CN108014782A - A kind of method of catalytic degradation lignin - Google Patents
A kind of method of catalytic degradation lignin Download PDFInfo
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- CN108014782A CN108014782A CN201711347661.1A CN201711347661A CN108014782A CN 108014782 A CN108014782 A CN 108014782A CN 201711347661 A CN201711347661 A CN 201711347661A CN 108014782 A CN108014782 A CN 108014782A
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
Abstract
The present invention provides a kind of method of catalytic degradation lignin, comprise the following steps：Using catalyst depolymerization lignin；The catalyst is layered solid acid catalyst.The present invention uses layered solid acid catalyst catalytic degradation lignin, and lignin conversion rate is higher, and the reaction was complete, and layered solid acid catalyst used in reaction can be recycled, and this method can also obtain higher liquid fuel component yield.The catalyst of the present invention separates simply with depolymerization product, environmental-friendly, has great importance to establishing sustainable energy system and preserving the ecological environment.
Description
Technical field
The present invention relates to biomass catalyzing transformation technology field, more particularly to a kind of method of catalytic degradation lignin.
Background technology
Lignin is a kind of unformed natural polymer with tridimensional network, substantially single by phenylpropyl alcohol alkyl
Member composition, is primarily present in lignum, is the main component for forming plant.Meanwhile in lignocellulosic, lignin
Content accounts for 15%~25%, but the energy that it is contained but has accounted for nearly 40%.Therefore, with fossil energy increasingly
Reduce, lignin is of increased attention.
Lignin is as a kind of natural aromatic high polymer with tridimensional network, mainly by coniferyl alcohol, sinapinic alcohol
It is formed by connecting, therefore can be obtained by depolymerization lignin by carbon-carbon bond and ehter bond with to three kinds of elementary cells of hydroxyl tonquinol
Take the compound of a variety of high added values.
At present, the lignin that annual paper-making industry produces can reach 50,000,000 tons, and the lignin that these waste liquids produce does not conform to
Reason utilizes and huge pollution is caused to environment.Had in recent years many researcher using Hydrolyze method, hydrogenolysis method and
A variety of thermochemical methods such as pyrolysismethod carry out the compound and liquid fuel that catalytic degradation lignin produces high added value, various
Catalyst have been used to the catalytic degradation of lignin.But the above method is there are severe reaction conditions, the problems such as product yield is low.
Lignin prepares liquid fuel and also obtain fast development in recent years, but yield is relatively low, and depolymerisation conditions are harsh, production
Thing is complicated, separation and purification difficult, it is difficult to industrialization.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of method of catalytic degradation lignin, has
Higher conversion ratio.
To solve above technical problem, the present invention provides a kind of method of catalytic degradation lignin, comprise the following steps：
Using catalyst depolymerization lignin；
The catalyst is layered solid acid catalyst.
The present invention avoids using fossil base product using biomass-based lignin as substrate, not only effectively realizes resource
Efficiently use, while also mitigate environmental problem, green is sustainable.The present invention has no special limit to the source of the lignin
It is fixed, can be obtained by method well known to those skilled in the art, such as papermaking lignin, corncob hydrolytic lignin, from eucalyptus
Dilute acid hydrolysis lignin, the lignin that organic solvent method obtains from pine in tree, the wood that organic solvent method obtains from apricot shell
Quality etc..
The layered solid acid catalyst that the present invention uses, has the advantages that heat endurance is high, and reusability is good, and layer
Specific layer structure can be such that this macromolecular of lignin is fully contacted with catalyst possessed by shape catalyst, and interlayer
The B acid of distribution can promote the depolymerization of lignin, and then improve the conversion ratio of reaction.Separated at the same time with product simply, environment
It is friendly.
Catalyst is specially used, catalytic degradation is carried out to lignin in a solvent.
Layered solid acid catalyst is the metal oxide after proton exchange, is specially HTaMoO6, HNbMoO6,
HTaWO6, HNbWO6And HTiNbO5In any one or more.
The present invention is to the preparation method of above-mentioned layered solid acid catalyst and is not particularly limited, and can be people in the art
Method known to member.
It is preferred that prepare in accordance with the following methods：
According to molecular formula, by one or more of tantalum source, niobium source, tungsten source, molybdenum source and titanium source, two kinds are preferably chosen, with lithium
Source mixes, and grinding is uniform, calcining, then carries out sour exchange with Bronsted acid, filters, dry, obtains layered solid acid catalysis
Agent.
The present invention is to the concrete mode of the calcining without restriction, method well known to those skilled in the art.Institute
The temperature for stating calcining is preferably 300~1000 DEG C；More preferably 550~900 DEG C；Most preferably 580~900 DEG C.The calcining
Time is preferably 5~80h；More preferably 20~72h；Most preferably 24~72h.
The Bronsted acid is preferably hydrochloric acid, nitric acid, any one or a few in sulfuric acid and phosphoric acid.It will be urged by Bronsted acid
The lithium ion of agent interlayer is replaced into hydrogen ion.The concentration of the Bronsted acid is preferably 1~13mol/L；More preferably 2~
3mol/L。
In some embodiments of the invention, acid further includes after exchanging：Add the step that organic base carries out dipping and stripping
Suddenly.
The organic base is preferably tetrabutylammonium hydroxide.
The present invention is not limited the source of above-mentioned Bronsted acid and organic base, commercially available.
Without limiting, those skilled in the art are known for concrete operations of the present invention to the dipping.The leaching
The time of stain is preferably 2h~30 day；More preferably 1~28 day；Most preferably 7~14 days；The temperature of the dipping is preferably 10
~200 DEG C, more preferably 20~40 DEG C.
It is currently preferred, carried out under conditions of the dipping earthquake.
For the present invention to the concrete operations mode of the concussion without limiting, those skilled in the art are known.
For the present invention to the separated concrete operations without limiting, those skilled in the art are known.Preferably from
The heart or suction filtration.
The present invention is to the concrete mode of the drying steps after the isolated solid without restriction, people in the art
Member is known.The temperature of the drying is preferably 40~80 DEG C, more preferably 60~70 DEG C；The time of the drying is preferably
6~24h；More preferably 12~20h；Most preferably 12~14h.
The present invention is to tantalum source without limiting, and the compound well known to those skilled in the art that can provide tantalum atom is i.e.
Can；Preferably tantalum pentoxide；
The present invention is to niobium source without limiting, and the compound well known to those skilled in the art that can provide niobium atom is i.e.
Can；Preferably niobium pentaoxide；
The present invention is to tungsten source without limiting, and the compound well known to those skilled in the art that can provide tungsten atom is i.e.
Can；Preferably tungstic acid；
The present invention is to molybdenum source without limiting, and the compound well known to those skilled in the art that can provide molybdenum atom is i.e.
Can；Preferably molybdenum trioxide；
The present invention is to titanium source without limiting, and the compound well known to those skilled in the art that can provide titanium atom is i.e.
Can；Preferably titanyl compound, such as titanium oxide；
The present invention is to lithium source without limiting, and the compound well known to those skilled in the art that can provide lithium atom is i.e.
Can；The preferably salt of lithium, such as lithium carbonate.
In some embodiments of the invention, using one kind in tantalum source or niobium source, and in tungsten source or molybdenum source
One kind, and lithium source mixing, prepare layered solid acid catalyst.The ratio of three is preferably 1:1：(1~1.2).
Depolymerization of the layered solid acid catalyst that the present invention is prepared using the above method to lignin works well, catalyst
It is simple with the separation of product, while the hydrothermal stability of catalyst is good, still there is higher activity at 320 DEG C.
Currently preferred, the catalyst further includes carbon metal supported catalyst.
The method that the present invention is used in combination using layered solid acid catalyst and carbon metal supported catalyst, catalytic degradation wood
Quality, improves the conversion ratio of reaction and the yield of petroleum ether extract.
Metal in the carbon metal supported catalyst is preferably the one or more in gold, silver and platinum group metal.It is described
Platinum group metal is preferably the one or more in rhodium, ruthenium, iridium, palladium, nickel and platinum.
It is furthermore preferred that the carbon metal supported catalyst is any one in palladium carbon, rhodium carbon, ruthenium carbon and platinum carbon or several
Kind.
The mass ratio of layered solid acid catalyst and carbon metal supported catalyst is preferably (1~10)：(1~10),
More preferably (1~7)：(1~7), is further preferably (1~5)：(1~5), is most preferably (1~3)：(1~3).
In the present invention, the mass ratio of the lignin and catalyst is preferably (1~100)：1.
Preferably, the solvent of the catalytic degradation is dioxane and the mixed solvent of water.The dioxane and water
Volume ratio is preferably (1~20)：1, more preferably (2~10)：1, it is further preferably (5~9)：1.
The temperature of the catalytic degradation is preferably 200~320 DEG C, and the pressure of depolymerization is preferably 1~8MPa, the time of depolymerization
Preferably 1~24h, more preferably 2~24h, are further preferably 6~24h.
The heating rate of the reaction is preferably 1~10 DEG C/min.
Container of the invention for the reaction is well known to those skilled in the art without limiting；It can be height
Press kettle.Hydrogen is preferably filled with reaction, is sealed.
Preferably system is cooled down after depolymerization reaction, the cooling is preferably cooled to room temperature.The present invention is for institute
The mode of cooling is stated without limiting.
After cooling, reaction solution is collected, isolates catalyst and residue, filtered, obtain filtrate, measured through gas phase, for virtue
Aroma compounds.
Aromatic compound of the present invention, which includes guaiacol, 4- ethyl -phenols, 4- methyl guaiacol and 4s, 4- ethyls, more to be created
The common monomers such as wooden phenol, 4- propyl guaiacols, vanillic aldehyde, vanillyl alcohol, Acetovanillone, homovanillic acid.
After reaction, filtrate can be divided into two parts of equity, after concentrating respectively, second is extracted with ethyl acetate to obtain in a part
Acetoacetic ester extract；Another part acetone solution, is then small molecule component with petroleum ether extraction.The mode of the concentration is excellent
Elect revolving as.
The complete conversion of the achievable lignin of the present invention, solves and converts incomplete ask during conventional lignin depolymerization
Topic, and most lignin can depolymerization be monomer and dimer, it is green renewable as liquid fuel component.
Compared with prior art, the present invention provides a kind of method of catalytic degradation lignin, comprise the following steps：Using
Catalyst depolymerization lignin；The catalyst is layered solid acid catalyst.The present invention uses layered solid acid catalyst
Catalytic degradation lignin, lignin conversion rate is higher, and the reaction was complete, and layered solid acid catalyst used in reaction is recycled
Use, this method can also obtain higher liquid fuel component yield.The catalyst of the present invention separates simply with depolymerization product, ring
Border is friendly, has great importance to establishing sustainable energy system and preserving the ecological environment.
Embodiment
In order to further illustrate the present invention, the method with reference to embodiment to catalytic degradation lignin provided by the invention
It is described in detail.
Embodiment 1
A certain amount of tantalum oxide is taken, molybdenum oxide and lithium carbonate, which are placed in mortar, to be fully ground uniformly, is then placed in porcelain boat,
The molar ratio of 600 DEG C of calcining 24h, tantalum oxide, molybdenum oxide and lithium carbonate is 1：2：2.Catalyst after calcining is put into 1mol/L
Salpeter solution in shake dipping, at normal temperatures it is light and slow concussion 2 weeks, the lithium ion between displacing catalyst layer with hydrogen ion, so
After centrifuge, with deionized water rinsing catalyst, dried in 70 DEG C of baking oven, grind pale yellow powder shape layered catalyst
HTaMoO6, then the preparation completion of catalyst.
Embodiment 2
A certain amount of niobium oxide is taken, molybdenum oxide and lithium carbonate, which are placed in mortar, to be fully ground uniformly, is then placed in porcelain boat,
The molar ratio of 580 DEG C of calcining 24h, niobium oxide, molybdenum oxide and lithium carbonate is 1：2：2.Catalyst after calcining is put into 1mol/L
Salpeter solution in shake dipping, at normal temperatures it is light and slow concussion 2 weeks, the lithium ion between displacing catalyst layer with hydrogen ion, so
After centrifuge, with deionized water rinsing catalyst, dried in 70 DEG C of baking oven, grind pale yellow powder shape layered catalyst
HNbMoO6, then the preparation completion of catalyst.
Embodiment 3
A certain amount of tantalum oxide is taken, tungsten oxide and lithium carbonate, which are placed in mortar, to be fully ground uniformly, is then placed in porcelain boat,
The molar ratio of 900 DEG C of calcining 24h, tantalum oxide, tungsten oxide and lithium carbonate is 1.1：2：2.Catalyst after calcining is put into 1mol/
Dipping is shaken in the salpeter solution of L, at normal temperatures light and slow concussion 2 weeks, the lithium ion between displacing catalyst layer with hydrogen ion, so
After centrifuge, with deionized water rinsing catalyst, dried in 70 DEG C of baking oven, grind pale yellow powder shape layered catalyst
HTaWO6, then the preparation completion of catalyst.
Embodiment 4
A certain amount of niobium oxide is taken, tungsten oxide and lithium carbonate, which are placed in mortar, to be fully ground uniformly, is then placed in porcelain boat,
The molar ratio of 760 DEG C of calcining 72h, niobium oxide, tungsten oxide and lithium carbonate is 1：2：2.Catalyst after calcining is put into 1mol/L
Salpeter solution in shake dipping, at normal temperatures it is light and slow concussion 2 weeks, the lithium ion between displacing catalyst layer with hydrogen ion, so
After centrifuge, with deionized water rinsing catalyst, dried in 70 DEG C of baking oven, grind pale yellow powder shape layered catalyst
HTaWO6, then the preparation completion of catalyst.
Embodiment 5
Take a certain amount of HTaMoO6It is placed in pure water, adds a certain amount of tetrabutylammonium hydroxide, at normal temperatures gently
Bradyseism, which is swung, carries out dipping and stripping for 2 weeks, and the rear salpeter solution for adding 0.1mol/L makes the nanometer sheet coagulation of stripping, is then centrifuged for, and uses
Deionized water rinsing catalyst, is dried in 70 DEG C of baking oven, grinds to obtain HTaMoO6Nanometer sheet, the then preparation of catalyst are completed.
Embodiment 6
Taking 0.4g lignin dissolutions, (dioxane solution and water volume ratio are 9 in dioxane solution-water:1) mix molten
In liquid, it is put into after dissolving in the autoclave of 50ml.At the same time by the layered solid acid catalyst produced in 0.1g above-described embodiments 1 and
The rhodium C catalyst of 0.1g purchases is placed in reaction kettle, and the hydrogen of 2Mpa is filled with after sealing；Stir speed (S.S.) is adjusted to 600rmp.With
Reaction kettle is warming up to 290 DEG C by the heating rate of 5 DEG C/min, and reaction time 2h, is cooled to room temperature after reaction.Collect anti-
Solution after answering；It is separated by filtration catalyst and recycles, while obtains filtrate.
Mark thing is added, takes micro filtrate to remove water, with the content of GC detection aromatic compounds.Testing conditions are：
SHIMADZU GC-2010, Agilent HP-5 capillary columns, detector FID, furnace temperature is 50 DEG C of maintenance 3min, with 10 DEG C/min
It is warming up to 280 DEG C and keeps the temperature 10min, nitrogen is as carrier gas.
Filtrate is divided into two parts of equity, and after concentrating respectively, acetic acid ethyl ester extract is extracted with ethyl acetate to obtain in a part；
Another part acetone solution, is then small molecule component with petroleum ether extraction.The result shows that can be true under the experiment condition
The yield of fixed aromatic compound is 7.3%, and petroleum ether extract yield is 26.0%.
Embodiment 7
Taking 0.4g lignin dissolutions, (dioxane solution and water volume ratio are 9 in dioxane solution-water:1) mix molten
In liquid, it is put into after dissolving in the autoclave of 50ml.At the same time by the layered solid acid catalyst produced in 0.1g above-described embodiments 2 and
The rhodium C catalyst of 0.1g purchases is placed in reaction kettle, and the hydrogen of 2Mpa is filled with after sealing；Stir speed (S.S.) is adjusted to 600rmp.With
Reaction kettle is warming up to 290 DEG C by the heating rate of 5 DEG C/min, and reaction time 2h, is cooled to room temperature after reaction.Collect anti-
Solution after answering；It is separated by filtration catalyst and recycles, while obtains filtrate.
Mark thing is added, takes micro filtrate to remove water, with the content of GC detection aromatic compounds.Testing conditions are：
SHIMADZU GC-2010, Agilent HP-5 capillary columns, detector FID, furnace temperature is 50 DEG C of maintenance 3min, with 10 DEG C/min
It is warming up to 280 DEG C and keeps the temperature 10min, nitrogen is as carrier gas.
Filtrate is divided into two parts of equity, and after concentrating respectively, acetic acid ethyl ester extract is extracted with ethyl acetate to obtain in a part；
Another part acetone solution, is then small molecule component with petroleum ether extraction.The result shows that can be true under the experiment condition
The yield of fixed aromatic compound is 7.1%, and petroleum ether extract yield is 22.7%.
Embodiment 8
Taking 0.4g lignin dissolutions, (dioxane solution and water volume ratio are 9 in dioxane solution-water:1) mix molten
In liquid, it is put into after dissolving in the autoclave of 50ml.At the same time by the layered solid acid catalyst produced in 0.1g above-described embodiments 3 and
The rhodium C catalyst of 0.1g purchases is placed in reaction kettle, and the hydrogen of 2Mpa is filled with after sealing；Stir speed (S.S.) is adjusted to 600rmp.With
Reaction kettle is warming up to 290 DEG C by the heating rate of 5 DEG C/min, and reaction time 2h, is cooled to room temperature after reaction.Collect anti-
Solution after answering；It is separated by filtration catalyst and recycles, while obtains filtrate.
Mark thing is added, takes micro filtrate to remove water, with the content of GC detection aromatic compounds.Testing conditions are：
SHIMADZU GC-2010, Agilent HP-5 capillary columns, detector FID, furnace temperature is 50 DEG C of maintenance 3min, with 10 DEG C/min
It is warming up to 280 DEG C and keeps the temperature 10min, nitrogen is as carrier gas.
Filtrate is divided into two parts of equity, and after concentrating respectively, acetic acid ethyl ester extract is extracted with ethyl acetate to obtain in a part；
Another part acetone solution, is then small molecule component with petroleum ether extraction.The result shows that can be true under the experiment condition
The yield of fixed aromatic compound is 6.4%, and petroleum ether extract yield is 21.9%.
Embodiment 9
Taking 0.4g lignin dissolutions, (dioxane solution and water volume ratio are 9 in dioxane solution-water:1) mix molten
In liquid, it is put into after dissolving in the autoclave of 50ml.At the same time by the layered solid acid catalyst produced in 0.1g above-described embodiments 4 and
The rhodium C catalyst of 0.1g purchases is placed in reaction kettle, and the hydrogen of 2Mpa is filled with after sealing；Stir speed (S.S.) is adjusted to 600rmp.With
Reaction kettle is warming up to 290 DEG C by the heating rate of 5 DEG C/min, and reaction time 2h, is cooled to room temperature after reaction.Collect anti-
Solution after answering；It is separated by filtration catalyst and recycles, while obtains filtrate.
Mark thing is added, takes micro filtrate to remove water, with the content of GC detection aromatic compounds.Testing conditions are：
SHIMADZU GC-2010, Agilent HP-5 capillary columns, detector FID, furnace temperature is 50 DEG C of maintenance 3min, with 10 DEG C/min
It is warming up to 280 DEG C and keeps the temperature 10min, nitrogen is as carrier gas.
Filtrate is divided into two parts of equity, and after concentrating respectively, acetic acid ethyl ester extract is extracted with ethyl acetate to obtain in a part；
Another part acetone solution, is then small molecule component with petroleum ether extraction.The result shows that can be true under the experiment condition
The yield of fixed aromatic compound is 6.0%, and petroleum ether extract yield is 19.6%.
Embodiment 10
Taking 0.4g lignin dissolutions, (dioxane solution and water volume ratio are 9 in dioxane solution-water:1) mix molten
In liquid, it is put into after dissolving in the autoclave of 50ml.At the same time by the layered solid acid catalyst produced in 0.1g above-described embodiments 5 and
The rhodium C catalyst of 0.1g purchases is placed in reaction kettle, and the hydrogen of 2Mpa is filled with after sealing；Stir speed (S.S.) is adjusted to 600rmp.With
Reaction kettle is warming up to 290 DEG C by the heating rate of 5 DEG C/min, and reaction time 2h, is cooled to room temperature after reaction.Collect anti-
Solution after answering；It is separated by filtration catalyst and recycles, while obtains filtrate.
Mark thing is added, takes micro filtrate to remove water, with the content of GC detection aromatic compounds.Testing conditions are：
SHIMADZU GC-2010, Agilent HP-5 capillary columns, detector FID, furnace temperature is 50 DEG C of maintenance 3min, with 10 DEG C/min
It is warming up to 280 DEG C and keeps the temperature 10min, nitrogen is as carrier gas.
Filtrate is divided into two parts of equity, and after concentrating respectively, acetic acid ethyl ester extract is extracted with ethyl acetate to obtain in a part；
Another part acetone solution, is then small molecule component with petroleum ether extraction.The result shows that can be true under the experiment condition
The yield of fixed aromatic compound is 6.2%, and petroleum ether extract yield is 20.9%.
The results are shown in Table 1, and table 1 is the reaction condition and result described in the embodiment of the present invention 6~10.
Reaction condition and result described in 1 embodiment of the present invention 6~10 of table collect
The above-mentioned extraction yield that rate is ethyl acetate that always depolymerizes, represents the conversion ratio of lignin.
Embodiment 6~10 the result shows that, in the case where other conditions are constant, the layered catalytic that is prepared in embodiment 1
Agent HTaMoO6Depolymerization effect to lignin is more preferable, the yield highest of aromatic compound yield and petroleum ether extract.
Embodiment 11
Taking 0.4g lignin dissolutions, (dioxane solution and water volume ratio are 9 in dioxane solution-water:1) mix molten
In liquid, it is put into after dissolving in the autoclave of 50ml.The layered solid acid catalyst that will be produced at the same time in the above-mentioned embodiments 1 of 0.1g
It is placed in the ruthenium C catalyst of 0.1g purchases in reaction kettle, the hydrogen of 2Mpa is filled with after sealing；Stir speed (S.S.) is adjusted to 600rmp.
Reaction kettle is warming up to 290 DEG C with the heating rate of 5 DEG C/min, reaction time 2h, is cooled to room temperature after reaction.Collect
Solution after reaction；It is separated by filtration catalyst and recycles, while obtains filtrate.
Mark thing is added, takes micro filtrate to remove water, with the content of GC detection aromatic compounds.Testing conditions are：
SHIMADZU GC-2010, Agilent HP-5 capillary columns, detector FID, furnace temperature is 50 DEG C of maintenance 3min, with 10 DEG C/min
It is warming up to 280 DEG C and keeps the temperature 10min, nitrogen is as carrier gas.
Filtrate is divided into two parts of equity, and after concentrating respectively, acetic acid ethyl ester extract is extracted with ethyl acetate to obtain in a part；
Another part acetone solution, is then small molecule component with petroleum ether extraction.The result shows that can be true under the experiment condition
The yield of fixed aromatic compound is 6.3%, and petroleum ether extract yield is 22.7%.
Embodiment 12
Taking 0.4g lignin dissolutions, (dioxane solution and water volume ratio are 9 in dioxane solution-water:1) mix molten
In liquid, it is put into after dissolving in the autoclave of 50ml.The layered solid acid catalyst that will be produced at the same time in the above-mentioned embodiments 1 of 0.1g
It is placed in the platinum carbon catalyst of 0.1g purchases in reaction kettle, the hydrogen of 2Mpa is filled with after sealing；Stir speed (S.S.) is adjusted to 600rmp.
Reaction kettle is warming up to 290 DEG C with the heating rate of 5 DEG C/min, reaction time 2h, is cooled to room temperature after reaction.Collect
Solution after reaction；It is separated by filtration catalyst and recycles, while obtains filtrate.
Mark thing is added, takes micro filtrate to remove water, with the content of GC detection aromatic compounds.Testing conditions are：
SHIMADZU GC-2010, Agilent HP-5 capillary columns, detector FID, furnace temperature is 50 DEG C of maintenance 3min, with 10 DEG C/min
It is warming up to 280 DEG C and keeps the temperature 10min, nitrogen is as carrier gas.
Filtrate is divided into two parts of equity, and after concentrating respectively, acetic acid ethyl ester extract is extracted with ethyl acetate to obtain in a part；
Another part acetone solution, is then small molecule component with petroleum ether extraction.The result shows that can be true under the experiment condition
The yield of fixed aromatic compound is 6.7%, and petroleum ether extract yield is 18.9%.
Embodiment 13
Taking 0.4g lignin dissolutions, (dioxane solution and water volume ratio are 9 in dioxane solution-water:1) mix molten
In liquid, it is put into after dissolving in the autoclave of 50ml.The layered solid acid catalyst that will be produced at the same time in the above-mentioned embodiments 1 of 0.1g
It is placed in the palladium-carbon catalyst of 0.1g purchases in reaction kettle, the hydrogen of 2Mpa is filled with after sealing；Stir speed (S.S.) is adjusted to 600rmp.
Reaction kettle is warming up to 290 DEG C with the heating rate of 5 DEG C/min, reaction time 2h, is cooled to room temperature after reaction.Collect
Solution after reaction；It is separated by filtration catalyst and recycles, while obtains filtrate.
Mark thing is added, takes micro filtrate to remove water, with the content of GC detection aromatic compounds.Testing conditions are：
SHIMADZU GC-2010, Agilent HP-5 capillary columns, detector FID, furnace temperature is 50 DEG C of maintenance 3min, with 10 DEG C/min
It is warming up to 280 DEG C and keeps the temperature 10min, nitrogen is as carrier gas.
Filtrate is divided into two parts of equity, and after concentrating respectively, acetic acid ethyl ester extract is extracted with ethyl acetate to obtain in a part；
Another part acetone solution, is then small molecule component with petroleum ether extraction.The result shows that can be true under the experiment condition
The yield of fixed aromatic compound is 6.8%, and petroleum ether extract yield is 17.4%.
The results are shown in Table 2, and table 2 is the reaction condition and result described in the embodiment of the present invention 6 and embodiment 11~13.
Reaction condition and result described in 2 embodiment of the present invention 9 of table and embodiment 13~15
Table 2 the result shows that, when layered catalyst is constant, use different hydrogenation catalysts, under conditions of current, this
The aromatic compound yield yield and petroleum ether extract yield highest obtained when invention is using rhodium carbon.
Embodiment 14
Taking 0.4g lignin dissolutions, (dioxane solution and water volume ratio are 9 in dioxane solution-water:1) mix molten
In liquid, it is put into after dissolving in the autoclave of 50ml.At the same time by the layered solid acid catalyst produced in 0.1g above-described embodiments 1 and
The rhodium C catalyst of 0.1g purchases is placed in reaction kettle, and the hydrogen of 2Mpa is filled with after sealing；Stir speed (S.S.) is adjusted to 600rmp.With
Reaction kettle is warming up to 250 DEG C by the heating rate of 5 DEG C/min, and reaction time 2h, is cooled to room temperature after reaction.Collect anti-
Solution after answering；It is separated by filtration catalyst and recycles, while obtains filtrate.
Mark thing is added, takes micro filtrate to remove water, with the content of GC detection aromatic compounds.Testing conditions are：
SHIMADZU GC-2010, Agilent HP-5 capillary columns, detector FID, furnace temperature is 50 DEG C of maintenance 3min, with 10 DEG C/min
It is warming up to 280 DEG C and keeps the temperature 10min, nitrogen is as carrier gas.
Filtrate is divided into two parts of equity, and after concentrating respectively, acetic acid ethyl ester extract is extracted with ethyl acetate to obtain in a part；
Another part acetone solution, is then small molecule component with petroleum ether extraction.The result shows that can be true under the experiment condition
The yield of fixed aromatic compound is 5.1%, and petroleum ether extract yield is 8.1%.
Embodiment 15~20
In addition to reaction temperature is different from embodiment 14, specific reaction process and detection method are identical with embodiment 14, described
Reaction temperature is respectively 260 DEG C, 270 DEG C, 280 DEG C, 300 DEG C, 310 DEG C, 320 DEG C.After measured, it may be determined that aromatic compound
The yield of thing is respectively 5.7%, 5.4%, 6.6%, 7.9%, 8.2%, 8.2%, and petroleum ether extract yield is respectively
15.1%, 20.2%, 22.7%, 30.0%, 38.1%, 41.0%.
The reaction condition of embodiment 6 and embodiment 14~20 and the results are shown in Table 3, table 3 are the embodiment of the present invention 6 and real
Apply the reaction condition and result described in example 14~20：
Reaction condition and result described in 3 embodiment of the present invention 6 of table and embodiment 14~20
Embodiment 6 and embodiment 14~20 the result shows that, in the case where other conditions are constant, temperature is more high more favourable
In the progress of reaction.
Embodiment 21~25
In addition to the reaction time is different from embodiment 20, specific reaction process and detection method are identical with embodiment 20, described
Reaction time takes 3h, 6h, 12h, 18h, 24h respectively, after measured, it may be determined that the yield of aromatic compound be respectively
8.7%, 9.1%, 8.3%, 9.6%, 10.4%, petroleum ether extract yield is respectively 43.9%, 45.35%, 54.0%,
56.1%, 58.7%.The reaction condition of embodiment 20 and embodiment 21~25 and the results are shown in Table 4, table 4 is implemented for the present invention
Reaction condition and result described in example 20 and embodiment 21~25：
Reaction condition and result described in 4 embodiment of the present invention 20 of table and embodiment 21~25
Table 4 the result shows that, when other conditions are constant, extend the reaction time be conducive to reaction progress, and react when
Between it is longer, the present invention in aromatic compound yield and petroleum ether extract yield it is higher.
From above-described embodiment, the present invention uses specific catalyst depolymerization lignin, has higher yield,
And easy to operate, mild condition.
The explanation of above example is only intended to help to understand method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
1. a kind of method of catalytic degradation lignin, comprises the following steps：
Using catalyst depolymerization lignin；
The catalyst is layered solid acid catalyst.
2. according to the method described in claim 1, it is characterized in that, layered solid acid catalyst is HTaMoO6,
HNbMoO6, HTaWO6, HNbWO6And HTiNbO5In any one or more.
3. according to the method described in claim 1, it is characterized in that, the catalyst further includes carbon metal supported catalyst.
4. according to the method described in claim 3, it is characterized in that, the metal in the carbon metal supported catalyst is gold, silver
With the one or more in platinum group metal；The platinum group metal is the one or more in rhodium, ruthenium, iridium, palladium and platinum.
5. according to the method described in claim 3, it is characterized in that, the carbon metal supported catalyst is palladium carbon, rhodium carbon, ruthenium carbon
With any one or a few in platinum carbon.
6. according to the method described in claim 3, it is characterized in that, layered solid acid catalyst and the catalysis of carbon carried metal
The mass ratio of agent is (1~10)：(1~10).
7. according to the method described in claim 1, it is characterized in that, the temperature of the catalytic degradation be 200~320 DEG C, the time
For 1~24h, pressure is 1~8MPa.
8. according to the method described in claim 1, it is characterized in that, the mass ratio of the lignin and catalyst for (1~
100)：1.
9. according to the method described in claim 1, it is characterized in that, the solvent of the catalytic degradation is the mixed of dioxane and water
Bonding solvent.
10. according to the method described in claim 9, it is characterized in that, the volume ratio of the dioxane and water is (1~20)：
1。
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