CN107321360B - A kind of bismuth-containing catalysts and preparation method thereof preparing glyceric acid for selective oxidation glycerol - Google Patents
A kind of bismuth-containing catalysts and preparation method thereof preparing glyceric acid for selective oxidation glycerol Download PDFInfo
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- CN107321360B CN107321360B CN201710468834.9A CN201710468834A CN107321360B CN 107321360 B CN107321360 B CN 107321360B CN 201710468834 A CN201710468834 A CN 201710468834A CN 107321360 B CN107321360 B CN 107321360B
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a kind of bismuth-containing catalysts and preparation method thereof that glyceric acid is prepared for selective oxidation glycerol, it is characterized in that, the catalyst is using bismuth as active component, and using layered hydroxide or laminated metal composite oxides as carrier, preparation method is the following steps are included: preparation bismuth salt solution；Prepare soluble metal salt solution, above two solution is slowly added into a certain amount of soluble carbonate salt solution and adjusts pH value, aging is stirred under constant temperature, cooling, washing to neutral, decompression filters, vacuum drying, calcining, catalyst prepared by the present invention prepares glyceric acid for selective oxidation glycerol, has the characteristics that glycerol conversion yield is high, glycerol production acid selectivity is good, preparation method is simple, repeat performance is good and low in cost.
Description
Technical field
The present invention relates to a kind of bismuth-containing catalysts and preparation method thereof that glyceric acid is prepared for selective oxidation glycerol, belong to
In selective glycerol catalyst technical field.
Background technique
Contain 3 hydroxy functional groups in glycerol molecule, theoretically, catalysis oxidation glycerol will generate a series of high added values
Chemical products.The conventional production practices of these chemicals traditional chemical oxidation process (such as Gao Meng mostly at high cost, seriously polluted
Sour potassium oxidizing process, nitric acid oxidation method and chromic acid oxidation) or low-yield fermentation process, their industrial application and yield have
Limit.The catalysis oxidation of glycerol is a kind of very complicated multiple parallel reactions and consecutive reaction process.On catalysis oxidation glycerol primary carbon
Hydroxy functional group can be generated glyceraldehyde (GLYD), glyceric acid (GLYA), sub- tartaric acid (TARAC), sub- tartaric acid can be into
The oxidation of one step generates oxalic acid (OXALA), glyoxalic acid (GLYCA), glycolic (GA) and mesoxalic acid (MESAC)；Catalysis oxidation is sweet
Hydroxy functional group in oily secondary carbon, then can be generated dihydroxyacetone (DHA) (DHA), and DHA can further be oxidized to malonaldehydic acid
(HYPAC), and the oxidation product of the above glycerol can by oxidation ultimately generate formic acid, carbon dioxide and carbon monoxide
Deng.Product in real reaction is mostly the mixing of above compound, therefore selectivity is during the catalytic oxidation of glycerol
It is particularly important, high efficiency selected catalyst system and catalyst should be selected, control the direction of catalyzing glycerol oxidation reaction.
O2It as oxidant, inexpensively, is easy to get, oxidized byproduct is only water, and is suitble to industrialized production.O2Oxidation system is normal
Catalyst includes metalloporphyrin, solid supported type metal complex, molecular sieve, oxide etc..Wherein, solid supported type metal complex
Catalyst system reaction condition is mild, reactivity preferable (glycerol conversion yield 82.5% or so), selectively higher (glyceric acid selects
Property 86.1% or so), catalyst easily separates with product.But initiator, co-catalyst or use need to be often added in reaction process to be had
Solvent, thus need to purify product.And catalyst efficiency and stability wait to further increase, and can be only achieved industry
The requirement of production, energy consumption, material consumption are still more serious.Higher cost.
Summary of the invention
High, the selective good, system of glycerol production acid that the technical problem to be solved by the invention is to provide a kind of glycerol conversion yields
Preparation Method is simple, repeat performance is good and the low-cost bismuth-containing for preparing glyceric acid for selective oxidation glycerol is urged
Agent and preparation method thereof.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of bismuth-containing catalysts preparing glyceric acid for selective oxidation glycerol, the catalyst is using bismuth as active group
Point, using layered hydroxide or laminated metal composite oxides as carrier.
A kind of preparation method for the bismuth-containing catalysts preparing glyceric acid for selective oxidation glycerol, comprising the following steps:
S01: preparation bismuth salt solution: a certain amount of bismuth salt is dissolved in organic solvent, the bismuth salt with it is described organic molten
The molal volume ratio of agent is 0.1-2mol:5-10L, and stirring at normal temperature 0.5-5.0h is to get the bismuth salt solution；
S02: it prepares soluble metal salt solution: a certain amount of soluble metallic salt is dissolved in deionized water, it is described
Soluble metallic salt and the molal volume ratio of the deionized water are that 3-15mol:6-12L is molten to get the soluble metallic salt
Liquid；
S03: two kinds of solution of S01 and S02 preparation are slowly added into the soluble carbonate salt of isometric 2-10mol/L
In solution, controlling to adjust pH value with lye during dropwise addition is 9-11, stirring aging 6-24h at 30-80 DEG C of constant temperature, cooling,
Washing to neutral, decompression filters, 40-120 DEG C of vacuum drying 8-24h to get bismuth-containing the more metal hydroxide catalysts of stratiform,
By the more metal hydroxides of the stratiform of the bismuth-containing in 250-1000 DEG C of N in heating furnace2Lower calcining 2-12h is to get bismuth-containing
Laminated metal composite oxide catalysts.
The bismuth salt includes one or both of bismuth nitrate or bismuth chloride.
The organic solvent includes one or both of dehydrated alcohol, ethylene glycol, glycerol.
The soluble carbonate salt includes one of ammonium carbonate, sodium carbonate or potassium carbonate or a variety of.
The lye includes one of ammonium hydroxide, sodium hydroxide solution or potassium hydroxide solution or a variety of.
The soluble metallic salt include copper nitrate, aluminum nitrate, nickel nitrate, ferric nitrate, cobalt nitrate, manganese nitrate, chromic nitrate,
Two kinds, three kinds in zinc nitrate, nitric acid vanadium, calcium nitrate, cerous nitrate, ammonium nitrate, cesium nitrate, barium nitrate, lanthanum nitrate or magnesium nitrate
Or four kinds；Two kinds, three kinds or four kinds either in the chloride of the above metal.
Catalyst of the invention is used to prepare glyceric acid, the preparation method is as follows:
By glycerol, dosage is that the catalyst of glycerol total weight 0.5-3.0% is added in stainless steel cauldron together, is filled with
The oxygen of 0.5~2.5MPa is warming up to 40-120 DEG C under agitation, 4-48h is reacted, after being centrifuged out catalyst
Obtain product.
Product analysis method is as follows:
It will be sent after product centrifugal filtration to being analyzed with external standard method on Agilent1200 type high performance liquid chromatograph.
Chromatographic condition is as follows: Aminex HPX-87H chromatographic column (U.S. Bole Bio-Rad, 300 × 7.8mm), column temperature 60
DEG C, 0.01mol/L H2SO4Mobile phase, flow velocity 0.5mL/min, ultraviolet and Composition distribution, ultraviolet detection wavelength 210nm, sample introduction
Measure 10 μ L.
Advantageous effects of the invention:
1, method for preparing catalyst is simple, easy to operate, and the fabulous Bi loaded catalyst of dispersion degree can be obtained.
2, it is generated in reaction in glyceric acid, glycerol conversion yield is high, and glycerol production acid selectivity is good.
3, catalyst repeat performance is good, and after reusing 8 times, reactivity is without significant decrease.
4, preparation cost is cheap, and reaction condition is mild, environmentally friendly.
5, carrier used by catalyst realizes freely regulating and controlling for Bi loaded catalyst acid-base property.
Specific embodiment
The invention will be further described below.Following embodiment is only used for clearly illustrating technical side of the invention
Case, and not intended to limit the protection scope of the present invention.
Embodiment 1
0.2mol bismuth chloride is dissolved in 5L dehydrated alcohol, stirring at normal temperature 0.5h is to get bismuth chloride ethanol solution.Then
3mol copper nitrate, 3mol nickel chloride and 3mol aluminum nitrate are dissolved in the deionized water of 6L to get more metal salt solutions.By 5L
It is molten that bismuth chloride ethanol solution and the more metal salt solutions of 6L are slowly added into a certain amount of concentration 12L 2mol/L ammonium carbonate in 1h
In liquid, and adjusting pH value with ammonium hydroxide is 9-11,60 DEG C of stirring aging 8h, and cooling, washing to neutral, decompression filters, 60 DEG C of vacuum
Dry 12h to get bismuth-containing the more metal hydroxide catalysts of stratiform, by the more metal hydroxides of the stratiform of the bismuth-containing in adding
In 250 DEG C of N in hot stove2Laminated metal composite oxide catalysts of the lower calcining 3h to get bismuth-containing, catalytic effect: glycerol turns
Rate 34.2%, glyceric acid selectivity 48.3%.
Embodiment 2
1mol bismuth nitrate is dissolved in 10L ethylene glycol, stirring at normal temperature 3h is to get bismuth nitrate ethylene glycol solution.Then will
1.5mol ferric nitrate and 1.5mol cobalt nitrate are dissolved in the deionized water of 6L to get more metal salt solutions.By 10L bismuth nitrate second
Glycol solution and the more metal salt solutions of 6L are slowly added into a certain amount of concentration 12L 2mol/L sodium carbonate liquor in 1h, and
Adjusting pH value with sodium hydroxide solution is 9-11, and for 24 hours, cooling, washing to neutral, decompression filters, and 110 DEG C true for 30 DEG C of stirring agings
The dry 8h of sky to get bismuth-containing the more metal hydroxide catalysts of stratiform, by the more metal hydroxides of the stratiform of the bismuth-containing in
In 450 DEG C of N in heating furnace2Laminated metal composite oxide catalysts of the lower calcining 4h to get bismuth-containing, catalytic effect: glycerol
Conversion ratio 67.4%, glyceric acid selectivity 34.9%.
Embodiment 3
1.5mol bismuth chloride is dissolved in 10L dehydrated alcohol and glycerol (volume ratio 1:1), stirring at normal temperature 2h is to get chlorine
Change bismuth ethyl alcohol glycerite.Then by 4.5mol copper chloride, 4.5mol zinc chloride and 1.5mol manganese nitrate be dissolved in 6L go from
To get more metal salt solutions in sub- water.10L bismuth chloride ethyl alcohol glycerite and the more metal salt solutions of 6L are slowly added in 1h
Into a certain amount of concentration 6L 5mol/L sodium carbonate liquor, and adjusting pH value with potassium hydroxide solution is 9-11, and 45 DEG C of stirrings are old
Change 18h, cooling, washing to neutral, decompression filters, and 90 DEG C of vacuum drying 10h urge to get the more metal hydroxides of stratiform of bismuth-containing
Agent, by the more metal hydroxides of the stratiform of the bismuth-containing in 600 DEG C of N in heating furnace2The lower 6h that calcines is to get the layer of bismuth-containing
Shape metal composite oxide catalyst, catalytic effect: glycerol conversion yield 76.2%, glyceric acid selectivity 58.4%.
Embodiment 4
2mol bismuth nitrate is dissolved in 10L ethylene glycol and glycerol (volume ratio 1:1), stirring at normal temperature 4h is to get bismuth nitrate
Glycol glycerin solution.Then 4.5mol copper nitrate, 4.5mol chromic nitrate and 1mol nitric acid vanadium are dissolved in the deionized water of 6L
In to get more metal salt solutions.10L bismuth nitrate glycol glycerin solution and the more metal salt solutions of 6L are slowly added into 1h
In a certain amount of concentration 6L 5mol/L solution of potassium carbonate, and adjusting pH value with sodium hydroxide solution is 9-11,55 DEG C of stirring agings
15h, cooling are washed to neutral, decompression suction filtration, and 120 DEG C are dried in vacuo 7h to get the more metal hydroxide catalysis of stratiform of bismuth-containing
Agent, by the more metal hydroxides of the stratiform of the bismuth-containing in 750 DEG C of N in heating furnace2The lower 5h that calcines is to get the stratiform of bismuth-containing
Metal composite oxide catalyst, catalytic effect: glycerol conversion yield 69.8%, glyceric acid selectivity 74.3%.
Embodiment 5
1mol bismuth chloride is dissolved in 5L glycerol, stirring at normal temperature 4.5h is to get bismuth chloride glycerite.Then by 3mol
Copper nitrate, 3mol barium nitrate, 3mol magnesium nitrate and 2mol cesium nitrate are dissolved in the deionized water of 6L molten to get more metal salts
Liquid.5L bismuth chloride glycerite and the more metal salt solutions of 6L are slowly added into a certain amount of concentration 6L 5mol/L carbon in 1h
In acid sodium solution, and adjusting pH value with ammonium hydroxide is 9-11,70 DEG C of stirring aging 16h, and cooling, washing to neutral, decompression filters, 75
DEG C vacuum drying 11h to get bismuth-containing the more metal hydroxide catalysts of stratiform, by the more metal hydroxides of the stratiform of the bismuth-containing
Object is in heating furnace in 800 DEG C of N2Laminated metal composite oxide catalysts of the lower calcining 8h to get bismuth-containing, catalytic effect:
Glycerol conversion yield 85.4%, glyceric acid selectivity 67.8%.
Embodiment 6
1mol bismuth nitrate is dissolved in 5L dehydrated alcohol, stirring at normal temperature 4h is to get bismuth nitrate ethanol solution.Then will
1.5mol copper chloride, 1.5mol nickel chloride, 6mol magnesium chloride and 2mol aluminium chloride are dissolved in the deionized water of 6L to get mostly golden
Belong to salting liquid.5L bismuth nitrate ethanol solution and the more metal salt solutions of 6L are slowly added into a certain amount of concentration 6L in 1h
In 5mol/L sal volatile, and adjusting pH value with sodium hydroxide solution is 9-11,80 DEG C of stirring aging 20h, and cooling, washing is extremely
Neutral, decompression filters, and 60 DEG C are dried in vacuo 18h to get the more metal hydroxide catalysts of stratiform of bismuth-containing, by the bismuth-containing
The more metal hydroxides of stratiform are in heating furnace in 900 DEG C of N2The lower 4h that calcines is to get the laminated metal composite oxides of bismuth-containing
Catalyst, catalytic effect: glycerol conversion yield 56.7%, glyceric acid selectivity 68.2%.
Embodiment 7
1mol bismuth chloride is dissolved in 5L ethylene glycol and dehydrated alcohol (volume ratio 1:1), stirring at normal temperature 3.5h is to get chlorine
Change bismuth ethylene glycol ethyl ethers alcoholic solution.Then 3mol copper nitrate, 3mol nickel nitrate, 3mol calcium nitrate and 2mol aluminum nitrate are dissolved in 6L
Deionized water in get more metal salt solutions.By 5L bismuth chloride ethylene glycol ethyl ethers alcoholic solution and the more metal salt solutions of 6L in 1h
It is slowly added into a certain amount of concentration 6L 5mol/L sodium carbonate liquor, and adjusting pH value with ammonium hydroxide is 9-11,60 DEG C of stirrings are old
Change for 24 hours, cooling, washing to neutral, decompression filters, and 110 DEG C of vacuum drying 8h urge to get the more metal hydroxides of stratiform of bismuth-containing
Agent, by the more metal hydroxides of the stratiform of the bismuth-containing in 450 DEG C of N in heating furnace2The lower 4h that calcines is to get the layer of bismuth-containing
Shape metal composite oxide catalyst, catalytic effect: glycerol conversion yield 67.7%, glyceric acid selectivity 78.1%.
Embodiment 8
1mol bismuth nitrate is dissolved in 5L dehydrated alcohol and glycerol (volume ratio 1:1), stirring at normal temperature 5h is to get bismuth nitrate
Ethyl alcohol glycerite.Then 1.5mol copper nitrate, 1.5mol cerous nitrate, 6mol barium nitrate and 2mol lanthanum nitrate are dissolved in 6L's
To get more metal salt solutions in deionized water.5L bismuth chloride ethanol solution and the more metal salt solutions of 6L are slowly added in 1h
Into a certain amount of concentration 6L 5mol/L solution of potassium carbonate, and adjusting pH value with sodium hydroxide solution is 9-11, and 75 DEG C of stirrings are old
Change 22h, cooling, washing to neutral, decompression filters, and 90 DEG C of vacuum drying 15h urge to get the more metal hydroxides of stratiform of bismuth-containing
Agent, by the more metal hydroxides of the stratiform of the bismuth-containing in 1000 DEG C of N in heating furnace2Lower calcining 6h is to get bismuth-containing
Laminated metal composite oxide catalysts, catalytic effect: glycerol conversion yield 94.2%, glyceric acid selectivity 38.7%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of bismuth-containing catalysts prepare the application in glyceric acid in selective oxidation glycerol, characterized in that the catalyst with
Bismuth is active component, using layered hydroxide or laminated metal composite oxides as carrier.
2. a kind of bismuth-containing catalysts according to claim 1 prepare the application in glyceric acid in selective oxidation glycerol,
Be characterized in, the bismuth-containing catalysts preparation method the following steps are included:
S01: preparation bismuth salt solution: a certain amount of bismuth salt is dissolved in organic solvent, the bismuth salt and the organic solvent
Molal volume ratio is 0.1-2mol:5-10L, and stirring at normal temperature 0.5-5.0h is to get the bismuth salt solution；
S02: it prepares soluble metal salt solution: a certain amount of soluble metallic salt is dissolved in deionized water, it is described solvable
Property metal salt and the deionized water molal volume ratio be 3-15mol:6-12L to get the soluble metal salt solution；
S03: two kinds of solution of S01 and S02 preparation are slowly added into the soluble carbonate salt solution of isometric 2-10mol/L
In, controlling to adjust pH value with lye during dropwise addition is 9-11, and aging 6-24h, cooling, washing are stirred at 30-80 DEG C of constant temperature
It is filtered to neutral, decompression, 40-120 DEG C is dried in vacuo 8-24h to get the more metal hydroxide catalysts of stratiform of bismuth-containing, by institute
The more metal hydroxides of stratiform of bismuth-containing are stated in heating furnace in 250-1000 DEG C of N2The lower 2-12h that calcines is to get the layer of bismuth-containing
Shape metal composite oxide catalyst.
3. a kind of bismuth-containing catalysts according to claim 2 prepare the application in glyceric acid in selective oxidation glycerol,
It is characterized in, the bismuth salt includes one or both of bismuth nitrate or bismuth chloride.
4. a kind of bismuth-containing catalysts according to claim 2 prepare the application in glyceric acid in selective oxidation glycerol,
It is characterized in, the organic solvent includes one or both of dehydrated alcohol, ethylene glycol, glycerol.
5. a kind of bismuth-containing catalysts according to claim 2 prepare the application in glyceric acid in selective oxidation glycerol,
It is characterized in, the soluble carbonate salt includes one of ammonium carbonate, sodium carbonate or potassium carbonate or a variety of.
6. a kind of bismuth-containing catalysts according to claim 2 prepare the application in glyceric acid in selective oxidation glycerol,
It is characterized in, the lye includes one of ammonium hydroxide, sodium hydroxide solution or potassium hydroxide solution or a variety of.
7. a kind of bismuth-containing catalysts according to claim 2 prepare the application in glyceric acid in selective oxidation glycerol,
Be characterized in, the soluble metallic salt include copper nitrate, aluminum nitrate, nickel nitrate, ferric nitrate, cobalt nitrate, manganese nitrate, chromic nitrate,
Two kinds, three kinds in zinc nitrate, nitric acid vanadium, calcium nitrate, cerous nitrate, ammonium nitrate, cesium nitrate, barium nitrate, lanthanum nitrate or magnesium nitrate
Or four kinds；Two kinds, three kinds or four kinds either in the chloride of the above metal.
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