CN105037103A - Method for efficiently depolymerizing lignin - Google Patents
Method for efficiently depolymerizing lignin Download PDFInfo
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- CN105037103A CN105037103A CN201510373024.6A CN201510373024A CN105037103A CN 105037103 A CN105037103 A CN 105037103A CN 201510373024 A CN201510373024 A CN 201510373024A CN 105037103 A CN105037103 A CN 105037103A
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- xylogen
- yield
- phenols
- adopt
- depolymerization
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 229920005610 lignin Polymers 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 10
- 150000002989 phenols Chemical class 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims description 18
- 150000002191 fatty alcohols Chemical class 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 150000003384 small molecules Chemical class 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012429 reaction media Substances 0.000 claims description 5
- 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 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000010970 precious metal Substances 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 27
- 229910052799 carbon Inorganic materials 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 238000004939 coking Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 238000000638 solvent extraction 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
- 239000003550 marker Substances 0.000 description 12
- 238000004451 qualitative analysis Methods 0.000 description 12
- 238000004445 quantitative analysis Methods 0.000 description 12
- 239000012453 solvate Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 229920002488 Hemicellulose Polymers 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
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 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
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000196324 Embryophyta Species 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
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002154 agricultural waste Substances 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
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- -1 methoxyl group Chemical group 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification 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
- 238000004227 thermal cracking Methods 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for efficiently depolymerizing lignin. The method is characterized in that by taking metal chlorides and precious metal as composite catalysts, and taking a small molecular organic solvent as a medium, efficient catalytic depolymerization of renewable energy sources such as the lignin, which are difficult to utilize, can be realized under mild conditions, and further phenolic chemicals with high added value and biological oil with high calorific value are prepared. The method disclosed by the invention has the obvious advantages of a simple process, mild conditions, high yield of monophenol, controllable products, recycling of the catalysts and the like; the defects of high requirement on equipment, high energy consumption, low yield of target products, serious catalyst deactivation and the like existing in the current production method can be avoided.
Description
Technical field
The invention belongs to environmental protection technology; agricultural waste effectively utilizes technology and new energy technology development and utilizes field; to act synergistically the composite catalyst formed in particular to a kind of metal chloride and precious metal of adopting; in Small molecule organic solvents, efficient depolymerization xylogen, obtains the fatty alcohol of high yield, hydrocarbon polymer, monomer phenols and phenols oligomer.
Background technology
Along with the exhaustion day by day of fossil oil, energy demand is more and more nervous.Meanwhile, the CO of a large amount of combustion of fossil fuels discharge
2, SO
2, NO and dust, cause Greenhouse effect more serious, environment sustainable development constituted a threat to.Therefore, seek low-carbon (LC), oligosaprobic reproducible substitute energy becomes the common recognition of countries in the world.Biomass are directed to the photosynthesis of plant, have rich carbon content, reserves are large, distribution is wide, pollute the advantages such as low, cheap and renewable, compared with fossil oil, its sulfur-bearing and nitrogen content are all lower, ash oontent is also very little simultaneously, is considered to a kind of potential petrochemical industry substitute energy.Current, most research concentrate on form Wooden Biomass three kinds of main components (Mierocrystalline cellulose, hemicellulose and xylogen) in be easier to transform Mierocrystalline cellulose and hemicellulose on.Remaining xylogen is then usually discharged with the form of refuse, only in biorefinery factory, provides energy and steam as fuel.But, by the xylogen of three kinds of random bondings of phenylpropyl alcohol alkyl structure unit, there is several functions group and the unsaturated double-bond isoreactivity sites such as aromatic base, methoxyl group, phenol (alcohol) hydroxyl, carbonyl and carboxyl, and the C/H content ratio close with oil, be the renewable resources that occurring in nature uniquely directly can provide aromatic ring.Therefore, development new technologies are to make full use of xylogen in renewable biomass and prepare biofuel and biochemicals seems particularly important.
In recent years, the serial lignin depolymerization such as biological enzymolysis, thermo-cracking, catalytic hydrogenolysis, catalyzed oxidation and conversion means are widely used, but it also exists more deficiency.As: biological enzymolysis is consuming time oversize; Thermal cracking temperature is high, energy consumption is large; The easy coking and deactivation of catalytic hydrogenolysis; Catalyzed oxidation needs to add oxygenant, high to equipment requirements; The strong acid catalyst of especially current many technical processes, easily causes equipment corrosion, and catalyst carbon deposition inactivation is serious.
Summary of the invention
In order to overcome the deficiencies in the prior art and shortcoming, primary and foremost purpose of the present invention is to provide a kind of metal chloride and precious metal of adopting to act synergistically the composite catalyst formed, in Small molecule organic solvents, efficient depolymerization xylogen, obtains the fatty alcohol of high yield, hydrocarbon polymer, monomer phenols and phenols oligomer.By the regulation and control to catalyzer and reaction medium, increase the contact between xylogen raw material and catalyzer, enhancement of heat transfer and mass transfer process, reduce process energy consumption, and suppress the deactivation phenomenom that catalyzer is caused by coking carbon distribution.
Object of the present invention is realized by following technical proposals:
The method of the efficient depolymerization of a kind of xylogen.The method utilizes metal chloride and noble metal catalyst to work in coordination with and forms composite catalyst, xylogen is realized and phenolic compound is prepared in the depolymerization of rich lignin matter waste effectively in Small molecule organic solvents, under mild conditions, reinforcing mass transfer and heat transfer, reduce process energy consumption, and suppress catalyst carbon deposition.The method mainly comprises the following steps:
In the nitrogen or hydrogen gas atmosphere of 2 ~ 5MPa, according to the ratio of 0.5 ~ 2mmol metal chloride catalyst, 0.01 ~ 0.2g noble metal hydrogenation catalyst, 0.5 ~ 1.0g xylogen and 40 ~ 80mL reaction medium, the each material of abundant mixing, be heated to 240 ~ 300 DEG C, under agitation react 3 ~ 6h and can obtain depolymerization product, through being separated modes such as () such as filtrations, solvent extractions, purification can obtain desired substance; Described metal chloride catalyst is selected from ZnCl
2, MgCl
2, AlCl
3, CrCl
3in one or both, described noble metal hydrogenation catalyst is selected from Pd/C, Pt/C or Ru/C (in noble metal hydrogenation catalyst, the charge capacity of active ingredient is preferably 5wt%), described reaction medium is the mixture of Small molecule organic solvents or Small molecule organic solvents and water.
Further, above-mentioned xylogen is selected from alkali lignin, sodium sulfonate xylogen, dealkalize xylogen, organic solvent xylogen (as organic molten Herba penniseti xylogen) or acidolysis xylogen (can derive from the rich lignin matter wastes such as maize straw hydrolytic residue).
Further, above-mentioned Small molecule organic solvents is selected from methyl alcohol, ethanol, n-propyl alcohol or ethylene glycol.For the mixture with water, particular methanol-water mixture (volume ratio is preferably 4:1).
Further, the solution product of above-mentioned reaction mainly comprises fatty alcohol, hydrocarbon polymer, monomer phenols and phenols oligomer.
Principle of the present invention is: metal chloride and the precious metal composite catalyst formed that acts synergistically has good catalytic performance and carbon accumulation resisting ability, in Small molecule organic solvents, under certain processing condition, the efficiently and directionally catalytic degradation realizing xylogen and rich lignin matter prepares fatty alcohol, hydrocarbon polymer, monomer phenols and phenols oligomer.
Hinge structure of the present invention has following advantage and effect:
(1) catalyst system that the inventive method builds has synergy catalytic effect, compared with existing catalyst system, have active high, carbon accumulation resisting ability strong, simple to operate, is easy to product separation, the remarkable advantages such as environmental friendliness;
(2) solvent of the present invention is the mixture of methyl alcohol, ethanol, n-propyl alcohol, ethylene glycol or above-mentioned substance and water, biomass can be directed to, therefore, there is the remarkable advantage such as renewable, green and above-mentioned solvent can realize recycle after simple separation;
(3) the inventive method can select alkali lignin, sodium sulfonate xylogen, dealkalize xylogen, the different materials such as organic solvent xylogen and acidolysis xylogen, and therefore, raw material sources are extensive, and rich content is cheap;
(4) the inventive method compared with prior art, and maximum advantage is that, in above-mentioned system, the transformation efficiency of xylogen is high, and the target product yield such as fatty alcohol, hydrocarbon polymer, monomer phenols are high, and effectively can suppress the formation of coking carbon distribution;
(5) catalyst system provided by the invention possesses and good recycles performance.
Embodiment
Below in conjunction with embodiment, further detailed description is done to the present invention, but embodiments of the present invention are not limited thereto.
Embodiment 1
Take 0.5g dealkalize xylogen and 1mmolCrCl
3be placed in 40mL methanol solvate with 0.1g5wt%Pd/C, system is through H
23MPa is inflated, in 280 DEG C of reaction 5h after replacing 3 times.Be cooled to room temperature fast, adopt the modes such as filtration, solvent extraction to be separated wherein product successively.Adopt GC-MS qualitative analysis, adopt GC to carry out quantitative analysis in conjunction with marker method to volatile products; The means such as GPC, FT-IR are adopted to characterize the molecular weight distribution of non-volatility product and essential building blocks.Result shows: after this catalytic treatment, and xylogen can realize 82.9% conversion, wherein fatty alcohol yield 3.1%, hydrocarbon polymer yield 1.7%, pockwood phenols yield 2.6%, phenol yield 13.5%, phenols oligomer yield 48.4%.Have no obvious coking carbon deposition phenomenon in this process.
Embodiment 2
Take 0.5g sodium sulfonate xylogen and 1mmolCrCl
3be placed in 40mL methanol solvate with 0.1g5wt%Pd/C, system is through H
23MPa is inflated, in 300 DEG C of reaction 5h after replacing 3 times.Be cooled to room temperature fast, adopt the modes such as filtration, solvent extraction to be separated wherein product successively.Adopt GC-MS qualitative analysis, adopt GC to carry out quantitative analysis in conjunction with marker method to volatile products; The means such as GPC, FT-IR are adopted to characterize the molecular weight distribution of non-volatility product and essential building blocks.Result shows: after this catalytic treatment, and xylogen can realize 81.0% conversion, wherein fatty alcohol yield 11.9%, hydrocarbon polymer yield 1.1%, pockwood phenols yield 1.1%, phenol yield 5.3%, phenols oligomer yield 44.8%.Have no obvious coking carbon deposition phenomenon in this process.
Embodiment 3
Take the organic molten Herba penniseti xylogen of 0.5g and 1mmolCrCl
3be placed in 40mL methanol solvate with 0.1g5wt%Ru/C, system is through H
24MPa is inflated, in 260 DEG C of reaction 5h after replacing 3 times.Be cooled to room temperature fast, adopt the modes such as filtration, solvent extraction to be separated wherein product successively.Adopt GC-MS qualitative analysis, adopt GC to carry out quantitative analysis in conjunction with marker method to volatile products; The means such as GPC, FT-IR are adopted to characterize the molecular weight distribution of non-volatility product and essential building blocks.Result shows: after this catalytic treatment, and xylogen can realize 65.3% conversion, wherein fatty alcohol yield 0.8%, hydrocarbon polymer yield 1.1%, pockwood phenols yield 1.8%, phenol yield 9.6%, phenols oligomer yield 42.6%.Have no obvious coking carbon deposition phenomenon in this process.
Embodiment 4
Take 0.5g alkali lignin and 1mmolCrCl
3be placed in 40mL methanol solvate with 0.1g5wt%Pd/C, system is through N
23MPa is inflated, in 260 DEG C of reaction 5h after replacing 3 times.Be cooled to room temperature fast, adopt the modes such as filtration, solvent extraction to be separated wherein product successively.Adopt GC-MS qualitative analysis, adopt GC to carry out quantitative analysis in conjunction with marker method to volatile products; The means such as GPC, FT-IR are adopted to characterize the molecular weight distribution of non-volatility product and essential building blocks.Result shows: after this catalytic treatment, and xylogen can realize 68.4% conversion, wherein fatty alcohol yield 11.9%, hydrocarbon polymer yield 3.2%, pockwood phenols yield 0.4%, phenol yield 7.4%, phenols oligomer yield 35.8%.Have no obvious coking carbon deposition phenomenon in this process.
Embodiment 5
Take 0.5g alkali lignin, 1mmolCrCl
3, 1mmolZnCl
2be placed in 40mL methanol solvate with 0.1g5wt%Pd/C, system is through H
24MPa is inflated, in 260 DEG C of reaction 5h after replacing 3 times.Be cooled to room temperature fast, adopt the modes such as filtration, solvent extraction to be separated wherein product successively.Adopt GC-MS qualitative analysis, adopt GC to carry out quantitative analysis in conjunction with marker method to volatile products; The means such as GPC, FT-IR are adopted to characterize the molecular weight distribution of non-volatility product and essential building blocks.Result shows: after this catalytic treatment, and xylogen can realize 67.4% conversion, wherein fatty alcohol yield 0.2%, hydrocarbon polymer yield 0.5%, pockwood phenols yield 1.7%, phenol yield 1.3%, phenols oligomer yield 27.3%.Have no obvious coking carbon deposition phenomenon in this process.
Embodiment 6
Take 0.5g alkali lignin, 1mmolCrCl
3be placed in 40mL methanol-water (4:1) mixed solvent with 0.1g5wt%Pd/C, system is through H
24MPa is inflated, in 260 DEG C of reaction 5h after replacing 3 times.Be cooled to room temperature fast, adopt the modes such as filtration, solvent extraction to be separated wherein product successively.Adopt GC-MS qualitative analysis, adopt GC to carry out quantitative analysis in conjunction with marker method to volatile products; The means such as GPC, FT-IR are adopted to characterize the molecular weight distribution of non-volatility product and essential building blocks.Result shows: after this catalytic treatment, and xylogen can realize 63.6% conversion, wherein fatty alcohol yield 0.1%, hydrocarbon polymer yield 0.1%, pockwood phenols yield 1.8%, phenol yield 2.4%, phenols oligomer yield 52.8%.
Embodiment 7
Take 0.5g alkali lignin, 0.5mmolMgCl
2be placed in 40mL alcohol solvent with 0.1g5wt%Pt/C, system is through H
24MPa is inflated, in 260 DEG C of reaction 5h after replacing 3 times.Be cooled to room temperature fast, adopt the modes such as filtration, solvent extraction to be separated wherein product successively.Adopt GC-MS qualitative analysis, adopt GC to carry out quantitative analysis in conjunction with marker method to volatile products; The means such as GPC, FT-IR are adopted to characterize the molecular weight distribution of non-volatility product and essential building blocks.Result shows: after this catalytic treatment, and xylogen can realize 81.5% conversion, wherein fatty alcohol yield 1.3%, hydrocarbon polymer yield 1.1%, pockwood phenols yield 2.6%, phenol yield 4.5%, phenols oligomer yield 51.1%.Have no obvious coking carbon deposition phenomenon in this process.
Embodiment 8
Take 0.75g alkali lignin, 1mmolAlCl
3be placed in 40mL n-propyl alcohol solvent with 0.1g5wt%Pd/C, system is through H
24MPa is inflated, in 260 DEG C of reaction 4h after replacing 3 times.Be cooled to room temperature fast, adopt the modes such as filtration, solvent extraction to be separated wherein product successively.Adopt GC-MS qualitative analysis, adopt GC to carry out quantitative analysis in conjunction with marker method to volatile products; The means such as GPC, FT-IR are adopted to characterize the molecular weight distribution of non-volatility product and essential building blocks.Result shows: after this catalytic treatment, and xylogen can realize 85.6% conversion, wherein fatty alcohol yield 5.6%, hydrocarbon polymer yield 1.3%, pockwood phenols yield 0.7%, phenol yield 4.6%, phenols oligomer yield 54.3%.Have no obvious coking carbon deposition phenomenon in this process.
Embodiment 9
Take 0.5g alkali lignin, 1mmolCrCl
3be placed in 40mL ethylene glycol solvent with 0.1g5wt%Pd/C, system is through H
23MPa is inflated, in 240 DEG C of reaction 6h after replacing 3 times.Be cooled to room temperature fast, adopt the modes such as filtration, solvent extraction to be separated wherein product successively.Adopt GC-MS qualitative analysis, adopt GC to carry out quantitative analysis in conjunction with marker method to volatile products; The means such as GPC, FT-IR are adopted to characterize the molecular weight distribution of non-volatility product and essential building blocks.Result shows: after this catalytic treatment, and xylogen can realize 56.0% conversion, wherein fatty alcohol yield 0.1%, hydrocarbon polymer yield 0.1%, pockwood phenols yield 0.8%, phenol yield 1.2%, phenols oligomer yield 44.6%.In this process, the side reaction caused by solvent increases.
Embodiment 10
Take 1g alkali lignin, 2mmolCrCl
3be placed in 80mL alcohol solvent with 0.2g5wt%Pd/C, system is through H
22MPa is inflated, in 260 DEG C of reaction 5h after replacing 3 times.Be cooled to room temperature fast, adopt the modes such as filtration, solvent extraction to be separated wherein product successively.Adopt GC-MS qualitative analysis, adopt GC to carry out quantitative analysis in conjunction with marker method to volatile products; The means such as GPC, FT-IR are adopted to characterize the molecular weight distribution of non-volatility product and essential building blocks.Result shows: after this catalytic treatment, and xylogen can realize 79.5% conversion, wherein fatty alcohol yield 1.1%, hydrocarbon polymer yield 1.2%, pockwood phenols yield 2.3%, phenol yield 4.1%, phenols oligomer yield 53.4%.Have no obvious coking carbon deposition phenomenon in this process.
Embodiment 11
Take 0.5g maize straw hydrolytic residue (acidolysis xylogen), 0.01g5wt%Pd/C and 1mmolCrCl
3be placed in 60mL methanol solvate, system is through H
25MPa is inflated, in 260 DEG C of reaction 3h after replacing 3 times.Be cooled to room temperature fast, adopt the modes such as filtration, solvent extraction to be separated wherein product successively.Adopt GC-MS qualitative analysis, adopt GC to carry out quantitative analysis in conjunction with marker method to volatile products; The means such as GPC, FT-IR are adopted to characterize the molecular weight distribution of non-volatility product and essential building blocks.Result shows: after this catalytic treatment, and xylogen can realize 71.2% conversion, wherein fatty alcohol yield 1.6%, hydrocarbon polymer yield 1.5%, pockwood phenols yield 3.6%, phenol yield 12.7%, phenols oligomer yield 48.0%.Have no obvious coking carbon deposition phenomenon in this process.
Reference examples 1
Take 0.5g alkali lignin, 1mmolCrCl
3and 1mmolZnCl
2be placed in 40mL methanol solvate, system is through H
24MPa is inflated, in 260 DEG C of reaction 5h after replacing 3 times.Be cooled to room temperature fast, adopt the modes such as filtration, solvent extraction to be separated wherein product successively.Adopt GC-MS qualitative analysis, adopt GC to carry out quantitative analysis in conjunction with marker method to volatile products; The means such as GPC, FT-IR are adopted to characterize the molecular weight distribution of non-volatility product and essential building blocks.Result shows: after this catalytic treatment, and xylogen can realize 42.9% conversion, wherein fatty alcohol yield 0.1%, hydrocarbon polymer yield 0.3%, pockwood phenols yield 1.6%, phenol yield 1.0%, phenols oligomer yield 29.1%.Have no obvious coking carbon deposition phenomenon in this process.
Can be found out by the contrast of embodiment and reference examples, by the synergy of metal chloride catalyst and noble metal hydrogenation catalyst, under the reaction conditions that the present invention limits, the transformation efficiency of xylogen can be significantly improved.
It is the present invention's preferably embodiment in above-described embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (4)
1. a method for the efficient depolymerization of xylogen, is characterized in that, comprise the following steps:
In the nitrogen or hydrogen gas atmosphere of 2 ~ 5MPa, according to the ratio of 0.5 ~ 2mmol metal chloride catalyst, 0.01 ~ 0.2g noble metal hydrogenation catalyst, 0.5 ~ 1.0g xylogen and 40 ~ 80mL reaction medium, the each material of abundant mixing, be heated to 240 ~ 300 DEG C, under agitation react 3 ~ 6h and namely obtain depolymerization product; Described metal chloride catalyst is selected from ZnCl
2, MgCl
2, AlCl
3, CrCl
3in one or both, described noble metal hydrogenation catalyst is selected from Pd/C, Pt/C or Ru/C, and described reaction medium is the mixture of Small molecule organic solvents or Small molecule organic solvents and water.
2. the method for the efficient depolymerization of xylogen as claimed in claim 1, it is characterized in that, described xylogen is selected from alkali lignin, sodium sulfonate xylogen, dealkalize xylogen, organic solvent xylogen or acidolysis xylogen.
3. the method for the efficient depolymerization of xylogen as claimed in claim 1 or 2, it is characterized in that, described Small molecule organic solvents is selected from methyl alcohol, ethanol, n-propyl alcohol or ethylene glycol.
4. the method for the efficient depolymerization of xylogen as claimed in claim 1 or 2, it is characterized in that, described depolymerization product comprises fatty alcohol, hydrocarbon polymer, monomer phenols and phenols oligomer.
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| CN114477083A (en) * | 2022-03-14 | 2022-05-13 | 东南大学 | Biomass refining method and system by utilizing waste self-supplied hydrogen and solvent |
| CN114805024A (en) * | 2022-04-07 | 2022-07-29 | 东南大学 | Method for preparing cyclic alcohol by catalytic conversion of lignin depolymerized bio-oil |
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| CN112844379B (en) * | 2020-12-31 | 2022-06-14 | 华南理工大学 | Method for preparing monophenol chemicals by catalyzing lignin depolymerization through ruthenium loaded on metal organic framework material derivative |
| CN114477083A (en) * | 2022-03-14 | 2022-05-13 | 东南大学 | Biomass refining method and system by utilizing waste self-supplied hydrogen and solvent |
| CN114805024A (en) * | 2022-04-07 | 2022-07-29 | 东南大学 | Method for preparing cyclic alcohol by catalytic conversion of lignin depolymerized bio-oil |
| CN114805024B (en) * | 2022-04-07 | 2024-04-26 | 东南大学 | Method for preparing cyclic alcohol by catalytic conversion of lignin depolymerization bio-oil |
| CN115970732A (en) * | 2023-03-20 | 2023-04-18 | 河北工业大学 | Preparation method and application of lignin-derived carbon-anchored monatomic catalyst |
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