CN102603515B - 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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CN102603515B
CN102603515B CN 201210039023 CN201210039023A CN102603515B CN 102603515 B CN102603515 B CN 102603515B CN 201210039023 CN201210039023 CN 201210039023 CN 201210039023 A CN201210039023 A CN 201210039023A CN 102603515 B CN102603515 B CN 102603515B
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mierocrystalline cellulose
acid
gluconic acid
cellulose
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CN102603515A (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 to85%.

Description

A kind of method for preparing gluconic acid with the Mierocrystalline cellulose direct oxidation
Technical field
The present invention relates to a kind of gluconic acid, especially relate to a kind of method for preparing gluconic acid with the Mierocrystalline cellulose direct oxidation.
Background technology
Gluconic acid and derivative thereof are the multiduty important Organic chemical products of a class.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 the 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 gluconic acid and production have vast potential for future development.
At present, gluconic acid generally is to be got by glucose oxidase, 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. gluconic acid production technique summary [J]. print during chemical industry, 1995,10:24-27).Multiplex biological oxidation process mainly is by the fermentative Production calglucon in China in the world, again calglucon is carried out acidification and obtains gluconic acid, and then make various gluconates.This method equipment is huge, and investment cost is high, and byproduct is many, and separation and purification of products is difficulty relatively, thereby production cost is higher.Wherein the heterogeneous catalytic oxidation research for preparing gluconic acid is mainly produced gluconic acid ([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, for improving the stability of gluconic acid, reduce gluconic acid poisoning and subsequent oxidation catalyzer, reaction often need to be carried out ([9] A.Mirescu under alkaline environment, H.Berndt, 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, ([10] X.S.Tan of Wang Ye group, 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 converted into gluconic acid take carbon nanotube as carrier loaded golden catalyzed oxidation cellobiose, reaction 6h gluconic acid yield reaches 80% in water medium.
Mierocrystalline cellulose is by 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, so that development and use difficulty.If the Mierocrystalline cellulose Direct Catalytic Oxidation can be generated gluconic acid, not only be conducive to 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 for cellulosic catalyzed conversion thus.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing gluconic acid with the Mierocrystalline cellulose direct oxidation.
The present invention includes following steps:
1) preparation of catalyzer:
(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 3Solution is denoted as solution a, with H 3.0PW 12O 40Be dissolved in and be mixed with H in the deionized water 3.0PW 12O 40Solution is denoted as solution b, and solution a is joined solution b, produces white precipitate, after the ageing white suspension liquid, take out after the centrifugation, remove supernatant liquid, the centrifugal solid drying that goes out is namely 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 as follows: 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, formed mixture leaves standstill, oven dry, pulverize last under hydrogen atmosphere with gold reduction, make Au catalyst;
2) Mierocrystalline cellulose: described Mierocrystalline cellulose comprises Microcrystalline Cellulose, acid treated fiber element and ball milling Mierocrystalline cellulose, described Microcrystalline Cellulose adopts commercially available commercial fibre element, described acid treated fiber element is processed the Mierocrystalline cellulose that obtains for Microcrystalline Cellulose with acid, and described ball milling Mierocrystalline cellulose is processed 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 reactor, again inner bag are put into reactor, drain air in the still with oxygen, namely get gluconic acid after being filled with oxygen reaction again.
In step 1) (1) part in, the concentration of described solution a can be 0.01～0.1mol/L, the concentration of described solution b can be 0.01～0.1mol/L; Described when solution a is joined solution b, can be 25～50 ℃ of lower stirrings, the volume ratio of described solution a and solution b can be 1: 1; The time of described ageing can be 0.5～2h.
In step 1) (2) part in, the volume ratio of described chlorauric acid solution and deionized water can be 1: (2～50); The temperature of described oven dry can be 80～100 ℃; The temperature of described gold reduction can be 200～500 ℃, and the time of gold reduction can be 0.5～2h.
In step 2) in, the concrete grammar that described Microcrystalline Cellulose is processed with acid can be: first 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 take water washing to pH again, drying is ground into powder, and gets the acid treated fiber element; The mass percentage concentration of phosphoric acid is preferably 43%～85%, in mass ratio, Microcrystalline Cellulose: phosphate aqueous solution=(0.01～10): 100, 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 described Microcrystalline Cellulose is processed with the method for mechanical ball milling can be: the commercial fibre element in ball mill grinding 1～3 day, is namely got the ball milling Mierocrystalline cellulose.
In step 3) in, described 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); Describedly drain with oxygen that air can repeat 10 times at least in the still, the pressure of described oxygen can be 0.1～2.0MPa; The condition of described reaction can be at 80～180 ℃ of reaction 0.2～48h.
Analyze with high performance liquid chromatography (HPLC) after the product centrifugation.
The present invention is take neutral water as medium, 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) common existence is lower, Mierocrystalline cellulose catalyzed oxidation preparation of gluconic acid, and the yield of its gluconic acid can reach 85%.
Description of drawings
Fig. 1 is the color atlas of the gluconic acid for preparing of the present invention.In Fig. 1, X-coordinate is time/min, and ordinate zou is for detecting voltage/mV; Chromatographic column: Shodex SH1011, retention time: 7.25min.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1
The preparation of catalyzer:
(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 centrifugation, remove supernatant liquid after taking out, 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.Under 80 ℃ and agitation condition 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.
The ball milling Mierocrystalline cellulose: with the commercial fibre element in ball mill grinding 2 days and get final product.
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 in the polytetrafluoro inner bag, inner bag put into the stainless steel autoclave again, drains air in the still with oxygen, repeat 10 times after, be filled with again the oxygen of 1.0MPa, stir, behind 145 ℃ of reaction 11h product.Analyze with high performance liquid chromatography (HPLC) after the product centrifugation.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
The preparation of catalyzer:
(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 centrifugation, remove supernatant liquid after taking out, 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.Under 80 ℃ and agitation condition 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.
The ball milling Mierocrystalline cellulose: with the commercial fibre element in ball mill grinding 2 days and get final product.
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 in the polytetrafluoro inner bag, inner bag put into the stainless steel autoclave again, drains air in the still with oxygen, repeat 10 times after, be filled with again the oxygen of 1.0MPa, stir, behind 145 ℃ of reaction 11h product.Analyze with high performance liquid chromatography (HPLC) after the product centrifugation.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 in the polytetrafluoro inner bag, inner bag put into the stainless steel autoclave again, drains air in the still with oxygen, repeat 10 times after, be filled with again the oxygen of 1.0MPa, stir, behind 145 ℃ of reaction 11h product.Analyze with high performance liquid chromatography (HPLC) after the product centrifugation.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
Embodiment 4
The preparation of catalyzer:
(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 centrifugation, remove supernatant liquid after taking out, can make Cs with 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.Under 80 ℃ and agitation condition 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.
The ball milling Mierocrystalline cellulose: with the commercial fibre element in ball mill grinding 2 days and get final product.
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 3.0PW 12O 40, H 3.0PW 12O 40, water and a magneton join in the polytetrafluoro inner bag, inner bag put into the stainless steel autoclave again, drains air in the still with oxygen, repeat 10 times after, be filled with again the oxygen of 1.0MPa, stir, behind 145 ℃ of reaction 11h product.Analyze with high performance liquid chromatography (HPLC) after the product centrifugation.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
Figure BDA0000137057790000061
Embodiment 5
The preparation of catalyzer:
(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 centrifugation, remove supernatant liquid after taking out, 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.Under 80 ℃ and agitation condition 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.
The ball milling Mierocrystalline cellulose: with the commercial fibre element in ball mill grinding 2 days and get final product.
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 in the polytetrafluoro inner bag, inner bag put into the stainless steel autoclave again, drains air in the still with oxygen, repeat 10 times after, be filled with again the oxygen of 1.0MPa, stir, behind 145 ℃ of reaction 11h product.Analyze with high performance liquid chromatography (HPLC) after the product centrifugation.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).
The ball milling Mierocrystalline cellulose: with the commercial fibre element in ball mill grinding 2 days and get final product.
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 in the polytetrafluoro inner bag, inner bag put into the stainless steel autoclave again, drains air in the still with oxygen, repeat 10 times after, be filled with again the oxygen of 1.0MPa, stir, behind 145 ℃ of reaction 11h product.Analyze with high performance liquid chromatography (HPLC) after the product centrifugation.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).
The ball milling Mierocrystalline cellulose: with the commercial fibre element in ball mill grinding 2 days and get final product.
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 in the polytetrafluoro inner bag, inner bag put into the stainless steel autoclave again, drains air in the still with oxygen, repeat 10 times after, be filled with again the oxygen of 1.0MPa, stir, behind 145 ℃ of reaction 11h product.Analyze with high performance liquid chromatography (HPLC) after the product centrifugation.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 is with embodiment 2 (i), (ii) and 1 (i).
The ball milling Mierocrystalline cellulose: with the commercial fibre element in ball mill grinding 2 days and get final product.
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 in the polytetrafluoro inner bag, inner bag put into the stainless steel autoclave again, drains air in the still with oxygen, repeat 10 times after, be filled with again the oxygen of 1.0MPa, stir, behind 145 ℃ of reaction 11h product.Analyze with high performance liquid chromatography (HPLC) after the product centrifugation.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
Embodiment 9
Catalyst preparation step with embodiment 4 (i) and (ii).
The ball milling Mierocrystalline cellulose: with the commercial fibre element in ball mill grinding 2 days and get final product.
Catalyzed reaction: with Mierocrystalline cellulose, 1.0wt%Au/Cs 3.0PW 12O 40, H 3.0PW 12O 40, water and a magneton join in the polytetrafluoro inner bag, inner bag put into the stainless steel autoclave again, drains air in the still with oxygen, repeat 10 times after, be filled with again the oxygen of 1.5MPa, stir, behind 145 ℃ of reaction 11h product.Analyze with high performance liquid chromatography (HPLC) after the product centrifugation.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 in the polytetrafluoro inner bag, inner bag put into the stainless steel autoclave again, drains air in the still with oxygen, repeat 10 times after, be filled with again the oxygen of 1.0MPa, stir, behind 145 ℃ of reaction 11h product.Analyze with high performance liquid chromatography (HPLC) after the product centrifugation.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
Figure BDA0000137057790000082
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 again phosphate aqueous solution, 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 take water washing to pH again, drying is ground into powder, and is for 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 ℃.In 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 in the polytetrafluoro inner bag, inner bag put into the stainless steel autoclave again, drains air in the still with oxygen, repeat 10 times after, be filled with again the oxygen of 1.0MPa, stir, behind 145 ℃ of reaction 11h product.Analyze with high performance liquid chromatography (HPLC) after the product centrifugation.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
Figure BDA0000137057790000091
Product is analyzed by HPLC, and as shown in Figure 1, transforming in the methods of the invention the primary product that Mierocrystalline cellulose obtains is gluconic acid (chromatographic column: Shodex SH1011, retention time: 7.25min).

Claims (9)

1. one kind prepares the method for gluconic acid with the Mierocrystalline cellulose direct oxidation, it is characterized in that may further comprise the steps:
1) preparation of catalyzer:
(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 3Solution is denoted as solution a, with H 3.0PW 12O 40Be dissolved in and be mixed with H in the deionized water 3.0PW 12O 40Solution is denoted as solution b, and solution a is joined solution b, produces white precipitate, after the ageing white suspension liquid, take out after the centrifugation, remove supernatant liquid, the centrifugal solid drying that goes out is namely 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 as follows: 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, formed mixture leaves standstill, oven dry, pulverize last under hydrogen atmosphere with gold reduction, make Au catalyst;
2) Mierocrystalline cellulose: described Mierocrystalline cellulose comprises Microcrystalline Cellulose, acid treated fiber element and ball milling Mierocrystalline cellulose, described Microcrystalline Cellulose adopts commercially available commercial fibre element, described acid treated fiber element is processed the Mierocrystalline cellulose that obtains for Microcrystalline Cellulose with acid, and described ball milling Mierocrystalline cellulose is processed the Mierocrystalline cellulose that obtains for the method with mechanical ball milling; The concrete grammar that described Microcrystalline Cellulose is processed take acid as: first the Microcrystalline Cellulose water is made its swollen, adds again phosphate aqueous solution, 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 take water washing to pH again, drying is ground into powder, and gets the acid treated fiber element; The mass percentage concentration of phosphoric acid is preferably 43%～85%, in mass ratio, Microcrystalline Cellulose: phosphate aqueous solution=(0.01～10): 100, the amount of water after leaving standstill and the volume ratio of phosphate aqueous solution are phosphate aqueous solution: water=1: (0.1～1);
3) catalyzed reaction: with Mierocrystalline cellulose, mAu/Cs xH 3-xPW 12O 40, Cs xH 3-xPW 12O 40Join in the inner bag of reactor with water, again inner bag is put into reactor, drain air in the still with oxygen, namely get gluconic acid after being filled with again oxygen reaction, wherein x=0～3.0.
2. as claimed in claim 1ly a kind ofly prepare the method for gluconic acid with the Mierocrystalline cellulose direct oxidation, it is characterized in that the concentration of described solution a is 0.01～0.1mol/L in step 1) (1) part, the concentration of described solution b is 0.01～0.1mol/L.
3. a kind of method for preparing gluconic acid with the Mierocrystalline cellulose direct oxidation as claimed in claim 1, it is characterized in that in step 1) (1) part, described when solution a is joined solution b, 25～50 ℃ of lower stirrings, the volume ratio of described solution a and solution b is 1: 1.
4. as claimed in claim 1ly a kind ofly prepare the method for gluconic acid with the Mierocrystalline cellulose direct oxidation, it is characterized in that the time of described ageing is 0.5～2h in step 1) (1) part.
5. as claimed in claim 1ly a kind ofly prepare the method for gluconic acid with the Mierocrystalline cellulose direct oxidation, it is characterized in that the volume ratio of described chlorauric acid solution and deionized water is 1: (2～50) in step 1) (2) part.
6. as claimed in claim 1ly a kind ofly prepare the method for gluconic acid with the Mierocrystalline cellulose direct oxidation, it is characterized in that the temperature of described oven dry is 80～100 ℃ in step 1) (2) part; The temperature of described gold reduction is 200～500 ℃, and the time of gold reduction is 0.5～2h.
7. a kind of method for preparing gluconic acid with the Mierocrystalline cellulose direct oxidation as claimed in claim 1, it is characterized in that in step 2) in, the concrete grammar that described Microcrystalline Cellulose is processed take the method for mechanical ball milling as: the commercial fibre element in ball mill grinding 1～3 day, is namely got the ball milling Mierocrystalline cellulose.
8. as claimed in claim 1ly a kind ofly prepare the method for gluconic acid with the Mierocrystalline cellulose direct oxidation, it is characterized in that in step 3) described Mierocrystalline cellulose: m Au/Cs 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).
9. as claimed in claim 1ly a kind ofly prepare the method for gluconic acid with the Mierocrystalline cellulose direct oxidation, it is characterized in that in step 3), describedly drain with oxygen that air repeats 10 times at least in the still, the pressure of described oxygen is 0.1～2.0MPa; The condition of described reaction is at 80～180 ℃ of reaction 0.2～48h.
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