CN106187738A - A kind of method that carbon nanotube loaded noble metal catalyst prepares glyoxalic acid - Google Patents
A kind of method that carbon nanotube loaded noble metal catalyst prepares glyoxalic acid Download PDFInfo
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- CN106187738A CN106187738A CN201610524251.9A CN201610524251A CN106187738A CN 106187738 A CN106187738 A CN 106187738A CN 201610524251 A CN201610524251 A CN 201610524251A CN 106187738 A CN106187738 A CN 106187738A
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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
- 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
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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
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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Abstract
The preparation that the present invention relates to a kind of carbon nanotube loaded noble metal catalyst and the method being applied to clean synthesizing glyoxalic acid thereof, comprise the following steps: the polarization of CNT processes, the CNT with special diameter is put in distilled water and stir 34 hours, filtration, washing and drying, stir 6 12 hours with nitric acid and sulphuric acid nitration mixture high temperature reflux, filter, wash to neutrality drying；Being carried in CNT of nano-metal particle, stirs 12 hours after adding processed CNT in the precursor water solution of metal ultrasonic 48 hours, reduces with under hydrazine hydrate solution or hydrogen atmosphere after filtration washing, refilters washing vacuum drying；Oxygen catalytic oxidation Biformyl generates the chemical reaction of glyoxalic acid, glyoxal water solution adds the carbon nanotube loaded metallic catalyst of preparation, heated and stirred is also passed through oxygen, and in course of reaction with the pH value of sodium hydroxide control system between 68, reaction end is filtrated to get glyoxylic acid solution.
Description
Technical field
The invention belongs to Chemical Engineering Technology and catalysis technical field, relate to a kind of catalytic oxidation and prepare the side of glyoxalic acid
Method.
Background technology
Glyoxalic acid is a kind of important industrial chemicals and intermediate, medicine, pesticide, spice, papermaking, food additive and
The application in the fields such as biochemistry constantly expands.It is currently used primarily in broad ectrum antibiotic amoxicillin, cefaparole, resists
During hypertension drug atenolol, spice vanillin, cosmetics additive allantoin and pesticide intermediate produce.According to oxidant
Selection with primary raw material is different, it has been reported that the method preparing glyoxalic acid mainly have: Biformyl nitric acid oxidation method, Biformyl
Precious metal catalyst dioxygen oxidation method, Biformyl electroxidation method, Biformyl hydrogen peroxide oxidation method, Biformyl sodium hypochlorite oxidization,
Biformyl dichloroacetate method, glycolic enzymatic oxidation method, acid by electrolytic reduction of oxalic method etc..
Biformyl nitric acid oxidation method is the current most common method of commercial production glyoxalic acid, and the method is former with Biformyl
Material, nitric acid is oxidant, and reaction condition is gentle, and technique is simple.But this technique still suffers from some drawbacks:
A () uses substantial amounts of nitric acid etc. to have the oxidant of severe corrosive, environment is had by the nitrogen oxides produced in production process
Certain pollution；
B after () oxidation reaction, Biformyl residual volume is higher, and be difficult to Ex-all in last handling process；
C the selectivity of () oxidation Biformyl is the highest, produce substantial amounts of oxalic acid by-product because of over oxidation, and cause glyoxalic acid to produce
Rate declines.
Existing many reported in literature Biformyls are oxidized by oxygen as glyoxalic acid under noble metal platinum or palladium chtalyst effect, also with
Shi Shengcheng oxalic acid and formic acid.These researchs also show to generate the conversion ratio of glyoxalic acid and selectivity be with metal species used, mix
The factors such as miscellaneous metal, the use of catalyst carrier/part and reaction condition (especially pH value and temperature) are closely-related.France
(white carbon black, graphite, oxidation activity are burnt, non-oxide for the catalyticing research currently used platinum of institute and oxide carrier (SiO2, TiO2) carbon carrier
Activated coke) Y-Shaped zeolite reached the selectivity of 98% conversion ratio and 73%.
Summary of the invention
Use CNT to prepare catalyst as carrier to load metal, instead of traditional nitre with air as oxidant
Acid oxidant, it is to avoid the discharge of nitrogen oxides.
A kind of carbon nanotube loaded noble metal catalyst prepares glyoxalic acid method, comprises the following steps:
Step one: the process of CNT, puts into CNT in distilled water and stirs 3-4 hour, and filtration, washing and drying add
Enter nitration mixture high temperature reflux to stir 6-12 hour, filter, wash to neutrality drying；
Step 2: stir 12 after processed CNT being added in the precursor water solution of metal ultrasonic 4-8 hour little
Time, reduce with hydrazine hydrate solution after filtration washing, refilter washing vacuum drying；
Step 3: catalysis glyoxalic acid synthesis, adds the carbon nanotube loaded metallic catalyst of preparation, heating in glyoxal water solution
Stirring and be passed through oxygen, in course of reaction with the pH value of sodium hydroxide control system between 6-8, reaction end is filtrated to get second
Aldehydic acid solution.
The beneficial effect that the present invention obtains:
1, precious metal catalyst synthesizing glyoxalic acid by oxidation of glyoxal of the present invention, not only has the reaction condition of gentleness, and environment is dirty
Contaminate minimum, also do not have prior synthesizing method product difficulty to separate, the defects such as equipment requirements is high.If suitable catalyst can be filtered out with anti-
Answer condition so that the selectivity of the conversion ratio of Biformyl and generation glyoxalic acid improves further, will obtain preferable result；
2, the present invention uses corrosion-resistant logical oxygen distribution device to make cheap oxygen form the most small bubble in reaction system,
And be evenly distributed in reactant liquor thus avoid system occurring local response cause productivity to decline and by-product increases；
3, the present invention use CNT as carrier, be first acidified, make the oxidized surface of CNT with carboxyl, this
Sample is catalyzed after oxidation becomes glyoxalic acid when Biformyl, the carboxyl owing to CNT shows negative electricity with carboxyl, to glyoxalic acid
There is repulsive interaction, it is to avoid glyoxalic acid is generated oxalic acid by catalysis oxidation further, improves the productivity of glyoxalic acid, reduces by-product oxalic acid
Yield.
Detailed description of the invention
Below by the technical scheme in the embodiment of the present invention is become apparent from, complete description, it is clear that described reality
Executing example is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area is general
All other embodiments that logical technical staff is obtained on the premise of not making creative work, broadly fall into present invention protection
Scope.
It is further described by following steps:
Step one: the process of CNT, weighs 1-3g CNT and puts into stirring 3-4 hour in distilled water, filter, wash baking
Dry, stir 6-12 hour with nitration mixture high temperature reflux, filter, wash to neutrality drying；
Step 2: stir 12-24 after adding processed CNT in the precursor water solution of metal ultrasonic 4-8 hour
Hour, reduce with hydrazine hydrate solution after filtration washing, refilter washing vacuum drying；
Step 3: catalysis glyoxalic acid synthesis, the glyoxal water solution of 10-40ml 40% adds in there-necked flask, dilute NaOH solution
Regulating its pH is between 6-8, adds the carbon nanotube loaded metallic catalyst 0.1-0.5g of preparation, sets heating-up temperature as 35-
75 DEG C are stirred and are passed through oxygen, and regulation oxygen flow is 10-50ml/min, control the pH of system in course of reaction with sodium hydroxide
Value is between 6-8, and reaction 3-9h terminates to be filtrated to get glyoxylic acid solution.
Further, it is desirable to the carrier of metallic catalyst is CNT.
Further, it is desirable to CNT is acidification to be carried out before load.
Further, it is desirable to the CNT that metal precursor processes with polarization is reducing after carrying out filtration washing after mixing
Process.
Further, it is desirable in catalytic reaction, system pH is maintained between 6-8.
Further, it is desirable to the device used during logical oxygen is porous corrosion-resistant gas distributor.
Embodiment 1
Step one: the process of CNT, weigh 1g CNT put in distilled water stir 4 hours, filter, washing and drying,
Add nitration mixture high temperature reflux to stir 6 hours, filter, wash to neutrality drying；
Step 2: stir 12 hours after adding processed CNT in the precursor water solution of metal ultrasonic 4 hours,
Reduce with hydrazine hydrate solution after filtration washing, refilter washing vacuum drying；
Step 3: catalysis glyoxalic acid synthesis, the glyoxal water solution of 10ml 40% adds in there-necked flask, and dilute NaOH solution regulates
Its pH is between 7.7, adds the carbon nanotube loaded metallic catalyst 0.2g of preparation, sets heating-up temperature and as 50 DEG C of stirrings and leads to
Entering oxygen, regulation oxygen flow is 20ml/min, in course of reaction with the pH value of sodium hydroxide control system between 6-8, instead
4h is answered to terminate to be filtrated to get glyoxylic acid solution.
Product checking result is: Biformyl residual quantity is 1.2%, and the conversion ratio of Biformyl is 91.2%；Determination of Glyoxalic
25.1%, the molar yield of glyoxalic acid is 77.3%.
Embodiment 2
Step one: the process of CNT, weigh 1g CNT put in distilled water stir 4 hours, filter, washing and drying,
Add nitration mixture high temperature reflux to stir 6 hours, filter, wash to neutrality drying；
Step 2: stir 12 hours after adding processed CNT in the precursor water solution of metal ultrasonic 4 hours,
Reduce with hydrazine hydrate solution after filtration washing, refilter washing vacuum drying；
Step 3: catalysis glyoxalic acid synthesis, the glyoxal water solution of 10ml 40% adds in there-necked flask, and dilute NaOH solution regulates
Its pH is between 7.0, adds the carbon nanotube loaded metallic catalyst 0.4g of preparation, sets heating-up temperature and as 60 DEG C of stirrings and leads to
Entering oxygen, regulation oxygen flow is 20ml/min, in course of reaction with the pH value of sodium hydroxide control system between 6-8, instead
4h is answered to terminate to be filtrated to get glyoxylic acid solution.
Product checking result is: Biformyl residual quantity is 0.8%, and the conversion ratio of Biformyl is 94.2%；Determination of Glyoxalic
24.3%, the molar yield of glyoxalic acid is 75.5%.
Embodiment 3
Step one: the process of CNT, weigh 1g CNT put in distilled water stir 4 hours, filter, washing and drying,
Add nitration mixture high temperature reflux to stir 8 hours, filter, wash to neutrality drying；
Step 2: stir 12 hours after adding processed CNT in the precursor water solution of metal ultrasonic 6 hours,
Reduce with hydrazine hydrate solution after filtration washing, refilter washing vacuum drying；
Step 3: catalysis glyoxalic acid synthesis, the glyoxal water solution of 10ml 40% adds in there-necked flask, and dilute NaOH solution regulates
Its pH is between 7.7, adds the carbon nanotube loaded metallic catalyst 0.3g of preparation, sets heating-up temperature and as 45 DEG C of stirrings and leads to
Entering oxygen, regulation oxygen flow is 30ml/min, in course of reaction with the pH value of sodium hydroxide control system between 6-8, instead
5h is answered to terminate to be filtrated to get glyoxylic acid solution.
Product checking result is: Biformyl residual quantity is 1.0%, and the conversion ratio of Biformyl is 93.4%；Determination of Glyoxalic
25.6%, the molar yield of glyoxalic acid is 78.3%.
This embodiment contrasts with existing production technology has following positive effect:
Send out synthesizing glyoxalic acid by noble metal Oxygen Catalytic Oxidation, replace nitric acid or the use of other severe corrosive oxidants, fall
Low to consersion unit with the loss of water conservancy diversion system, it is to avoid to produce substantial amounts of nitric oxide, be substantially reduced environmental protection operating cost and tail
Gas discharges the environmental pollution brought.Oxygen is cheap and easily-available, safety and environmental protection, is substantially reduced traditional mode of production cost.The present invention uses
The corrosion-resistant logical oxygen equipment of speciality material, i.e. cheap oxygen is converted into a large amount of small oxygen bubbles and is evenly distributed in reactant liquor.This
The conversion ratio of outer Biformyl improves, and reduces the content of Biformyl in glyoxylic acid solution, successfully solves later stage Biformyl difficulty
The problem of reason；Improve the productivity of glyoxalic acid, be substantially reduced the content of by-product oxalic acid.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (4)
1. glyoxalic acid method prepared by carbon nanotube loaded noble metal (platinum, gold, silver, a palladium) catalyst, it is characterised in that include
Following steps: step one: the polarization of CNT processes, put into CNT in distilled water and stir 3-4 hour, filter, wash
Wash drying, stir 6-12 hour with nitration mixture high temperature reflux, filter, wash to neutrality drying；Step 2: nanometer
Metallic particles loads on CNT, and by adding in the precursor water solution of metal, the ultrasonic 4-8 of processed CNT is little
Stir 12 hours time after, reduce with hydrazine hydrate solution after filtration washing, refilter washing vacuum drying；Step 3: catalysis
Dioxygen oxidation Biformyl generates the chemical reaction of glyoxalic acid, and the carbon nanotube loaded metal adding preparation in glyoxal water solution is urged
Agent, heated and stirred is also passed through oxygen, and in course of reaction with the pH value of sodium hydroxide control system between 6-8, reaction terminates
It is filtrated to get glyoxylic acid solution.
Glyoxalic acid method prepared by catalyst the most according to claim 1, it is characterised in that require the carrier of metallic catalyst
It it is the CNT of special polarization process.
Glyoxalic acid method prepared by catalyst the most according to claim 1, it is characterised in that nano-metal particle is carried on pole
In the CNT that change processes.
Glyoxalic acid method prepared by catalyst the most according to claim 1, it is characterised in that require the dress used during logical oxygen
It is set to porous corrosion-resistant gas distributor.
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| CN201610524251.9A CN106187738A (en) | 2016-07-06 | 2016-07-06 | A kind of method that carbon nanotube loaded noble metal catalyst prepares glyoxalic acid |
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| CN201610524251.9A CN106187738A (en) | 2016-07-06 | 2016-07-06 | A kind of method that carbon nanotube loaded noble metal catalyst prepares glyoxalic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047026A (en) * | 2017-12-15 | 2018-05-18 | 武汉工程大学 | A kind of method that glyoxal catalytic oxidation extraction prepares glyoxalic acid |
| CN115745774A (en) * | 2022-12-07 | 2023-03-07 | 临沂市金沂蒙生物科技有限公司 | Preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid |
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|---|---|---|---|---|
| CN101462946A (en) * | 2008-12-30 | 2009-06-24 | 上海华谊（集团）公司 | Method for preparing ethanol acid by catalytic oxidation of biformyl |
| CN105669424A (en) * | 2016-03-03 | 2016-06-15 | 武汉科技大学 | Glyoxalic acid and preparation method thereof |
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2016
- 2016-07-06 CN CN201610524251.9A patent/CN106187738A/en active Pending
Patent Citations (2)
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| CN101462946A (en) * | 2008-12-30 | 2009-06-24 | 上海华谊（集团）公司 | Method for preparing ethanol acid by catalytic oxidation of biformyl |
| CN105669424A (en) * | 2016-03-03 | 2016-06-15 | 武汉科技大学 | Glyoxalic acid and preparation method thereof |
Non-Patent Citations (2)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047026A (en) * | 2017-12-15 | 2018-05-18 | 武汉工程大学 | A kind of method that glyoxal catalytic oxidation extraction prepares glyoxalic acid |
| CN115745774A (en) * | 2022-12-07 | 2023-03-07 | 临沂市金沂蒙生物科技有限公司 | Preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid |
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