CN109806886A - A kind of glycerol oxidation prepares catalyst of dihydroxyacetone (DHA) and its preparation method and application - Google Patents
A kind of glycerol oxidation prepares catalyst of dihydroxyacetone (DHA) and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to the catalyst and its preparation method and application that a kind of glycerol oxidation prepares dihydroxyacetone (DHA), belong to chemical catalysis technical field, catalyst of the invention is the catalyst that a kind of glycerol oxidation prepares dihydroxyacetone (DHA), wherein: the catalyst is Au base catalyst, the carrier of catalyst is copper zirconium mixed oxide, and the molar ratio of copper and zr element is 1:100-100:1 in the carrier of catalyst.Also correspondingly provided catalyst preparation method and its application in dihydroxyacetone (DHA) is prepared in glycerol oxidation.Supported Au catalysts prepared by the present invention can prepare dihydroxyacetone (DHA) (DHA) by efficiently catalyzing and oxidizing glycerol in heterogeneous alkaline media, and the selectivity that glycerol conversion yield can achieve 80%, DHA can achieve 95% or more.Reaction process mild condition, equipment corrosion are small, environmental-friendly, and the industrialization amplification for having reached current requires, and have broad application prospects.
Description
Technical field
The invention belongs to chemical catalysis technical fields, and in particular to be that a kind of glycerol oxidation prepares urging for dihydroxyacetone (DHA)
Agent and its preparation method and application.
Background technique
Dihydroxyacetone (DHA) (Dihydroxyacetone;It DHA), is a kind of important industrial chemicals, medicine intermediate and function
Energy additive, is widely used in cosmetics.There is special-effect especially as suncream, the excessive steaming of moisture of skin can be prevented
Hair, plays the role of moisturizing, sun-proof and ultraviolet radiation preventing；Also the coverture that can be used as leucoderma disease application on human skin makes patient's skin
Skin is in normal color；As a kind of important medicine intermediate, DHA has been successfully applied to the treatment of diabetes at present, acts on
Similar to glucose, respiratory rate and oxygen consumption can be greatly enhanced, effectively inhibit the generation of excessive acetoacetate；In leather
In manufacture, DHA is used as the protective agent of leather and fur products；In addition, DHA also act as fruits and vegetables, aquatic products, meat products it is fresh-keeping
Agent has the function of anti-corrosive fresh-keeping.Glycerol is as a kind of important biomass plateform molecules, and production capacity is significantly superfluous at present, with sweet
Oil is raw material, catalysis oxidation is carried out to it prepares dihydroxyacetone (DHA) to can be improved glycerol added value, alleviate overstock problem, be one
Environmentally protective and mild condition synthetic route has important application value to promoting biomass efficient to convert.
Bertland in 1986 etc. successfully synthesizes DHA(AppliedMicrobiologyand by fermentation method for the first time
Biotechnology, 1994,41,359-365), microbe fermentation method accounts for leading role in preparation DHA method so far, at present
Commercially available DHA is mainly derived from glycerol fermentation, but the low yield of such method target product, fermentation period are long, point of product
It is low from cost for purification height, reaction substrate concentration, and since enzyme or thallus cause it to be easy to the sensibility of solution environmental
It inactivates and obtains in reaction and is difficult.Direct Catalytic Oxidation method be under the action of catalyst and oxidant, it is straight by single step reaction
The method for delivering a child into DHA.1993, carrier loaded Pt catalyst (Pt/ was in the first time discovery of Kimura seminar of carbon black
AC) glycerol can be oxidized to DHA, but the yield of DHA is only 4% (JournaloftheAmericanOilChemistsSocie
ty,1993,70,1027-1030).Carrier, auxiliary agent of Pt base catalyst etc. are all studied in detail later.Pd base Dan Jin
Principal product of metal catalyst in the presence of no auxiliary agent is glyceric acid, and Ag's is added with the conversion ratio and DHA for being conducive to improve glycerol
Selectivity.Hirasawa etc. is to Pd-Ag/C catalyst the study found that in neutral conditions, Pd-Ag/C (Pd/Ag=1) is urged
The glycerol conversion yield of agent reached the yield of 52%, DHA up to 44% (JournalofCatalysis, 2013,300,205-
216).Claus in 2007 etc. has successfully synthesized DHA on Au base catalyst for the first time, and the selectivity of DHA is 26%, addition
After Pt the selectivity and glycerol conversion yield of DHA all increase (AppliedCatalysisB:Environmental, 2007,70
(1-4), 637-643), but still well below the catalytic activity of Bi-Pt/C catalyst.In addition to this, many metals are organic matches
Mixture catalyst, heteropolyacid catalyst are also applied to glycerol oxidation and prepare dihydroxyacetone (DHA) reaction, but metal organic complexes
The preparation process of object catalyst is more complicated, and recycles difficulty, and the introducing of organic solvent also increases the subsequent place of product
Science and engineering skill；And the stability of heteropolyacid catalyst is poor, active component is easy to run off, and the by-product reacted is more, after increasing product
The difficulty of processing.Au base catalyst compared with the great advantage of Pt, Pd base catalyst can be overcome when selecting oxygen is oxidant
Oxygen-intoxication, but reaction need to carry out in alkaline medium.For this problem, it would be highly desirable to one kind is developed suitable for non-alkaline medium,
Produce green, the efficient Au base catalyst of dihydroxyacetone (DHA).
Summary of the invention
That the object of the present invention is to provide a kind of reaction conditions is mild, efficiently, stability is good, reproducible can be used in non-alkali
Glycerol oxidation prepares catalyst of dihydroxyacetone (DHA) and its preparation method and application in property medium.
The present invention is using glycerol as raw material, and under mild reaction conditions, oxidation prepares dihydroxy third on Au base catalyst
Ketone (DHA).
Catalyst of the invention is a kind of supported Au catalysts that DHA is prepared for glycerol oxidation, and carrier is compound gold
Belong to oxide.
A kind of glycerol oxidation prepares the catalyst of dihydroxyacetone (DHA), in which: the catalyst is Au base catalyst, catalyst
Carrier be copper zirconium mixed oxide, the molar ratio of copper and zr element is 1:100-100:1 in the carrier of catalyst.
A kind of glycerol oxidation prepares the preparation method of the catalyst of dihydroxyacetone (DHA), comprising the following steps:
S1, copper nitrate, zirconium nitrate and water are mixed according to following mass ratio: copper nitrate: zirconium nitrate: water=1-28.7:25-1:
100, it is configured to solution A；
S2, by sodium carbonate and water according to mass ratio it is 1.325-26.5:100, is configured to B solution；
S3, the step S2 B solution prepared is added rapidly in the solution A of step S1 preparation, after mixing evenly, in 70 DEG C of temperature
Under the conditions of water-bath aging 1-12h, then product repeated filtration, the washing after aging will until the pH value of filtrate is in neutrality
Ageing products after washing dry 12h under the conditions of 110 DEG C of temperature；
S4, the sample after drying is ground into powder, powder is then roasted into 4h under the conditions of 400-700 DEG C of temperature, after remaining
Step uses；
S5, by step S4 roasting after powder, Au and urea be in mass ratio that 1:0-0.05:0-6.1 is distributed in 50g water, mix
After conjunction liquid stirs 0-30min at room temperature, mixed liquor is warming up to 80 DEG C, and stir 0-12h under the conditions of 80 DEG C of temperature, finally,
By mixed liquor aging 0-24h at room temperature；
S6, the solution obtained after step S5 aging is filtered, filtrate is washed repeatedly into filtrate without chlorine using deionized water
Filtrate is taken out and filter cake is made by ion；
S7, the filter cake for obtaining step S6 dry 4h under the conditions of 110 DEG C of temperature, the sample after drying is in 110-400 DEG C of temperature
Under the conditions of roast 5h, be made catalyst.
A kind of catalyst prepares the application in dihydroxyacetone (DHA) in glycerol oxidation, comprising the following steps: catalyst and glycerol
Molar ratio be 1:10-1000, reaction temperature be 10-180 DEG C, reaction time 1-12h, pressure 0.1-0.5MPa.
Compared with prior art the invention has the benefit that
Supported Au catalysts prepared by the present invention can prepare dihydroxy by efficiently catalyzing and oxidizing glycerol in heterogeneous alkaline media
Benzylacetone (DHA), the selectivity that glycerol conversion yield can achieve 80%, DHA can achieve 95% or more.Reaction process condition temperature
Small, environmental-friendly with equipment corrosion, the industrialization amplification for having reached current requires, and has broad application prospects.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.The method and step that the present invention mentions is only used for
The bright present invention rather than the limitation present invention, the embodiment described is only a part of the embodiments of the present invention, rather than all real
Apply example；Meanwhile the step of involved in the present embodiment, is not precluded and intermediate also can be inserted into other method and steps；Moreover, except no special
Illustrate, the present embodiment number is only used for distinguishing each embodiment, arrangement order or implementation model not for limitation various method steps
It encloses, the change and adjustment of corresponding relationship also will be regarded as practical range of the invention under the premise of without substantive innovation work.
The chemical reagent that following embodiments are related to can be commercially available unless otherwise specified in chemical reagents corporation.Instead
Product is answered to pass through high performance liquid chromatography detection (LC-10Avp), chromatographic column Aminex®HPX-87H, differential refraction detector
(RID-10A) and UV detector (SPD-10Avp) sulfuric acid is mobile phase, flow velocity 0.6mL/min, column temperature 60oC。
Glycerol conversion yield, dihydroxyacetone (DHA) selectivity and yield are calculated according to the following equation:
Embodiment 1:
28.69g copper nitrate, 2.46g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-1.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 2:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-2.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 3:
24.16g copper nitrate, 9.83g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-3.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 4:
18.12g copper nitrate, 19.66g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbon
Sour sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly,
70 DEG C of water-bath aging 1h are placed in, are filtered, deionized water washs to filtrate and be in neutrality, and blue-green bulk sample is obtained, 110 in baking oven
DEG C dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-4.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 5:
15.1g copper nitrate, 24.58g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-5.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 6:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 0.1ml is added40.122g urea is added later, is stirred at room temperature for (10mg/mL) precursor water solution
After 30min, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion,
110 DEG C of dry 4h, 200 DEG C of roasting 5h in tube furnace, obtain catalyst C-6.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 7:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 1ml is added41.22g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-7.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 8:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 3ml is added43.66g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-8.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 9:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 10ml is added412.2g urea is added later, is stirred at room temperature for (10mg/mL) precursor water solution
After 30min, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion,
110 DEG C of dry 4h, 200 DEG C of roasting 5h in tube furnace, obtain catalyst C-9.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 10:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 400 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-10.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 11:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 700 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-11.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 12:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 300 in tube furnaceoC roasts 5h, obtains catalyst C-12.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 13:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 1.325g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-13.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 14:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 26.5g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-14.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 15:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 12h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 in baking oven
DEG C dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-15.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 16:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, is warming up to 80 DEG C and stirs for (10mg/mL) precursor water solution
6h is mixed, hereafter aged at room temperature 12h, the Cl of noresidue is then washed with deionized water into filtrate—Ion, 110 DEG C of dry 4h, tubular type
200 DEG C of roasting 5h, obtain catalyst C-16 in furnace.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 17:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 12h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C
4h is dried, 200 DEG C of roasting 5h in tube furnace obtain catalyst C-17.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 18:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 12h, are then washed with deionized water the Cl of the noresidue into filtrate—Ion, 110 DEG C of dry 4h, in tube furnace
200 DEG C of roasting 5h, obtain catalyst C-18.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 19:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter for 24 hours, the Cl of the noresidue into filtrate is then washed with deionized water in aged at room temperature-Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-19.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.2MPa, 50 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Embodiment 20:
27.18g copper nitrate, 4.92g zirconium nitrate are dissolved in 100g deionized water, and stirring 0.5h is made into solution A.By 13.25g carbonic acid
Sodium is dissolved in 100g deionized water, and stirring 0.5h is made into B solution.B solution is added rapidly in solution A, after mixing evenly, is set
In 70 DEG C of water-bath aging 1h, filtering, deionized water is washed to filtrate and is in neutrality, and obtains blue-green bulk sample, 110 DEG C in baking oven
Dry 12h, pulverizing is placed in 600 DEG C of roasting 4h in Muffle furnace and obtains carrier finished product.The above-mentioned carrier finished product of 1g is taken, is distributed to
In 50g water, the NaAuCl of 2ml is added42.44g urea is added later, 30min is stirred at room temperature for (10mg/mL) precursor water solution
Afterwards, 80 DEG C of stirring 6h, hereafter aged at room temperature 12h, is then washed with deionized water the Cl of the noresidue into filtrate-Ion, 110 DEG C dry
Dry 4h, 200 DEG C of roasting 5h in tube furnace, obtains catalyst C-2.
By the above-mentioned catalyst of 0.39g, 19.5g glycerine water solution (0.1M/Kg) is fitted into reaction kettle, in 0.3MPa, 60 DEG C
Lower reaction 4h.Mixed liquor is centrifuged after reaction, a small amount of supernatant liquor is taken out and carries out efficient liquid phase chromatographic analysis, analyze result such as table
Shown in 1.
Glycerol oxidation prepares the reaction result of DHA in 1 different catalysts of table
In conclusion support type Au base catalyst prepared by the present invention, can realize mild condition, height in non-alkaline medium
Effect catalysis oxidation glycerol prepares the target of dihydroxyacetone (DHA).Using above-mentioned catalyst, it can effectively reduce environmental pollution, be stale-proof
Erosion equipment, catalyst are easily recycled, and the selectivity that glycerol conversion yield is up to 82%, DHA is up to 95% or more.Present invention catalysis
Agent is low for equipment requirements, and catalyst regeneration is convenient, is suitable for industrialized production.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
It is familiar with those skilled in the art in the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (3)
1. the catalyst that a kind of glycerol oxidation prepares dihydroxyacetone (DHA), it is characterised in that: the catalyst is Au base catalyst, is urged
The carrier of agent is copper zirconium mixed oxide, and the molar ratio of copper and zr element is 1:100-100:1 in the carrier of catalyst.
2. a kind of glycerol oxidation as described in claim 1 prepares the preparation method of the catalyst of dihydroxyacetone (DHA), feature exists
In the following steps are included:
S1, copper nitrate, zirconium nitrate and water are mixed according to following mass ratio: copper nitrate: zirconium nitrate: water=1-28.7:25-1:
100, it is configured to solution A；
S2, by sodium carbonate and water according to mass ratio it is 1.325-26.5:100, is configured to B solution；
S3, the step S2 B solution prepared is added rapidly in the solution A of step S1 preparation, after mixing evenly, in 70 DEG C of temperature
Under the conditions of water-bath aging 1-12h, then product repeated filtration, the washing after aging will until the pH value of filtrate is in neutrality
Ageing products after washing dry 12h under the conditions of 110 DEG C of temperature；
S4, the sample after drying is ground into powder, powder is then roasted into 4h under the conditions of 400-700 DEG C of temperature, after remaining
Step uses；
S5, by step S4 roasting after powder, Au and urea be in mass ratio that 1:0-0.05:0-6.1 is distributed in 50g water, mix
After conjunction liquid stirs 0-30min at room temperature, mixed liquor is warming up to 80 DEG C, and stir 0-12h under the conditions of 80 DEG C of temperature, finally,
By mixed liquor aging 0-24h at room temperature；
S6, the solution obtained after step S5 aging is filtered, filtrate is washed repeatedly into filtrate without chlorine using deionized water
Filtrate is taken out and filter cake is made by ion；
S7, the filter cake for obtaining step S6 dry 4h under the conditions of 110 DEG C of temperature, the sample after drying is in 110-400 DEG C of temperature
Under the conditions of roast 5h, be made catalyst.
3. a kind of catalyst as described in claim 1 prepares the application in dihydroxyacetone (DHA) in glycerol oxidation, it is characterised in that
The following steps are included: the molar ratio of catalyst and glycerol is 1:10-1000, reaction temperature is 10-180 DEG C, reaction time 1-
12h, pressure 0.1-0.5MPa.
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