CN109701654A - A kind of method of Non-precious Metal Catalysts lignin selection depolymerization - Google Patents
A kind of method of Non-precious Metal Catalysts lignin selection depolymerization Download PDFInfo
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Abstract
The present invention relates to lignin to select depolymerization, the method for specifically a kind of complex-catalyzed lignin selection hydrogenolysis aromatic compound of base metal bipyridyl.This method realizes that highly selective cracking aryl oxide key obtains phenolic compound using lignin as raw material in 80 DEG C -200 DEG C, the nitrogen atmosphere of 0.1MPa.β-O-4 Model Molecule conversion ratio is up to 100%, and guaiacol yield is up to 95%, and styrene yield is up to 71%;When being converted using different lignin as raw material, aromatic series biology oil yield is 34-71%.The present invention is raw material using renewable natural biomass, and raw material is cheap and from a wealth of sources;Catalyst is non-precious metal catalyst;Without using inorganic acid, alkali, the generation that conventional wooden element is catalyzed a large amount of lye is avoided;Have many characteristics, such as that reaction condition is mild, do not consume hydrogen source, activity and selectivity is high, reaction process is environmental-friendly.
Description
Technical field
The present invention relates to lignin depolymerizations to prepare aromatic compound, specifically a kind of not consume hydrogen source and oxygen
M (mpo) under the conditions of sourcenComposition catalyst (M=Fe, Co, n=3;M=Ni, n=2) catalyst Liginon Resource splits
The method that solution prepares phenols aromatic compound.
Background technique
The high speed development of world economy has benefited from the extensive use of fossil energy.As fossil resource constantly consumes, the energy
Crisis and environmental problem are increasingly serious.Developing renewable new energy substitution fossil resource becomes the certainty of sustainable society development
Trend.
Biomass resource is renewable resource that is most abundant, most cheap and meeting sustainable development requirement on the earth.In life
In the component of substance, the content of lignin is only second to cellulose, is all regenerated every year with 50,000,000,000 tons of speed, be in nature most
Aromatic compound resource abundant.However, due to the physicochemical properties of lignin stubbornness, lignin conversion has using shortage
Effect approach, during biomass economy, the lignin more than 95% is discharged into rivers or burn-up in the form of " black liquor ", not only
Biomass resource is wasted, and is had seriously polluted the environment, resulting waste water accounts for the 30% of national amount of industrial wastewater, is
First object of China's industrial wastewater control.
Aromatic compound has a particularly important application in chemical industry, such as phenol and terephthalic acid (TPA) and its spreads out
Biology is not only widely used bulk chemical, while being also production resin, rubber, medicine intermediate and other finings
The important source material of product.Structurally, lignin is the three-dimensional network polymer using aromatic ring as main structure body, structural unit
Between be connected by ehter bond or carbon-carbon bond.Link between selective rhizotomy lignin structure unit can be achieved to be provided by lignin
Source prepares aromatic compound, so that the substitute as fossil resource is applied, mitigates world energy sources to a certain extent
The awkward situation of crisis, while also avoiding discarding the discharge of " black liquor ".
The selection depolymerization of lignin at present mainly includes reduction depolymerization, oxidative degradation, high temperature pyrolysis and biocatalysis depolymerization
Equal several methods (Chemical Reviews, 2015,15,11559-11624).World patent (WO99/10450) is in 260-
310 DEG C add hydrogen to prepare gasoline component in nitrogen atmosphere with base catalysis lignin, but phenyl ring complete hydrogenation needs more hydrogen sources, and
Base catalyst generates a large amount of waste liquids, pollutes environment.United States Patent (USP) (US 4,900,873) uses biphenyl or naphthalene at 300-400 DEG C
Aromatic compound is prepared for solvent pyrolysis lignin, but yield is less than 20%.United States Patent (USP) (US 5,807,952) is in 400-
The pyrolysis under air atmosphere of the strong base catalysts such as KOH lignin prepares phenolic compound at 600 DEG C, phenol maximum output up to 60%,
But severe reaction conditions, and generate a large amount of spent lyes.It is main that Chinese patent (CN 101768052A), which is described with zeroth order Ni,
The Catalyzed by Pt/M Bimetallic Nano lignin of active component adds hydrogen, and raw material maximum conversion reaches 53%.Canadian Patent is using gold
Belonging to sulfide is that catalyst Catalytic lignin degradation under 250-450 DEG C and 15-45 MPa obtains phenolic compound, and highest obtains
40% phenol yield.In terms of the finding of document, the lignin hydrodepolymerization and oxidative degradation reported at present are mostly with Pd, Pt etc.
Noble metal is catalyst, and reaction condition is relatively harsh, it usually needs additional addition acid or alkali, and need to consume hydrogen source or oxygen
Source.
Summary of the invention
The purpose of the present invention is to provide one kind under the conditions of not consuming hydrogen source and oxygen source M (mpo)nComposition catalyst
(M=Fe, Co, n=3;M=Ni, n=2) the Catalytic lignin resource depolymerization method for preparing phenols aromatic compound.It realizes
In different solvents Catalytic lignin and its modelling substrate in high yield, be converted into phenols aromatic compound with high selectivity
Object.
To achieve the above object, the technical scheme adopted by the invention is as follows:
A kind of method of Non-precious Metal Catalysts lignin selection depolymerization, with M (mpo)nOne of complex or two kinds with
The method that the selection depolymerization of upper catalyst lignin prepares aromatic compound, wherein M=Fe, Co or Ni, M=Fe or Co
When, n=3;N=2 when M=Ni, at M (mpo)nUnder effect, have form bonding ability polar solvent in, lignin or
One of lignin Model Molecule or two kinds or more react in closed reactor under inert atmosphere conditions, cracking preparation virtue
Fragrant compounds of group.
The lignin is one of organosolv lignin, sodium lignin sulfonate and alkali lignin or two kinds or more;It is described
Lignin Model Molecule is the compound with β-O-4 structure.
It is described that there is the polar solvent for forming bonding ability, specially water, methanol, dioxane, tetrahydrofuran, ethyl alcohol
One of or two kinds or more.
The mass ratio of the lignin and Model Molecule raw material and catalyst is 100:1-2:1, and the inert atmosphere is nitrogen
Gas, the initial pressure for filling nitrogen in reaction kettle at room temperature is 0.1MPa-5MPa;Reaction temperature is 80-200 DEG C;Reaction time
For 4h -48h.
The preferred 10:1 of the mass ratio of the lignin and Model Molecule raw material and catalyst, in the reaction kettle at room temperature
The initial pressure for filling nitrogen is preferably 0.1MPa;Preferably 200 DEG C of reaction temperature;Reaction time is preferably for 24 hours.
The M (mpo)nComposition catalyst specifically: Co (mpo)3,Fe(mpo)3,Ni(mpo)2One of or two
Kind or more, catalyst structure formula is shown below:
The aromatic compound is one kind or two of phenylol, lilac base and guaiaci lignum phenolic group aromatic compound
Kind or more.
Compared with prior art, the present invention has the following advantages:
1. raw material wood element of the invention is the most abundant natural reproducible aromatic compound resource, source in nature
Extensively, low in cost.Compared with existing petroleum base industrial production prepares aromatic compound, the present invention does not consume fossil money
Source has the advantages that raw material is reproducible, meets the requirement of sustainable development.
2. the present invention provides new way for the utilization of industrial lignin such as lignosulfonates, alkali lignin, reduce
Pollution caused by discharging and burn because of industrial lignin.
3. catalyst is using iron, cobalt, nickel as main active component, low in cost, activity and selectivity is high.
4. reaction system is environmental-friendly when taking water as a solvent, pollution-free;Inorganic acid, alkali are not used in reaction process, are avoided
Common problem of environmental pollution in lignin degradation technique.
5. reaction condition is mild, does not consume hydrogen source and oxygen source.
It is further described in detail below by specific embodiment.
Specific embodiment
Embodiment 1
M(mpo)nComposition catalyst (M=Fe, Co, n=3;M=Ni, n=2) it is specific the preparation method is as follows:
Fe(mpo)3Preparation: the anhydrous frerrous chloride of 1.0g and 3.0g 2,2'- bis- thio two (pyridine -1- oxide),
30h is stirred at room temperature in 0.43g sodium methoxide in 200ml methanol, filters after reaction, blue brown filtrate in 5 DEG C of refrigerated overnights,
Crystalline solid is obtained, liquid is separated, crystal is collected and is dried in vacuo up to 2.41g brown solid catalyst Fe (mpo)3, yield:
70%.
Co(mpo)3Preparation: waterless cobaltous chloride 2.0g, pyrithione sodium salt 2.3g are in 300ml tetrahydro furan
It is stirred at room temperature in muttering for 24 hours, then filters, brown-green filtrate obtains crystalline solid, liquid is separated in 5 DEG C of refrigerated overnights, collects
Crystal is dried in vacuo up to 5.28g solid catalyst Co (mpo)3, mol yield: 77%.
Ni(mpo)2Preparation: 2,2'- bis- thio two (pyridine -1- oxide) 0.38g be dissolved in 50ml methanol/acetonitrile (1:
1, v/v) in the mixed solvent, sequentially adds 0.24g Nickel dichloride hexahydrate after completely dissolution, and 0.10g sodium methoxide is stirred at room temperature
20h, solution become brown, filtering, and subsequent 5 DEG C of refrigerated overnights obtain brown water chestnut shape crystal, collect crystal and are dried in vacuo to obtain the final product
0.19g solid catalyst Co (mpo)3, mol yield: 60%.
Embodiment 2-10
M(mpo)nThe depolymerization of complex-catalyzed lignin Model Molecule 2- (2- methoxyphenoxy) -1- phenylethanol
Reaction: in a kettle by 50mg lignin Model Molecule and M (mpo)nComplex 5mg is dissolved in respectively in 10ml methanol, uses nitrogen
Gas is closed by reaction kettle in normal pressure state after replacing five times and is warming up to 80 DEG C -200 DEG C, with the speed progress of 1000 turns/min
It is stirred to react 4h-24h.After reaction, room temperature, sampling analysis after supernatant liquor filtering are down to.Product qualitative analysis passes through
GC-MS joint technology and standard specimen control, quantitative analysis are realized by gas chromatogram fixative.Reaction result is shown in Table 1.
M (mpo) under 1 different condition of tablenComplex-catalyzed lignin Model Molecule 2- (2- methoxyphenoxy) -1- benzene
Base ethyl alcohol depolymerization reaction result
As can be seen from the table, synthesized M (mpo)nComposition catalyst can Catalytic lignin Model Molecule 2-
(2- methoxyphenoxy) -1- phenylethanol depolymerization obtains three kinds of guaiacol, styrene and ethylbenzene aromatic compounds, different
Catalyst activity difference.
Embodiment 11-10
Ni(mpo)2Catalytic lignin Model Molecule 2- (2- methoxyphenoxy) -1- phenylethanol at different conditions
Depolymerization reaction: in a kettle by the lignin Model Molecule of certain mass and M (mpo)nComplex is dissolved in 30ml first respectively
In alcohol, nitrogen is filled with to pressure is set after being replaced five times with nitrogen, reaction kettle is warming up to 150 DEG C, with the speed of 1000 turns/min
Degree is stirred to react for 24 hours.After reaction, room temperature, sampling analysis after supernatant liquor filtering are down to.Product qualitative analysis is logical
It crosses GC-MS joint technology and standard specimen control, quantitative analysis is realized by gas chromatogram fixative.Reaction result is shown in Table 2.
Ni (mpo) under 2 different condition of table2Complex-catalyzed lignin Model Molecule 2- (2- methoxyphenoxy) -1-
Phenylethanol depolymerization reaction result
Embodiment 17-21
Ni(mpo)2The depolymerization reaction of complex-catalyzed difference lignin Model Molecule: in a kettle that 50 mg are wooden
Prime model molecule (being denoted as a-e respectively, structural formula is shown in attached formula 1) and Ni (mpo)25 mg of complex is dissolved in respectively in 10ml methanol,
It is in normal pressure state that reaction kettle is closed and be warming up to 150 DEG C after being replaced five times with nitrogen, it is stirred with the speed of 1000 turns/min
Mix reaction for 24 hours.After reaction, room temperature, sampling analysis after supernatant liquor filtering are down to.Product qualitative analysis is joined by GC-MS
It is compareed with technology and standard specimen, quantitative analysis is realized by gas chromatogram fixative.Reaction equation is as shown in Equation 1:
Formula 1:Ni (mpo)2It is catalyzed different beta-O-4 Model Molecule reaction equation
Reaction result is as shown in table 3.
Table 3Ni (mpo)2Complex-catalyzed difference lignin Model Molecule depolymerization reaction result
Embodiment 22-26
In a kettle by 50mg lignin Model Molecule and Ni (mpo)2It is molten that complex 5mg is dissolved in 10ml reaction respectively
In agent (respectively water, ethyl alcohol, tetrahydrofuran, dioxane, toluene), it will be reacted after being replaced five times with nitrogen in normal pressure state
Kettle is closed and is warming up to 150 DEG C, is stirred to react for 24 hours with the speed of 1000 turns/min.After reaction, it is down to room temperature, on
Sampling analysis after layer clear liquid filtering.Product qualitative analysis is compareed by GC-MS joint technology and standard specimen, and quantitative analysis passes through gas
Phase chromatography internal standard method is realized.It the results are shown in Table 4.
Table 4.Ni (mpo)2Catalytic lignin Model Molecule 2- (2- methoxyphenoxy) -1- phenylethanol is different molten
Reaction result in agent
Embodiment 27-39
True lignin reaction result
Be separately added into 50mg lignin, 5mg catalyst and 10ml methanol in a kettle, with nitrogen replace five times after in
Normal pressure state is closed by reaction kettle and is warming up to goal response temperature, is stirred to react with the speed of 1000 turns/min to setting
Determine the reaction time.After reaction, it is down to room temperature, reaction solution filtering, 50 DEG C of rotary evaporations of filtrate are gone out solvent, and fragrance is obtained
The weighing of compound bio oil calculates bio oil yield.The component that bio oil is included is compareed by GC-MS joint technology and standard specimen
It is analyzed.The result shows that in addition to guaiacyl propane, lilac base propane, guaiacyl propyl alcohol and lilac in bio oil
It further include the phenolic compound of the C6-C9 such as phenol, 2- methylphenol, 4- ethyl -phenol other than base propyl alcohol.Embodiment 27-39's
Reaction result is shown in Table 5.
Table 5M (mpo) n catalyst is catalyzed different lignin depolymerization activities and compares
The present invention realizes that highly selective cracking aryl oxide key obtains phenolic compound.β-O-4 Model Molecule conversion ratio is up to
100%, guaiacol yield is up to 95%, and styrene yield is up to 71%;When being converted using different lignin as raw material,
Aromatic series biology oil yield is 34-71%.The present invention is raw material using renewable natural biomass, and raw material is cheap and source is wide
It is general;Catalyst is non-precious metal catalyst;Without using inorganic acid, alkali, the production that conventional wooden element is catalyzed a large amount of lye is avoided
It is raw;Have many characteristics, such as that reaction condition is mild, do not consume hydrogen source, activity and selectivity is high, reaction process is environmental-friendly.
Claims (7)
1. a kind of method of Non-precious Metal Catalysts lignin selection depolymerization, it is characterised in that: with M (mpo)nOne of complex
Or the method that the selection depolymerization of two kinds or more catalyst lignin prepares aromatic compound, wherein M=Fe, Co or Ni, M=
When Fe or Co, n=3;N=2 when M=Ni, at M (mpo)nIt is wooden in there is the polar solvent for forming bonding ability under effect
Element or one of lignin Model Molecule or two kinds or more react, cracking is made under inert atmosphere conditions in closed reactor
Standby aromatic compound.
2. according to the method for claim 1, it is characterised in that: the lignin is organosolv lignin, sodium lignin sulfonate
And one of alkali lignin or two kinds or more;The lignin Model Molecule is the compound with β-O-4 structure.
3. according to the method for claim 1, it is characterised in that: it is described that there is the polar solvent for forming bonding ability, specifically
For one of water, methanol, dioxane, tetrahydrofuran, ethyl alcohol or two kinds or more.
4. according to the method for claim 1, it is characterised in that: the matter of the lignin and Model Molecule raw material and catalyst
For amount than being 100:1-2:1, the inert atmosphere is nitrogen, and the initial pressure for filling nitrogen in reaction kettle at room temperature is 0.1MPa-
5MPa;Reaction temperature is 80-200 DEG C;Reaction time is 4h -48h.
5. according to method described in claim 1 or 4, it is characterised in that: the lignin and Model Molecule raw material and catalyst
The preferred 10:1 of mass ratio, the initial pressure that nitrogen is filled in the reaction kettle at room temperature is preferably 0.1MPa;Reaction temperature is excellent
Select 200 DEG C;Reaction time is preferably for 24 hours.
6. according to the method for claim 1, it is characterised in that: the M (mpo)nComposition catalyst specifically: Co
(mpo)3,Fe(mpo)3,Ni(mpo)2One of or two kinds or more, catalyst structure formula is shown below:
7. according to the method for claim 1, it is characterised in that: the aromatic compound be phenylol, lilac base and
The one or two or more kinds of guaiaci lignum phenolic group aromatic compound.
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CN112759619A (en) * | 2021-02-25 | 2021-05-07 | 福建农林大学 | Process for the one-pot conversion of lignocellulose to phenolic compounds, polyols and organic acids |
CN113666845A (en) * | 2021-07-21 | 2021-11-19 | 南京工业大学 | Lignin-based diphenylmethane diisocyanate and preparation method and application thereof |
CN114618548A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Cobalt-based catalyst, preparation method thereof and application of cobalt-based catalyst in catalytic oxidative cracking of lignin |
CN115160382A (en) * | 2022-07-28 | 2022-10-11 | 中国科学技术大学 | Method for catalytic depolymerization of lignin |
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CN112441888A (en) * | 2019-09-04 | 2021-03-05 | 中国科学院大连化学物理研究所 | Pd-ReOx/CeO2Method for preparing nitrogen-containing aromatic compound by catalyzing lignin ammoniation reaction |
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CN112625764A (en) * | 2019-09-24 | 2021-04-09 | 南阳师范学院 | Method for producing biofuel by efficiently converting lignin |
CN114618548A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Cobalt-based catalyst, preparation method thereof and application of cobalt-based catalyst in catalytic oxidative cracking of lignin |
CN112759619A (en) * | 2021-02-25 | 2021-05-07 | 福建农林大学 | Process for the one-pot conversion of lignocellulose to phenolic compounds, polyols and organic acids |
CN112759619B (en) * | 2021-02-25 | 2023-10-20 | 山东百沃生物科技有限公司 | Method for converting lignocellulose into phenolic compounds, polyalcohol and organic acid by one-pot method |
CN113666845A (en) * | 2021-07-21 | 2021-11-19 | 南京工业大学 | Lignin-based diphenylmethane diisocyanate and preparation method and application thereof |
CN115160382A (en) * | 2022-07-28 | 2022-10-11 | 中国科学技术大学 | Method for catalytic depolymerization of lignin |
CN115160382B (en) * | 2022-07-28 | 2024-03-26 | 中国科学技术大学 | Method for catalytic depolymerization of lignin |
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