CN115304470B - Method for preparing formic acid by catalytic oxidation of glucose in microchannel reactor - Google Patents
Method for preparing formic acid by catalytic oxidation of glucose in microchannel reactor Download PDFInfo
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 92
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 62
- 239000008103 glucose Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 49
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 46
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 239000007789 gas Substances 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 29
- 239000012071 phase Substances 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 16
- 239000007791 liquid phase Substances 0.000 claims description 9
- SPFMQWBKVUQXJV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;hydrate Chemical compound O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O SPFMQWBKVUQXJV-BTVCFUMJSA-N 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 238000010574 gas phase reaction Methods 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000004581 coalescence Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing formic acid by catalytic oxidation of glucose in a microchannel reactor. The method comprises the steps of dissolving a sodium metavanadate catalyst, a catalytic auxiliary agent sulfuric acid and glucose in deionized water, and injecting the solution into a microchannel through a continuous feed pump. The gas phase is high-purity oxygen, the flow is regulated by a gas mass flow controller, and the high-purity oxygen is continuously injected into the micro-channel. The reaction temperature of the method is controlled at 80-180 ℃, the addition amount of sulfuric acid in an aqueous solution is 0.1-3 wt%, the reaction pressure is 0.5-3.5 MPa, the inner diameter of a microchannel mixer is 0.1-1 mm, the inner diameter of a microchannel reactor is 0.1-1 mm, the length of a reaction microchannel is 2000-40000 mm, and the residence time of reaction materials in the microchannel is 2-10 min. Compared with the traditional batch kettle type process, the method has the advantages that the reaction rate can be obviously improved, the safety of the reaction process is essentially improved, and the process continuity can be realized.
Description
Technical Field
The invention relates to a method for preparing formic acid by catalytic oxidation of glucose in a microchannel reactor, belonging to the field of organic synthesis.
Background
Formic acid is an important basic chemical raw material and is widely applied to industries such as textile, leather manufacturing, pharmacy and the like. In recent years, formic acid becomes an ideal fuel for excellent hydrogen storage energy and fuel cells by virtue of the advantages of being liquid at normal temperature and pressure, being convenient for storage and transportation, and the like. At present, the most mainstream formic acid production process at home and abroad is a methyl formate hydrolysis method, and the reaction raw material CH utilized by the method 3 The main sources of OH and CO are fossil energy, and along with the gradual consumption of fossil energy, the development of a new environment-friendly technology with high efficiency, low pollution and sustainable formic acid preparation becomes an important task for researchers.
Glucose (C) 6 H 12 O 6 ) Is a polyhydroxy compound rich in reducing groups, and can be obtained by biomass hydrolysis, and formic acid (CH) is produced by using the polyhydroxy compound as a raw material 2 O 2 ) Has the advantages of natural molecular structure and good atom economy, and brings a new opportunity for developing a novel formic acid production route. Jin et al (Energy Environ Sci, 2011, 4:382-397) use a conventional hydrothermal oxidation process using NaOH as a catalyst to utilize H 2 O 2 As an oxidant, the yield of formic acid reaches 75% under the high-temperature condition (250 ℃). However, this method is limited in practical industrial application due to high reaction temperature and high alkali consumption. Choudhary et al (appl. Catalyst. B: environ., 2015, 162: 1-10) uses MgO-supported CuO as a catalyst, utilizing H 2 O 2 As an oxidizing agent, glucose was catalytically oxidized to formic acid using a conventional tank reactor, with a yield of 65%. The above study shows that, in H 2 O 2 As an oxidizing agent, glucose can be oxidized efficiently to obtain formic acid, but H 2 O 2 The cost is higher, and the further industrial popularization of the method is not facilitated.
Thus, researchers have developed 5 PV 2 Mo 10 O 40 、NaVO 3 /H 2 SO 4 The vanadium-containing compounds are used as catalysts, and the low-cost and easily available O 2 A vanadium-containing hydrothermal catalytic oxidation system that is an oxidant. The route has the advantages of mild reaction conditions, low production cost, environmental friendliness and the like, and is widely focused by industry and academia. However, use O 2 The reaction for preparing formic acid by oxidizing glucose belongs to a typical gas-liquid multiphase reaction process, the mass transfer process of oxygen to glucose aqueous solution is a control step of the whole reaction system, and the phase dispersion effect and the phase boundary area are key for determining the mass transfer rate and the reaction performance. Aiming at the gas-liquid heterogeneous oxidation reaction system, the reaction equipment adopted in the prior art is a traditional stirred tank reactor, and the reaction equipment has the advantages of small contact specific phase boundary area, poor mass transfer performance, serious material back mixing, wide reaction residence time distribution, low material concentration and poor process controllability (such as bubbles/liquid drops)Wide size distribution, random dispersion and coalescence processes), etc., resulting in low space-time yield in the whole process, prominent amplifying effect, and difficult effective control of process safety.
Disclosure of Invention
The invention aims to provide a novel process for preparing formic acid by catalytic oxidation of glucose in a microchannel reactor aiming at the defects of the current process and technology for preparing formic acid by glucose. By virtue of the advantages of high-efficiency heat transfer and mass transfer performance, controllable reaction process and the like of the microchannel reactor, the synchronous improvement of the conversion rate of glucose and the yield of formic acid is realized.
In order to achieve the above purpose, the invention provides a method for preparing formic acid by catalytic oxidation of glucose in a microchannel reactor system, which adopts the following technical scheme:
after glucose aqueous solution and oxygen with dispersed catalyst are mixed and distributed by a micro-channel mixer, glucose aqueous solution-oxygen two-phase material flowing out of the micro-channel mixer enters the micro-channel reactor, the reaction process is completed at preset temperature and pressure, the reacted material enters a gas-liquid separation tank for gas-liquid separation, gas phase enters a gas collector from the top of the gas-liquid separation tank after passing through a back pressure valve, and liquid phase is put into a sample collector from the bottom of the gas-liquid separation tank.
The microchannel reactor system relates to a raw material storage tank, an oxygen bottle, a gas mass flow controller, a continuous feed pump, a microchannel mixer, a microchannel reactor, a reaction temperature control device, a gas-liquid separation tank, a back pressure valve and a product collecting tank.
The raw material storage tank, the continuous feed pump, the micro-channel mixer, the micro-channel reactor, the gas-liquid separation tank, the back pressure valve and the product collection tank are connected in series, the gas phase branch oxygen bottle, the gas mass flow controller and the micro-channel mixer are connected in series, and the gas phase branch and the liquid phase branch are connected in parallel through the micro-mixer.
The micro-channel mixer and the micro-channel reactor are both arranged in a reaction temperature control device, and the rest parts do not perform any temperature control treatment.
In the method provided by the invention, a micro-channel mixer andthe temperature of the micro-channel reactor is controlled to be 80-180 DEG o C, preferably at a temperature of 140 to 160 DEG C oC 。
The pressure of the reaction system is controlled by a back pressure valve connected to a gas phase outlet pipeline at the top of the gas-liquid separation tank, and the reaction pressure is 0.5-3.5 MPa, preferably 2.5-3.5 MPa.
The glucose is added in an amount of 0.5-3 wt% based on the amount of the solvent, and the solvent is deionized water.
The addition amount of the catalyst sodium metavanadate is 0.1-1 wt%, preferably 0.3-0.6 wt%, based on the amount of the solvent.
The pH value of the aqueous solution of the reaction system is regulated and controlled by adding sulfuric acid, wherein the adding amount of the sulfuric acid is 0.1-3 wt%, preferably 1-2 wt%, based on the amount of the solvent.
The residence time of the reaction materials in the microchannel reaction channel is 2-10 min, preferably 4-8 min, and the residence time is controlled by changing the inner diameter of the microchannel reactor and adjusting the flow of glucose aqueous solution and oxygen.
The diameter of the internal through hole of the micro-channel mixer is 0.1-1 mm, preferably 0.25-0.60 mm; the internal hydrodynamic diameter of the microchannel reactor is 0.1-1 mm, preferably 0.4-0.8 mm, and the length of the microchannel reactor is 2000-40000 mm, preferably 6000-20000 mm.
Compared with the prior art, the invention has the beneficial effects that:
(1) In the method provided by the invention, the micro-channel mixer is provided with a sub-millimeter internal through hole, so that the glucose aqueous solution and the gas phase oxidant oxygen can be dispersed into a liquid plug and a bubble which are small in size, uniform in size and controllable; the micro-channel reactor can limit the dispersed bubbles and the liquid plug of the micro-channel mixer in the micro-channel, thereby avoiding the coalescence of micro-bubbles, greatly increasing the specific phase boundary area of materials, shortening the diffusion distance and improving the transfer rate; in addition, the micro-channel reactor can be regarded as a micro-tube type plug flow reactor, so that the problems of wide reaction residence time distribution, low selectivity and the like caused by material back mixing can be effectively avoided, and the instantaneous liquid holdup of the micro-channel reactor is low, so that the process safety is effectively ensured. Regarding the productivity problem of the reaction system, the method can adjust the productivity of the apparatus by a simple parallel number amplifying means.
(2) Compared with the reaction process carried out by adopting an intermittent kettle type reactor in the literature, the method has the following advantages: the gas-liquid phase is uniformly dispersed and controllable, the specific phase interface area is large, the heat/mass transfer rate and the reaction rate are high, the residence time distribution is narrow, the reaction selectivity is high, the process continuity can be realized, the amplifying effect of the process is small, and the process is intrinsically safe.
Drawings
FIG. 1 is a schematic flow chart of the method of the present invention, wherein:
1 is a glucose aqueous solution raw material storage tank; 2 is a continuous feed pump; 3 is an oxygen bottle; 4 is a gas mass flow controller; 5 is a microchannel mixer; 6 is a microchannel reactor; 7 is a reaction temperature control device; 8 is a gas-liquid separation tank; 9 is a back pressure valve; 10 is a two-way ball valve; 11 is a gas phase product collector; 12 is a liquid phase product collection tank.
Detailed Description
The process for achieving the catalytic oxidation of glucose to formic acid in a microchannel reactor is shown in FIG. 1. The glucose aqueous solution containing the catalyst and the catalyst auxiliary agent is stored in a raw material storage tank 1, and the raw material liquid is pumped into one inlet of a microchannel mixer 5 along a pipeline through a continuous feed pump 2; high pressure oxygen is discharged from the oxygen bottle 3 through a pressure reducing valve, flows into a gas mass flow controller 7 along a pipeline, adjusts the oxygen flow required by the reaction through the gas mass flow controller, and then flows into the other inlet of the microchannel mixer 5 along the pipeline; after the two materials are mixed and dispersed in the micro-channel mixer, the two materials enter a micro-channel reactor 6 connected with the outlet of the micro-channel mixer, the two inlet pipelines of the micro-channel mixer, the micro-channel mixer and the micro-channel reactor are all used for regulating and controlling the temperature through a reaction temperature control device 7, and the pressure of a reaction system is controlled through a back pressure valve 9. Under the preset temperature and pressure, the gas-liquid two-phase material completes the reaction process in the microchannel reactor, the reacted material enters the gas-liquid separation tank 8 for gas-liquid separation, the gas phase enters the gas phase product collector 11 from the top of the gas-liquid separation tank through the back pressure valve, and the liquid phase is put into the liquid phase product collection tank 12 from the bottom of the gas-liquid separation tank.
The present invention is described above, and specific examples of the present invention are given below. The specific examples are provided only for further elaboration of the invention and do not limit the scope of the claims of the present application.
Example 1
Deionized water is used as a solvent to prepare an aqueous solution of glucose required by the reaction. Based on the amount of the solvent, the mass fraction of glucose in the aqueous solution is 1. 1 wt%, the mass fraction of sodium metavanadate as a catalyst is 0.35 wt%, and the mass fraction of sulfuric acid as a catalyst auxiliary agent is 2 wt%; the oxidant of the reaction is high-purity oxygen. The reaction of preparing formic acid by catalytic oxidation of glucose is carried out by adopting the process flow shown in figure 1. Wherein, the micro-channel mixers all adopt T-shaped mixing mode, and the diameter of the internal through hole of the micro-channel mixer is 0.45 and mm; the inner diameter of the microchannel reactor was 0.6. 0.6 mm and the length of the microchannel was 10000 mm.
At a reaction pressure of 3.0 MPa and a reaction temperature of 160 o C. And (3) carrying out a reaction for preparing formic acid by catalytic oxidation of glucose under the conditions of a gas-liquid volume flow ratio of 50:1 and a residence time of 6 min, and carrying out liquid chromatography analysis on the collected liquid phase product. The results show that: the conversion of glucose was 97.89% and the yield of formic acid was 71.80%.
Example 2
The pressure of the reaction system was adjusted to 2.0 MPa, and the other conditions were the same as in example 1. The results show that: the conversion of glucose was 89.62% and the yield of formic acid was 65.23%.
Example 3
The pressure of the reaction system was adjusted to 3.5 MPa, and the other conditions were the same as in example 1. The results show that: the conversion of glucose was 99.23%, and the yield of formic acid was 69.47%.
Example 4
Changing the reaction temperature to 120 o C, the rest of the conditions are the same as in example 1. The results show that: the conversion of glucose was 83.73% and the yield of formic acid was 55.85%.
Example 5
Changing the reaction temperature to 140 o C, the rest of the conditions are the same as in example 1. The results show that: the conversion of glucose was 93.14% and the yield of formic acid was 67.47%.
Example 6
Changing the reaction temperature to 180 DEG o C, the rest of the conditions are the same as in example 1. The results show that: the conversion of glucose was 99.65% and the yield of formic acid was 68.32%.
Example 7
The mass fraction of the catalyst sodium metavanadate was changed to 0.20% wt%, and the other conditions were the same as in example 1. The results show that: the conversion of glucose was 87.95% and the yield of formic acid was 65.96%.
Example 8
The mass fraction of the catalyst sodium metavanadate was changed to 0.80. 0.80 wt%, and the other conditions were the same as in example 1. The results show that: the conversion of glucose was 87.95% and the yield of formic acid was 65.96%.
Example 9
The procedure was as in example 1, except that the mass fraction of glucose in the aqueous solution was changed to 0.5. 0.5 wt%, the diameter of the internal through-hole of the microchannel mixer was 0.6. 0.6 mm, and the other conditions were the same as in example 1. The results show that: the conversion of glucose was 95.27%, and the yield of formic acid was 69.55%.
Example 10
The mass fraction of the catalyst auxiliary sulfuric acid was changed to 0.5. 0.5 wt%, and the other conditions were the same as in example 9. The results show that: the conversion of glucose was 93.63% and the yield of formic acid was 68.81%.
Example 11
The mass fraction of the catalyst auxiliary sulfuric acid was changed to 3 wt%, and the other conditions were the same as in example 9. The results show that: the conversion of glucose was 96.54% and the yield of formic acid was 68.85%.
Example 12
The internal through-hole diameter of the microchannel mixer was changed to 1 mm, and the other conditions were the same as in example 9. The results show that: the conversion of glucose was 94.12% and the yield of formic acid was 68.71%.
Example 13
The procedure was as in example 1, except that the mass fraction of glucose in the aqueous solution was changed to 2. 2 wt% and the internal hydrodynamic diameter of the microchannel reactor was 0.4. 0.4 mm, with the other conditions being the same as in example 1. The results show that: the conversion of glucose was 94.34% and the yield of formic acid was 68.87%.
Example 14
The internal hydrodynamic diameter of the microchannel reactor was changed to 1 mm, and the other conditions were the same as in example 13. The results show that: the conversion of glucose was 89.38% and the yield of formic acid was 65.25%.
Example 15
The residence time of the reaction mass inside the microchannel reactor was varied to 2 min, the rest of the conditions being the same as in example 13. The results show that: the conversion of glucose was 58.60% and the yield of formic acid was 20.91%.
Example 16
The residence time of the reaction mass inside the microchannel reactor was varied to 10 min, the rest of the conditions being the same as in example 13. The results show that: the conversion of glucose was 100%, and the yield of formic acid was 66.39%.
Comparative example 1
The prepared glucose aqueous solution required by the reaction is the same as that of the example 1, the glucose aqueous solution is added into a batch reaction kettle, the gas in the kettle is replaced for three times by adopting high-purity oxygen, and finally the oxygen is filled to 3.0 MPa. The reaction process adopts magnetic stirring, and the reaction temperature is 160 DEG C o C, reaction time 1 h. The results show that: the conversion of glucose was 88.41% and the yield of formic acid was 53.45%.
Although the invention and its practical results have been described in detail in the foregoing description, those skilled in the art should understand that the invention can be practiced with modification and alteration within the scope of the invention, and therefore the scope of the invention shall be determined by the appended claims.
Claims (8)
1. A method for preparing formic acid by catalytic oxidation of glucose in a microchannel reactor, which is characterized by comprising the following steps:
(1) Dissolving a catalyst, a catalyst auxiliary agent and glucose in deionized water, and fully stirring until the dissolution is completed to obtain a homogeneous glucose aqueous solution, and pumping the glucose aqueous solution into a microchannel mixer through a continuous feed pump, wherein the diameter of an internal through hole of the microchannel mixer is 0.1-1 mm;
the catalyst is sodium metavanadate, the catalytic auxiliary agent is sulfuric acid, and the mass fraction of the addition amount of the catalyst, the catalytic auxiliary agent and glucose is 0.1-1 wt%, 0.1-3 wt% and 0.5-3 wt% based on the amount of deionized water;
(2) The gas phase is high-purity oxygen, the flow is regulated by a gas mass flow controller, the gas phase is continuously injected into a microchannel mixer, two materials are mixed and redistributed in the microchannel mixer, the gas phase is dispersed into small bubbles with uniform size and interval, glucose aqueous solution-oxygen two-phase materials flowing out of the microchannel mixer enter the microchannel reactor, the internal hydrodynamic diameter of the microchannel reactor is 0.1-1 mm, and the length of the microchannel is 2000-40000 mm;
(3) And (3) completing the reaction process of glucose aqueous solution-oxygen two-phase materials at the preset temperature and pressure in the microchannel reactor, enabling the reacted materials to enter a gas-liquid separation tank for gas-liquid separation, enabling a gas phase to enter a gas collector from the top of the gas-liquid separation tank after passing through a back pressure valve, and enabling a liquid phase to be placed into a sample collector from the bottom of the gas-liquid separation tank.
2. The method for preparing formic acid by catalytic oxidation of glucose according to claim 1, wherein the method comprises the following steps: the gas-liquid two phases of oxygen and glucose water solution are respectively preheated to the reaction temperature by a reaction temperature control device, then are mixed and dispersed by a micro-channel mixer, and the dispersed gas-liquid two-phase fluid enters a micro-channel reactor.
3. The method for preparing formic acid by catalytic oxidation of glucose according to claim 2, wherein the method comprises the following steps: the preheating pipeline, the micro-channel mixer and the micro-channel reactor of the reaction materials are all arranged in a reaction temperature control device, and the reaction temperature is 80-180 ℃.
4. The method for preparing formic acid by catalytic oxidation of glucose according to claim 1, wherein the method comprises the following steps: the adding amount of the catalyst sodium metavanadate is 0.3-0.6wt%.
5. The method for preparing formic acid by catalytic oxidation of glucose according to claim 1, wherein the method comprises the following steps: the diameter of the inner through hole of the micro-channel mixer is 0.25-0.60 mm.
6. The method for preparing formic acid by catalytic oxidation of glucose according to claim 1, wherein the method comprises the following steps: the internal hydrodynamic diameter of the microchannel reactor is 0.4-0.8 mm, and the length of the microchannel is 6000-20000 mm.
7. The method for preparing formic acid by catalytic oxidation of glucose according to claim 1, wherein the method comprises the following steps: the pressure of the micro-channel reaction system is 0.5-3.5 MPa.
8. The method for preparing formic acid by catalytic oxidation of glucose according to claim 1, wherein the method comprises the following steps: the volume flow rate of the liquid phase reaction material is 50-1000 mu l/min, the volume flow rate of the gas phase reaction material is 1-10 ml/min, and the residence time of the oxygen and glucose aqueous solution gas-liquid two-phase material in the reaction system is 2-10 min.
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| CN102464521A (en) * | 2010-11-04 | 2012-05-23 | 中国科学院大连化学物理研究所 | Method for synthesizing cyclic carbonate ester in micro reactor system |
| CN104177247A (en) * | 2013-05-28 | 2014-12-03 | 北京化工大学 | Method for preparation of formic acid by catalytic oxidation of biomass |
| WO2021218669A1 (en) * | 2020-04-29 | 2021-11-04 | 西安交通大学 | Method for realizing high-efficiency circulation of vanadium and sulfuric acid with trace dmso to catalyze biomass in order to prepare formic acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464521A (en) * | 2010-11-04 | 2012-05-23 | 中国科学院大连化学物理研究所 | Method for synthesizing cyclic carbonate ester in micro reactor system |
| CN104177247A (en) * | 2013-05-28 | 2014-12-03 | 北京化工大学 | Method for preparation of formic acid by catalytic oxidation of biomass |
| WO2021218669A1 (en) * | 2020-04-29 | 2021-11-04 | 西安交通大学 | Method for realizing high-efficiency circulation of vanadium and sulfuric acid with trace dmso to catalyze biomass in order to prepare formic acid |
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