier alkalinity - Google Patents
A kind of metal cooperates with efficient catalytic glycerol to prepare the catalyst and preparation method thereof of DHA with carrier alkalinity Download PDFInfo
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 10
- 239000010931 gold Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 9
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 9
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 235000009508 confectionery Nutrition 0.000 description 4
- 238000007210 heterogeneous catalysis Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 150000004054 benzoquinones Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002539 nanocarrier Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 229910020252 KAuCl4 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013376 functional food Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical class O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052725 zinc 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
- B01J23/007—Mixed salts
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of metal cooperates with efficient catalytic glycerol to prepare the catalyst and preparation method thereof of DHA with carrier alkalinity, belongs to biomass catalyzing transformation technology and related chemistry technical field.The catalyst is made of evenly dispersed gold nano grain and double-metal hydroxide.Catalyst is carrier by double-metal hydroxide, and the precipitation method of being taken advantage of the occasion and liquid-phase reduction are made, advantage be by control hydrotalcite precursor preparation method can regulating catalyst alkaline density, intensity.Catalyst is used for selective glycerol oxidation preparation DHA, when 60 DEG C, 0.5Mpa, reaction 4h, the yield of DHA is up to 44.1%.
Description
Technical field
The invention belongs to biomass catalyzing transformation technology and related chemistry technical fields, and it is sweet in particular, provide a kind of catalysis
Oily selective oxidation prepares 1,3-Dihydroxyacetone (DHA) catalyst, preparation and application.
Background technique
The features such as biomass energy is green, sustainable because of it, is widely paid close attention to and is developed.Biodiesel is because of its former material
Expect that source is wide, becomes the Typical Representative in biomass energy.Glycerol is a kind of biggish pair of yield in biodiesel conversion process
Product (every one ton of biodiesel of production generates 100Kg glycerol), however conversion capability is insufficient downstream, excess capacity occurs.Cause
This, catalyzing glycerol conversion high added value product is of great significance.It is its conversion that selective glycerol oxidation, which prepares target product,
It is important by way of.1,3-Dihydroxyacetone (DHA) is used as chemical intermediate, in pharmaceutical synthesis, cosmetic field, leather industry, food
The fields such as product anti-corrosion and functional food, which have, to be widely applied.
Glycerin catalytic conversion preparation DHA is broadly divided into homogeneous catalysis method, heterogeneous catalysis method.Currently, since heterogeneous catalysis exists
Easy to operate on reaction controlling, process flow is simple, green, therefore heterogeneous catalysis is always by the favor of researcher.In recent years, sweet
The heterogeneous catalytic oxidation preparation target of oil becomes research hotspot.Also there are many problems in research report, not such as catalytic activity
Height, poor selectivity, reaction condition limit (exogenously added alkali, high pressure) etc..
Glycerol oxidation preparation DHA preparation DHA needs Selective activation secondary hydroxyl, inhibits deep oxidation and avoids C-C key
Fracture.In current research report, preparing DHA catalyst from glycerol mainly has homogeneous catalyst and heterogeneous catalyst.Its
Middle homogeneous catalyst is mainly that Pd, Fe metal complex catalysts are catalyzed reaction in organic solvent, with [(neocuproine)
Pd(OAc)]2(OTf)2The cationic Pd of coordination is catalyst, and benzoquinones makees oxidant, CH3CN realizes glycerol height as solvent
Selectivity preparation DHA is learned, and passes through adjusting solvent CH3CN/H2The ratio of O, in 5mol%Pd, 0.7ml solvent, 0.1mmol is sweet
Oil, 0.3mmol benzoquinones react 3 hours at room temperature, the conversion ratio for realizing 100% and selectivity greater than 95%
(Angew.Chem.,2010,49:9456-9459).Iron [the Fe (BPA) being coordinated with BPA2(OTf)2As catalyst, with MeCN/
H2O=2/1 solvent, 30% hydrogen peroxide as oxidant react 90 minutes 17% glycerol conversion yields realized at room temperature, DHA's
Selectivity is but up to 100% (J.Mol.Catal.A:Chem., 2015,396:353-359).However having of using of homogeneous catalysis
Solvent and organic oxidizing agent have biggish harm to environment, and homogeneous catalyst preparation process is complex, catalyst
Recycling difficulty is big after the reaction, these factors increase cost, unfavorable industrialized production.The oxidation of heterogeneous catalysis glycerol
Catalyst mainly with carbon material (active carbon (AC), carbon nanotube (MNCT), graphite etc.), metal oxide (CeO2、ZnO、
CuO, MgO etc.) it is the noble metal catalysts such as carrier loaded Au, Pt, Pd.Wherein PtBi/C obtains preferable catalytic performance,
And the glycerol conversion yield of 49.0%DHA selectivity and 91.5% is obtained for most ratio of greater inequality with Pt/Bi=1:1
(Chin.J.Catal., 2011,32:1831-1837), but the selectivity of DHA is to be improved.In PtSb/MWCNTs catalyst,
PtSb forms single alloy mutually its structure, (60 DEG C, O under optimal experiment condition2flow 150cm3/ min) it obtains
90% glycerol conversion yield and 51.4% DHA selectivity (Appl.Catal.B:Environ., 2012,127:212-220).Pt
Base catalyst is generally lower to the selectivity of target product, and transition oxidation is serious.Pd-Ag/C catalyst, in 0.3Mpa O2, 80
DEG C, reaction obtains 44% DHA yield for 24 hours, and glycerol conversion yield 52%, reactivity is to be improved
(Catal.Sci.Technol.,2012,2,1150–1152).Some researches show that Au to be conducive to the Selective activation of secondary hydroxyl, and
In Au/CuO catalyst, when reaction condition is 80 DEG C, 4h, 2Mpa, higher yield 80% is obtained, however glycerol conversion yield master
If improving (glycerol/Au feed ratio is 20~50) (ACS Catal.2014,4,2226- by the dosage for increasing catalyst
2230).Although Pd, Au catalyst performance are improved but its reaction efficiency is still to be improved.
Summary of the invention
The purpose of the present invention is to provide a kind of catalyzing glycerol selective oxidations to prepare 1,3-Dihydroxyacetone (DHA) catalysis
Agent, preparation and application.
Catalyst of the invention is made of evenly dispersed gold nano grain and double-metal hydroxide (LDHs), the catalysis
Agent is carrier, the deposited precipitation method and liquid-phase reduction preparation by double-metal hydroxide.
The activated centre of catalyst by even particulate dispersion Au metal active centres nano particles and hydrotalcite supports
Basic site composition.Catalyst active center is that Au metal active centres and basic active center act synergistically.
In catalyst the content of Au metal active centres be 0.5~2.0wt%, Au metal active centres particle size 2~
5nm。
The preparation of the catalyst: hydrotalcite (Layered Double is also known as with double metal composite hydroxide
Hydroxides is abbreviated as LDHs) it is carrier, neatly stone veneer bivalent cation selects Zn2+、Co2+、Ni2+、Mg2+, trivalent sun
Ion selects Fe3+、Ga3+、Al3+、Mn3+、Ti3+、Cr3+, molar ratio M2+/M3+=(0~5): 1 does not include 0, the water of preparation
Steatite support impregnates Au by the method for deposition sedimentation3+Solution will impregnate Au3+Hydrotalcite sample afterwards is with toluene and ethyl alcohol
Solvent, NaBH4For reducing agent, load Au catalyst is made in liquid-phase reduction.Toluene and ethyl alcohol are arbitrary proportion.
The catalyst is used for glycerol oxidation reaction, especially selective glycerol oxidation preparation DHA.
The above-mentioned catalyst of the present invention aoxidizes the method for preparing DHA for selective glycerol, and it is sweet that substrate is added in aqueous solution
The mass ratio of the material of oil and catalyst, catalyst charge and institute's glycerol adding is 1:100~1:500 (activated centre Au and glycerol
Molar ratio), reaction temperature is 30-90 DEG C, and reaction pressure is that 0~3Mpa does not include 0, and reaction time 1-8h can also be online
Catalysis reaction.
Remarkable advantage of the invention is the synergistic effect between Au nano particle and carrier alkalinity, metallic particles and carrier alkali
Property it is adjustable for quantity, selective glycerol oxidation preparation DHA performance is good, and DHA yield is up to 44.8%.
The present invention has the advantage that the advantage is that catalyst metals activated centre Au nano particle and carrier basic active
Center synergistic effect, is that Au nanoparticle size and carrier basic active centric quantity and intensity are adjustable, to realize efficiently choosing
Selecting property oxidation preparation DHA.
Detailed description of the invention
The ZnAl-LDHs of (a) coprecipitation preparation synthesized in Fig. 1 case study on implementation 1 of the present invention and case study on implementation；(b)Au/
ZnAl-LDHs XRD spectra.Wherein abscissa is 2 θ, unit: degree；Ordinate is intensity.Specification catalyst carrier does not become,
Au nano particle is evenly dispersed, to be not reflected.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
Step A: Zn (NO is weighed3)2·6H2O、Al(NO3)3·9H2O (molar ratio of Zn and Al are 3) is dissolved in deionized water
In, it stirs and ultrasound is to being completely dissolved, solution clear (solution A)；Weigh Na2CO3200mL deionized water (solution C) is added to set
It in 1000mL four-hole boiling flask, and weighs NaOH and is dissolved in 200mL deionized water, be configured to aqueous slkali (solution B).In room temperature magnetic
Power stirring under, solution A and solution B are slowly dropped into four-hole boiling flask, control for pH value it is constant.It is dripped completely to metal salt solution A
After complete, thermostatic crystallization in oil bath.It being filtered by decompression and obtains solid sample, then deionized water washing is dried in an oven,
Grind to obtain ZnAl-CO3- LDHs powder, kept dry.
Step B: by the ZnAl-CO of above-mentioned preparation3- LDHs is put in a round bottom flask, and deionized water dispersion is added, weighs
KAuCl4, deionized water dissolving ultrasonic disperse is added dropwise in the round-bottomed flask for having dispersed hydrotalcite supports, weighs urea, is added
To round-bottomed flask, the reflux digestion in constant temperature oil bath, then by centrifugation, deionized water washing, dry catalyst precarsor Au3 +/ZnAl-LDHs。
Step C: by Au obtained above3+/ ZnAl-LDHs, through NaBH4Au catalyst Au/ZnAl- is obtained after liquid-phase reduction
LDHs (load capacity of Au is 1.09wt%).
Step D: accurately weighing weighed catalyst, glycerine water solution into stainless steel kettle, closed, is oxygenated replacement reaction kettle
Middle air, is repeated 8 times, and rises to reaction temperature from room temperature, starts clock reaction.It at the end of reaction, is cooled to room temperature, using liquid phase
Chromatography, glycerol conversion yield 53.3%, DHA selectively reaches 70.1%.
Step E: accurately weighing weighed catalyst, Catalyst packing is entered trickle bed reactor, glycerine water solution is through high pressure
Squeeze into reaction system, mass space velocity 0.2h-1, 60 DEG C of reaction temperature are risen to from room temperature, starts to keep the temperature clock reaction, take per hour
Sample, using liquid-phase chromatographic analysis, glycerol conversion yield 11.2%, DHA selectively reaches 92.9%.
Embodiment 2
Step A: Zn (NO is weighed3)2·6H2O、Ga(NO3)3·9H2O(Zn(NO3)2·6H2O、Ga(NO3)3·9H2O's rubs
3) your ratio is dissolved in deionized water, stir and ultrasonic to being completely dissolved, solution clear (solution A)；Weigh Na2CO3Add
200mL deionized water (solution C) is placed in 1000mL four-hole boiling flask, and is weighed NaOH and be dissolved in 200mL deionized water, is configured to
Aqueous slkali (solution B).Under room temperature magnetic agitation, solution A and solution B are slowly dropped into four-hole boiling flask, controlled as pH value perseverance
It is fixed.After metal salt solution A is dripped off completely, thermostatic crystallization in oil bath.It is filtered by decompression and obtains solid sample, deionized water
Washing, then dries in an oven, grinds to obtain ZnGa-CO3- LDHs powder, kept dry.
Step B: by the Zn of above-mentioned preparation2Ga1-CO3- LDHs is put in a round bottom flask, and deionized water dispersion is added, weighs
KAuCl4, deionized water dissolving ultrasonic disperse is added dropwise in the round-bottomed flask for having dispersed hydrotalcite supports, weighs urea, is added
To round-bottomed flask, the reflux digestion in constant temperature oil bath, then by centrifugation, deionized water washing, dry catalyst precarsor Au3 +/ZnGa-LDHs。
Step C: by Au obtained above3+/ ZnGa-LDHs, through NaBH4Au catalyst Au/ZnGa- is obtained after liquid-phase reduction
LDHs (load capacity of Au is 0.98wt%).
Step D: accurately weighing weighed catalyst, glycerine water solution into stainless steel kettle, closed, is oxygenated replacement reaction kettle
Middle air, is repeated 8 times, and rises to reaction temperature from room temperature, starts clock reaction.It at the end of reaction, is cooled to room temperature, using liquid phase
Chromatography, glycerol conversion yield 73.1%, DHA selectively reaches 60.4%.
Step E: accurately weighing weighed catalyst, Catalyst packing is entered trickle bed reactor, glycerine water solution is through high pressure
Squeeze into reaction system, mass space velocity 0.2h-1, 60 DEG C of reaction temperature are risen to from room temperature, starts clock reaction, is taken per hour primary
Sample, using liquid-phase chromatographic analysis, glycerol conversion yield 15.4%, DHA selectively reaches 87.1%.
Embodiment 3
Step A: Mg (NO is weighed3)2·6H2O、Al(NO3)3·9H2O is dissolved in deionized water (Mg (NO3)2·6H2O、Al
(NO3)3·9H2The molar ratio 3 of O), it stirs and ultrasound is to being completely dissolved, solution clear (solution A)；Weigh Na2CO3Add
200mL deionized water (solution C) is placed in 1000mL four-hole boiling flask, and is weighed NaOH and be dissolved in 200mL deionized water, is configured to
Aqueous slkali (solution B).Under room temperature magnetic agitation, solution A and solution B are slowly dropped into four-hole boiling flask, controlled as pH value perseverance
It is fixed.After metal salt solution A is dripped off completely, thermostatic crystallization in oil bath.It is filtered by decompression and obtains solid sample, deionized water
Washing, then dries in an oven, grinds to obtain MgAl-CO3- LDHs powder, kept dry.
Step B: by the MgAl-CO of above-mentioned preparation3- LDHs is put in a round bottom flask, and deionized water dispersion is added, weighs
KAuCl4, deionized water dissolving ultrasonic disperse is added dropwise in the round-bottomed flask for having dispersed hydrotalcite supports, weighs urea, is added
To round-bottomed flask, the reflux digestion in constant temperature oil bath, then by centrifugation, deionized water washing, dry catalyst precarsor Au3 +/MgAl-LDHs。
Step C: by Au obtained above3+/ MgAl-LDHs, through NaBH4Au catalyst Au/MgAl- is obtained after liquid-phase reduction
LDHs (load capacity of Au is 0.98wt%).
Step D: accurately weighing weighed catalyst, glycerine water solution into stainless steel kettle, closed, is oxygenated replacement reaction kettle
Middle air, is repeated 8 times, and rises to reaction temperature from room temperature, starts clock reaction.It at the end of reaction, is cooled to room temperature, using liquid phase
Chromatography, glycerol conversion yield 71.2%, DHA selectively reaches 55.8%.
Step E: accurately weighing weighed catalyst, Catalyst packing is entered trickle bed reactor, glycerine water solution is through high pressure
Squeeze into reaction system, mass space velocity 0.2h-1, 60 DEG C of reaction temperature are risen to from room temperature, starts clock reaction, is taken per hour primary
Sample, using liquid-phase chromatographic analysis, glycerol conversion yield 14.1%, DHA selectively reaches 70.6%.
Claims (6)
1. a kind of metal cooperates with efficient catalytic glycerol to prepare the catalyst of DHA with carrier alkalinity, which is characterized in that catalyst is by equal
The gold nano grain and double-metal hydroxide (LDHs) of even dispersion form, which is carrier by double-metal hydroxide,
The deposited precipitation method and liquid-phase reduction preparation.
2. a kind of metal described in accordance with the claim 1 cooperates with efficient catalytic glycerol to prepare the catalyst of DHA with carrier alkalinity,
Be characterized in that, the activated centre of catalyst by even particulate dispersion Au metal active centres nano particle and hydrotalcite supports
Basic site composition；Catalyst active center is that Au metal active centres and basic active center act synergistically.
3. a kind of metal described in accordance with the claim 1 cooperates with efficient catalytic glycerol to prepare the catalyst of DHA with carrier alkalinity,
Be characterized in that, in catalyst the content of Au metal active centres be 0.5~2.0wt%, Au metal active centres particle size 2~
5nm。
4. the preparation method of any one of the claim 1-3 catalyst, which is characterized in that again with double metal composite hydroxide
Referred to as hydrotalcite (Layered Double Hydroxides, be abbreviated as LDHs) is carrier, the choosing of neatly stone veneer bivalent cation
Select Zn2+、Co2+、Ni2+、Mg2+, Tricationic selection Fe3+、Ga3+、Al3+、Mn3+、Ti3+、Cr3+, molar ratio M2+/M3+=
(0~5): 1 does not include 0, and the hydrotalcite supports of preparation impregnate Au by the method for deposition sedimentation3+Solution will impregnate Au3+Afterwards
Hydrotalcite sample, using toluene and ethyl alcohol as solvent (any ratio), NaBH4For reducing agent, load Au catalyst is made in liquid-phase reduction.
5. the application of any one of the claim 1-3 catalyst is used for glycerol oxidation reaction, especially selective glycerol and aoxidizes
Prepare DHA.
6. applying according to claim 5, the method for preparing DHA is aoxidized for selective glycerol, is added in aqueous solution
The mass ratio of the material of substrate glycerol and catalyst, catalyst charge and institute's glycerol adding is 1:100~1:500, and reaction temperature is
30-90 DEG C, reaction pressure is that 0~3Mpa does not include 0, reaction time 1-8h, or online catalysis reaction.
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| CN110882701A (en) * | 2019-12-13 | 2020-03-17 | 北京化工大学 | Gold-based bimetallic/ZnO-CuO catalyst for preparing dihydroxyacetone from glycerol and preparation method thereof |
| CN114396868A (en) * | 2022-01-18 | 2022-04-26 | 陕西科技大学 | alpha-MWCNTs/MgAl-LDH/leather flexible wearable strain sensing material and preparation method thereof |
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