CN106187736A - A kind of method that carbon-supported transition-metal catalyst catalytic oxidation of glucose prepares sodium gluconate - Google Patents

A kind of method that carbon-supported transition-metal catalyst catalytic oxidation of glucose prepares sodium gluconate Download PDF

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Publication number
CN106187736A
CN106187736A CN201610511036.5A CN201610511036A CN106187736A CN 106187736 A CN106187736 A CN 106187736A CN 201610511036 A CN201610511036 A CN 201610511036A CN 106187736 A CN106187736 A CN 106187736A
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catalyst
reaction
sodium gluconate
activated carbon
carbon
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Inventor
丑凌军
赵军
宋焕玲
杨建�
赵华华
闫亮
梁宁
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Gansu Institute Of Business Technology Co ltd
Lanzhou Institute of Chemical Physics LICP of CAS
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Gansu Institute Of Business Technology Co ltd
Lanzhou Institute of Chemical Physics LICP of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of method that carbon-supported transition-metal catalyst catalytic oxidation of glucose prepares sodium gluconate, concretely comprise the following steps: X/C catalyst is sufficiently mixed with D/W, controlling reaction temperature is 45 ~ 65 DEG C, oxygen is passed through mixture system by reaction continuously, and add 30%(mass concentration under agitation) NaOH aqueous solution, maintaining pH value of reaction system is 7.5 ~ 9.0, isothermal reaction is until keeping constant in system pH 30min, by gained solution left standstill, filter and separate out catalyst in case reusing, filtrate is by concentrating, crystallization, air-dried process i.e. obtains product sodium gluconate；X/C catalyst, X is main active component, one or both in Co, Ag, Cu and Ni, and X is 1:2.5 ~ 10 with the atomic ratio of activated carbon；C is carrier, and for the activated carbon through pretreatment, its specific surface area is 500 ~ 2000 m2/g.Production technology of the present invention is simple, and product is easily isolated, and catalyst is with low cost, and regeneration easily, can be recycled, three-waste free discharge.

Description

A kind of carbon-supported transition-metal catalyst catalytic oxidation of glucose prepares gluconic acid The method of sodium
Technical field
The present invention relates to a kind of carbon-supported transition-metal catalyst catalytic oxidation of glucose and prepare the side of sodium gluconate Method, belongs to catalysis technical field.
Background technology
Gluconic acid and derivant (gluconate, gluconic acid lactone etc.) thereof are important multiduty organic of a class Chemical products, the nutritional supplement during wherein sodium gluconate can be used as medicine intermediate, food industry, additive, day chemical industry The cement retarder in complexation cleaning agent, steel surface abluent, anti-incrustation corrosion inhibitor, chelating agen and building industry in industry Deng, also act as and prepare the high added value such as gluconic acid lactone, gluconate (such as zinc salt, calcium salt, magnesium salt, ferrous salt) product The basic material of product, has purposes widely in industries such as chemical industry, food, medicine, light industrys.
In recent years, the main method of domestic and international industrialized production sodium gluconate has: biological fermentation process, eletrooxidation Method and heterogeneous catalytic oxidation method.Gluconic acid commercial production mainly uses biological fermentation process at present, and the method is to production process Asepticization degree require higher, the cycle is long, and by-product is many, and product purity is low, and product color is wayward, and subsequent fine is made This height, it addition, there is also the series of problems such as spawn culture, selection-breeding and waste water process in Technology.Eletrooxidation Method mainly includes sodium hypochlorite oxidization and hydrogen peroxide oxidation process, and the method is the oxidability ensureing oxidant, it is desirable to anti- Answering system is strong basicity, need to strictly control the concentration of oxidant, cause byproduct of reaction many, and product yield is low and separates more tired Difficulty, catalyst is difficult to reclaiming, and environmental pollution is serious.It is high that heterogeneous catalytic oxidation method has productivity, and by-product is few, and product is easy In the advantage separated, so starting the most gradually to cause the concern of people from the 70's of twentieth century.Study more having at present The catalyst such as nanometer gold, Pt/C, Pd/C (CN 1594265, CN 101249443, GB 1208101, JP 8007230), nanometer Au catalyst complicated process of preparation, activity is affected very big by the factor such as preparation method, carrier, and current large-scale industrial production depends on Old have difficulties；Palladium system, platinum group catalyst have good selectivity and low temperature active, but inactivation is very fast；And above-mentioned your gold Metal catalyst there is also the problems such as with high costs, catalyst how recycling.
Summary of the invention
It is an object of the invention to provide a kind of carbon-supported transition-metal catalyst catalytic oxidation of glucose and prepare Fructus Vitis viniferae The method of sodium saccharate.
The present invention utilizes Pre-Treatment of Activated charcoal loading transition metallic catalyst, is simply and efficiently prepared glucose by glucose Acid sodium, has production technology simple, and product is easily isolated, and catalyst is with low cost, regeneration is easy, can be recycled, without the three wastes Discharge, the feature such as environmental protection.
A kind of method that carbon-supported transition-metal catalyst catalytic oxidation of glucose prepares sodium gluconate, its feature exists In concretely comprising the following steps: be sufficiently mixed with D/W by X/C catalyst, controlling reaction temperature is 45 ~ 65 DEG C, will in reaction Oxygen is passed through mixture system continuously, and adds 30% (mass concentration) NaOH aqueous solution under agitation, maintains reaction System pH value is 7.5 ~ 9.0, and isothermal reaction is until keeping constant, by gained solution left standstill, filtration in system pH 30min Precipitation catalyst is in case reusing, and filtrate i.e. obtains product sodium gluconate by concentrating, crystallize, air-dry process；Described X/C urges Agent, X is main active component, one or both in Co, Ag, Cu and Ni, the atomic ratio of X and activated carbon be 1:2.5 ~ 10；C is carrier, and for the activated carbon through pretreatment, its specific surface area is 500 ~ 2000 m2/g。
Described glucose is 5 ~ 50:1 with the mass ratio of catalyst.
The mass concentration of described D/W is 10% ~ 35%.
The preparation method of described X/C catalyst: activated carbon granule is done pre-with sodium hydroxide, nitric acid, deionized water successively Process, in 100 DEG C ~ 200 DEG C drying for standby；XNO is weighed when 40 DEG C3, add deionized water wiring solution-forming, by activated carbon It is suspended in above-mentioned solution, uses solution incipient impregnation, dipper precipitation, colloidal sol absorption to prepare support type X/C catalyst；By X/ C catalyst under nitrogen protection, 100 DEG C ~ 450 DEG C roastings 2 ~ 6 hours；At 180 DEG C ~ 350 DEG C, use 15%(volumetric concentration) hydrogen Gas reductase 12 ~ 6 hour, obtain finished catalyst.
Described X/C catalyst is suspended in deionized water, heated and boiled, drips reproducibility formalin, while hot sucking filtration, Washing, can recycle after above-mentioned Regeneration Treatment.
Present invention process step is simple, and product is easily isolated, three-waste free discharge, environmental protection, and catalyst is with low cost, again Raw easy, can be recycled.
Detailed description of the invention
Below by way of specific embodiment, the preparation method and technology process that the present invention relates to is described in detail.
Embodiment 1:
1) carrier active carbon pretreatment
First preparation 5%(mass concentration) salpeter solution, 5%(mass concentration) sodium hydroxide solution；Weigh absorbent charcoal carrier 50g in 85 DEG C of low suspensions are in appropriate 5%(mass concentration) in sodium hydroxide solution, stir, wash 1h, sucking filtration under room temperature, be dried, will at The carrier managed is suspended in appropriate 5%(mass concentration at 75 DEG C) in salpeter solution, it is passed through nitrogen bubble, stirs, wash 1h, room The lower sucking filtration of temperature, deionized water wash, is dried, 180 DEG C of roasting 2 h under nitrogen protection, obtains Pre-Treatment of Activated high-area carbon, standby With；
2) prepared by catalyst
Weigh the AgNO of 17.5 g3(A.R), add 50 mL deionized waters, be configured to AgNO3Solution, adds 37%(volume dense Degree) formalin 15 g, deionized water 200 g；Weigh the 7 Pre-Treatment of Activated high-area carbon of g to be suspended in above-mentioned solution, in water-bath It is warming up to 40 DEG C, continuously stirred, it is slowly added dropwise 30%(mass concentration) NaOH solution 20 g, continue heated and stirred 2h, stand 2h, deionized water wash, sucking filtration, it is dried at 100 DEG C, 180 DEG C of roasting 1h in the protection of last nitrogen, obtains the catalysis of Ag/C finished product Agent.
3) catalytic oxidation of glucose prepares the technical process of sodium gluconate
Being sufficiently mixed with D/W by the Ag/C finished catalyst of preparation, in catalyst, Ag with the mass ratio of glucose is 1:50, D/W concentration is 30%(mass concentration), controlling reaction mixture temperature is 55 DEG C, in reaction by oxygen even Continue and be passed through mixture system, and be added dropwise to NaOH(5mol/mL under agitation) aqueous solution, maintain reaction system pH Value is 8.5, and isothermal reaction is until keeping constant in system pH 30min.Reaction terminates, and by gained solution left standstill, filters out and urges Agent is in case reusing, and filtrate obtains product sodium gluconate by process steps such as concentrating, crystallize, air-dry.Reaction time consumption 3.5 hours, record sodium gluconate yield 51.5%.
Embodiment 2:
1) carrier active carbon pretreatment
Pretreatment mode in embodiment 1 is used to prepare absorbent charcoal carrier, standby；
2) prepared by catalyst
Weigh 10g Co (NO3)26H2O (A.R), adds deionized water and is configured to solution；Weigh the Pre-Treatment of Activated charcoal of 10.7g to carry Body, is warming up to 60 DEG C in water-bath, with the Co (NO prepared3) 2Solution incipient impregnation absorbent charcoal carrier, products therefrom 120 DEG C Under be dried 4h, 380 DEG C of roasting 4h in the protection of last nitrogen, at 280 DEG C, use 15%(volumetric concentration) hydrogen reducing 4h obtains Co/ C finished catalyst.
3) catalytic oxidation of glucose prepares the technical process of sodium gluconate
Being sufficiently mixed with D/W by the Co/C finished catalyst of preparation, in catalyst, Co with the mass ratio of glucose is 1:50, D/W concentration is 30%(mass concentration), controlling reaction mixture temperature is 55 DEG C, in reaction by oxygen even Continue and be passed through mixture system, and be added dropwise to NaOH(5mol/mL under agitation) aqueous solution, maintain reaction system pH value Being 8.5, isothermal reaction is until keeping constant in system pH 30min.Reaction terminates, and by gained solution left standstill, filters out catalysis Agent is in case reusing, and filtrate concentrates, crystallizes, air-dry and obtain product sodium gluconate.Reaction time consumption 4 hours, records glucose Yield 40.2%.
Embodiment 3:
1) carrier active carbon pretreatment
Pretreatment mode in embodiment 1 is used to prepare absorbent charcoal carrier, standby；
2) prepared by catalyst
Weigh the Cu (NO of 10g/L3) 2(A.R) solution 8.3 mL, weighs the Ni (NO of 10g/L3) 2(A.R) solution 7.8 ML, adds deionized water mix homogeneously；Weigh the Pre-Treatment of Activated high-area carbon of 3.0g, water-bath is warming up to 60 DEG C, with prepare Cu, Ni mixed solution incipient impregnation absorbent charcoal carrier, is dried 4h, 380 DEG C of roastings in the protection of last nitrogen at products therefrom 120 DEG C Burning 4h, at 280 DEG C, use 15%(volumetric concentration) hydrogen reducing 4h obtains Cu-Ni/C finished catalyst.
3) catalytic oxidation of glucose prepares the technical process of sodium gluconate
Being sufficiently mixed with D/W by the Cu-Ni/C finished catalyst of preparation, catalyst with the mass ratio of glucose is 1:10, D/W concentration is 30%(mass concentration), controlling reaction mixture temperature is 55 DEG C, in reaction by oxygen even Continue and be passed through mixture system, and be added dropwise to NaOH(5mol/mL under agitation) aqueous solution, maintain reaction system pH Value is 8.5, and isothermal reaction is until keeping constant in system pH 30min.Reaction terminates, and by gained solution left standstill, filters out and urges Agent is in case reusing, and filtrate obtains product sodium gluconate by process steps such as concentrating, crystallize, air-dry.Reaction time consumption 4 Hour, record glucose yield 35.6%.
Embodiment 4:
Catalyst regeneration cycle reacts
Weigh reacted Ag/C finished catalyst 7g in embodiment 1, be suspended in 100mL deionized water, heated and boiled 30min, after the whole bubbling of catalyst suspends, dropping 10g formalin (volumetric concentration 37%), sucking filtration while hot, deionization Water washs, and uses 5 times through above-mentioned Regeneration Treatment Posterior circle, and catalyst activity is without significant change.

Claims (4)

1. the method that a carbon-supported transition-metal catalyst catalytic oxidation of glucose prepares sodium gluconate, it is characterised in that Concretely comprising the following steps: be sufficiently mixed with D/W by X/C catalyst, controlling reaction temperature is 45 ~ 65 DEG C, by oxygen in reaction Gas is passed through mixture system continuously, and adds 30wt% NaOH aqueous solution under agitation, maintains reaction system pH value Being 7.5 ~ 9.0, isothermal reaction, until keeping constant in system pH 30min, by gained solution left standstill, filters precipitation catalyst In case reusing, filtrate i.e. obtains product sodium gluconate by concentrating, crystallize, air-dry process；Described X/C catalyst, X is main Wanting active component, one or both in Co, Ag, Cu and Ni, X is 1:2.5 ~ 10 with the atomic ratio of activated carbon；C is for carrying Body, for the activated carbon through pretreatment, its specific surface area is 500 ~ 2000 m2/g。
2. the method for claim 1, it is characterised in that described glucose is 5 ~ 50:1 with the mass ratio of catalyst.
3. the method described in claim 1, it is characterised in that the mass concentration of described D/W is 10% ~ 35%.
4. the method for claim 1, it is characterised in that the preparation method of described X/C catalyst: activated carbon granule is depended on Secondary sodium hydroxide, nitric acid, deionized water do pretreatment, in 100 DEG C ~ 200 DEG C drying for standby；Weigh when 40 DEG C XNO3, add deionized water wiring solution-forming, activated carbon be suspended in above-mentioned solution, use solution incipient impregnation, dipping heavy Form sediment, support type X/C catalyst is prepared in colloidal sol absorption；By X/C catalyst under nitrogen protection, 100 DEG C ~ 450 DEG C roastings 2 ~ 6 are little Time；At 180 DEG C ~ 350 DEG C, it is 15% hydrogen reducing 2 ~ 6 hours by volumetric concentration, obtains finished catalyst.
CN201610511036.5A 2016-07-04 2016-07-04 A kind of method that carbon-supported transition-metal catalyst catalytic oxidation of glucose prepares sodium gluconate Pending CN106187736A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250069A (en) * 2018-01-22 2018-07-06 万华化学集团股份有限公司 A kind of preparation method of isooctyl acid
CN108262040A (en) * 2018-01-29 2018-07-10 云南森博混凝土外加剂有限公司 A kind of catalyst for being used to prepare sodium gluconate
CN108863756A (en) * 2018-08-07 2018-11-23 陈华明 A method of preparing gluconic acid

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250069A (en) * 2018-01-22 2018-07-06 万华化学集团股份有限公司 A kind of preparation method of isooctyl acid
CN108250069B (en) * 2018-01-22 2021-01-15 万华化学集团股份有限公司 Preparation method of isooctanoic acid
CN108262040A (en) * 2018-01-29 2018-07-10 云南森博混凝土外加剂有限公司 A kind of catalyst for being used to prepare sodium gluconate
CN108863756A (en) * 2018-08-07 2018-11-23 陈华明 A method of preparing gluconic acid

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Application publication date: 20161207