CN104557514B - A kind of biomass-making by rich cellulose is for the method for oxyacetic acid - Google Patents
A kind of biomass-making by rich cellulose is for the method for oxyacetic acid Download PDFInfo
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- CN104557514B CN104557514B CN201310475557.6A CN201310475557A CN104557514B CN 104557514 B CN104557514 B CN 104557514B CN 201310475557 A CN201310475557 A CN 201310475557A CN 104557514 B CN104557514 B CN 104557514B
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- 239000002253 acid Substances 0.000 title claims abstract description 53
- 229920002678 cellulose Polymers 0.000 title claims abstract description 40
- 239000001913 cellulose Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002028 Biomass Substances 0.000 claims abstract description 17
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 150000003751 zinc Chemical class 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000005286 illumination Methods 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 235000010980 cellulose Nutrition 0.000 claims description 37
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 17
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 10
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 10
- 241001330002 Bambuseae Species 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 10
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 10
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 10
- 239000011425 bamboo Substances 0.000 claims description 10
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 10
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 10
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical group [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 150000003384 small molecules Chemical class 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 14
- 239000011521 glass Substances 0.000 description 10
- 241000219000 Populus Species 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 239000011094 fiberboard Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 238000001782 photodegradation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 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 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- -1 hydroxyl free radical Chemical class 0.000 description 1
- JYVNDCLJHKQUHE-UHFFFAOYSA-N hydroxymethyl acetate Chemical compound CC(=O)OCO JYVNDCLJHKQUHE-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000003466 welding Methods 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
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
Abstract
The invention discloses the method for a kind of biomass-making by rich cellulose for oxyacetic acid, with the biomass of rich cellulose for raw material, infiltrated and be adjusted in weakly acidic oxygenant through pH value regulator, take ferrous salt as Fenton's reaction catalyzer, zinc salt is secondary catalysts, under illumination condition, carry out Fenton's reaction, after reaction terminates, be separated by filtration and obtain described oxyacetic acid.The present invention urgees Fenton's reaction by light to produce free radical, coordinates simultaneously, realize the selective regulation of product with secondary catalysts.The step that present method prepares oxyacetic acid is simple, does not need heating and pressurizing, is easy to control; Used catalyst cheap, degradation process is without the need to organic solvent; Namely the preparation achieving product in a mild condition transforms, and the small-molecule starting material conversion method comparing existing petroleum-based sources has clear superiority, be a kind ofly to have a high potential, the oxyacetic acid production method of efficient economy.
Description
Technical field
The present invention relates to the preparation method of oxyacetic acid, particularly relate to the method for a kind of biomass-making by rich cellulose for oxyacetic acid.
Background technology
Oxyacetic acid another name oxyacetic acid or glycolic acid, be the acid of the simplest aliphatic hydroxyl, be mainly present in sugarcane beet and immature grape, but content be lower at occurring in nature.Oxyacetic acid is a kind of important organic synthesis intermediate and Chemicals, it is of wide application: can be used as clean-out system (be a kind of cost-effective clean-out system as the oxyacetic acid of 2% and the formic acid of 1% are made into mixing acid, be suitable for clean air conditioning machinery and remove the incrustation scale of super critical boiler), the batching of sterilant, fiber dyeing agent, purification agent, welding compound, varnish batching, copper erosion agent, tackiness agent, petroleum demulsifier and metal chelator etc.Sodium salt, the sylvite of oxyacetic acid can be used as electroplate liquid additive, for the production of organic synthesis platform chemicals such as ethylene glycol.Oxyacetic acid is still for the preparation of the important source material of biological degradation novel material simultaneously.Country is one of basic chemical industry product oxyacetic acid being classified as main exploitation in 10th Five-Year Plan, is enough to illustrate its importance in chemical industry.
Domestic oxyacetic acid market potential demand is about 100,000 tons, market value aspect domestic at about 20000 yuan/ton, import at about 30000 yuan/ton.At present, the technology of preparing of domestic oxyacetic acid mainly contains two kinds of methods.First method is, take Mono Chloro Acetic Acid as raw material, under sodium hydroxide and methyl alcohol exist, be obtained by reacting hydroxy methyl acetate, and then hydrolysis obtains oxyacetic acid.This technical process is long, and yield is low, and has the defects such as the serious and environmental pollution of small scale, equipment corrosion, makes the cost of production oxyacetic acid high.The cyanide process that another kind is raw material with formaldehyde and prussic acid (or sodium-chlor), owing to using the prussiate of severe toxicity, in production operation, security requirement is higher.Due to above two kinds of methods be all based on small molecules between conversion prepare oxyacetic acid, technique falls behind, yield poorly, environmental pollution is serious, the second-rate demand that far can not meet market, therefore inhibits widely using of oxyacetic acid to a certain extent.
As can be seen here, prepare oxyacetic acid based on the conversion of small-molecule chemical product and also there is certain technological deficiency, do not have feasible technology to coordinate the greenization and the recyclability that realize raw material sources yet.
As everyone knows, renewable natural polymer the abundantest in the Mierocrystalline cellulose world today that to be plant and algae etc. synthesized by photosynthesis, its annual production reaches more than one hundred billion ton according to estimates.Though it is the important chemical such as ethanol, ethylene glycol, lactic acid that prior art to have related to Mierocrystalline cellulose through conversion of glucose, be that the technology that oxyacetic acid prepared by raw material does not also have report with Mierocrystalline cellulose.
Summary of the invention
For the deficiencies in the prior art, the invention provides the novel method that a kind of biomass degradation based on rich cellulose prepares oxyacetic acid.Present method implementation condition is gentle, simple to operate, is easy to regulating and controlling, again because raw material sources are extensive, cheap, has wide industrial prospect.
The invention discloses the method for a kind of biomass-making by rich cellulose for oxyacetic acid, comprise the steps: with the biomass of rich cellulose as raw material, infiltrated and be adjusted in weakly acidic oxygenant through pH value regulator, take ferrous salt as Fenton's reaction catalyzer, zinc salt is secondary catalysts, under illumination condition, carry out Fenton's reaction, after reaction terminates, be separated by filtration and obtain described oxyacetic acid.
The effective ways of to be the Fenton's reaction of the superoxide of representative with hydrogen peroxide by Fenton's reaction catalyzer-ferrous salt catalytic decomposition the be hydroxyl free radical generating strong oxidizing property, the radiation of light can accelerate the self-decomposition of Fenton's reaction and hydrogen peroxide, the degraded of the biomass of further acceleration rich cellulose, improves reaction efficiency; Zinc salt as secondary catalysts has the effect that selective regulation product generates, and it adds the generation that can suppress by-product acetic acid, thus impels DeR to carry out to the direction generating oxyacetic acid.
The biomass of rich cellulose that the present invention uses can be commercial natural celluloses as absorbent cotton or containing the higher wood powder, bamboo powder etc. of cellulose components, also can be through the paper pulp fiber of process or the Microcrystalline Cellulose of recrystallization.
As preferably, when the biomass degradation carrying out above-mentioned rich cellulose is produced, with the biomass of rich cellulose for benchmark, by mass percentage: the total addition level of oxygenant is 20% ~ 1000%; The total addition level of Fenton's reaction catalyzer ferrous salt is 0.1% ~ 10%; The total addition level of zinc salt is 5 ~ 50%.Ferrous salt catalyzer is very few and the too much speed of reaction that all causes is on the low side; And zinc salt to cross selectivity of product at least poor, too high then speed of reaction is on the low side.Only under above-mentioned optimum condition, rate of decomposition can reach best with selectivity of product.
As preferably, described oxygenant is superoxide, and its general formula is R-O-O-R', and wherein, R and R' is respectively H, C
1~ C
5alkyl or metal ion, the alkyl selecting carbon number to be less than 5 is to guarantee its solubleness in water.Further preferably, described oxygenant is hydrogen peroxide or sodium peroxide.
As preferably, described Fenton's reaction catalyzer is ferrous sulfate or iron protochloride.
As preferably, described pH value regulator is mineral acid or organic acid, for the pH value of oxygenant is adjusted to 3 ~ 6.Wherein the representative of mineral acid is sulfuric acid, hydrochloric acid etc., and organic acid representative is acetic acid.The form of DeR speed and gained degraded product can be regulated and controled by the adjustment of pH.
Zinc salt add the generation that can suppress other by products, for requirement solubleness and not introducing being difficult to the foreign ion removed, preferred secondary catalysts is zinc chloride or zinc sulfate.
Carry out in illumination degrading process, as preferably, described light source is visible ray or UV-light, and the power of light source is 10W ~ 1000W, and the time of illumination degrading is 1 ~ 10 hour.
Degraded product of the present invention mainly oxyacetic acid and byproduct formic acid after testing.Because oxyacetic acid fusing point is 75 ~ 80 DEG C and difficult volatilization, and formic acid boiling point is lower and volatile.Therefore formic acid can be separated by the method for distillation or underpressure distillation at about 80 DEG C.And metal salt catalyst remaining in solution can be removed by adding the method precipitation of basic cpd as soda ash; Also according to metal-salt and oxyacetic acid solvability difference in organic solvent, repeatedly can extract by adding ethyl acetate and purify.
The preparation method of the oxyacetic acid that the present invention proposes is the principle of the biomass degradation based on rich cellulose, be characterized in the mixed catalyst employing ferrous salt and zinc salt, urge Fenton's reaction to the biomass of rich cellulose of degrading through light, and regulation and control reaction is carried out to the direction generating oxyacetic acid.The step that the method prepares oxyacetic acid is simple, and be easy to control, degradation process is not with an organic solvent, the catalyzer used is cheap, without the need to heating and pressurizing, achieving the condition gentleer than existing small molecules method for transformation, is the oxyacetic acid production method of efficient economy.
Embodiment
For a better understanding of the present invention, set forth technical scheme of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
The biomass of the rich cellulose that the present embodiment is used are the fiber board after baking oven is dried at 80 DEG C.
Mierocrystalline cellulose photodegradation reaction is carry out in the disc open glass container of 10cm at a diameter.Reactor is placed in immediately below ultraviolet lamp source, and ultraviolet lamp wavelength is 365nm, and power is 500W, and the distance between cardboard surfaces and ultraviolet lamp source is 8cm.
The implementation step of the present embodiment is as follows:
First 1g fiber board is placed in disc Glass Containers, then container is placed in ice-water bath.Be about the pH regulator to 4 of the hydrogen peroxide of 30% by mass concentration with dilute hydrochloric acid, then get the hydrogen peroxide being equivalent to 1000% fiber board quality to add fiber board complete wetting in container, add the zinc chloride of 20% fiber board quality again, last 1% solution of ferrous chloride (being equivalent to 1% fiber board quality) slowly adding 1mL again, after being added dropwise to complete, container is placed in irradiation under UV-light, the irradiation-induced degradation time is 2 hours.
Cleaned twice and be placed in baking oven drying by undissolved solid distilled water after having reacted and weigh, the degradation rate of fiber board is 65%, and the productive rate of oxyacetic acid is 43%.
Embodiment 2:
The biomass of the rich cellulose that the present embodiment is used are the medical absorbent cotton after baking oven is dried at 80 DEG C.
Mierocrystalline cellulose photodegradation reaction is carry out in the disc open glass container of 10cm at a diameter.Reactor is placed in immediately below ultraviolet lamp source, and ultraviolet lamp wavelength is 365nm, and power is 500W, and the distance between absorbent cotton surface and ultraviolet lamp source is 8cm.
The implementation step of the present embodiment is as follows:
1g absorbent cotton is placed in disc Glass Containers, then disk is placed in ice-water bath.Be about the pH regulator to 5 of the hydrogen peroxide of 30% by mass concentration with dilute sulphuric acid, then get the hydrogen peroxide being equivalent to 500% absorbent cotton quality to add absorbent cotton complete wetting in container, add the zinc sulfate of 30% absorbent cotton quality again, last 2% copperas solution (being equivalent to 2% absorbent cotton quality) slowly adding 1ml again, after being added dropwise to complete, container is placed in irradiation under UV-light, the irradiation-induced degradation time is 3 hours.
Cleaned twice and be placed in baking oven drying by undissolved solid distilled water after having reacted and weigh, the degradation rate of absorbent cotton is 73%, and the productive rate of oxyacetic acid is 52%.
Embodiment 3:
The biomass of the rich cellulose that the present embodiment is used are the Poplar Powder after baking oven is dried at 80 DEG C.
Mierocrystalline cellulose photodegradation reaction is carry out in the disc open glass container of 10cm at a diameter.Reactor is placed in immediately below ultraviolet lamp source, and ultraviolet lamp wavelength is 365nm, and power is 500W, and the distance between Poplar Powder surface and ultraviolet lamp source is 8cm.
The implementation step of the present embodiment is as follows:
1g Poplar Powder is placed in disc Glass Containers, then disk is placed in ice-water bath.Be about the pH regulator to 3 of the hydrogen peroxide of 30% by mass concentration with dilute sulphuric acid, then get the hydrogen peroxide being equivalent to 1000% Poplar Powder quality to add Poplar Powder complete wetting in container, add the zinc sulfate of 50% Poplar Powder quality again, last 4% copperas solution (being equivalent to 4% Poplar Powder quality) slowly adding 1ml again, after being added dropwise to complete, container is placed in irradiation under UV-light, the irradiation-induced degradation time is 2 hours.
Cleaned twice and be placed in baking oven drying by undissolved solid distilled water after having reacted and weigh, the degradation rate of Poplar Powder is 77%, and the productive rate of oxyacetic acid is 32%.
Embodiment 4:
The biomass of the rich cellulose that the present embodiment is used are the bamboo powder after baking oven is dried at 80 DEG C.
Mierocrystalline cellulose photodegradation reaction is carry out in the disc open glass container of 10cm at a diameter.Reactor is placed in immediately below ultraviolet lamp source, and ultraviolet lamp wavelength is 365nm, and power is 50W, and the distance between bamboo powder surface and ultraviolet lamp source is 8cm.
The implementation step of the present embodiment is as follows:
1g bamboo powder is placed in disc Glass Containers, then disk is placed in ice-water bath.Be about the pH regulator to 4 of the hydrogen peroxide of 30% by mass concentration with dilute hydrochloric acid, then get the hydrogen peroxide being equivalent to 1000% bamboo opaque amount to add bamboo powder complete wetting in container, add the zinc chloride of 30% bamboo opaque amount again, last 1% solution of ferrous chloride (being equivalent to 3% bamboo opaque amount) slowly adding 3mL again, after being added dropwise to complete, container is placed in irradiation under UV-light, the irradiation-induced degradation time is 10 hours.
Cleaned twice and be placed in baking oven drying by undissolved solid distilled water after having reacted and weigh, the degradation rate of bamboo powder is 53%, and the productive rate of oxyacetic acid is 24%.
Embodiment 5:
The biomass of the rich cellulose that the present embodiment is used are the Microcrystalline Cellulose after baking oven is dried at 80 DEG C.
Mierocrystalline cellulose photodegradation reaction is carry out in the disc open glass container of 10cm at a diameter.Reactor is placed in immediately below ultraviolet lamp source, and ultraviolet lamp wavelength is 365nm, and power is 500W, and the distance between Microcrystalline Cellulose surface and ultraviolet lamp source is 8cm.
The implementation step of the present embodiment is as follows:
1g Microcrystalline Cellulose is placed in disc Glass Containers, then disk is placed in ice-water bath.Be about the pH regulator to 5 of the hydrogen peroxide of 30% by mass concentration with dilute hydrochloric acid, then get the hydrogen peroxide being equivalent to 800% Microcrystalline Cellulose quality to add Microcrystalline Cellulose complete wetting in container, add the zinc chloride of 30% Microcrystalline Cellulose quality again, last 1% solution of ferrous chloride (being equivalent to 3% Microcrystalline Cellulose quality) slowly adding 3mL again, after being added dropwise to complete, container is placed in irradiation under UV-light, the irradiation-induced degradation time is 3 hours.
Cleaned twice and be placed in baking oven drying by undissolved solid distilled water after having reacted and weigh, the degradation rate of Microcrystalline Cellulose is 61%, and the productive rate of oxyacetic acid is 45%.
Claims (8)
1. one kind by the biomass-making of rich cellulose for the method for oxyacetic acid, it is characterized in that, comprise the steps: with the biomass of rich cellulose as raw material, infiltrated and be adjusted in weakly acidic oxygenant through pH value regulator, take ferrous salt as Fenton's reaction catalyzer, zinc salt is secondary catalysts, under illumination condition, carry out Fenton's reaction, after reaction terminates, be separated by filtration and obtain described oxyacetic acid; Described oxygenant is superoxide, and its general formula is R-O-O-R', and wherein, R and R' is respectively H, C
1~ C
5alkyl or metal ion.
2. the biomass-making by rich cellulose according to claim 1 is for the method for oxyacetic acid, and it is characterized in that, the biomass of described rich cellulose are absorbent cotton, cardboard, wood powder, bamboo powder or Microcrystalline Cellulose.
3. the biomass-making by rich cellulose according to claim 1 is for the method for oxyacetic acid, it is characterized in that, with the biomass of rich cellulose for benchmark, by mass percentage: the total addition level of oxygenant is 20% ~ 1000%; The total addition level of ferrous salt is 0.1% ~ 10%; The total addition level of zinc salt is 5 ~ 50%.
4. the biomass-making by rich cellulose according to claim 1 is for the method for oxyacetic acid, and it is characterized in that, described oxygenant is hydrogen peroxide or sodium peroxide.
5. the biomass-making by rich cellulose according to claim 1 is for the method for oxyacetic acid, and it is characterized in that, described ferrous salt is ferrous sulfate or iron protochloride.
6. the biomass-making by rich cellulose according to claim 1 is for the method for oxyacetic acid, and it is characterized in that, described zinc salt is zinc chloride or zinc sulfate.
7. the biomass-making by rich cellulose according to claim 1 is for the method for oxyacetic acid, and it is characterized in that, described pH value regulator is mineral acid or organic acid.
8. the biomass-making by rich cellulose according to claim 1 is for the method for oxyacetic acid, and it is characterized in that, the light source of described illumination is visible ray or UV-light, and the power of light source is 10W ~ 1000W, and light application time is 1 ~ 10 hour.
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| CN101184717A (en) * | 2005-05-27 | 2008-05-21 | 旭化成化学株式会社 | Method for producing glycolic acid |
| JP2009137891A (en) * | 2007-12-06 | 2009-06-25 | Lion Corp | Method for producing dihydroxyacetone or glycolic acid |
| JP2011016782A (en) * | 2009-07-10 | 2011-01-27 | Lion Corp | Method for producing glycolic acid, and glycolic acid-containing composition |
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| CN101184717A (en) * | 2005-05-27 | 2008-05-21 | 旭化成化学株式会社 | Method for producing glycolic acid |
| JP2009137891A (en) * | 2007-12-06 | 2009-06-25 | Lion Corp | Method for producing dihydroxyacetone or glycolic acid |
| JP2011016782A (en) * | 2009-07-10 | 2011-01-27 | Lion Corp | Method for producing glycolic acid, and glycolic acid-containing composition |
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