CN102653506B - Method for preparing catechol from lignin - Google Patents
Method for preparing catechol from lignin Download PDFInfo
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- CN102653506B CN102653506B CN201210073796.4A CN201210073796A CN102653506B CN 102653506 B CN102653506 B CN 102653506B CN 201210073796 A CN201210073796 A CN 201210073796A CN 102653506 B CN102653506 B CN 102653506B
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- hydroxyanisole
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229920005610 lignin Polymers 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000012298 atmosphere Substances 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000010792 warming Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000010025 steaming Methods 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003929 acidic solution Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 9
- 229960001867 guaiacol Drugs 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000002803 fossil fuel Substances 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 230000009466 transformation Effects 0.000 description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- BWUICJCIIJZMPE-UHFFFAOYSA-N benzene-1,2-diol;2-methoxyphenol Chemical compound OC1=CC=CC=C1O.COC1=CC=CC=C1O BWUICJCIIJZMPE-UHFFFAOYSA-N 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950009195 phenylpropanol Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
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Abstract
The invention discloses a method for preparing catechol from lignin, which comprises the following steps: after mixing alkali lignin and a solution, adding the mixture into a high-pressure reaction kettle, and reacting in an inert gas atmosphere to generate guaiacol; and hydrolyzing the guaiacol to obtain the catechol. The invention overcomes the defect of low selectivity in the prior art, solves the problem that the raw material phenol is derived from non-renewable fossil fuels, and provides a method for preparing catechol from the reactant guaiacol prepared by degrading lignin, which is often used as waste in renewable biomass.
Description
Technical field
The present invention relates to the preparation method of pyrocatechol, more particularly, a kind of xylogen that adopts is the method for waste pyrocatechol.
Background technology
Pyrocatechol is chemical important in chemical industry.50% pyrocatechol is as producing sterilant, and remaining,, as producing spices or medicine, can also be used as photographic developer.By the ethylize thanatol obtain of pyrocatechol, can be used for producing vanillin food grade,1000.000000ine mesh, vanillin food grade,1000.000000ine mesh is to produce chocolate important component.Piperonylaldehyde is also that raw material makes by pyrocatechol, and piperonylaldehyde is typically used as seasonings.The industrialized preparing process of pyrocatechol is hydoxylating phenol at present, and its process is that phenol can make neighbour, Resorcinol through oxide compound (peroxy acid, hydrogen peroxide etc.) oxidation, through separation, can obtain pyrocatechol.The shortcoming of this method is poor selectivity, has by product Resorcinol to generate.
Along with fossil oil approach exhaustion day by day, this renewable energy source of biomass is paid close attention to widely.Lignocellulose three major polymers: cellulose, hemicellulose and xylogen form.There is extensive work report to obtain ethanol by cellulose degradation, sugar, the chemical such as furfural, and xylogen has just gone out of use.In addition, a large amount of nights containing xylogen also can be discharged in paper mill.At present, there is a small amount of xylogen for combustion heat supplying.Due to the complex construction of xylogen, increased the difficulty of studying and utilize it.Xylogen is to be formed by connecting by three kinds of phenyl propanol monomers, and mode of connection has ehter bond connection to be connected with C-C key.Therefore by lignin degradation, obtaining phenols chemical is a green, continuable route, but by the pyrocatechol that hydroxyanisole obtains high yield, there is no at present report.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, overcome the not high problem of selectivity of prior art, solve the problem that raw material phenol derives from non-renewable fossil oil simultaneously, providing a kind of is that reactant is prepared pyrocatechol based on the reproducible biomass hydroxyanisole that wherein the long lignin degradation for the treatment of as waste obtains, this be one renewable, green technique, yield reaches 90%.
Object of the present invention is achieved by following technical proposals:
By xylogen, produced a method for pyrocatechol, according to following step, carry out:
First, after alkali lignin is mixed with solution, add in autoclave, utilize rare gas element protection, making original pressure in reactor is 0MPa, is warming up to 250-350 ℃, and stirring reaction 1h-5h, after reaction finishes, suction filtration, with dichloromethane extraction, then revolves steaming, obtains hydroxyanisole;
Adopt again hydroxyanisole hydrolysis to produce pyrocatechol, according to following step, carry out: hydroxyanisole and acidic solution are joined in reaction vessel, after closed reaction vessel, utilize rare gas element or hydrogen to purge, to get rid of oxygen, keep reaction vessel internal pressure stable, then after temperature reaction certain hour, can obtain pyrocatechol.
In technique scheme, the solution mixing with alkali lignin is the mixing solutions of deionized water or ethanol or water and ethanol (volume ratio 1: 1), and the solution that is preferably 0.5g alkali lignin and 70mL mixes; Described rare gas element is selected nitrogen, argon gas or helium.
In such scheme, described acidic solution is salt aqueous acid or the aqueous solution that presents acid salt, for example iron(ic) chloride or cupric chloride, it should be noted that in the present invention program, the hydrolysis that acidic solution is hydroxyanisole provides acid water surrounding atmosphere, and (in the aqueous hydrochloric acid of low pH, acid catalysis is principal reaction path to carry out corresponding catalysis, approaching under neutrality or solutions of weak acidity, is water catalyzed reaction).Need to guarantee that reaction system is mixed in the add-on of acidic solution after, in reaction vessel, the pH of reaction system is 1.0-2.0, is preferably 1.5-2.0.
In such scheme, after encloses container, need oxygen wherein to be got rid of, can select rare gas element (for example nitrogen, argon gas, helium) to carry out, also can select hydrogen to carry out; After getting rid of oxygen, need to utilize the gas using to maintain certain pressure in reaction vessel, and within the reaction times continual and steady (not occurring significantly changing), for the hydrolysis of hydroxyanisole provides atmosphere.By experimental data, found, hydrogen is that reaction atmosphere is done the high twice of yield of reaction atmosphere than nitrogen; Therefore and hydrogen pressure is higher, yield is higher, can select first to utilize rare gas element to carry out oxygen eliminating, and then pass into hydrogen, and relief reaction is carried out in atmosphere of hydrogen, and container inner pressure is stabilized in 0-2MPa, is more preferably 0-1MPa.
In such scheme, after container inner pressure is stable, heats up and react, temperature is 280-350 ℃, the reaction times is 1h-5h, can in reaction process, by machinery or magnetic force, stir.
In sum, the reaction conditions of whole reaction system is following one of several:
(1) selecting rare gas element is atmosphere, and in reaction vessel, the pH of reaction system is 1.0-2.0, is preferably 1.5-2.0; Container inner pressure is stabilized in 0-2MPa, is more preferably 0-1MPa; Temperature is 280-350 ℃, preferably 280-300 ℃; Reaction times is 1h-5h, preferably 1h-3h
(2) selecting hydrogen gas is atmosphere, and in reaction vessel, the pH of reaction system is 1.0-2.0, is preferably 1.5-2.0; Container inner pressure is stabilized in 0-2MPa, is more preferably 0-1MPa; Temperature is 280-350 ℃, preferably 280-300 ℃; Reaction times is 1h-5h, preferably 1h-3h
In technique scheme, after the first step reaction finishes, Agilent gas chromatography combined with mass spectrometry (Agilent 6890-5973 for last solution, 30m * 0.25mm * 0.25 μ m HP-5MS capillary column, it is 60 degree that post case is set to starting temperature, temperature rise rate is 10 degree per minutes, is warming up to 250 degree) do qualitative sign, qualitative results is that product is pyrocatechol.Quantivative approach is marker method, and use Agilent chromatogram (Agilent 6890, GC-FID, and 50m * 0.2mm * 0.25 μ m HP-5capillary column, it is 60 degree that post case is set to starting temperature, temperature rise rate is 10 degree per minutes, is warming up to 250 degree).The color atlas of the Gc-ms of dichloromethane extraction liquid after Tu1Shi lignin reaction (X-coordinate is time (min), and ordinate zou is the intensity at peak).Climax about 6.2 minutes is the peak of hydroxyanisole.Two peaks of 8 minutes are 4 (3)-methyl, 2-methoxyphenol, and the peak about 10 minutes is 4-ethyl, 2-methoxyphenol, the peak of 11 minutes is 4-propyl group, 2-methoxyphenol.Fig. 2 is the bar graph (X-coordinate is nuclear-cytoplasmic ratio, and ordinate zou is intensity) of 6.2 minutes hydroxyanisoles in figure A.Fig. 3 is the standard bar graph of hydroxyanisole in spectrum storehouse.Comparison diagram 2 and Fig. 3, can see three standard fragments of hydroxyanisole, 81,109 and 124.
In such scheme, after second step reaction finishes, Agilent gas chromatography combined with mass spectrometry (Agilent 6890-5973 for reaction soln, 30m * 0.25mm * 0.25 μ m HP-5MS capillary column, it is 60 degree that post case is set to starting temperature, temperature rise rate is 10 degree per minutes, is warming up to 250 degree) do qualitative sign, qualitative results is that product is pyrocatechol.Quantivative approach is marker method, and use Agilent chromatogram (Agilent 6890, GC-FID, and 50m * 0.2mm * 0.25 μ mHP-5capillary column, it is 60 degree that post case is set to starting temperature, temperature rise rate is 10 degree per minutes, is warming up to 250 degree).As shown in accompanying drawing 1-3, Fig. 1 is the color atlas (X-coordinate is time (min), and ordinate zou is the intensity at peak) of the GC-MS of solution after hydroxyanisole reaction.The peak of 5 minutes is internal standard substance ethylbenzene, and the peak of 6.5 minutes is reactant hydroxyanisole, and the peak of 8 minutes is product pyrocatechol.Fig. 2 be 8 minutes peak (pyrocatechol) bar graph (X-coordinate is nuclear-cytoplasmic ratio, and ordinate zou is intensity).Fig. 3 is the standard bar graph of pyrocatechol in spectrum storehouse.Comparison diagram 2 and Fig. 3, can see three fragment peaks of pyrocatechol, 64,81 and 110.
The industrialized preparing process of pyrocatechol is hydoxylating phenol at present, and its process is that phenol can make neighbour, Resorcinol through oxide compound (peroxy acid, hydrogen peroxide etc.) oxidation, through separation, can obtain pyrocatechol.The shortcoming of this method is poor selectivity, has by product Resorcinol to generate.And prior art is the method based on hydroxylation phenol, and phenol derives from non-renewable fossil oil.The reaction production line of the technical scheme " xylogen-hydroxyanisole-pyrocatechol " that the present invention proposes, generally be divided into the first step for " xylogen-hydroxyanisole ", second step is " hydroxyanisole-pyrocatechol ", it is a reproducible production line, method than the existing phenol based on fossil oil refining is wanted environmental protection, sustainable.
Accompanying drawing explanation
Fig. 1 is the color atlas (X-coordinate is time (min), and ordinate zou is the intensity at peak) of the Gc-ms of dichloromethane extraction liquid after alkali lignin reaction
Fig. 2 is the bar graph (X-coordinate is nuclear-cytoplasmic ratio, and ordinate zou is intensity) of 6.2 minutes hydroxyanisoles in Fig. 1
Fig. 3 is the standard bar graph (X-coordinate is nuclear-cytoplasmic ratio, and ordinate zou is intensity) of hydroxyanisole in spectrum storehouse
Fig. 4 is the color atlas (X-coordinate is time (min), and ordinate zou is the intensity at peak) of the GC-MS of solution after hydroxyanisole reaction
Fig. 5 be 8 minutes peak (pyrocatechol) bar graph (X-coordinate is nuclear-cytoplasmic ratio, and ordinate zou is intensity)
Fig. 6 is the standard bar graph (X-coordinate is nuclear-cytoplasmic ratio, and ordinate zou is intensity) of pyrocatechol in spectrum storehouse
Embodiment
Below in conjunction with specific embodiment, further illustrate technical scheme of the present invention.
Embodiment 1
First, after 0.5g alkali lignin is mixed with 70mL deionized water, add in autoclave, utilize nitrogen protection, making original pressure in reactor is 0MPa, is warming up to 250 ℃, and stirring reaction 5h, after reaction finishes, suction filtration, with dichloromethane extraction, then revolves steaming, obtains hydroxyanisole;
The aqueous hydrochloric acid 70mL of 0.5g hydroxyanisole and pH=1.8 is joined in reactor, when reaction atmosphere is H
2, original pressure 1MPa, is warming up to 280 ℃, and the reaction times is 3h, and the transformation efficiency of hydroxyanisole is 100%, and the yield of pyrocatechol is 90%.
First, after 0.5g alkali lignin is mixed with 70mL deionized water, add in autoclave, utilize nitrogen protection, making original pressure in reactor is 0MPa, is warming up to 350 ℃, and stirring reaction 3h, after reaction finishes, suction filtration, with dichloromethane extraction, then revolves steaming, obtains hydroxyanisole;
The aqueous hydrochloric acid 70mL of 0.5g hydroxyanisole and pH=1.5 is joined in reactor, when reaction atmosphere is H
2, original pressure 0.5MPa, is warming up to 280 ℃, and the reaction times is 3h, and the transformation efficiency of hydroxyanisole is 93%, and the yield of pyrocatechol is 84%.
Embodiment 3
First, after 0.5g alkali lignin is mixed with 70mL deionized water, add in autoclave, utilize nitrogen protection, making original pressure in reactor is 0MPa, is warming up to 300 ℃, and stirring reaction 4h, after reaction finishes, suction filtration, with dichloromethane extraction, then revolves steaming, obtains hydroxyanisole;
The aqueous hydrochloric acid 70mL of 0.5g hydroxyanisole and pH=1.8 is joined in reactor, when reaction atmosphere is H
2, original pressure 0MPa, is warming up to 300 ℃, and the reaction times is 1h, and the transformation efficiency of hydroxyanisole is 83%, and the yield of pyrocatechol is 76%.
First, after 0.5g alkali lignin is mixed with 70mL ethanol, add in autoclave, utilize nitrogen protection; making original pressure in reactor is 0MPa, is warming up to 320 ℃, and stirring reaction 1h, after reaction finishes; suction filtration, with dichloromethane extraction, then revolves steaming, obtains hydroxyanisole
The aqueous hydrochloric acid 70mL of 0.5g hydroxyanisole and pH=2.0 is joined in reactor, when reaction atmosphere is H
2, original pressure 2MPa, is warming up to 350 ℃, and the reaction times is 5h, and the transformation efficiency of hydroxyanisole is 97%, and the yield of pyrocatechol is 87%.
Embodiment 5
First; after 0.5g alkali lignin is mixed with the mixing solutions (volume ratio is 1: 1) of 70mL second alcohol and water, add in autoclave, utilize nitrogen protection; making original pressure in reactor is 0MPa; be warming up to 350 ℃, stirring reaction 1h, after reaction finishes; suction filtration; with dichloromethane extraction, then revolve steaming, obtain hydroxyanisole
The aqueous hydrochloric acid 70mL of 0.5g hydroxyanisole and pH=1.5 is joined in reactor, when reaction atmosphere is H
2, original pressure 1.5MPa, is warming up to 280 ℃, and the reaction times is 5h, and the transformation efficiency of hydroxyanisole is 92%, and the yield of pyrocatechol is 83%.
Embodiment 6
First; after 0.5g alkali lignin is mixed with the mixing solutions (volume ratio is 1: 1) of 70mL second alcohol and water, add in autoclave, utilize argon gas protection; making original pressure in reactor is 0MPa; be warming up to 280 ℃, stirring reaction 1h, after reaction finishes; suction filtration; with dichloromethane extraction, then revolve steaming, obtain hydroxyanisole
The aqueous hydrochloric acid 70mL of 0.5g hydroxyanisole and pH=1.0 is joined in reactor, when reaction atmosphere is H
2, original pressure 0MPa, is warming up to 300 ℃, and the reaction times is 2h, and the transformation efficiency of hydroxyanisole is 66%, and the yield of pyrocatechol is 64%.
Embodiment 7
First; after 0.5g alkali lignin is mixed with the mixing solutions (volume ratio is 1: 1) of 70mL second alcohol and water, add in autoclave, utilize helium protection; making original pressure in reactor is 0MPa; be warming up to 320 ℃, stirring reaction 1h, after reaction finishes; suction filtration; with dichloromethane extraction, then revolve steaming, obtain hydroxyanisole
The aqueous hydrochloric acid 70mL of 0.5g hydroxyanisole and pH=1.2 is joined in reactor, when reaction atmosphere is H
2, original pressure 0MPa, is warming up to 280 ℃, and the reaction times is 3h, and the transformation efficiency of hydroxyanisole is 75%, and the yield of pyrocatechol is 73%.
Adopt nitrogen atmosphere to carry out the hydrolysising experiment of hydroxyanisole as follows
Embodiment 8
First, after 0.5g alkali lignin is mixed with 70mL ethanol, add in autoclave, utilize nitrogen protection; making original pressure in reactor is 0MPa, is warming up to 250 ℃, and stirring reaction 1h, after reaction finishes; suction filtration, with dichloromethane extraction, then revolves steaming, obtains hydroxyanisole
The aqueous hydrochloric acid 70mL of 0.5g hydroxyanisole and pH=1.8 is joined in reactor, when reaction atmosphere is N
2, original pressure 0MPa, is warming up to 280 ℃, and the reaction times is 3h, and the transformation efficiency of hydroxyanisole is 55%, and the yield of pyrocatechol is 53%.
Embodiment 9
First; after 0.5g alkali lignin is mixed with the mixing solutions (volume ratio is 1: 1) of 70mL second alcohol and water, add in autoclave, utilize nitrogen protection; making original pressure in reactor is 0MPa; be warming up to 300 ℃, stirring reaction 1h, after reaction finishes; suction filtration; with dichloromethane extraction, then revolve steaming, obtain hydroxyanisole
The aqueous hydrochloric acid 70mL of 0.5g hydroxyanisole and pH=2.0 is joined in reactor, when reaction atmosphere is N
2, original pressure 1MPa, is warming up to 280 ℃, and the reaction times is 3h, and the transformation efficiency of hydroxyanisole is 23%, and the yield of pyrocatechol is 22%.
First, after 0.5g alkali lignin is mixed with 70mL deionized water, add in autoclave, utilize nitrogen protection; making original pressure in reactor is 0MPa, is warming up to 320 ℃, and stirring reaction 1h, after reaction finishes; suction filtration, with dichloromethane extraction, then revolves steaming, obtains hydroxyanisole
The aqueous hydrochloric acid 70mL of 0.5g hydroxyanisole and pH=1.9 is joined in reactor, when reaction atmosphere is N
2, original pressure 1.5MPa, is warming up to 280 ℃, and the reaction times is 3h, and the transformation efficiency of hydroxyanisole is 29%, and the yield of pyrocatechol is 28%.
Embodiment 11
First; after 0.5g alkali lignin is mixed with the mixing solutions (volume ratio is 1: 1) of 70mL second alcohol and water, add in autoclave, utilize nitrogen protection; making original pressure in reactor is 0MPa; be warming up to 320 ℃, stirring reaction 1h, after reaction finishes; suction filtration; with dichloromethane extraction, then revolve steaming, obtain hydroxyanisole
The aqueous hydrochloric acid 70mL of 0.5g hydroxyanisole and pH=1.5 is joined in reactor, when reaction atmosphere is N
2, original pressure 0MPa, is warming up to 280 ℃, and the reaction times is 3h, and the transformation efficiency of hydroxyanisole is 23%, and the yield of pyrocatechol is 22%.
Above the present invention has been done to exemplary description; should be noted that; in the situation that not departing from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (7)
1. by xylogen, produced a method for pyrocatechol, it is characterized in that, according to following step, carry out:
First, after alkali lignin is mixed with solution, add in autoclave, utilize rare gas element protection, making original pressure in reactor is 0MPa, is warming up to 250-350 ℃, stirring reaction 1h-5h, after reaction finishes, suction filtration, with dichloromethane extraction, revolve again steaming, obtain hydroxyanisole, the solution wherein mixing with alkali lignin is the mixing solutions of deionized water or ethanol or water and ethanol, and the volume ratio of described second alcohol and water is 1:1; Described rare gas element is selected nitrogen, argon gas or helium;
Adopt again hydroxyanisole hydrolysis to produce pyrocatechol, according to following step, carry out: hydroxyanisole and acidic solution are joined in reaction vessel, after closed reaction vessel, utilize rare gas element or hydrogen to purge, to get rid of oxygen, keep reaction vessel internal pressure stable, then after temperature reaction certain hour, can obtain pyrocatechol; Wherein said rare gas element is selected nitrogen, argon gas or helium; Described acidic solution is salt aqueous acid or the aqueous solution that presents acid salt; Need to guarantee that reaction system is mixed in the add-on of acidic solution after, in reaction vessel, the pH of reaction system is 1.0-2.0; Selecting rare gas element is atmosphere, in reaction vessel, the pH of reaction system is 1.0-2.0, container inner pressure is stabilized in 0-2MPa, temperature is 280-350 ℃, and the reaction times is 1h-5h, or to select hydrogen gas be atmosphere, in reaction vessel, the pH of reaction system is 1.0-2.0, container inner pressure is stabilized in 0-2MPa, and temperature is 280-350 ℃, and the reaction times is 1h-5h.
2. a kind of method of being produced pyrocatechol by xylogen according to claim 1, is characterized in that, the solution that is preferably 0.5g alkali lignin and 70mL mixes.
3. a kind of method of being produced pyrocatechol by xylogen according to claim 1, is characterized in that, described in to present acid salt be iron(ic) chloride or cupric chloride.
4. a kind of method of being produced pyrocatechol by xylogen according to claim 1, is characterized in that, need to guarantee that reaction system is mixed in the add-on of acidic solution after, in reaction vessel, the pH of reaction system is preferably 1.5-2.0.
5. a kind of method of being produced pyrocatechol by xylogen according to claim 1, is characterized in that, in reaction process, by machinery or magnetic force, stirs.
6. a kind of method of being produced pyrocatechol by xylogen according to claim 1, is characterized in that, selecting rare gas element is atmosphere, and in reaction vessel, the pH of reaction system is preferably 1.5-2.0; Container inner pressure is stabilized in 0-1MPa; The preferred 280-300 ℃ of temperature; Preferred 1h-3h of reaction times.
7. a kind of method of being produced pyrocatechol by xylogen according to claim 1, is characterized in that, selecting hydrogen gas is atmosphere, and in reaction vessel, the pH of reaction system is preferably 1.5-2.0; Container inner pressure is stabilized in 0-1MPa; The preferred 280-300 ℃ of temperature; Preferred 1h-3h of reaction times.
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| WO2019025535A1 (en) | 2017-08-03 | 2019-02-07 | Universiteit Antwerpen | Method for the deacylation and/or dealkylation of compounds |
| CN109680296B (en) * | 2018-12-24 | 2020-11-03 | 河北工业大学 | Method for preparing eugenol by reacting ortho-methoxyphenol group decomposed from lignin with additional allyl |
| KR102196174B1 (en) * | 2019-10-31 | 2020-12-30 | 한국과학기술연구원 | Method for producing catechol and catechol derivatives from lignin |
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| US3577467A (en) * | 1968-05-29 | 1971-05-04 | Continental Can Co | Process for the hydrolysis of lignin |
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| Comparative studies of oil compositions produced from sawdust,rice husk, lignin and cellulose by hydrothermal treatment;Selhan Karagoz等;《Fuel》;20050119;第84卷;第875-884页 * |
| Selhan Karagoz等.Comparative studies of oil compositions produced from sawdust,rice husk, lignin and cellulose by hydrothermal treatment.《Fuel》.2005,第84卷第875-884页. |
| Vapor-phase hydrolysis of methoxyphenols.I.Hydrolysis of guaiacol on silica gel;美国化学学会;《美国化学文摘》;19651231;第62卷;摘要 * |
| 木质素溶剂热降解研究;陈啸;《浙江大学硕士学位论文》;20120213;第22页倒数第2段、第25页3.1实验步骤及定量方法、第30页第1段、表4.1、图3.1 * |
| 美国化学学会.Vapor-phase hydrolysis of methoxyphenols.I.Hydrolysis of guaiacol on silica gel.《美国化学文摘》.1965,第62卷全文. |
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