CN102603515A - Method for preparing gluconic acid by direct oxidization of cellulose - Google Patents

Method for preparing gluconic acid by direct oxidization of cellulose Download PDF

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CN102603515A
CN102603515A CN2012100390234A CN201210039023A CN102603515A CN 102603515 A CN102603515 A CN 102603515A CN 2012100390234 A CN2012100390234 A CN 2012100390234A CN 201210039023 A CN201210039023 A CN 201210039023A CN 102603515 A CN102603515 A CN 102603515A
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mierocrystalline cellulose
glucono
cellulose
water
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CN102603515B (en
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安冬丽
邓卫平
叶爱华
张庆红
王野
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Xiamen University
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Abstract

The invention discloses a method for preparing gluconic acid by direct oxidization of cellulose, and relates to gluconic acid. The method comprises the steps of preparing a catalyst comprising synthesis of cesium 12-tungstophosphate (PWC) and preparation of a gold (Au) catalyst; selecting cellulose; and performing a catalytic reaction: adding m Au/CsxH3-xPW12O40, CsxH3-xPW12O40 and water into an inner container of a reaction kettle, wherein x is equal to 0-3.0, placing the inner container into the reaction kettle, evacuating the air in the reaction kettle with oxygen, then introducing oxygen, and allowing for a reaction to obtain gluconic acid. The method disclosed by the invention uses neutral water as a medium, performs catalytic oxidation of cellulose to prepare gluconic acid in the presence of the metal Au-loaded PWC catalyst or in the presence of the metal Au-loaded PWC catalyst and CsxH(3-x)PW12O40, wherein x is equal to 0-3.0, and the highest yield of gluconic acid can be up to 85%.

Description

A kind of method for preparing glucono-with the Mierocrystalline cellulose direct oxidation
Technical field
The present invention relates to a kind of glucono-, especially relate to a kind of method for preparing glucono-with the Mierocrystalline cellulose direct oxidation.
Background technology
Glucono-and verivate thereof are one type of multiduty important organic chemical industry's products.They are as complexing agent, the grease-removing agent of iron and steel, aluminium, glass surface, and washing auxiliary detergent, foodstuff additive and accessory substance etc. are widely used in fields such as metal processing, plating, food, building, weaving, daily-use chemical industry.The U.S. and Japan and other countries just began to produce in enormous quantities as far back as the 1950's, at present.About 40,000 tons of the output of world's gluconate, and the not enough kiloton of China ultimate production, so the research of glucono-and production have vast potential for future development.
At present, glucono-generally is to be got by glucose oxidase, and method has biological oxidation process (fermentation method and oxidation enzyme process), chemical catalytic oxidation method and electrolytic oxidation ([3] Zhu Jianliang; Appoint forever; Ouyang Pingkai. glucono-production technique summary [J]. print during chemical industry, 1995,10:24-27).Use biological oxidation process in the world, mainly be through the fermentative Production calglucon in China more, again calglucon carried out acidification and obtain glucono-, and then process various gluconates.This method equipment is huge, and investment cost is high, and sub product is many, and separation and purification of products is difficulty relatively, thereby production cost is higher.Wherein the heterogeneous catalytic oxidation research for preparing glucono-is mainly produced glucono-([4] C.Baatz with noble metal catalyst catalytic oxidation of glucose such as Pd, Pt, Au; N.Decker; Prube U, New innovative gold catalysts prepared by an improved incipientwetness method [J], J.Catal.; 2008,258:165-169; [5] C.Baatz, U.Prube, Preparation of goldcatalysts for glucose oxidation by incipient wetness [J], J.Catal., 2007,249:34-40; [6] X.Liang, C.J.Liu, P.Y.Kuai, Selective oxidation of glucose to gluconic acid over argon plasma reducedPd/Al 2O 3[J], Green Chem., 2008,10:1318-1322; [7] A.Abbadi, H.Beckkum, Effect of pHin the Pt-catalyzed oxidation of D-glucose to D-gluconic acid [J], J.Mol.Catal.A:Chem., 1995,97:111-118; [8] S.Hermans, M.Devillers, On the role of ruthenium associated with Pd and/orBi incarbon-supported catalysts for the partial oxidation of glucose [J]; Appl.Catal., A, 2002; 235:253-264), and in the process of catalytic oxidation of glucose, be the stability that improves glucono-; The minimizing glucono-poisons and subsequent oxidation catalyzer, and reaction often need be carried out ([9] A.Mirescu, H.Berndt under alkaline environment; A.Martin, Long-term stability of a 0.45%Au/TiO 2Catalyst in the selective oxidation of glucose atoptimised reaction conditions [J], Appl.Catal.A, 2007,317:204-209).2009, Wang Ye group ([10] X.S.Tan, W.P.Deng; M.Liu; Q.H.Zhang, Y.Wang, Carbon nanotube-supported goldnanoparticles as efficient catalysts for selective oxidation of cellobiose into gluconic acid in watermedium. [J]; Chem.Commun.; 2009,46:7179-7181) reported first be that carrier loaded golden catalyzed oxidation cellobiose is converted into glucono-with carbon nanotube, reaction 6h glucono-yield reaches 80% in water medium.
Mierocrystalline cellulose is through β-1 by glucose; The high molecular polymer that 4 glycosidic links are formed by connecting; Also being the abundantest biomass of nature, being mainly derived from trees, cotton, fibre of flax for textile material and other agricultural byproducts, is the inexhaustible renewable resources of occurring in nature.Annual nearly 1.5 * 10 12Ton synthesizes through photosynthesis.But because the densification of its structural form makes development and use difficult.If can the direct catalyzed oxidation of Mierocrystalline cellulose be generated glucono-, not only help the requirement of Sustainable development, also significant to safeguarding ecotope.Because crystalline structure and water insoluble and most of solvent of Mierocrystalline cellulose stabilizer pole, it is less to generate micromolecular organic acid report to cellulosic catalyzed conversion thus.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing glucono-with the Mierocrystalline cellulose direct oxidation.
The present invention includes following steps:
1) Preparation of catalysts:
(1) phosphorus heteropoly tungstic acid cesium salt (Cs xH 3-xPW 12O 40, x=0～3.0) synthetic: with Cs 2CO 3Be dissolved in and be mixed with Cs in the deionized water 2CO 3The solution note is made solution a, with H 3.0PW 12O 40Be dissolved in and be mixed with H in the deionized water 3.0PW 12O 40Solution note is made solution b, and solution a is joined solution b, produces white precipitate, after the ageing white suspension liquid, take out after the spinning, remove supernatant liquid, the centrifugal solid drying that goes out is promptly made phosphorus heteropoly tungstic acid cesium salt (Cs xH 3-xPW 12O 40, x=0～3.0);
(2) preparation of Au catalyst: the chemical constitution of catalyzer is mAu/Cs xH 3-xPW 12O 40, m is the mass percent of metallic gold in catalyzer, m is 0.1%～5%, Cs xH 3-xPW 12O 40(x=0～3.0) are the phosphorus heteropoly tungstic acid cesium salt;
Its concrete preparation process is following: be the chlorauric acid solution of 0.001～0.005g/ml with gold content; Add deionized water and be diluted to 10～50ml; Prepared phosphorus heteropoly tungstic acid cesium salt is joined in the above-mentioned chlorauric acid solution, and formed mixture leaves standstill, oven dry; Pulverize last under hydrogen atmosphere with gold reduction, make Au catalyst;
2) Mierocrystalline cellulose: said Mierocrystalline cellulose comprises Microcrystalline Cellulose, acid treated fiber element and ball milling Mierocrystalline cellulose; Said Microcrystalline Cellulose adopts commercially available commercial fibre plain; Said acid treated fiber is plain handles the Mierocrystalline cellulose that obtains for Microcrystalline Cellulose with acid, and said ball milling Mierocrystalline cellulose is handled the Mierocrystalline cellulose that obtains for the method with mechanical ball milling;
3) catalyzed reaction: with Mierocrystalline cellulose, m Au/Cs xH 3-xPW 12O 40, Cs xH 3-xPW 12O 40(x=0～3.0) and water join in the inner bag of reaction kettle, again inner bag are put into reaction kettle, drain air in the still with oxygen, promptly get glucono-after charging into oxygen reaction again.
In step 1) (1) part, the concentration of said solution a can be 0.01～0.1mol/L, and the concentration of said solution b can be 0.01～0.1mol/L; Said when solution a is joined solution b, can stir down at 25～50 ℃, the volume ratio of said solution a and solution b can be 1: 1; The said aged time can be 0.5～2h.
In step 1) (2) part, the volume ratio of said chlorauric acid solution and deionized water can be 1: (2～50); The temperature of said oven dry can be 80～100 ℃; Said golden reductive temperature can be 200～500 ℃, and the golden reductive time can be 0.5～2h.
In step 2) in, the concrete grammar that said Microcrystalline Cellulose is handled with acid can be: earlier the Microcrystalline Cellulose water is made its swollen, add phosphate aqueous solution again, to forming transparent dope solution; Sticky thing solution is placed 0～100 ℃ of water-bath, leave standstill 10～60min after, add entry, with Cellulose precipitates regeneration, be 7 with water washing to pH value of solution value again, drying is ground into powder, acid treated fiber is plain; The mass percentage concentration of phosphoric acid is preferably 43%～85%, presses mass ratio, Microcrystalline Cellulose: phosphate aqueous solution=(0.01～10): 100, and the amount of water after leaving standstill and the volume ratio of phosphate aqueous solution are phosphate aqueous solution: water=1: (0.1～1); The concrete grammar that said Microcrystalline Cellulose is handled with the method for mechanical ball milling can be: the commercial fibre element in ball mill grinding 1～3 day, is promptly got the ball milling Mierocrystalline cellulose.
In step 3), said Mierocrystalline cellulose: m Au/Cs xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40: the mass ratio of water can be 1: (0.05～1): (0～1): (50～250); Saidly drain with oxygen that air can repeat 10 times at least in the still, the pressure of said oxygen can be 0.1～2.0MPa; The condition of said reaction can be at 80～180 ℃ of reaction 0.2～48h.
Analyze with performance liquid chromatography (HPLC) after the product spinning.
The present invention is medium with the neutral water, is carried on phosphorus heteropoly tungstic acid cesium salt catalyzer or metallic gold is carried on phosphorus heteropoly tungstic acid cesium salt catalyzer and Cs in metallic gold xH 3-xPW 12O 40(x=0～3.0) are common to be existed down, Mierocrystalline cellulose catalyzed oxidation preparation of gluconic acid, and the yield of its glucono-can reach 85%.
Description of drawings
Fig. 1 is the color atlas of the glucono-of the present invention's preparation.In Fig. 1, X-coordinate is time/min, and ordinate zou is for detecting voltage/mV; Chromatographic column: Shodex SH1011, RT: 7.25min.
Embodiment
Through embodiment the present invention is described further below.
Embodiment 1
Preparation of catalysts:
(i) with Cs 2CO 3Be dissolved in the Cs that is mixed with 0.02mol/L in the deionized water 2CO 3Solution a.With H 3.0PW 12O 40Be dissolved in the H that is mixed with 0.1mol/L in the deionized water 3.0PW 12O 40Solution b.Under 25～50 ℃ and intense agitation, solution a125mL slowly is added drop-wise among the solution b of 50mL volume, produce white precipitate, ageing 1h.White suspension liquid is put into the whizzer spinning, take out the back and remove supernatant liquid, the centrifugal solid that goes out is put into the baking oven drying can make Cs 1.2H 1.8PW 12O 40
(ii) pipette the chlorauric acid solution that the 2.1ml gold content is 0.0048g/ml, add deionized water and be diluted to 15ml.Cs that 1g is prepared under the vigorous stirring 1.2H 1.8PW 12O 40Join in the above-mentioned chlorauric acid solution.After stirring 4h under the formed mixture room temperature, hold over night.80 ℃ with agitation condition under with the mixture evaporate to dryness, dry 1h in 80 ℃ baking oven again.Fully grind behind this powder under 300 ℃ of hydrogen atmospheres golden reductase 12 h, can make 1.0wt%Au/Cs 1.2H 1.8PW 12O 40Catalyzer.
Ball milling Mierocrystalline cellulose: the commercial fibre element was promptly got in ball mill grinding in 2 days.
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 1.2H 1.8PW 12O 40, Cs 1.2H 1.8PW 12O 40, water and a magneton join and gather in the tetrafluoro inner bag, again inner bag put into the stainless steel autoclave, drains air in the still with oxygen, repeat 10 times after, charge into the oxygen of 1.0MPa again, stir, behind 145 ℃ of reaction 11h product.Analyze with performance liquid chromatography (HPLC) after the product spinning.Mierocrystalline cellulose: m Au/Cs xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40(x=0-3.0): the quality of the water ratio that feeds intake is 0.20: 0.20: 0: 10.Cellulosic catalytic oxidation performance is referring to table 1.
Table 1
Figure BDA0000137057790000041
Embodiment 2
Preparation of catalysts:
(i) with Cs 2CO 3Be dissolved in the Cs that is mixed with 0.02mol/L in the deionized water 2CO 3Solution a.With H 3.0PW 12O 40Be dissolved in the H that is mixed with 0.1mol/L in the deionized water 3.0PW 12O 40Solution b.Under 25～50 ℃ and intense agitation, solution a250mL slowly is added drop-wise among the solution b of 50mL volume, produce white precipitate, ageing 1h.White suspension liquid is put into the whizzer spinning, take out the back and remove supernatant liquid, the centrifugal solid that goes out is put into the baking oven drying can make Cs 2.2H 0.8PW 12O 40
(ii) pipette the chlorauric acid solution that the 2.1ml gold content is 0.0048g/ml, add deionized water and be diluted to 15ml.Cs that 1g is prepared under the vigorous stirring 2.2H 0.8PW 12O 40Join in the above-mentioned chlorauric acid solution.After stirring 4h under the formed mixture room temperature, hold over night.80 ℃ with agitation condition under with the mixture evaporate to dryness, dry 1h in 80 ℃ baking oven again.Fully grind behind this powder under 300 ℃ of hydrogen atmospheres golden reductase 12 h, can make 1.0wt%Au/Cs 2.2H 0.8PW 12O 40Catalyzer.
Ball milling Mierocrystalline cellulose: the commercial fibre element was promptly got in ball mill grinding in 2 days.
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 2.2H 0.8PW 12O 40, Cs 1.2H 1.8PW 12O 40, water and a magneton join and gather in the tetrafluoro inner bag, again inner bag put into the stainless steel autoclave, drains air in the still with oxygen, repeat 10 times after, charge into the oxygen of 1.0MPa again, stir, behind 145 ℃ of reaction 11h product.Analyze with performance liquid chromatography (HPLC) after the product spinning.Mierocrystalline cellulose: m Au/Cs xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40(x=0-3.0): the quality of the water ratio that feeds intake is 0.20: 0.20: 0: 10.Cellulosic catalytic oxidation performance is referring to table 2.
Table 2
Figure BDA0000137057790000051
Embodiment 3
Catalyst preparation step with embodiment 2 (i) and (ii).
Mierocrystalline cellulose: adopt the commercial goods Mierocrystalline cellulose.
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 2.2H 0.8PW 12O 40, Cs 1.2H 1.8PW 12O 40, water and a magneton join and gather in the tetrafluoro inner bag, again inner bag put into the stainless steel autoclave, drains air in the still with oxygen, repeat 10 times after, charge into the oxygen of 1.0MPa again, stir, behind 145 ℃ of reaction 11h product.Analyze with performance liquid chromatography (HPLC) after the product spinning.Mierocrystalline cellulose: m Au/Cs xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40(x=0-3.0): the quality of the water ratio that feeds intake is 0.20: 0.20: 0: 10.The catalytic oxidation performance of commercial fibre element is referring to table 3.
Table 3
Figure BDA0000137057790000052
Embodiment 4
Preparation of catalysts:
(i) with Cs 2CO 3Be dissolved in the Cs that is mixed with 0.02mol/L in the deionized water 2CO 3Solution a.With H 3.0PW 12O 40Be dissolved in the H that is mixed with 0.1mol/L in the deionized water 3.0PW 12O 40Solution b.Under 25～50 ℃ and intense agitation, solution a400mL slowly is added drop-wise among the solution b of 50mL volume, produce white precipitate, ageing 1h.White suspension liquid is put into the whizzer spinning, take out the back and remove supernatant liquid, can make Cs putting into the baking oven drying behind the centrifugal solid centrifuge washing that goes out 3 to 4 times 3.0PW 12O 40
(ii) pipette the chlorauric acid solution that the 2.1m1 gold content is 0.0048g/ml, add deionized water and be diluted to 15ml.Cs that 1g is prepared under the vigorous stirring 3.0PW 12O 40Join in the above-mentioned chlorauric acid solution.After stirring 4h under the formed mixture room temperature, hold over night.80 ℃ with agitation condition under with the mixture evaporate to dryness, dry 1h in 80 ℃ baking oven again.Fully grind behind this powder under 300 ℃ of hydrogen atmospheres golden reductase 12 h, can make 1.0wt%Au/Cs 3.0PW 12O 40Catalyzer.
Ball milling Mierocrystalline cellulose: the commercial fibre element was promptly got in ball mill grinding in 2 days.
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 3.0PW 12O 40, H 3.0PW 12O 40, water and a magneton join and gather in the tetrafluoro inner bag, again inner bag put into the stainless steel autoclave, drains air in the still with oxygen, repeat 10 times after, charge into the oxygen of 1.0MPa again, stir, behind 145 ℃ of reaction 11h product.Analyze with performance liquid chromatography (HPLC) after the product spinning.Mierocrystalline cellulose: m Au/Cs xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40(x=0-3.0): the quality of the water ratio that feeds intake is 0.20: 0.08: 0.10: 10.Cellulosic catalytic oxidation performance is referring to table 4.
Table 4
Embodiment 5
Preparation of catalysts:
(i) with Cs 2CO 3Be dissolved in the Cs that is mixed with 0.02mol/L in the deionized water 2CO 3Solution a.With H 3.0PW 12O 40Be dissolved in the H that is mixed with 0.1mol/L in the deionized water 3.0PW 12O 40Solution b.Under 25～50 ℃ and intense agitation, solution a313mL slowly is added drop-wise among the solution b of 50mL volume, produce white precipitate, ageing 1h.White suspension liquid is put into the whizzer spinning, take out the back and remove supernatant liquid, the centrifugal solid that goes out is put into the baking oven drying can make Cs 2.6H 0.4PW 12O 40
(ii) pipette the chlorauric acid solution that the 2.1ml gold content is 0.0048g/ml, add deionized water and be diluted to 15ml.Cs that 1g is prepared under the vigorous stirring 2.6H 0.4PW 12O 40Join in the above-mentioned chlorauric acid solution.After stirring 4h under the formed mixture room temperature, hold over night.80 ℃ with agitation condition under with the mixture evaporate to dryness, dry 1h in 80 ℃ baking oven again.Fully grind behind this powder under 300 ℃ of hydrogen atmospheres golden reductase 12 h, can make 1.0wt%Au/Cs 2.6H 0.4PW 12O 40Catalyzer.
Ball milling Mierocrystalline cellulose: the commercial fibre element was promptly got in ball mill grinding in 2 days.
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 2.6H 0.4PW 12O 40, H 3.0PW 12O 40, water and a magneton join and gather in the tetrafluoro inner bag, again inner bag put into the stainless steel autoclave, drains air in the still with oxygen, repeat 10 times after, charge into the oxygen of 1.0MPa again, stir, behind 145 ℃ of reaction 11h product.Analyze with performance liquid chromatography (HPLC) after the product spinning.Mierocrystalline cellulose: m Au/Cs xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40(x=0-3.0): the quality of the water ratio that feeds intake is 0.20: 0.08: 0.10: 10.Cellulosic catalytic oxidation performance is referring to table 5.
Table 5
Figure BDA0000137057790000062
Embodiment 6
Catalyst preparation step with embodiment 2 (i) and (ii).
Ball milling Mierocrystalline cellulose: the commercial fibre element was promptly got in ball mill grinding in 2 days.
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 2.2H 0.4PW 12O 40, H 3.0PW 12O 40, water and a magneton join and gather in the tetrafluoro inner bag, again inner bag put into the stainless steel autoclave, drains air in the still with oxygen, repeat 10 times after, charge into the oxygen of 1.0MPa again, stir, behind 145 ℃ of reaction 11h product.Analyze with performance liquid chromatography (HPLC) after the product spinning.Mierocrystalline cellulose: m Au/Cs xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40(x=0-3.0): the quality of the water ratio that feeds intake is 0.20: 0.08: 0.10: 10.Cellulosic catalytic oxidation performance is referring to table 6.
Table 6
Figure BDA0000137057790000071
Embodiment 7
Catalyst preparation step with embodiment 1 (i) and (ii).
Ball milling Mierocrystalline cellulose: the commercial fibre element was promptly got in ball mill grinding in 2 days.
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 1.2H 0.4PW 12O 40, H 3.0PW 12O 40, water and a magneton join and gather in the tetrafluoro inner bag, again inner bag put into the stainless steel autoclave, drains air in the still with oxygen, repeat 10 times after, charge into the oxygen of 1.0MPa again, stir, behind 145 ℃ of reaction 11h product.Analyze with performance liquid chromatography (HPLC) after the product spinning.Mierocrystalline cellulose: m Au/Cs xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40(x=0-3.0): the quality of the water ratio that feeds intake is 0.20: 0.08: 0.10: 10.Cellulosic catalytic oxidation performance is referring to table 7.
Table 7
Figure BDA0000137057790000072
Embodiment 8
Catalyst preparation step with embodiment 2 (i), (ii) with 1 (i).
Ball milling Mierocrystalline cellulose: the commercial fibre element was promptly got in ball mill grinding in 2 days.
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 2.2H 0.8PW 12O 40, Cs 1.2H 1.8PW 12O 40, water and a magneton join and gather in the tetrafluoro inner bag, again inner bag put into the stainless steel autoclave, drains air in the still with oxygen, repeat 10 times after, charge into the oxygen of 1.0MPa again, stir, behind 145 ℃ of reaction 11h product.Analyze with performance liquid chromatography (HPLC) after the product spinning.Mierocrystalline cellulose: m Au/Cs xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40(x=0-3.0): the quality of the water ratio that feeds intake is 0.20: 0.08: 0.20: 10.Cellulosic catalytic oxidation performance is referring to table 8.
Table 8
Figure BDA0000137057790000073
Embodiment 9
Catalyst preparation step with embodiment 4 (i) and (ii).
Ball milling Mierocrystalline cellulose: the commercial fibre element was promptly got in ball mill grinding in 2 days.
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 3.0PW 12O 40, H 3.0PW 12O 40, water and a magneton join and gather in the tetrafluoro inner bag, again inner bag put into the stainless steel autoclave, drains air in the still with oxygen, repeat 10 times after, charge into the oxygen of 1.5MPa again, stir, behind 145 ℃ of reaction 11h product.Analyze with performance liquid chromatography (HPLC) after the product spinning.Mierocrystalline cellulose: m Au/Cs xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40(x=0-3.0): the quality of the water ratio that feeds intake is 0.20: 0.08: 0.10: 10.Cellulosic catalytic oxidation performance is referring to table 9.
Table 9
Figure BDA0000137057790000081
Embodiment 10
Catalyst preparation step with embodiment 4 (i) and (ii).
Mierocrystalline cellulose: adopt the commercial goods Mierocrystalline cellulose.
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 3.0PW 12O 40, H 3.0PW 12O 40, water and a magneton join and gather in the tetrafluoro inner bag, again inner bag put into the stainless steel autoclave, drains air in the still with oxygen, repeat 10 times after, charge into the oxygen of 1.0MPa again, stir, behind 145 ℃ of reaction 11h product.Analyze with performance liquid chromatography (HPLC) after the product spinning.Mierocrystalline cellulose: m Au/Cs xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40(x=0-3.0): the quality of the water ratio that feeds intake is 0.20: 0.08: 0.10: 10.The catalytic oxidation performance of commercial fibre element is referring to table 10.
Table 10
Embodiment 11
Catalyst preparation step with embodiment 4 (i) and (ii).
Mierocrystalline cellulose: in the Mierocrystalline cellulose pre-treatment, the Mierocrystalline cellulose water is made its swollen, add phosphate aqueous solution again, to the dope solution that forms transparent homogeneous; Sticky thing solution is placed 0～100 ℃ of water-bath, leave standstill 10～60min after, add entry, with Cellulose precipitates regeneration, be 7 with water washing to pH value of solution value again, drying is ground into powder, and is subsequent use.Mierocrystalline cellulose is preferably Microcrystalline Cellulose.The mass percentage concentration of phosphoric acid is preferably 43%～85%.Pretreated temperature can be 0～100 ℃, is preferably 0～50 ℃.Press mass ratio, Mierocrystalline cellulose: phosphate aqueous solution=(0.01～10): 100, the amount of water after leaving standstill and the proportioning of phosphate aqueous solution are phosphate aqueous solution: water=100: (10～100).
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 3.0PW 12O 40, H 3.0PW 12O 40, water and a magneton join and gather in the tetrafluoro inner bag, again inner bag put into the stainless steel autoclave, drains air in the still with oxygen, repeat 10 times after, charge into the oxygen of 1.0MPa again, stir, behind 145 ℃ of reaction 11h product.Analyze with performance liquid chromatography (HPLC) after the product spinning.Mierocrystalline cellulose: m Au/Cs xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40(x=0-3.0): the quality of the water ratio that feeds intake is 0.20: 0.08: 0.10: 10.The catalytic oxidation performance of cellobiose is referring to table 11.
Table 11
Product is analyzed by HPLC, and is as shown in Figure 1, and transforming the primary product that Mierocrystalline cellulose obtains in the methods of the invention is glucono-(chromatographic column: Shodex SH1011, RT: 7.25min).

Claims (10)

1. one kind prepares the method for glucono-with the Mierocrystalline cellulose direct oxidation, it is characterized in that may further comprise the steps:
1) Preparation of catalysts:
(1) the phosphorus heteropoly tungstic acid cesium salt is synthetic: with Cs 2CO 3Be dissolved in and be mixed with Cs in the deionized water 2CO 3The solution note is made solution a, with H 3.0PW 12O 40Be dissolved in and be mixed with H in the deionized water 3.0PW 12O 40Solution note is made solution b, and solution a is joined solution b, produces white precipitate, after the ageing white suspension liquid, take out after the spinning, remove supernatant liquid, the centrifugal solid drying that goes out is promptly made the phosphorus heteropoly tungstic acid cesium salt;
(2) preparation of Au catalyst: the chemical constitution of catalyzer is mAu/Cs xH 3-xPW 12O 40, m is the mass percent of metallic gold in catalyzer, m is 0.1%～5%, Cs xH 3-xPW 12O 40Be the phosphorus heteropoly tungstic acid cesium salt, wherein x=0～3.0;
Its concrete preparation process is following: be the chlorauric acid solution of 0.001～0.005g/ml with gold content; Add deionized water and be diluted to 10～50ml; Prepared phosphorus heteropoly tungstic acid cesium salt is joined in the above-mentioned chlorauric acid solution, and formed mixture leaves standstill, oven dry; Pulverize last under hydrogen atmosphere with gold reduction, make Au catalyst;
2) Mierocrystalline cellulose: said Mierocrystalline cellulose comprises Microcrystalline Cellulose, acid treated fiber element and ball milling Mierocrystalline cellulose; Said Microcrystalline Cellulose adopts commercially available commercial fibre plain; Said acid treated fiber is plain handles the Mierocrystalline cellulose that obtains for Microcrystalline Cellulose with acid, and said ball milling Mierocrystalline cellulose is handled the Mierocrystalline cellulose that obtains for the method with mechanical ball milling;
3) catalyzed reaction: with Mierocrystalline cellulose, m Au/Cs xH 3-xPW 12O 40, Cs xH 3-xPW 12O 40Join in the inner bag of reaction kettle with water, again inner bag is put into reaction kettle, drain air in the still, promptly get glucono-after charging into oxygen reaction again, wherein x=0～3.0 with oxygen.
2. as claimed in claim 1ly a kind ofly prepare the method for glucono-with the Mierocrystalline cellulose direct oxidation, it is characterized in that the concentration of said solution a is 0.01～0.1mol/L in step 1) (1) part, the concentration of said solution b is 0.01～0.1mol/L.
3. a kind of method for preparing glucono-with the Mierocrystalline cellulose direct oxidation as claimed in claim 1; It is characterized in that in step 1) (1) part; Said when solution a is joined solution b, stir down at 25～50 ℃, the volume ratio of said solution a and solution b is 1: 1.
4. as claimed in claim 1ly a kind ofly prepare the method for glucono-, it is characterized in that the said aged time is 0.5～2h in step 1) (1) part with the Mierocrystalline cellulose direct oxidation.
5. as claimed in claim 1ly a kind ofly prepare the method for glucono-, it is characterized in that the volume ratio of said chlorauric acid solution and deionized water is 1: (2～50) in step 1) (2) part with the Mierocrystalline cellulose direct oxidation.
6. as claimed in claim 1ly a kind ofly prepare the method for glucono-, it is characterized in that the temperature of said oven dry is 80～100 ℃ in step 1) (2) part with the Mierocrystalline cellulose direct oxidation; Said golden reductive temperature is 200～500 ℃, and the golden reductive time is 0.5～2h.
7. a kind of method for preparing glucono-with the Mierocrystalline cellulose direct oxidation as claimed in claim 1; It is characterized in that in step 2) in; The concrete grammar that said Microcrystalline Cellulose is handled with acid is: earlier the Microcrystalline Cellulose water is made its swollen; Add phosphate aqueous solution again, to forming transparent dope solution; Sticky thing solution is placed 0～100 ℃ of water-bath, leave standstill 10～60min after, add entry, with Cellulose precipitates regeneration, be 7 with water washing to pH value of solution value again, drying is ground into powder, acid treated fiber is plain; The mass percentage concentration of phosphoric acid is preferably 43%～85%, presses mass ratio, Microcrystalline Cellulose: phosphate aqueous solution=(0.01～10): 100, and the amount of water after leaving standstill and the volume ratio of phosphate aqueous solution are phosphate aqueous solution: water=1: (0.1～1).
8. a kind of method for preparing glucono-with the Mierocrystalline cellulose direct oxidation as claimed in claim 1; It is characterized in that in step 2) in; The concrete grammar that said Microcrystalline Cellulose is handled with the method for mechanical ball milling is: the commercial fibre element in ball mill grinding 1～3 day, is promptly got the ball milling Mierocrystalline cellulose.
9. as claimed in claim 1ly a kind ofly prepare the method for glucono-, it is characterized in that in step 3) said Mierocrystalline cellulose: m Au/Cs with the Mierocrystalline cellulose direct oxidation xH 3-xPW 12O 40: Cs xH 3-xPW 12O 40: the mass ratio of water is 1: (0.05～1): (0～1): (50～250).
10. as claimed in claim 1ly a kind ofly prepare the method for glucono-with the Mierocrystalline cellulose direct oxidation, it is characterized in that in step 3), saidly drain with oxygen that air repeats 10 times at least in the still, the pressure of said oxygen is 0.1～2.0MPa; The condition of said reaction is at 80～180 ℃ of reaction 02～48h.
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CN103882157A (en) * 2012-12-21 2014-06-25 中国科学院大连化学物理研究所 Method for oxidation treatment of cellulose by molecular oxygen to hydrolyze cellulose into monosaccharide
CN106755611A (en) * 2017-03-01 2017-05-31 中国科学技术大学 A kind of method of heteropoly acid catalysis lignocellulosic hydrolysis
CN107029705A (en) * 2017-05-18 2017-08-11 厦门大学 The preparation and its application of a kind of load type metal catalyst
CN107029705B (en) * 2017-05-18 2020-01-31 厦门大学 Preparation and application of supported metal catalysts
CN108863756A (en) * 2018-08-07 2018-11-23 陈华明 A method of preparing gluconic acid
CN109020800A (en) * 2018-08-07 2018-12-18 陈华明 A method of gluconic acid is prepared with cellulose direct oxidation
CN111617802A (en) * 2020-06-24 2020-09-04 新疆农业大学 Combined supported catalyst and preparation method and application thereof

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