CN110128247A - A kind of method of catalytic lignin depolymerization - Google Patents
A kind of method of catalytic lignin depolymerization Download PDFInfo
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- CN110128247A CN110128247A CN201910437164.3A CN201910437164A CN110128247A CN 110128247 A CN110128247 A CN 110128247A CN 201910437164 A CN201910437164 A CN 201910437164A CN 110128247 A CN110128247 A CN 110128247A
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- 229920005610 lignin Polymers 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims abstract description 26
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical group CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229960001867 guaiacol Drugs 0.000 claims abstract description 13
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006731 degradation reaction Methods 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 9
- 230000002195 synergetic effect Effects 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 244000050510 Cunninghamia lanceolata Species 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000000539 dimer Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 239000013067 intermediate product Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920002488 Hemicellulose Polymers 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
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- WDFZWSZNOFELJY-OLQVQODUSA-N (1R,6S)-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical group C1=CC=C[C@H]2O[C@H]21 WDFZWSZNOFELJY-OLQVQODUSA-N 0.000 description 1
- HJFNQXYLCLOQJK-UHFFFAOYSA-N 2-methoxy-4-phenylphenol Chemical compound C1=C(O)C(OC)=CC(C=2C=CC=CC=2)=C1 HJFNQXYLCLOQJK-UHFFFAOYSA-N 0.000 description 1
- HZQXTPJMQFOCDY-UHFFFAOYSA-N 6-phenyl-7-oxabicyclo[4.1.0]hepta-2,4-dien-3-ol Chemical group OC1=CC2OC2(C=C1)c1ccccc1 HZQXTPJMQFOCDY-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 101000713585 Homo sapiens Tubulin beta-4A chain Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 244000297179 Syringa vulgaris Species 0.000 description 1
- 235000004338 Syringa vulgaris Nutrition 0.000 description 1
- 241000425573 Talanes Species 0.000 description 1
- 102100036788 Tubulin beta-4A chain Human genes 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods of catalytic lignin depolymerization, belong to technical field of biomass resource utilization.Lignin is added in the reaction vessel equipped with solvent, is reacted under the synergistic effect of iron powder and palladium carbon, realizes the degradation of lignin.Lignin conversion rate is at least 99%；Product is acetophenone and guaiacol, and yield respectively reaches 99% or more and 90% or more.The method of the present invention green high-efficient, the catalyst after reaction, which can recycle, to be recycled, and still keeps greater activity.This method produces high valuable chemicals for effective use lignin and provides a kind of new technical solution.
Description
Technical field
The invention belongs to technical field of biomass resource utilization, and in particular to a kind of method of catalytic lignin depolymerization.
Background technique
Lignin (abbreviation lignin), cellulose and hemicellulose are three kinds of masters in high terrestrial plant vascular tissue
Want constituent.Wherein, lignin is the natural polymer phenol polymer abundant of content second in nature, by three kinds of allusion quotations
Type phenylpropyl alcohol alkyl structure unit (guaiacyl benzene oxide unit, lilac base benzene oxide unit and p-hydroxyphenyl benzene oxide unit)
Pass through ehter bond and carbon-carbon bond link composition.
The industrial lignin that the whole world is discharged every year according to estimates is more than 1.5 hundred million tons, while with agricultures such as stalk, bagasse, rice husks
Woods waste is that the second generation alcohol fuel production process of primary raw material can also generate a large amount of lignin byproduct.Although wooden
Quality has the advantages such as from a wealth of sources, renewable, rich reserves, cheap, but by its structure is complicated, physicochemical properties
The influence of the factors such as inhomogenous, it is most only to be used as low calorie fuels, still fail to be utilized effectively so far,
Also the research of its splitting mechanism is greatly hindered.Lignin is applied in various industry because of its polyphenol class formation.It is wooden
The utilization method of element can be summarized as two major classes first is that changing lignin degradation to be used as after small molecule using chemistry or biological method
Work raw material, such as using lignin as raw material for producing vanillic aldehyde and phenolic compound aromatics chemicals；Second is that with macromolecular
Form directly utilizes, such as manufacturing dispersing agent, surfactant, flocculant, active carbon.Lignin is in answering agriculturally
With also very extensive, the additive, pesticide slow-releasing agent, plant growth regulator, soil improvement of fertilizer and various fertilizer can be used as
Agent etc..Further, since cellulose and hemicellulose oxygen content are higher, liquefaction products calorific value is low, and the C/Hratio of lignin most connects
It is bordering on natural oil, it can be with preparing liquid fuel by liquefaction lignin.
Currently, domestic and foreign scholars have been achieved for being mainly manifested in compared with quantum jump to lignin research: (1) modern elder generation
It is widely applied in lignin research into analysis instrument and has played important function；(2) resource of lignin-base material
Change to utilize and has certain progress；Lignin model compound be it is similar to macromolecular structures certain in lignin and function or
Similar artificial synthesized compound.Because its structure and function determines, splitting mechanism is easier to study relative to lignin,
It can provide fundamental basis for the research of lignin splitting mechanism.It is big that common lignin model compound is broadly divided into following 9
Class: simple phenolic and non-phenolic (also referred to as lignin monomer model object), β-O-4 type, α-O-4 type, β -5 type, β-β type, β -1
Type and 5-5 type, quinoid, 1,2- talan etc..Monomer, dimer, tripolymer, four can be divided into again according to its degree of polymerization is different
Aggressiveness.What application was more at present is the oligomers model compound such as monomer, dimer.The wooden prime model object of polymer is closer
The real structure of lignin, in order to it is truer, correctly reflect lignin degradation mechanism, it is necessary to use polymer lignin mould
Research object of the type object as lignin reaction mechanism.Currently, lignin and wooden prime model object cracking mode are broadly divided into and urge
Change hydrogenolysis, pyrolysis, alcohol
The lignin monomer model object of most study is guaiacol at present, and cracking mode is mainly catalytic hydrogenolysis, is made
It is noble metal catalyst and sulphided state Mo base catalyst with most catalyst, the catalytic effect of catalyst depends on carrier material
Material.Transiting state metal phosphide is a kind of very promising catalyst.Other cracking modes are such as pyrolyzed, oxidative degradation
It is very effective to the pollutant process in paper waste；The structure and molecular weight of polymer lignin model compound all most connect
Nearly natural lignin, however, the report in relation to its cracking reaction is rare so far.The wooden prime model of the oligomers such as monomer, dimer
Although object can represent lignin to a certain degree, because its structure is simple, and lignin structure is extremely complex, represents limitation,
Therefore, the cracking of polymer lignin model compound is following important research direction.
Summary of the invention
Goal of the invention: the deficiencies in the prior art are directed to, the purpose of the present invention is to provide a kind of catalytic lignins
The method of depolymerization.The efficiency for the β-O-4 key that content is most in fracture lignin is improved, it is high attached for effective use lignin production
Value added chemicals provides a technical strategies.
Technical solution: to solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
A kind of method of catalytic lignin depolymerization lignin is added in the reaction vessel equipped with solvent, in iron powder and palladium
It is reacted under the synergistic effect of carbon, realizes the degradation of lignin；The mass volume ratio of lignin and solvent is (20-25) mg/
mL；The molar ratio of lignin and iron powder is 1: the mass ratio of (1-2), lignin and palladium carbon is 10: (6-7)；Solvent is tetrahydro furan
It mutters, any one of dioxane, methanol, ethyl alcohol or isopropanol；Reaction temperature is 80-160 DEG C, reaction time 4-12h.
The method of the catalytic lignin depolymerization, lignin are China fir lignin or lignin dimer model compound.
The method of the catalytic lignin depolymerization, reaction temperature are 140 DEG C, reaction time 10h.
The molar ratio of the method for the catalytic lignin depolymerization, lignin and iron powder is 1: 2.
The mass ratio of the method for the catalytic lignin depolymerization, lignin and palladium carbon is 10: 7.
The method of the catalytic lignin depolymerization, solvent are methanol.
The mass volume ratio of the method for the catalytic lignin depolymerization, lignin and solvent is 25mg/mL.
A kind of method of catalytic lignin depolymerization, takes lignin to be dissolved in the reaction vessel equipped with methanol, be added iron powder with
Palladium carbon, reacts 10h at 140 DEG C, and the mass volume ratio of lignin and methanol is 25mg/mL, the molar ratio of lignin and iron powder
It is 1: 2, the mass ratio of lignin and palladium carbon is 10: 7；Lignin conversion rate is at least up to 99%, acetophenone yield be 99% with
On, guaiacol yield reaches 90% or more.
The utility model has the advantages that compared with prior art, the invention has the advantages that
(1) compared with existing wooden prime model object biodegrading process, the present invention, can under the synergistic effect of iron powder and palladium carbon
To obtain high efficiency of pcr product, high valuable chemicals are produced for effective use lignin, one technical strategies is provided.
(2) catalytic degradation system of the invention is not necessarily to carry out any pretreatment to lignin, directly to unpretreated wood
Quality is degraded, and operating method is simple, and reaction condition is controllable, realizes the degradation of lignin, and obtained degradation produces
Object can be used as a kind of important organic synthesis intermediate.
(3) reaction of the invention is not necessarily to logical H2, effectively reduce reaction cost；And catalyst can be recycled more
It is secondary, still there is high reactivity.
Detailed description of the invention
Fig. 1 is the reaction process flow chart of 1 model compound of embodiment degradation；
Fig. 2 is that embodiment 6 is applied to gel permeation chromatography (GPC) figure before and after the reaction of China fir lignin, wherein 2A is China fir
GPC curve before the wooden lignin reaction, 2B are GPC curve after China fir lignin reaction；
Fig. 3 is that embodiment 6 is applied to infrared spectrogram before and after the reaction of China fir lignin, wherein 3A is China fir lignin
Infrared spectrum curve before reacting, 3B are infrared spectrum curve after China fir lignin reaction.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, right combined with specific embodiments below
A specific embodiment of the invention is described in detail.
Efficiency of pcr product calculation method in the present invention: first according to the standard items of acetophenone and guaiacol, pass through gas phase color
The standard curve that (GC) draws acetophenone and guaiacol is composed, internal standard is done with naphthalene, then by the face of the area of reaction product and naphthalene
Quality of the product than can be calculated product on standard curve, the quality of product and theoretical mass percent are obtaining for product
Rate.Obtained by conversion ratio area percentage as shared by substrate in GC.
Embodiment 1
Model compound and catalytic degradation reaction process flow chart are as shown in Figure 1.
It takes lignin dimer model compound raw material 100mg to be dissolved in the pressure pipe equipped with 4mL methanol, 70mg palladium is added
Carbon and 46mg iron powder, react 10h at 140 DEG C, reaction solution are filtered centrifugation, supernatant is obtained, is quantified by GC
Characterization, testing result discovery, when solvent is methanol, the high conversion rate of model compound is up to 99%, acetophenone yield
99.2%, guaiacol yield reaches 90.3%, and intermediate product and by-product are also very low.
Embodiment 2
For the method for catalytic lignin depolymerization with embodiment 1, solvent is respectively tetrahydrofuran, dioxane, ethyl alcohol or isopropyl
Alcohol.
Reaction solution is filtered centrifugation, obtains supernatant, quantitatively characterizing is carried out by GC, experimental result is as shown in table 1.
1 experimental result in conjunction with the embodiments as shown in Table 1 can have an impact to conversion ratio and products collection efficiency using variety classes solvent.
Wherein, when solvent is dioxane and methanol, conversion ratio reaches up to 99%, and raw material almost converts；When solvent is
When methanol, acetophenone and guaiacol yield reach maximum value, and respectively 99.2% and 90.3%, intermediate product and other at this time
The amount of substance is also minimum.
Products collection efficiency result in 1 embodiment 2 of table
| Number | Solvent | Acetophenone yield/% | Guaiacol yield/% | Conversion ratio/% | Intermediate product/% | Other/% |
| 1 | Tetrahydrofuran | 52.3 | 45.2 | 98 | 22.1 | 1.2 |
| 2 | Dioxane | 91.2 | 88 | 99 | 9.4 | 0.3 |
| 3 | Ethyl alcohol | 76.2 | 86.1 | 89 | 4.3 | 0.8 |
| 4 | Isopropanol | 53.5 | 87.5 | 85.3 | 12 | 1.3 |
Embodiment 3
For the method for catalytic lignin depolymerization with embodiment 1, the reaction time is respectively 4,6,8 and 12h.
Reaction solution is filtered centrifugation, obtained supernatant carries out quantitatively characterizing, testing result such as 2 institute of table by GC
Show.1 experimental result in conjunction with the embodiments, as shown in Table 2, when reacted between when reaching 8h, conversion ratio has reached 99%.Even if
Reaction time continues growing, and conversion ratio is still constant, but the yield of acetophenone and guaiacol, can be with the increasing in reaction time
Add presentation first to increase the variation tendency reduced afterwards, reaches maximum value, respectively 99.2% He when the reaction time is 10h
90.3%.
Products collection efficiency result in 2 embodiment 3 of table
| Number | Time/h | Acetophenone yield/% | Guaiacol yield/% | Conversion ratio/% | Intermediate product/% | Other/% |
| 1 | 4 | 85.9 | 64.1 | 92 | 13 | 1.6 |
| 2 | 6 | 95 | 87.9 | 97 | 8 | 1.1 |
| 3 | 8 | 97.8 | 88.4 | 99 | 6 | 0.9 |
| 4 | 12 | 94 | 82.6 | 99 | 0.4 | 3.7 |
Embodiment 4
For the method for catalytic lignin depolymerization with embodiment 1, reaction temperature is respectively 80,100,120 and 160 DEG C.
Reaction solution is filtered centrifugation, obtained supernatant carries out quantitatively characterizing, testing result such as 3 institute of table by GC
Show.1 experimental result in conjunction with the embodiments, as shown in Table 3, the variation of reaction temperature have very big shadow to conversion ratio and products collection efficiency
It rings, when reaction temperature is 140 DEG C, conversion ratio and products collection efficiency highest are optimal reaction temperature.
Products collection efficiency result in 3 embodiment 4 of table
| Number | Temperature/DEG C | Acetophenone yield/% | Guaiacol yield/% | Conversion ratio/% | Intermediate product/% | Other/% |
| 1 | 80 | 15 | 13 | 84.5 | 62 | 3 |
| 2 | 100 | 42.6 | 37.3 | 92.6 | 30.8 | 2.4 |
| 3 | 120 | 98.2 | 86.3 | 97.3 | 16 | 2.2 |
| 4 | 160 | 98.8 | 88 | 99 | 0.6 | 2.6 |
Embodiment 5
The catalyst after 1 first set reaction of embodiment is collected, it is after methanol washs (5*10mL) and dry, again by it
Secondary to be catalyzed in reaction for second, method is the same as embodiment 1；Again by the catalyst after second of catalysis reaction by identical
It is catalyzed reaction for third time after processing, is repeated according to this, catalyst uses 5 times altogether, obtains that the results are shown in Table 4.
As shown in Table 4, it can be recycled and reused in reaction after being recycled to catalyst, with catalyst number of repetition
Increase, products collection efficiency and conversion ratio can be declined, but conversion ratio can achieve 99% after being repeated once, and repeat 5
After secondary, conversion ratio still can achieve 88.6%, and products collection efficiency illustrates that catalyst of the present invention can weigh 75% or more
It is multiple to use and still there is very high reactivity.
Products collection efficiency result in 4 embodiment 5 of table
| Number | Number | Acetophenone yield/% | Guaiacol yield/% | Conversion ratio/% | Intermediate product/% | Other/% |
| Embodiment 1 | 1 | 99.2 | 90.3 | 99 | 0.4 | 0.1 |
| 1 | 2 | 93.1 | 88.6 | 98.2 | 0.7 | 0.2 |
| 2 | 3 | 90.4 | 82.9 | 94.5 | 1.1 | 0.6 |
| 3 | 4 | 85.7 | 79.8 | 90 | 1.9 | 0.7 |
| 4 | 5 | 81.3 | 76.4 | 88.6 | 4.7 | 1.2 |
Embodiment 6
It takes 100mg China fir lignin to be dissolved in the reaction flask equipped with 4mL methanol, 70mg palladium carbon and 46mg iron powder is added,
Under 140 DEG C of reaction temperature, react 10h, reaction solution be filtered centrifugation, obtained solid residue carry out GPC detection with it is red
Outer detection, testing result are as shown in Figures 2 and 3.As shown in Figure 2, molecular weight drops to 1344 by 2190, in the reaction condition
Under, there is monomer generation.From the figure 3, it may be seen that the peak position that goes out of phenols and carbonyl complex is remarkably reinforced.Illustrate the method for the present invention
It can be used for the catalytic pyrolysis of polymer lignin.
Claims (8)
1. a kind of method of catalytic lignin depolymerization, which is characterized in that lignin is added in the reaction vessel equipped with solvent,
It is reacted under the synergistic effect of iron powder and palladium carbon, realizes the degradation of lignin；The quality volume amount ratio of lignin and solvent
For (20-25) mg/mL, the molar ratio of lignin and iron powder is 1: the mass ratio of (1-2), lignin and palladium carbon is 10: (6-7),
Solvent is any one of tetrahydrofuran, dioxane, methanol, ethyl alcohol or isopropanol, and reaction temperature is 80-160 DEG C, when reaction
Between be 4-12h.
2. the method for catalytic lignin depolymerization according to claim 1, which is characterized in that lignin be China fir lignin or
Lignin dimer model compound.
3. the method for catalytic lignin depolymerization according to claim 1, which is characterized in that reaction temperature is 140 DEG C, reaction
Time is 10h.
4. the method for catalytic lignin depolymerization according to claim 1, which is characterized in that the molar ratio of lignin and iron powder
It is 1: 2.
5. the method for catalytic lignin depolymerization according to claim 1, which is characterized in that the mass ratio of lignin and palladium carbon
It is 10: 7.
6. the method for catalytic lignin depolymerization according to claim 1, which is characterized in that solvent is methanol.
7. the method for catalytic lignin depolymerization according to claim 1, which is characterized in that the mass body of lignin and solvent
Product is than being 25mg/mL.
8. the method for catalytic lignin depolymerization according to claim 1, which is characterized in that lignin is taken to be dissolved in equipped with methanol
Reaction vessel in, iron powder and palladium carbon is added, reacts 10h at 140 DEG C, the mass volume ratio of lignin and methanol is 25mg/
The molar ratio of mL, lignin and iron powder is 1: 2, and the mass ratio of lignin and palladium carbon is 10: 7；Lignin conversion rate is at least up to
99%, acetophenone yield is 99% or more, and guaiacol yield reaches 90% or more.
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