CN111454139A - Method for preparing formic acid by vanadium and sulfuric acid efficient circulating catalysis of biomass through trace DMSO (dimethyl sulfoxide) - Google Patents
Method for preparing formic acid by vanadium and sulfuric acid efficient circulating catalysis of biomass through trace DMSO (dimethyl sulfoxide) Download PDFInfo
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 276
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 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 137
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 137
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000002028 Biomass Substances 0.000 title claims abstract description 56
- 229910052720 vanadium Inorganic materials 0.000 title claims description 32
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims description 31
- 238000006555 catalytic reaction Methods 0.000 title claims description 18
- 239000012452 mother liquor Substances 0.000 claims abstract description 80
- 239000000413 hydrolysate Substances 0.000 claims abstract description 73
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 60
- 230000003647 oxidation Effects 0.000 claims abstract description 58
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 239000001913 cellulose Substances 0.000 claims abstract description 33
- 229920002678 cellulose Polymers 0.000 claims abstract description 33
- 210000002196 fr. b Anatomy 0.000 claims abstract description 32
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 238000004821 distillation Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000010902 straw Substances 0.000 claims description 41
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 241000209140 Triticum Species 0.000 claims description 18
- 235000021307 Triticum Nutrition 0.000 claims description 18
- 238000006400 oxidative hydrolysis reaction Methods 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 17
- 239000000123 paper Substances 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 235000014676 Phragmites communis Nutrition 0.000 claims description 10
- 239000001117 sulphuric acid Substances 0.000 claims description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims description 10
- 241000609240 Ambelania acida Species 0.000 claims description 9
- 240000008042 Zea mays Species 0.000 claims description 9
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 9
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 9
- 239000010905 bagasse Substances 0.000 claims description 9
- 235000005822 corn Nutrition 0.000 claims description 9
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 241000274582 Pycnanthus angolensis Species 0.000 claims description 3
- 239000011087 paperboard Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 30
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 30
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 229940013688 formic acid Drugs 0.000 description 120
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 34
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- 239000011521 glass Substances 0.000 description 13
- 239000011111 cardboard Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 241000209094 Oryza Species 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229910019501 NaVO3 Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Processing Of Solid Wastes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing formic acid by efficiently and circularly catalyzing biomass by using trace DMSO (dimethyl sulfoxide) and sulfuric acid comprises the steps of putting biomass or household garbage into dilute sulfuric acid, adding sodium metavanadate and DMSO, performing oxidation hydrolysis, and quantitatively converting cellulose and hemicellulose into formic acid to obtain oxidation hydrolysate A; then carrying out reduced pressure distillation to separate the oxidized hydrolysate A to obtain a fraction B and a mother liquor C, wherein the fraction B is an aqueous solution of formic acid, and the aqueous solution of formic acid is subjected to subsequent separation or application; adding DMSO and water into the mother liquor C, heating and stirring to combine the DMSO and the water to obtain active mother liquor D; then putting the biomass or the household garbage into the active mother liquor D for oxidation and hydrolysis, and quantitatively converting the cellulose and the hemicellulose into a formic acid solution to obtain an oxidation hydrolysate; finally, adding the oxidation hydrolysate into the oxidation hydrolysate A, and repeatedly realizing the circulation of the system; the method has the advantages of good compatibility, high yield of the prepared formic acid, simple post-treatment, no reduction of the yield of the formic acid after multiple cycles, and reduction of the cost and environmental pollution.
Description
Technical Field
The invention belongs to the technical field of formic acid preparation, and particularly relates to a method for preparing formic acid by efficiently and circularly catalyzing biomass with vanadium and sulfuric acid by using trace DMSO (dimethyl sulfoxide).
Background
Formic acid is one of basic chemical raw materials, and has wide application in various fields such as medicine, papermaking, agriculture, textile printing and dyeing and the like. In recent years, formic acid has attracted a great deal of attention from scientists as a potential hydrogen storage material. At present, the industrial preparation methods of formic acid are mainly a formamide method and a methyl formate method. The raw materials (high pressure carbon monoxide and methanol) used in these traditional methods are from non-renewable fossil resources, and the toxicity of carbon monoxide is high, thus prompting researchers to develop a green and sustainable formic acid production method. The biomass is renewable, low in cost, low in pollution and wide in distribution, and can be developed into raw materials for producing chemicals. At present, the preparation of formic acid by using biomass as a raw material is still in a research stage, and if the formic acid can be prepared from the biomass under mild conditions with high efficiency, high yield and low energy consumption, the industrial production of the formic acid is promoted.
At present, two main methods for preparing formic acid by using biomass are provided, wherein the first method is an alkali-hydrogen oxidation method, and the second method is a hydrothermal oxidation method using vanadium as a catalyst. The alkali-hydrogen oxidation process is carried out with H2O2(hydrogen peroxide) as oxidant, water as solvent, sodium hydroxide as stabilizing reagent and catalyst, and the Formic acid (chemical of acid/base-catalyzed and oxidation reactions) obtained by chemical of acid/base-catalyzed Conversion of two organic in value-amplified products in hydrodynamics, 4,382-397. Jun Yun, Guodong Yao, growing Jin, et al, L ow-Temperature and high efficiency Conversion of chemical of reaction of organic in acid, scientific of organic in acid, chemical of reaction of organic in acid, chemical of reaction, ChE J.3663, 62,3657-3663, Qi-chemical of organic in reaction of chemical of organic in reaction, and chemical of organic in reaction of organic in acid, III of organic in reaction, III of organic in acid, III of organic in reaction, III, IV, V.V.V.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S. 7, H.S.S.S.S. 7, S.S.S.S.S.S. 7, S.S.S.S.S.S.S.S.S.S.S.S.S2O2The oxidation is strong, and the formic acid generated in the reaction can be further oxidized, so that a large amount of alkali is added in the reaction to improve the selectivity and yield of the formic acid, and the formate is generated instead of the formic acid in the reaction, thereby limiting the limitation of the reactionDirectly applying the subsequent reaction formic acid; the method has limited conversion degree of cellulose in the original ecological biomass, and a large amount of alkali and an oxidant H are required to be added in each circulation2O2And is not favorable for industrial cycle application.
The hydrothermal oxidation method using vanadium as catalyst uses vanadium-containing compound as catalyst, water as solvent and oxygen as oxidant, and makes the vanadium-containing compound mainly include heteropolyacid (HPA-x, x ═ 0-6) and VOSO at below 200 deg.C4，NaVO3And (4) three types.
Heteropoly acids are oxo acids formed by connecting various atoms (e.g., V, Mo, P, etc.) through oxygen bridges according to a certain rule. The heteropoly acid has good catalytic effect on small molecular sugar monomers, but has very limited conversion and decomposition on cellulose in the original ecological biomass. Therefore, the addition of auxiliary agents such as p-toluenesulfonic acid (TSA) and organic solvents such as n-hexanol, n-heptanol and the like to these systems further increases the reaction yield (Albert J,
R,BosmannA,et al.Selectiveoxidation ofcomplex,water-insoluble biomass to formic acid using additives asreactionaccelerators.EnergyEnviron.Sci.2012,5,7956–7962.
R,Taccardi N,
A,et al.Selective catalytic conversion ofbiobased carbohydrates toformic acidusingmolecularoxygen.Green Chem.2011,13,2759–2763.AlbertJ,LüdersD,
A,etal.Spectroscopic andelectrochemical characterizationofheteropolyacids for theiroptimizedapplicationinselectivebiomass oxidationto formicacid.Green Chem.2014,16,226–237.Jenny Reichert,Birgit Brunner,Andreas Jess,etal.,Biomass oxidation to formic acid in aqueous media using polyoxometalate analytes-boosting FA selection by in-situ extraction EnergyEnviron. Sci.2015,8, 2985-2990.). The selectivity of the heteropoly acid catalytic biomass for preparing formic acid is not high, and a large amount of organic acid auxiliary agents and organic solvents are added, so that the cost of the reaction is increased invisibly, and the purification of the formic acid is not facilitated.
VOSO4The catalytic system is in VOSO4Alcohol compounds such as ethanol are added to the system, thereby reducing formic acid over-oxidation and improving formic acid yield (TangZ, DengW, WangY, et., transformational of cell and derivatives of carbohydrates into micro and lactic acids catalysis. ChemSus Chem2014,7, 1557-and 1567.). The method has low concentration of reaction raw materials, and the water and a large amount of alcohol substances required by the same raw material amount increase the reaction cost and are also not beneficial to separation and large-scale circulation of formic acid.
NaVO3/H2SO4The catalytic system is to dilute H2SO4Adding NaVO into the aqueous solution3Formic acid is prepared, and the Conversion of cellulose in the original ecological biomass, such as biomass like wheat straw (WangWH, NiuM G, HouYC, et al, Catalytic Conversion of biomasses-derived carbohydrates to biological acid formation molecular chemistry. Green chem.2014,16,2614-2618. NiuM G, HouY C, Ren S H, et al, Conversion of straw sludge into biological acid in NaVO3-H2SO4aqueous solution with molecular xygen, Green chem.2015,17, 453-459.). The method realizes the separation of the formic acid by using an ether extraction mode, and the yield of the formic acid is only 47 percent to be further improved, thereby being not beneficial to the wide application in industry.
Although the method for preparing formic acid by using non-food biomass has made a certain progress in the alkali-peroxidation method using hydrogen peroxide as an oxidant or the hydrothermal oxidation method using vanadium with oxygen as an oxidant, the method still has great limitation in practical application. In the existing method, the aims of high-yield conversion of glucose, conversion of original ecological biomass and recycling are respectively realized at present, but how to simultaneously realize high-yield preparation of formic acid from the original ecological biomass and high-efficiency recycling of a catalytic system is a very challenging subject. The realization of this topic will show its potential industrial application prospects.
In conclusion, the existing technologies for preparing formic acid from biomass have the problems that the conversion of high yield of glucose, the conversion of high yield of original ecological biomass, low catalytic cycle cost and the like cannot be simultaneously met.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing formic acid by efficiently circularly catalyzing biomass with vanadium and sulfuric acid by using trace DMSO, and the method is used for efficiently circularly catalyzing biomass and domestic garbage with vanadium and sulfuric acid to prepare formic acid by using trace DMSO under mild conditions.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing formic acid by vanadium and sulfuric acid efficient circulating catalysis of biomass through trace DMSO comprises the following steps:
1) placing biomass or domestic garbage in dilute sulfuric acid with mass concentration of 0.5-1.5%, then adding sodium metavanadate and DMSO, and carrying out oxidative hydrolysis at the temperature of 140-;
wherein, 15-45m L dilute sulphuric acid, 0.05-0.15g sodium metavanadate and 0-2m L DMSO are added into each 1g biomass or domestic garbage;
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 45-65 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is an aqueous solution of formic acid, the aqueous solution of formic acid is subjected to subsequent separation or application, and the mother liquor C is a catalytic system of concentrated sulfuric acid and sodium metavanadate;
3) adding a trace amount of DMSO and water required by the reaction into the mother liquor C, heating to 50-95 ℃, stirring for five minutes to one hour to fully combine the DMSO and the water to obtain active mother liquor D, wherein 0.1-0.5m L DMSO is added into each 1g of biomass or household garbage;
4) putting the biomass or the household garbage with the same mass as that in the step 1) into the active mother liquor D, and carrying out oxidative hydrolysis at the temperature of 140-170 ℃ under the pressure of 2.0-7.0MPa to quantitatively convert cellulose and hemicellulose into a formic acid solution to obtain an oxidative hydrolysate.
Adding the oxidation hydrolysate obtained in the step 4) into the oxidation hydrolysate A obtained in the step 2), and circulating the step 2), the step 3) and the step 4) to realize the circulation of the system.
The biomass adopts wheat straw, corn straw, rice straw or reed straw.
The domestic garbage is bagasse, boxboard paper or waste newspaper.
The oxidative hydrolysis of the step 1) and the step 4) is carried out in oxygen or air.
The water supplemented in the step 3) is distilled circulating water.
The invention has the beneficial effects that:
the method for preparing the formic acid by efficiently and circularly catalyzing the biomass with the vanadium and the sulfuric acid by adopting the trace DMSO has good compatibility. Compared with the prior art, the yield of the formic acid prepared from the original ecological biomass is high, the post-treatment is simple, the yield of the formic acid prepared from the wheat straw is not reduced after multiple cycles, and the yield of the formic acid prepared from the wheat straw is more than or equal to 95 percent; the invention is a water phase reaction system, does not need a large amount of organic solvents, and reduces the cost and the environmental pollution. Compared with other catalytic systems, the catalytic system has the advantages of strong compatibility (compatibility with various biomasses and household garbage), high selectivity (more than or equal to 95 percent) and low circulating cost (simple reduced pressure distillation and addition of trace DMSO).
Drawings
FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Example 1, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass with trace DMSO comprises the following steps:
1) adding wheat straw 0.94g of 200 mesh sieve, dilute sulphuric acid 30m L with mass concentration of 0.7%, sodium metavanadate 0.08g and DMSO 0.31m L into a glass reactor, magnetically stirring at room temperature until the sodium metavanadate is fully dissolved, placing into a high-pressure kettle, heating to 160 deg.COxidizing and hydrolyzing in 3.0MPa air to obtain oxidized hydrolysate A of wheat straw, adding 1, 4-dioxane as internal standard, and treating with water1The content of formic acid in the oxidation hydrolysate A is 18mmol by HNMR determination, and the yield of the formic acid is 100% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 55 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding a trace amount of 0.31m L DMSO and water required by the reaction into the mother liquor C, heating to 90 ℃, and stirring for ten minutes to fully react to obtain active mother liquor D;
4) placing 0.94g of wheat straw with 200 mesh sieve in active mother liquor D, placing in a high-pressure kettle, heating to 160 deg.C, performing oxidation hydrolysis in 3.0MPa air to obtain oxidation hydrolysis solution of wheat straw, adding 1, 4-dioxane as internal standard, and using1The content of formic acid in the hydrolysate is 18mmol by HNMR determination, and the yield of the formic acid is 100% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
5) adding the oxidation hydrolysate obtained in the step 4) into the oxidation hydrolysate A obtained in the step 2), and circulating the step 2), the step 3) and the step 4) for 3 times, wherein the yield of formic acid is 100%, 99% and 100% respectively.
Example 2, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass with trace DMSO comprises the following steps:
1) adding 2.82g of wheat straw with a 200-mesh sieve, 90m L of dilute sulfuric acid with the mass concentration of 0.7%, 0.24g of sodium metavanadate and 0.93m L of DMSO into a glass reactor, magnetically stirring at room temperature until the sodium metavanadate is fully dissolved, placing into a high-pressure kettle, heating to 160 ℃, carrying out oxidative hydrolysis in oxygen at 3.0MPa to obtain an oxidative hydrolysate A of the wheat straw, adding 1, 4-dioxane into the oxidative hydrolysate A as an internal standard, and using the 1, 4-dioxane as the internal standard1H NMR measurement shows that the content of formic acid in the hydrolysate is 53mmol, and the yield of the formic acid is 99% (calculated on the basis of C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 55 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding 0.93m L DMSO and water required by the reaction into the mother liquor C, heating to 90 ℃, stirring for ten minutes, and fully reacting to obtain active mother liquor D;
4) placing 2.82g of wheat straw with 200 mesh sieve in medium-activity mother liquor D, placing in a high-pressure kettle, heating to 160 deg.C, performing oxidation hydrolysis in 3.0MPa oxygen to obtain oxidation hydrolysate of wheat straw, adding 1, 4-dioxane as internal standard into the oxidation hydrolysate, and using1The content of formic acid in the hydrolysate is 53mmol by HNMR determination, and the yield of the formic acid is 99% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
5) adding the oxidation hydrolysate obtained in the step 4) into the oxidation hydrolysate A obtained in the step 2), and circulating the step 2), the step 3) and the step 4) for 3 times, wherein the yield of formic acid is 100%, 99% and 100% respectively.
Example 3, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass with trace DMSO comprises the following steps:
1) in a glass reactor, 9.42g of chopped wheat straws, 300m L of dilute sulphuric acid with the mass concentration of 0.7%, 0.81g of sodium metavanadate and 3.1m L DMSO are magnetically stirred at room temperature until the sodium metavanadate is fully dissolved, the mixture is placed in a high-pressure kettle, the high-pressure kettle is heated to 160 ℃, the oxidation hydrolysis is carried out in oxygen at the pressure of 5.0MPa to obtain oxidation hydrolysis liquid A of the wheat straws, 1, 4-dioxane is added into the oxidation hydrolysis liquid A to be used as an internal standard, and the internal standard is added1Measuring the content of formic acid in the oxidized hydrolysate A by HNMR to be 179mmol, and the yield of the formic acid is 99% (based on C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 55 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding 3.1m L DMSO and water required by the reaction into the mother liquor C, heating to 90 ℃, and stirring for thirty minutes to fully react to obtain active mother liquor D;
4) placing 9.42g of chopped wheat straw in active mother liquor D, placing in a high-pressure kettle, heating to 160 deg.C, performing oxidation hydrolysis in 5.0MPa oxygen to obtain oxidation hydrolysis solution of wheat straw, adding 1, 4-dioxane as internal standard, and using1The content of formic acid in the hydrolysate is 179mmol by HNMR determination, and the yield of formic acid is 99% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
5) adding the oxidation hydrolysate obtained in the step 4) into the oxidation hydrolysate A obtained in the step 2), and circulating the step 2), the step 3) and the step 4) for 3 times, wherein the yield of formic acid is 99%, 99% and 98% respectively.
Example 4, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass with trace DMSO includes the following steps:
1) adding 3.03g of corn straw with a 200-mesh sieve, 90m L of dilute sulfuric acid with the mass concentration of 0.7%, 0.24g of sodium metavanadate and 0.93m L of DMSO into a glass reactor, magnetically stirring at room temperature until the sodium metavanadate is fully dissolved, placing into a high-pressure kettle, heating to 160 ℃, carrying out oxidative hydrolysis in oxygen at 3.0MPa to obtain an oxidative hydrolysate A of the corn straw, adding 1, 4-dioxane as an internal standard, and using the 1, 4-dioxane as the internal standard1The content of formic acid in the oxidized hydrolysate A is 43mmol by HNMR measurement, and the yield of the formic acid is 79% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 55 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding 0.93m L DMSO and water required by the reaction into the mother liquor C, heating to 90 ℃, stirring for ten minutes, and fully reacting to obtain active mother liquor D;
4) placing 3.03g of corn straw with 200 meshes in active mother liquor D, placing in a high-pressure kettle, heating to 160 ℃, and carrying out oxidative hydrolysis in 3.0MPa oxygen to obtain cornAdding 1, 4-dioxane as internal standard into the oxidized hydrolysate of straw1The HNMR determined the formic acid content of the hydrolysate to be 52mmol and the formic acid yield to be 78% (calculated on the C atoms of cellulose and hemicellulose in the charge).
Example 5, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass through trace DMSO comprises the following steps:
1) adding rice straw 3.10g of 200 mesh sieve, dilute sulphuric acid 90m L with mass concentration of 0.7%, sodium metavanadate 0.24g and DMSO 0.93m L into a glass reactor, magnetically stirring at room temperature until the sodium metavanadate is fully dissolved, placing into a high-pressure kettle, heating to 160 ℃, carrying out oxidative hydrolysis in oxygen at 3.0MPa to obtain oxidative hydrolysate A of the rice straw, adding 1, 4-dioxane as an internal standard, and adding into the oxidative hydrolysate A1The content of formic acid in the oxidation hydrolysate A is 46mmol by HNMR measurement, and the yield of the formic acid is 85% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 55 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding 0.93m L DMSO and water required by the reaction into the mother liquor C, heating to 90 ℃, stirring for ten minutes, and fully reacting to obtain active mother liquor D;
4) putting 3.10g of rice straw with 200 meshes into active mother liquor D, putting into a high-pressure kettle, heating to 160 ℃, carrying out oxidation hydrolysis in 3.0MPa oxygen to obtain oxidation hydrolysis liquid of the rice straw, adding 1, 4-dioxane as an internal standard, and using1The HNMR determined the formic acid content of the hydrolysate to be 47mmol and the formic acid yield to be 87% (calculated on the C atoms of cellulose and hemicellulose in the charge).
Example 6, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass with trace DMSO comprises the following steps:
1) adding reed straw 3.64g of 200 mesh sieve with mass concentration of 0.7 percent into a glass reactorStirring with dilute sulfuric acid 90m L, sodium metavanadate 0.24g and DMSO 0.93m L at room temperature under magnetic force until sodium metavanadate is fully dissolved, placing in a high-pressure kettle, heating to 160 deg.C, performing oxidative hydrolysis in oxygen at 3.0MPa to obtain oxidative hydrolysate A of reed straw, adding 1, 4-dioxane as internal standard, and adding 1, 4-dioxane as internal standard1The content of formic acid in the oxidation hydrolysate A is 46mmol by HNMR measurement, and the yield of the formic acid is 85% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 55 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding 0.93m L DMSO and water required by the reaction into the mother liquor C, heating to 90 ℃, stirring for ten minutes, and fully reacting to obtain active mother liquor D;
4) placing 3.64g of reed straw with 200 mesh sieve in active mother liquor D, placing in a high-pressure kettle, heating to 160 ℃, carrying out oxidation hydrolysis in 3.0MPa oxygen to obtain oxidation hydrolysis liquid of reed straw, adding 1, 4-dioxane as internal standard, and using1The HNMR determined the formic acid content of the hydrolysate to be 46mmol and the formic acid yield to be 85% (calculated on the C atoms of cellulose and hemicellulose in the charge).
Example 7, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass through trace DMSO comprises the following steps:
1) adding 2.80g of bagasse with a 200-mesh sieve, 90m L of dilute sulfuric acid with the mass concentration of 0.7%, 0.24g of sodium metavanadate and 0.93m L of DMSO into a glass reactor, magnetically stirring at room temperature until the sodium metavanadate is fully dissolved, placing into an autoclave, heating to 160 ℃, carrying out oxidative hydrolysis in oxygen at 3.0MPa to obtain an oxidative hydrolysate A of the bagasse, adding 1, 4-dioxane as an internal standard, and using the 1, 4-dioxane as an internal standard1The content of formic acid in the oxidized hydrolysate A is 57mmol by HNMR measurement, and the yield of the formic acid is 106% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 55 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding a trace amount of 0.93m L DMSO and water required by the reaction into the mother liquor C, heating to 90 ℃, and stirring for ten minutes to fully react to obtain active mother liquor D;
4) placing 2.80g of bagasse with 200 mesh sieve in active mother liquor D, placing in a high-pressure kettle, heating to 160 deg.C, performing oxidation hydrolysis in 3.0MPa oxygen to obtain oxidation hydrolysis solution of bagasse, adding 1, 4-dioxane as internal standard, and using1HNMR determination of formic acid content in the hydrolysate of 55mmol and formic acid yield of 101% based on C atoms of cellulose and hemicellulose in the charge).
Example 8, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass with trace DMSO includes the following steps:
1) in a glass reactor, 2.60g of crushed cardboard paper, 90m L of dilute sulphuric acid with the mass concentration of 0.7%, 0.24g of sodium metavanadate and 0.93m L of DMSO are magnetically stirred at room temperature until the sodium metavanadate is fully dissolved, the cardboard paper is placed in an autoclave and heated to 160 ℃, and the cardboard paper is subjected to oxidative hydrolysis in oxygen at the pressure of 3.0MPa to obtain an oxidative hydrolysate A of the cardboard paper, 1, 4-dioxane is added as an internal standard, and the cardboard paper is subjected to oxidative hydrolysis by using the 1, 4-dioxane as the internal standard1The content of formic acid in the oxidized hydrolysate A is 59mmol by HNMR measurement, and the yield of the formic acid is 90% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 55 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding a trace amount of 0.93m L DMSO and water required by the reaction into the mother liquor C, heating to 90 ℃, and stirring for ten minutes to fully react to obtain active mother liquor D;
4) placing 2.60g of the crushed boxboard paper into the active mother liquor D, placing the box paper into a high-pressure kettle, heating the box paper to 160 ℃, and carrying out oxidative hydrolysis in 3.0MPa oxygen to obtain the boxboardOxidizing hydrolysis solution of paper, adding 1, 4-dioxane as internal standard, and treating with ethanol1HNMR determined the formic acid content of the hydrolysate to be 50mmol, and the formic acid yield to be 92% (calculated based on the C atoms of the cellulose and hemicellulose in the fed amount).
Example 9, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass with trace DMSO includes the following steps:
1) in a glass reactor, 2.89g of crushed waste newspaper, 90m L of dilute sulphuric acid with the mass concentration of 0.7%, 0.24g of sodium metavanadate and 0.93m L of DMSO are magnetically stirred at room temperature until the sodium metavanadate is fully dissolved, the mixture is placed in a high-pressure kettle, the high-pressure kettle is heated to 160 ℃, the oxidation hydrolysis is carried out in oxygen at the pressure of 3.0MPa to obtain oxidation hydrolysis liquid A of the waste newspaper, 1, 4-dioxane is added as an internal standard, and the internal standard is used1The content of formic acid in the oxidized hydrolysate A is 46mmol by HNMR measurement, and the yield of the formic acid is 86% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 55 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding 0.93m L DMSO and water required by the reaction into the mother liquor C, heating to 90 ℃, stirring for ten minutes, and fully reacting to obtain active mother liquor D;
4) placing 2.89g of crushed waste newspaper into active mother liquor D, placing the mother liquor into a high-pressure kettle, heating to 160 ℃, carrying out oxidation hydrolysis in 3.0MPa oxygen to obtain oxidation hydrolysis liquid of the waste newspaper, adding 1, 4-dioxane as an internal standard, and using1The HNMR determined the formic acid content of the hydrolysate to be 46mmol and the formic acid yield to be 86% (calculated on the C atoms of cellulose and hemicellulose in the charge).
Example 10, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass with trace DMSO includes the following steps:
1) 1.03g of corn straw with a 200-mesh sieve, 15m of dilute sulphuric acid L with the mass concentration of 0.5 percent and 0.07 percent are added into a glass reactorg sodium metavanadate and 1.00m L DMSO, magnetically stirring at room temperature until sodium metavanadate is fully dissolved, placing in a high-pressure kettle, heating to 140 deg.C, performing oxidation hydrolysis in air at 3.0MPa to obtain oxidation hydrolysate A of corn stalk, adding 1, 4-dioxane as internal standard, and adding 1, 4-dioxane as internal standard1The content of formic acid in the oxidized hydrolysate A is 10mmol by HNMR measurement, and the yield of the formic acid is 56% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 45 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding 1.00m L DMSO and water required by reaction into the mother liquor C, heating to 50 ℃, stirring for sixty minutes, and fully reacting to obtain active mother liquor D;
4) placing 1.03g of corn stalk with 200 mesh sieve in active mother liquor D, placing in a high-pressure kettle, heating to 140 deg.C, performing oxidation hydrolysis in 3.0MPa oxygen to obtain oxidation hydrolysis solution of corn stalk, adding 1, 4-dioxane as internal standard, and using1The HNMR determined the formic acid content of the hydrolysate to be 10mmol and the formic acid yield to be 56% (calculated on the C atoms of cellulose and hemicellulose in the charge).
Example 11, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass with trace DMSO includes the following steps:
1) adding 1.20g of reed straw with 200 meshes, 20m L of dilute sulphuric acid with the mass concentration of 0.8%, 0.05g of sodium metavanadate and 0.50m L DMSO into a glass reactor, magnetically stirring at room temperature until the sodium metavanadate is fully dissolved, placing the mixture into a high-pressure kettle, heating to 150 ℃, carrying out oxidative hydrolysis in air at 5.0MPa to obtain an oxidative hydrolysate A of the reed straw, adding 1, 4-dioxane as an internal standard, and using the 1, 4-dioxane as the internal standard1The content of formic acid in the oxidized hydrolysate A is 12mmol by HNMR measurement, and the yield of the formic acid is 60% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 50 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding 1.00m L DMSO and water required by the reaction into the mother liquor C, heating to 70 ℃, and stirring for thirty minutes to fully react to obtain active mother liquor D;
4) placing 1.20g of reed straw with 200 mesh sieve in active mother liquor D, placing in a high-pressure kettle, heating to 150 deg.C, performing oxidation hydrolysis in 5.0MPa air to obtain oxidation hydrolysis solution of reed straw, adding 1, 4-dioxane as internal standard, and using1The HNMR determined the formic acid content of the hydrolysate to be 12mmol and the formic acid yield to be 60% (calculated on the C atoms of cellulose and hemicellulose in the charge).
Example 12, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass with trace DMSO includes the following steps:
1) adding 0.92g of bagasse with a 200-mesh sieve, 40m L of dilute sulfuric acid with the mass concentration of 1.2%, 0.12g of sodium metavanadate and 0.31m L of DMSO into a glass reactor, magnetically stirring at room temperature until the sodium metavanadate is fully dissolved, placing into an autoclave, heating to 160 ℃, carrying out oxidative hydrolysis in air at 7.0MPa to obtain an oxidative hydrolysate A of the bagasse, adding 1, 4-dioxane as an internal standard, and using the 1, 4-dioxane as the internal standard1The content of formic acid in the oxidation hydrolysate A is 15mmol by HNMR measurement, and the yield of the formic acid is 83% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 60 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding 1.5m L DMSO and water required by the reaction into the mother liquor C, heating to 80 ℃, and stirring for twenty minutes to fully react to obtain active mother liquor D;
4) placing 0.92g of bagasse sieved by a 200 mesh sieve in an active mother liquor D, placing in a high-pressure kettle, heating to 160 ℃, and carrying out oxidative hydrolysis in 7.0MPa air to obtain the wheat strawAdding 1, 4-dioxane as internal standard into the oxidized hydrolysate of stalk1The HNMR determined the formic acid content of the hydrolysate to be 14mmol and the formic acid yield to be 80% (calculated on the C atoms of cellulose and hemicellulose in the charge).
Example 13, referring to fig. 1, a method for preparing formic acid by vanadium and sulfuric acid high-efficiency circulating catalysis of biomass with trace DMSO includes the following steps:
1) in a glass reactor, 0.85g of crushed cardboard paper, 45m L of dilute sulphuric acid with the mass concentration of 1.2%, 0.15g of sodium metavanadate and 2.00m L of DMSO are magnetically stirred at room temperature until the sodium metavanadate is fully dissolved, the crushed cardboard paper is placed in a high-pressure kettle and heated to 180 ℃, and the crushed cardboard paper is subjected to oxidation hydrolysis in oxygen at the pressure of 3.0MPa to obtain oxidation hydrolysis liquid A of the cardboard paper, 1, 4-dioxane is added as an internal standard, and the internal standard is used1The content of formic acid in the oxidation hydrolysate A is 12mmol by HNMR measurement, and the yield of the formic acid is 67% (calculated based on C atoms of cellulose and hemicellulose in the fed amount);
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 90 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is mainly an aqueous solution of formic acid, the solution can be subjected to subsequent separation or application, and the mother liquor C contains sulfuric acid and sodium metavanadate;
3) adding 0.5m L DMSO and water required by the reaction into the mother liquor C, heating to 95 ℃, and stirring for five minutes to fully react to obtain active mother liquor D;
4) placing 0.85g of pulverized cardboard paper in active mother liquor D, placing in a high-pressure kettle, heating to 180 deg.C, performing oxidation hydrolysis in 3.0MPa oxygen to obtain oxidation hydrolysis solution of cardboard paper, adding 1, 4-dioxane as internal standard, and adding water1HNMR determined that the formic acid content of the hydrolysate was 11mmol and the formic acid yield was 63% (calculated on the C atoms of cellulose and hemicellulose in the charge).
Claims (6)
1. A method for preparing formic acid by vanadium and sulfuric acid efficient circulating catalysis biomass with trace DMSO is characterized by comprising the following steps:
1) placing biomass or domestic garbage in dilute sulfuric acid with mass concentration of 0.5-1.5%, then adding sodium metavanadate and DMSO, and carrying out oxidative hydrolysis at the temperature of 140-;
wherein, 15-45m L dilute sulphuric acid, 0.05-0.15g sodium metavanadate and 0-2m L DMSO are added into each 1g biomass or domestic garbage;
2) separating the oxidized hydrolysate A by a reduced pressure distillation method at 45-65 ℃ to obtain a fraction B and a mother liquor C, wherein the fraction B is an aqueous solution of formic acid, the aqueous solution of formic acid is subjected to subsequent separation or application, and the mother liquor C is a catalytic system of concentrated sulfuric acid and sodium metavanadate;
3) adding a trace amount of DMSO and water required by the reaction into the mother liquor C, heating to 50-95 ℃, stirring for five minutes to one hour, and fully combining to obtain active mother liquor D;
wherein 0.1-0.5m L DMSO is added into each 1g biomass or domestic garbage;
4) putting the biomass or the household garbage with the same mass as that in the step 1) into the active mother liquor D, and carrying out oxidative hydrolysis at the temperature of 140-170 ℃ under the pressure of 2.0-7.0MPa to quantitatively convert cellulose and hemicellulose into a formic acid solution to obtain an oxidative hydrolysate.
2. The method for preparing formic acid by using vanadium and sulfuric acid to efficiently catalyze biomass in a circulating manner through trace DMSO according to claim 1, which is characterized in that: adding the oxidation hydrolysate obtained in the step 4) into the oxidation hydrolysate A obtained in the step 2), and circulating the step 2), the step 3) and the step 4) to realize the circulation of the system.
3. The method for preparing formic acid by using vanadium and sulfuric acid to efficiently catalyze biomass in a circulating manner through trace DMSO according to claim 1, which is characterized in that: the biomass adopts wheat straw, corn straw, rice straw or reed straw.
4. The method for preparing formic acid by using vanadium and sulfuric acid to efficiently catalyze biomass in a circulating manner through trace DMSO according to claim 1, which is characterized in that: the domestic garbage is bagasse, boxboard paper or waste newspaper.
5. The method for preparing formic acid by using vanadium and sulfuric acid to efficiently catalyze biomass in a circulating manner through trace DMSO according to claim 1, which is characterized in that: the oxidative hydrolysis of the step 1) and the step 4) is carried out in oxygen or air.
6. The method for preparing formic acid by using vanadium and sulfuric acid to efficiently catalyze biomass in a circulating manner through trace DMSO according to claim 1, which is characterized in that: the water supplemented in the step 3) is distilled circulating water.
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| CN106966359A (en) * | 2017-03-28 | 2017-07-21 | 西安交通大学 | The method that the catalysis of transition metal iridium prepares hydrogen from the hydrolyzate of biomass and house refuse |
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| CN113264504B (en) * | 2021-06-08 | 2024-02-06 | 西咸新区青氢华屹能源科技有限公司 | Method for recycling biomass efficient hydrogen production catalytic system |
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