CN105037103B - A kind of method of the efficient depolymerization of lignin - Google Patents
A kind of method of the efficient depolymerization of lignin Download PDFInfo
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- CN105037103B CN105037103B CN201510373024.6A CN201510373024A CN105037103B CN 105037103 B CN105037103 B CN 105037103B CN 201510373024 A CN201510373024 A CN 201510373024A CN 105037103 B CN105037103 B CN 105037103B
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- lignin
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- 229920005610 lignin Polymers 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000002989 phenols Chemical class 0.000 claims abstract description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 12
- 239000011636 chromium(III) chloride Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 14
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 9
- 150000003384 small molecules Chemical class 0.000 abstract description 8
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000002779 inactivation Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012075 bio-oil Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 17
- 150000002191 fatty alcohols Chemical class 0.000 description 16
- 238000004939 coking Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 12
- 230000008021 deposition Effects 0.000 description 12
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000000638 solvent extraction Methods 0.000 description 12
- 238000010813 internal standard method Methods 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000004445 quantitative analysis Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- -1 methoxyl group Chemical group 0.000 description 5
- 239000012453 solvate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 239000005456 alcohol based solvent Substances 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 244000062720 Pennisetum compressum Species 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 238000009825 accumulation Methods 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
- 230000009849 deactivation Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 235000009973 maize Nutrition 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000002918 Fraxinus excelsior 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000003416 augmentation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
- C07C37/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes by hydrolysis of lignin or sulfite waste liquor
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B01J35/19—
Abstract
The invention discloses a kind of method of the efficient depolymerization of lignin.This method is using metal chloride and noble metal as composite catalyst, using Small molecule organic solvents as medium, the efficient catalytic depolymerization for the regenerative resource that lignin etc. is difficult by can be realized under mild conditions, prepare the phenols chemicals and high heating value bio oil of high added value.The present invention possesses that technique simple, mild condition, single phenol high income, product be controllable, catalyst can realize the remarkable advantages such as recycling.Equipment requirement present in current production method can be avoided high, energy consumption is big, and target product yield is low, catalyst inactivation seriously waits not enough.
Description
Technical field
The invention belongs to environmental protection technology, agricultural waste effectively is using technology and new energy technology development and utilizes neck
Domain, more particularly to a kind of use metal chloride and noble metal act synergistically the composite catalyst to be formed, organic molten in small molecule
Efficient depolymerization lignin in agent, obtains fatty alcohol, hydrocarbon, monomer phenols and phenols oligomer in high yield.
Background technology
With the increasingly depleted of fossil fuel, energy demand is more and more nervous.At the same time, a large amount of combustion of fossil fuels rows
The CO put2、SO2, NO and dust, cause greenhouse effects more serious, environment sustainable development constituted a threat to.Therefore, seek low
Carbon, low stain reproducible alternative energy source becomes the common recognition of countries in the world.Biomass is directed to the photosynthetic of plant
Effect, has the advantages that rich carbon content, reserves are big, distribution is wide, it is low, cheap and renewable to pollute, compared with fossil fuel, its
Sulfur-bearing and nitrogen content are relatively low, while content of ashes also very little, it is considered to be a kind of potential petrochemical industry alternative energy source.Currently, greatly
Partial research is concentrated on to be easier in the three kinds of main components (cellulose, hemicellulose and lignin) for constituting Wooden Biomass
On the cellulose and hemicellulose of conversion.Remaining lignin is then usually discharged in the form of waste, only in biorefinery factory
In be used as fuel to provide energy and steam.However, the lignin being bonded at random by three kinds of phenylpropyl alcohol alkyl structure units, with virtue
A variety of functional groups and the unsaturated double-bond isoreactivity sites, Yi Jiyu such as perfume base, methoxyl group, phenol (alcohol) hydroxyl, carbonyl and carboxyl
The close C/H contents ratio of oil, is that uniquely can directly provide the renewable resource of aromatic ring in nature.Therefore, new technology is developed
To make full use of, lignin prepares bio-fuel in renewable biomass and biochemicals is particularly important.
In recent years, the serial lignin depolymerization such as biological enzymolysis, thermal cracking, catalytic hydrogenolysis, catalysis oxidation and conversion means quilt
Extensively utilize, but its there is also more deficiency.Such as：Biological enzymolysis takes oversize；Thermal cracking temperature is high, energy consumption is big；It is catalyzed hydrogen
Solve easy coking and deactivation；Catalysis oxidation needs addition oxidant, to equipment requirement height；Especially current many technical processes it is strong
Acid catalyst, easily causes equipment corrosion, and catalyst carbon deposition inactivation is serious.
The content of the invention
In order to overcome the deficiencies in the prior art and shortcoming, primary and foremost purpose of the invention is to provide a kind of using gold
Category chloride and noble metal are acted synergistically the composite catalyst to be formed, and efficient depolymerization lignin, is obtained in Small molecule organic solvents
Obtain fatty alcohol, hydrocarbon, monomer phenols and phenols oligomer in high yield.Pass through the tune to catalyst and reaction medium
Control, the contact between increase lignin raw material and catalyst, augmentation of heat transfer and mass transport process, reduce process energy consumption, and suppress to urge
Agent deactivation phenomenom as caused by coking carbon distribution.
The purpose of the present invention is realized by following technical proposals：
A kind of method of the efficient depolymerization of lignin.This method is cooperatively formed multiple using metal chloride and noble metal catalyst
Catalyst is closed, lignin and rich lignin matter waste effectively solution are realized in Small molecule organic solvents, under temperate condition
It is poly- to prepare phenolic compound, reinforcing heat and mass transport, reduction process energy consumption, and suppress catalyst carbon deposition.This method mainly includes
Following steps：
In 2~5MPa nitrogen or hydrogen gas atmosphere, according to 0.5~2mmol metal chloride catalysts, 0.01~
The ratio of 0.2g noble metal hydrogenation catalysts, 0.5~1.0g lignin and 40~80mL reaction mediums, is sufficiently mixed each material,
240~300 DEG C are heated to, it is that can obtain depolymerization product that 3~6h is reacted under agitation, by separation (such as filtering, solvent extraction
Etc. mode), purification can obtain required material；The metal chloride catalyst is selected from ZnCl2、MgCl2、AlCl3、CrCl3In
One or two, the noble metal hydrogenation catalyst be selected from Pd/C, Pt/C or Ru/C (in noble metal hydrogenation catalyst, activity
The load capacity of component is preferably 5wt%), the reaction medium is the mixed of Small molecule organic solvents or Small molecule organic solvents and water
Compound.
Further, above-mentioned lignin is wooden selected from alkali lignin, sodium sulfonate lignin, dealkalize lignin, organic solvent
Plain (such as organic molten Chinese pennisetum lignin) or acidolysis lignin (can be from the rich lignins of maize straw hydrolytic residue
Matter discarded object).
Further, above-mentioned Small molecule organic solvents are selected from methanol, ethanol, normal propyl alcohol or ethylene glycol.For mixed with water
(volume ratio is preferably 4 for compound, preferably methanol-water mixtures:1).
Further, the solution product of above-mentioned reaction is mainly low including fatty alcohol, hydrocarbon, monomer phenols and phenols
Aggressiveness.
The present invention principle be：The metal chloride composite catalyst to be formed that acted synergistically with noble metal has good urge
Change performance and carbon accumulation resisting ability, in Small molecule organic solvents, under certain process conditions, realize lignin and rich lignin
The efficiently and directionally catalytic degradation of matter prepares fatty alcohol, hydrocarbon, monomer phenols and phenols oligomer.
The present invention has the following advantages and effect compared with the prior art：
(1) catalyst system and catalyzing that the inventive method is built has synergy catalytic effect, compared with existing catalyst system and catalyzing,
Active high, carbon accumulation resisting ability is strong, simple to operate, it is easy to which product is separated, environment-friendly to wait remarkable advantage；
(2) solvent of the present invention is the mixture of methanol, ethanol, normal propyl alcohol, ethylene glycol or above-mentioned substance and water,
Biomass can be directed to, therefore, with the remarkable advantage such as renewable, green and above-mentioned solvent can be real after simple separation
Now recycle；
(3) the inventive method can select alkali lignin, sodium sulfonate lignin, dealkalize lignin, organic solvent lignin
With the different material such as acidolysis lignin, therefore, extensively, rich content is cheap for raw material sources；
(4) compared with prior art, maximum advantage is in above-mentioned system the inventive method, the conversion ratio of lignin
Height, the target product yield such as fatty alcohol, hydrocarbon, monomer phenols is high, and can effectively suppress the formation of coking carbon distribution；
(5) catalyst system and catalyzing that the present invention is provided possesses good recycling performance.
Embodiment
Further detailed description is done to the present invention with reference to embodiment, but the implementation of the present invention is not limited to this.
Embodiment 1
Weigh 0.5g dealkalizes lignin and 1mmol CrCl3It is placed in 0.1g 5wt%Pd/C in 40mL methanol solvates, body
System is through H23MPa is inflated after replacing 3 times, 5h are reacted in 280 DEG C.Room temperature quickly is cooled to, successively using filtering, solvent extraction
The mode such as take to be separated to wherein product.Volatile products are carried out using GC-MS qualitative analyses, using GC combinations internal standard method
Quantitative analysis；The molecular weight distribution and essential building blocks of fixedness product are characterized using means such as GPC, FT-IR.
As a result show：After the catalytic treatment, lignin can realize 82.9% conversion, wherein fatty alcohol yield 3.1%, hydrocarbon
Yield 1.7%, guaiaci lignum phenols yield 2.6%, phenol yield 13.5%, phenols oligomer yield 48.4%.In the process
In have no obvious coking carbon deposition phenomenon.
Embodiment 2
Weigh 0.5g sodium sulfonates lignin and 1mmol CrCl3It is placed in 0.1g 5wt%Pd/C in 40mL methanol solvates,
System is through H23MPa is inflated after replacing 3 times, 5h are reacted in 300 DEG C.Room temperature quickly is cooled to, successively using filtering, solvent
The modes such as extraction are separated to wherein product.Volatile products are entered using GC-MS qualitative analyses, using GC combination internal standard methods
Row quantitative analysis；Table is carried out to the molecular weight distribution and essential building blocks of fixedness product using means such as GPC, FT-IR
Levy.As a result show：After the catalytic treatment, lignin can realize 81.0% conversion, wherein fatty alcohol yield 11.9%, hydrocarbonization
Compound yield 1.1%, guaiaci lignum phenols yield 1.1%, phenol yield 5.3%, phenols oligomer yield 44.8%.In the mistake
Obvious coking carbon deposition phenomenon is had no in journey.
Embodiment 3
Weigh 0.5g organic molten Chinese pennisetum lignin and 1mmol CrCl3It is molten that 40mL methanol is placed in 0.1g 5wt%Ru/C
In agent, system is through H24MPa is inflated after replacing 3 times, 5h are reacted in 260 DEG C.Quickly be cooled to room temperature, successively using filtering,
The modes such as solvent extraction are separated to wherein product.Volatility is produced using GC-MS qualitative analyses, using GC combinations internal standard method
Thing carries out quantitative analysis；The molecular weight distribution and essential building blocks of fixedness product are entered using means such as GPC, FT-IR
Row is characterized.As a result show：After the catalytic treatment, lignin can realize 65.3% conversion, wherein fatty alcohol yield 0.8%, carbon
Hydrogen compound yield 1.1%, guaiaci lignum phenols yield 1.8%, phenol yield 9.6%, phenols oligomer yield 42.6%.
Obvious coking carbon deposition phenomenon is had no during being somebody's turn to do.
Embodiment 4
Weigh 0.5g alkali lignins and 1mmol CrCl3It is placed in 0.1g 5wt%Pd/C in 40mL methanol solvates, system
Through N23MPa is inflated after replacing 3 times, 5h are reacted in 260 DEG C.Room temperature quickly is cooled to, successively using filtering, solvent extraction
Wherein product is separated etc. mode.Volatile products are determined using GC-MS qualitative analyses, using GC combination internal standard methods
Amount analysis；The molecular weight distribution and essential building blocks of fixedness product are characterized using means such as GPC, FT-IR.Knot
Fruit shows：After the catalytic treatment, lignin can realize 68.4% conversion, wherein fatty alcohol yield 11.9%, hydrocarbon
Yield 3.2%, guaiaci lignum phenols yield 0.4%, phenol yield 7.4%, phenols oligomer yield 35.8%.In this process
Have no obvious coking carbon deposition phenomenon.
Embodiment 5
Weigh 0.5g alkali lignins, 1mmol CrCl3, 1mmol ZnCl2It is molten that 40mL methanol is placed in 0.1g 5wt%Pd/C
In agent, system is through H24MPa is inflated after replacing 3 times, 5h are reacted in 260 DEG C.Quickly be cooled to room temperature, successively using filtering,
The modes such as solvent extraction are separated to wherein product.Volatility is produced using GC-MS qualitative analyses, using GC combinations internal standard method
Thing carries out quantitative analysis；The molecular weight distribution and essential building blocks of fixedness product are entered using means such as GPC, FT-IR
Row is characterized.As a result show：After the catalytic treatment, lignin can realize 67.4% conversion, wherein fatty alcohol yield 0.2%, carbon
Hydrogen compound yield 0.5%, guaiaci lignum phenols yield 1.7%, phenol yield 1.3%, phenols oligomer yield 27.3%.
Obvious coking carbon deposition phenomenon is had no during being somebody's turn to do.
Embodiment 6
Weigh 0.5g alkali lignins, 1mmol CrCl340mL methanol-waters (4 are placed in 0.1g 5wt%Pd/C:1) mix molten
In agent, system is through H24MPa is inflated after replacing 3 times, 5h are reacted in 260 DEG C.Quickly be cooled to room temperature, successively using filtering,
The modes such as solvent extraction are separated to wherein product.Volatility is produced using GC-MS qualitative analyses, using GC combinations internal standard method
Thing carries out quantitative analysis；The molecular weight distribution and essential building blocks of fixedness product are entered using means such as GPC, FT-IR
Row is characterized.As a result show：After the catalytic treatment, lignin can realize 63.6% conversion, wherein fatty alcohol yield 0.1%, carbon
Hydrogen compound yield 0.1%, guaiaci lignum phenols yield 1.8%, phenol yield 2.4%, phenols oligomer yield 52.8%.
Embodiment 7
Weigh 0.5g alkali lignins, 0.5mmol MgCl2It is placed in 0.1g 5wt%Pt/C in 40mL alcohol solvents, system
Through H24MPa is inflated after replacing 3 times, 5h are reacted in 260 DEG C.Room temperature quickly is cooled to, successively using filtering, solvent extraction
Wherein product is separated etc. mode.Volatile products are determined using GC-MS qualitative analyses, using GC combination internal standard methods
Amount analysis；The molecular weight distribution and essential building blocks of fixedness product are characterized using means such as GPC, FT-IR.Knot
Fruit shows：After the catalytic treatment, lignin can realize 81.5% conversion, wherein fatty alcohol yield 1.3%, and hydrocarbon is received
Rate 1.1%, guaiaci lignum phenols yield 2.6%, phenol yield 4.5%, phenols oligomer yield 51.1%.In this process not
See obvious coking carbon deposition phenomenon.
Embodiment 8
Weigh 0.75g alkali lignins, 1mmol AlCl3It is placed in 0.1g 5wt%Pd/C in 40mL normal propyl alcohol solvents, body
System is through H24MPa is inflated after replacing 3 times, 4h are reacted in 260 DEG C.Room temperature quickly is cooled to, successively using filtering, solvent extraction
The mode such as take to be separated to wherein product.Volatile products are carried out using GC-MS qualitative analyses, using GC combinations internal standard method
Quantitative analysis；The molecular weight distribution and essential building blocks of fixedness product are characterized using means such as GPC, FT-IR.
As a result show：After the catalytic treatment, lignin can realize 85.6% conversion, wherein fatty alcohol yield 5.6%, hydrocarbon
Yield 1.3%, guaiaci lignum phenols yield 0.7%, phenol yield 4.6%, phenols oligomer yield 54.3%.In this process
Have no obvious coking carbon deposition phenomenon.
Embodiment 9
Weigh 0.5g alkali lignins, 1mmol CrCl3It is placed in 0.1g 5wt%Pd/C in 40mL ethylene glycol solvents, system
Through H23MPa is inflated after replacing 3 times, 6h are reacted in 240 DEG C.Room temperature quickly is cooled to, successively using filtering, solvent extraction
Wherein product is separated etc. mode.Volatile products are determined using GC-MS qualitative analyses, using GC combination internal standard methods
Amount analysis；The molecular weight distribution and essential building blocks of fixedness product are characterized using means such as GPC, FT-IR.Knot
Fruit shows：After the catalytic treatment, lignin can realize 56.0% conversion, wherein fatty alcohol yield 0.1%, and hydrocarbon is received
Rate 0.1%, guaiaci lignum phenols yield 0.8%, phenol yield 1.2%, phenols oligomer yield 44.6%.In this process,
The side reaction triggered by solvent increases.
Embodiment 10
Weigh 1g alkali lignins, 2mmol CrCl3It is placed in 0.2g 5wt%Pd/C in 80mL alcohol solvents, system is through H2
2MPa is inflated after replacing 3 times, 5h are reacted in 260 DEG C.Room temperature quickly is cooled to, successively using the side such as filtering, solvent extraction
Formula is separated to wherein product.Quantitatively divided using GC-MS qualitative analyses, using GC combinations internal standard method to volatile products
Analysis；The molecular weight distribution and essential building blocks of fixedness product are characterized using means such as GPC, FT-IR.As a result table
It is bright：After the catalytic treatment, lignin can realize 79.5% conversion, wherein fatty alcohol yield 1.1%, hydrocarbon yield
1.2%, guaiaci lignum phenols yield 2.3%, phenol yield 4.1%, phenols oligomer yield 53.4%.Have no in this process
Obvious coking carbon deposition phenomenon.
Embodiment 11
Weigh 0.5g maize straws hydrolytic residue (acidolysis lignin), 0.01g 5wt%Pd/C and 1mmol CrCl3With put
In 60mL methanol solvates, system is through H25MPa is inflated after replacing 3 times, 3h are reacted in 260 DEG C.Room temperature quickly is cooled to,
Wherein product is separated using modes such as filtering, solvent extractions successively.Combined using GC-MS qualitative analyses, using GC interior
Mark method carries out quantitative analysis to volatile products；Using means such as GPC, FT-IR to the molecular weight distribution of fixedness product and
Essential building blocks are characterized.As a result show：After the catalytic treatment, lignin can realize 71.2% conversion, wherein fat
Alcohol yield 1.6%, hydrocarbon yield 1.5%, guaiaci lignum phenols yield 3.6%, phenol yield 12.7%, phenols is oligomeric
Body yield 48.0%.Obvious coking carbon deposition phenomenon is had no in this process.
Reference examples 1
Weigh 0.5g alkali lignins, 1mmol CrCl3With 1mmol ZnCl2It is placed in 40mL methanol solvates, system is through H2Put
4MPa is inflated after changing 3 times, 5h is reacted in 260 DEG C.Room temperature quickly is cooled to, successively using modes such as filtering, solvent extractions
Wherein product is separated.Quantitatively divided using GC-MS qualitative analyses, using GC combinations internal standard method to volatile products
Analysis；The molecular weight distribution and essential building blocks of fixedness product are characterized using means such as GPC, FT-IR.As a result table
It is bright：After the catalytic treatment, lignin can realize 42.9% conversion, wherein fatty alcohol yield 0.1%, hydrocarbon yield
0.3%, guaiaci lignum phenols yield 1.6%, phenol yield 1.0%, phenols oligomer yield 29.1%.Have no in this process
Obvious coking carbon deposition phenomenon.
It can be seen that and be catalyzed by metal chloride catalyst and noble metal hydrogenation by the contrast of embodiment and reference examples
The synergy of agent, under the reaction condition that the present invention is limited, can significantly improve the conversion ratio of lignin.
It is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention in above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, it is simple
Change, should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (2)
1. a kind of method of the efficient depolymerization of lignin, it is characterised in that comprise the following steps：
In 3MPa nitrogen or hydrogen gas atmosphere, according to 1mmol CrCl3, 0.1g 5wt%Pd/C, 0.5g dealkalize lignin
With the ratio of 40mL methanol, each material is sufficiently mixed, 280 DEG C are heated to, it is to obtain depolymerization product that 5h is reacted under agitation.
2. the method for the efficient depolymerization of lignin as claimed in claim 1, it is characterised in that the depolymerization product includes fat
Alcohol, hydrocarbon, monomer phenols and phenols oligomer.
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| CN107417498B (en) * | 2017-05-24 | 2020-01-31 | 中国科学技术大学 | method for catalytic depolymerization of lignin |
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