CN115819219A - Method for preparing formic acid by hydrothermal oxidation and catalysis of biomass through CuO - Google Patents
Method for preparing formic acid by hydrothermal oxidation and catalysis of biomass through CuO Download PDFInfo
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- CN115819219A CN115819219A CN202211478836.3A CN202211478836A CN115819219A CN 115819219 A CN115819219 A CN 115819219A CN 202211478836 A CN202211478836 A CN 202211478836A CN 115819219 A CN115819219 A CN 115819219A
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- cuo
- biomass
- formic acid
- hydrogen peroxide
- hydrothermal
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 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 35
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 35
- 239000002028 Biomass Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229960001867 guaiacol Drugs 0.000 claims description 18
- 229920005610 lignin Polymers 0.000 claims description 13
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 32
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 27
- 239000000126 substance Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 6
- JMSVCTWVEWCHDZ-UHFFFAOYSA-N syringic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1O JMSVCTWVEWCHDZ-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 3
- YIBXWXOYFGZLRU-UHFFFAOYSA-N syringic aldehyde Natural products CC12CCC(C3(CCC(=O)C(C)(C)C3CC=3)C)C=3C1(C)CCC2C1COC(C)(C)C(O)C(O)C1 YIBXWXOYFGZLRU-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 carboxylic acid compound Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing formic acid by utilizing CuO hydrothermal oxidation catalysis biomass, which comprises the steps of putting biomass, cuO and hydrogen peroxide solution into a reaction kettle, and carrying out hydrothermal reaction on the mixture to prepare formic acid; the method utilizes CuO as an alkali catalyst, overcomes the defects of strong corrosion and the like of the conventional alkali, realizes the rapid resource conversion of biomass, saves the cost, has no secondary pollution, uses the CuO as a cheap and easily available catalyst, can be recycled, and has better application prospect in the actual production; the method has the characteristics of high efficiency, greenness and the like, and is a method for producing formic acid by high-selectivity hydrothermal oxidation of a novel catalyst.
Description
Technical Field
The invention relates to a method for preparing formic acid by utilizing CuO hydrothermal oxidation catalysis biomass, which utilizes CuO and H 2 O 2 Realizes high-efficiency and high-selectivity water in a short time under the synergistic catalytic action of hydrothermal conditionsThermal conversion of biomass into formic acid belongs to the technical field of biomass resource treatment.
Background
With the development of economy, people rely on fossil energy more and more, and with the continuous exhaustion of fossil energy caused by the increase of energy demand, the energy crisis has become a great problem, and in order to deal with the consumption problem of fossil energy and a series of environmental problems brought by the consumption problem, a suitable new energy is urgently needed to be searched to replace non-renewable energy. Various forms of energy have been developed as substitutes for clean energy such as wind energy, solar energy, hydrogen energy, and biomass energy, and the biomass energy is attracting attention of researchers due to its advantages such as renewability and abundant reserves. Lignin is the second most abundant component in lignocellulosic biomass next to cellulose. And lignin is a polymeric aromatic organic substance containing many oxygen-based functional groups and has great potential as a renewable resource for producing valuable chemicals.
Formic acid is a simple carboxylic acid compound, has the characteristics of no toxicity, no corrosiveness, biodegradability and the like, is environment-friendly, has weak acidity, can be used as an acidifier and a cleaning agent, can be used for dyeing leather, rubber, textiles and the like, and is widely applied to various chemical fields of medicine synthesis, pesticide production, chemical products and the like. In addition, formic acid is also an environment-friendly hydrogen storage carrier, and the volume capacity of the formic acid reaches 53g H 2 L, and the hydrogen production method by formic acid dehydrogenation is simple, mild and easy to control, so formic acid is considered as a value-added carrier for hydrogen energy utilization.
Among the wide range of oxygenated chemicals, lignin-based biomass has received much attention because of its abundant functional groups to produce organic acids. At present, the prior art for producing formic acid by using a biomass chemical method mostly uses a large amount of alkaline catalysts or has long time, high cost and easy secondary pollution.
Disclosure of Invention
The invention provides a method for preparing formic acid by utilizing CuO hydrothermal oxidation catalysis biomass, which utilizes a hydrothermal technology, takes CuO as a catalyst, and utilizes CuO and H 2 O 2 Synergistic catalytic action, realizes short timeThe biomass is oxidized and converted into the formic acid with high efficiency and high selectivity.
The invention is realized by the following technical scheme:
a method for preparing formic acid by utilizing CuO hydrothermal oxidation catalysis biomass comprises the following steps:
and (2) putting the biomass, cuO and hydrogen peroxide solution into a reaction kettle for mixing, adding deionized water to enable the filling rate of the reaction kettle to reach 40%, and carrying out hydrothermal reaction on the mixture to obtain the formic acid.
The biomass is lignin, the lignin comprises G-type lignin monomer-guaiacol, S-type lignin monomer-syringic acid or H-type lignin monomer-p-hydroxybenzoic acid, and the system has universality.
The mass fraction of the hydrogen peroxide solution is 30%.
The biomass, the hydrogen peroxide aqueous solution, and the CuO are mixed in such a ratio that the ratio of the amounts of the hydrogen peroxide and the CuO in the biomass and the hydrogen peroxide aqueous solution is 1 to 16.
The hydrothermal reaction temperature is 200-300 ℃.
The hydrothermal reaction time is 1-20 min.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes CuO as an alkali catalyst, overcomes the defects of strong corrosion and the like of the conventional alkali (NaOH, KOH and the like), and utilizes CuO and H 2 O 2 Under the synergistic catalytic action under the hydrothermal condition, the high-efficiency and high-selectivity hydrothermal conversion of lignin biomass to formic acid is realized in a short time, and the yield and the selectivity are high; saving cost, no secondary pollution and good practical application prospect.
Drawings
FIG. 1 is a high performance liquid chromatogram of hydrothermal oxidation of lignin to formic acid in example 1.
Detailed Description
Other features, objects, and advantages of the invention will be apparent from the detailed description of the invention that follows, taken in conjunction with the accompanying drawings.
Example 1
A method for preparing formic acid by utilizing CuO hydrothermal oxidation catalytic oxidation guaiacol comprises the following steps:
putting 0.5mmol of guaiacol, 120mgCuO and hydrogen peroxide solution into a 5mL reaction kettle, wherein the mass fraction of the hydrogen peroxide solution is 30%, and the guaiacol and the hydrogen peroxide (H) in the hydrogen peroxide solution are 2 O 2 ) And the ratio of the amount of CuO substances is 1.
FIG. 1 is a high performance liquid chromatogram of hydrothermal oxidation of lignin to formic acid in example 1, and it is understood from the chromatogram that formic acid is reliably produced.
Example 2
A method for preparing formic acid by utilizing CuO hydrothermal oxidation catalysis guaiacol comprises the following steps:
putting 0.5mmol of guaiacol, 120mgCuO and hydrogen peroxide solution into a 5mL reaction kettle, wherein the mass fraction of the hydrogen peroxide solution is 30%, and the guaiacol and the hydrogen peroxide (H) in the hydrogen peroxide solution are 2 O 2 ) And the proportion of the CuO substance is 1.
Example 3
A method for preparing formic acid by utilizing CuO hydrothermal oxidation catalysis guaiacol comprises the following steps:
putting 0.5mmol of guaiacol, 120mgCuO and hydrogen peroxide solution into a 5mL reaction kettle, wherein the mass fraction of the hydrogen peroxide solution is 30%, and the guaiacol and the hydrogen peroxide (H) in the hydrogen peroxide solution are 2 O 2 ) And the ratio of the amount of CuO substances is 1And sealing the reactor, carrying out hydrothermal reaction on the mixture at 230 ℃ after 10min, analyzing the reaction product by using a high performance liquid chromatography, and converting by qualitative and quantitative analysis to obtain the formic acid with the yield of 5% and the selectivity of 7.1%.
Example 4
A method for preparing formic acid by utilizing CuO hydrothermal oxidation catalysis guaiacol comprises the following steps:
putting 0.5mmol of guaiacol, 40mg of CuO and hydrogen peroxide solution into a 5mL reaction kettle, wherein the mass fraction of the hydrogen peroxide solution is 30%, and the guaiacol and the hydrogen peroxide (H) in the hydrogen peroxide solution are 2 O 2 ) And the ratio of the amount of CuO substances is 1.
Example 5
A method for preparing formic acid by utilizing CuO hydrothermal oxidation catalysis guaiacol comprises the following steps:
putting 0.5mmol of guaiacol, 200mgCuO and hydrogen peroxide solution into a 5mL reaction kettle, wherein the mass fraction of the hydrogen peroxide solution is 30%, and the guaiacol and the hydrogen peroxide (H) in the hydrogen peroxide solution are 2 O 2 ) And the proportion of the CuO substance is 1.
Comparative example 1
Adding 0.5mmol of guaiacol, hydrogen peroxide (H) solution and 0.5mL of 4mol/L NaOH solution into a 5mL reaction kettle, wherein the mass fraction of the hydrogen peroxide solution is 30 percent 2 O 2 ) Is/are as followsThe mass ratio of the substances is 1.
After the sodium hydroxide is used for a period of time, the reaction kettle is seriously corroded, and the sodium hydroxide is difficult to separate from the solution after reaction and cannot be reused.
Example 6
A method for preparing formic acid by utilizing CuO hydrothermal oxidation catalysis syringic acid comprises the following steps:
taking 0.5mmol of syringic acid, 120mgCuO and hydrogen peroxide (H) 2 O 2 ) Putting the solution into a 5mL reaction kettle, wherein the mass fraction of the hydrogen peroxide solution is 30 percent, and the syringic acid and the hydrogen peroxide (H) in the hydrogen peroxide solution are 2 O 2 ) And the ratio of the amount of CuO substances is 1.
Example 7
A method for preparing formic acid by utilizing CuO hydrothermal oxidation catalysis p-hydroxybenzoic acid comprises the following steps:
putting 0.5mmol of p-hydroxybenzoic acid, 120mgCuO and hydrogen peroxide solution into a 5mL reaction kettle, wherein the mass fraction of the hydrogen peroxide solution is 30%, and hydrogen peroxide (H) in the p-hydroxybenzoic acid and the hydrogen peroxide solution is 2 O 2 ) And the proportion of the CuO substance is 1.
In the above examples 1-7, after the hydrothermal reaction is completed, the mixture in the reaction kettle is filtered, and the copper oxide obtained after the water washing is regenerated can be recycled, and the reaction kettle is not corroded.
It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (5)
1. A method for preparing formic acid by utilizing CuO hydrothermal oxidation catalysis biomass is characterized in that biomass, cuO and hydrogen peroxide solution are put into a reaction kettle to be mixed for hydrothermal reaction to prepare formic acid.
2. The method for preparing formic acid by utilizing CuO hydrothermal oxidation catalysis biomass as claimed in claim 1, wherein the biomass is lignin, and the lignin comprises G type monolignol-guaiacol, S type monolignol-syringic acid or H type monolignol-p-hydroxybenzoic acid.
3. The method for preparing formic acid by hydrothermal oxidation and catalysis of biomass through CuO according to claim 2, wherein the biomass, the aqueous hydrogen peroxide solution and the CuO are mixed in a ratio of the biomass to the hydrogen peroxide to the CuO of 1.
4. The method for preparing formic acid by utilizing CuO to hydrothermally oxidize and catalyze biomass according to claim 1, wherein the mass fraction of the hydrogen peroxide solution is 30%.
5. The method for preparing formic acid by utilizing CuO to hydrothermally oxidize and catalyze biomass according to claim 1, wherein the hydrothermal reaction temperature is 200-300 ℃ and the time is 1-20 min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211478836.3A CN115819219A (en) | 2022-11-23 | 2022-11-23 | Method for preparing formic acid by hydrothermal oxidation and catalysis of biomass through CuO |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211478836.3A CN115819219A (en) | 2022-11-23 | 2022-11-23 | Method for preparing formic acid by hydrothermal oxidation and catalysis of biomass through CuO |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005200340A (en) * | 2004-01-15 | 2005-07-28 | Heiji Enomoto | Method for producing monocarboxylic acid |
| JP2015134324A (en) * | 2014-01-17 | 2015-07-27 | 国立大学法人北陸先端科学技術大学院大学 | Copper-supported catalyst and method of producing the same, method of producing lactic acid, and method of producing formic acid |
| CN107118092A (en) * | 2017-05-25 | 2017-09-01 | 华南理工大学 | A kind of method that carbon dioxide collaboration metal oxide oxidation catalyst converts carbohydrate |
| CN107522611A (en) * | 2017-10-13 | 2017-12-29 | 厦门大学 | A kind of method that guaiacol prepares formic acid |
| CN107746375A (en) * | 2017-09-15 | 2018-03-02 | 上海交通大学 | A kind of method of house refuse optional water thermal oxide conversion production formic acid |
-
2022
- 2022-11-23 CN CN202211478836.3A patent/CN115819219A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005200340A (en) * | 2004-01-15 | 2005-07-28 | Heiji Enomoto | Method for producing monocarboxylic acid |
| JP2015134324A (en) * | 2014-01-17 | 2015-07-27 | 国立大学法人北陸先端科学技術大学院大学 | Copper-supported catalyst and method of producing the same, method of producing lactic acid, and method of producing formic acid |
| CN107118092A (en) * | 2017-05-25 | 2017-09-01 | 华南理工大学 | A kind of method that carbon dioxide collaboration metal oxide oxidation catalyst converts carbohydrate |
| CN107746375A (en) * | 2017-09-15 | 2018-03-02 | 上海交通大学 | A kind of method of house refuse optional water thermal oxide conversion production formic acid |
| CN107522611A (en) * | 2017-10-13 | 2017-12-29 | 厦门大学 | A kind of method that guaiacol prepares formic acid |
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