CN105503540A - Method for preparation of benzene ring phenol compound from alkali lignin - Google Patents
Method for preparation of benzene ring phenol compound from alkali lignin Download PDFInfo
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Abstract
The invention relates to a method for preparation of a benzene ring phenol compound from alkali lignin. At a reaction temperature of 150DEG C-300DEG C, under a hydrogen pressure of 0.1MPa-13Mpa, under the action of a metal catalyst, in a solvent containing choline ionic liquid, alkali lignin is taken as the reaction raw material, hydrogenation degradation of alkali lignin is carried out to prepare the benzene ring phenol compound. Specifically, the solvent containing choline ionic liquid can be one of a solvent only containing choline ionic liquid, a mixed solvent composed of choline ionic liquid and an inorganic solvent, or a mixed solvent composed of choline ionic liquid and an organic solvent; and the metal catalyst is raney nickel and/or loaded metal catalyst. The method provided by the invention has the significant advantages of cheap and easily available raw materials, simple catalyst preparation process, easy recovery, easy separation of product and the like.
Description
Technical field
The present invention relates to the method preparing benzene ring phenolic compound with alkali lignin.One in the mixed solvent that the mixed solvent formed with cholinium ion liquid, cholinium ion liquid and inorganic solvent or cholinium ion liquid and organic solvent form is for reaction medium, under the effect of load type metal catalyst, hydrogenation degraded alkali lignin prepares benzene ring phenolic compound.
Background technology
Xylogen is that nature is only second to cellulosic biomass-based material, and the whole world produces about 50,000,000,000 tons per year.China is as agricultural and forestry big country, and annual agriculture and forestry organic waste material reaches 700,000,000 tons.One of main component is wherein exactly xylogen.Also lignin component is included in the waste that people's daily life produces and the industrial residue of part.Xylogen is converted into efficiently energy chemistry product and not only effectively can alleviates the increasingly serious energy shortage problem of China, also can reduce the pressure of environmental improvement simultaneously.
Xylogen contains abundant aromatic functional groups and higher ratio of carbon-hydrogen, is that the high heating value liquid fuel of representative also can obtain and comprises the Chemicals that phenols etc. has high added value by both having obtained with aromatic hydrocarbons the degraded of xylogen and catalyzed conversion.At present, the transform mode of xylogen is mainly undertaken by the route of catalytic reduction, but the reaction conditions adopting High Temperature High Pressure, cause generating a large amount of by products, be difficult to be separated. moreDocument (Angew.Chem.Int.Ed., 2014,53,1) adopt Supercritical Ethanol method lignin degrading, temperature of reaction is 553K, and reaction pressure is 10.5MPa, take MoC/AC as the micromolecular compound that catalyzer can obtain more than 25 kinds, but be difficult to control its selectivity.Patent CN102676202 discloses utilization and to support on molecular sieve Ni base or Pd is catalyst based a step xylogen cracking can be converted into C6-C9 naphthenic hydrocarbon and aromatic hydrocarbon, and C12-C20 bicyclic alkane; In addition, document (Appl.Catal.B:Environ., 2014,146,289) is 673K in temperature of reaction, and the yield that lignin conversion generates phenolic compound is only 17%.More than the reaction high-temperature high-voltage reaction condition that adopts obtains reaction product through hydrogenolysis more.These class methods easily cause reactant to form carbon distribution along with the carrying out coking polymerization of time, and then reduce reactive behavior and selectivity, improve reaction danger coefficient.
Therefore development is a kind of environmentally friendly, and safety simple to operate, the reaction scheme that Atom economy is high has very important meaning.
Summary of the invention
The object of the invention is to the waste alkali lignin in industrial production for raw material, by cholinium ion liquid carrying height alkali lignin solubleness in the liquid phase, adopt metal catalyst, under suitable reaction conditions, generate benzene ring phenolic compound by hydrogenolysis, primary product is phenol and p-ethyl phenol compound.
For achieving the above object, the present invention is by the following technical solutions:
Temperature of reaction be 150 DEG C-300 DEG C, under hydrogen pressure is 0.1MPa-13MPa condition, under the effect of metal catalyst, in the solvent containing cholinium ion liquid, take alkali lignin as reaction raw materials, carry out hydrogenation degraded alkali lignin and prepare benzene ring phenolic compound;
Wherein can be the one in mixed solvent or cholinium ion liquid that the solvent, cholinium ion liquid and the inorganic solvent that only contain cholinium ion liquid form and the mixed solvent that organic solvent forms containing the solvent of cholinium ion liquid.
In reaction system, the mass concentration of alkali lignin is 0.1-200%, and preferred mass concentration is 10-100%.
Reaction is carried out in high-pressure reactor, and the reaction times is 0.5h-24h, and the preferred reaction time is 3h-12h;
Preferable reaction temperature is 180 DEG C-250 DEG C; Preferred hydrogen pressure is 1MPa-4MPa.
Metal catalyst is Raney's nickel and/or load type metal catalyst;
Load type metal catalyst is that active constituent loading is on carrier with one or two or more kinds in metallic iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, tungsten, copper, silver or gold; Carrier is one or two or more kinds in silicon oxide, silicon carbide, gac, aluminum oxide, zinc oxide, ferric oxide, titanium oxide or zirconium white; In load type metal catalyst, the mass content of metal active constituent is 0.5-40%, is preferably 10-20%;
The mass concentration of metal catalyst in reaction system is 0.001-5%, is preferably 0.1-1%.
Preferred load type metal catalyst is for active constituent loading is on carrier with one or more in metallic nickel, rhodium, gold or palladium; Preferred vector is one or two or more kinds of titanium oxide, gac or ferric oxide.
Metal catalyst is more preferably the one in Raney's nickel and loaded catalyst palladium carbon.
Cholinium ion liquid of the present invention is choline chloride 60, bursine, trifluoroacetic acid choline, levulinic acid choline, trifluoromethanesulfonic acid choline, methylsulphonic acid choline, Phenylsulfonic acid choline, phosphorylcholine or choline sulfate;
Inorganic solvent is water;
Organic solvent is one or two or more kinds in ethyl acetate, methylene dichloride, methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, propylene glycol, toluene, dimethylbenzene, tetrahydrofuran (THF), methyltetrahydrofuran or ether;
When described solvent is mixed solvent, cholinium ion liquid is 100:1 to 1:100 with inorganic solvent or organic solvent volume ratio.
Cholinium ion liquid is methylsulphonic acid choline or phosphorylcholine;
Inorganic solvent is water;
Organic solvent is one or both in ethyl acetate or ethanol;
When described solvent is mixed solvent, cholinium ion liquid is 10:1 to 1:10 with inorganic solvent or organic solvent volume ratio.
Benzene ring phenolic compound of the present invention is mainly phenol, pyrocatechol, p-ethyl phenol, methyl catechol, 4-ethyl guaiacol and 4-ethyl pyrocatechol.
In the present invention, Raney's nickel is commodity purchasing, and producer is the many power catalyst plants in Anshan, model ZL-N311.
Advantageous Effects
1) in cholinium ion liquid, use Biological resources to prepare phenolic compound, raw material is renewable, and cost is low, and Sustainable development;
2) selectivity of effective control C-C key and C-O cleavage reaction, highly selective prepares benzene ring type compounds;
3) the present invention has that cheaper starting materials is easy to get, catalyst preparation process is simple, reclaim the remarkable advantages such as easy, product is easily separated.
Accompanying drawing explanation
Fig. 1 is alkali lignin depolymerization reaction after product color atlas in embodiment 23; Wherein retention time t=5.473min is mark in p-Xylol, t=6.749min is phenol, t=7.989min is methyl catechol, t=8.732min is 4-ethylphenol, t=9.036min is pyrocatechol, t=9.846min is 4-ethyl guaiacol, and t=10.728min is 4-ethyl-pyrocatechol;
Fig. 2 is the mass spectrum of primary product phenol in embodiment 23;
Fig. 3 is the mass spectrum of primary product methyl catechol in embodiment 23;
Fig. 4 is the mass spectrum of primary product 4-ethylphenol in embodiment 23;
Fig. 5 is the mass spectrum of primary product pyrocatechol in embodiment 23;
Fig. 6 is the mass spectrum of primary product 4-ethyl guaiacol in embodiment 23;
Fig. 7 is the mass spectrum of primary product 4-ethyl pyrocatechol in embodiment 23;
Embodiment
The following example will contribute to understanding the present invention, but protection scope of the present invention is not limited to these embodiments.
Embodiment 1
Metal catalyst: can commodity in use catalyzer, as: the catalyzer Raney's nickel used in embodiment is commodity purchasing, and producer is the many power catalyst plants in Anshan, model ZL-N311, Ni content >=90%.
Also pickling process can be adopted, according to different loadings, get the metal precursor of different concns, self-control load type metal catalyst, example is prepared as: at the metal precursor Palladous chloride of correspondence and the aqueous solution medium volume Immesion active carbon carrier of ruthenium trichloride, in 60 DEG C of oven dry after stirring, then in 120 DEG C of dryings 12 hours with Pd/C and Ru/C, last 450 DEG C of reduction 1 hour in hydrogen atmosphere, use O after cooling again
2content is the O of 1%
2/ N
2gas mixture passivation 6 hours, can obtain metal catalyst.
Embodiment 2-10
Taking total amount is that the phosphorylcholine of 10 grams or mixed solvent proceed in 75 milliliters of reactors, add 0.25 gram of alkali lignin and 0.05 gram of Raney's nickel catalyst, pass into hydrogen exchange 3 times, be filled with the hydrogen of a certain amount of pressure, temperature of reaction is risen to certain temperature, rapid stirring 800rpm, react after 6 hours and stop heating, blow-off valve is opened when temperature is down to room temperature, still internal pressure is made to be down to normal pressure, collect product, by the product extracted into EtOAc that obtains 3 times, adopt gas chromatographic analysis products distribution, and steam instrument removing ethyl acetate with revolving, be weighed as total product weight.
The account form of transformation efficiency X (%):
Reaction conditions and reaction result refer to table 1.
Table 1
As table 1 result shows, the reaction medium used, between the interval and hydrogen pressure 1MPa-3MPa of temperature of reaction 180 DEG C-220 DEG C, all serves promoter action to hydrogenolysis.The mixed solvent adopting ethanol and phosphorylcholine to form significantly improves the transformation efficiency of alkali lignin, reaches as high as 56%.In addition under low cost, nickel catalyzator effect simple and easy to get, alkali lignin highly selective can generate benzene ring phenolic compound, and the highest overall selectivity can close to 90%.
Embodiment 11-16
Adopt the reaction conditions of embodiment 2-10, only change catalyzer, reaction conditions and reaction result refer to table 2.
Table 2
As shown in table 2, alkali lignin can in catalytic process involved in the present invention, and in different catalysts, highly selective is converted into ethylphenol.Wherein, on Raney's nickel catalyst and Pd catalyzer, the selectivity of ethylphenol can reach 47% and 48%, significantly shows the performance being better than other catalyzer in phosphorylcholine complex media.
Embodiment 17-27
Taking total amount is that the methylsulphonic acid choline of 10 grams or mixed solvent proceed in 75 milliliters of reactors, add 0.25 gram of alkali lignin and 0.05 gram of metal catalyst, pass into hydrogen exchange 3 times, be filled with the hydrogen of a certain amount of pressure, temperature of reaction is risen to certain temperature, rapid stirring 800rpm, react after 6 hours and stop heating, open blow-off valve when temperature is down to room temperature, make still internal pressure be down to normal pressure, collect product, by the product extracted into EtOAc that obtains 3 times, adopt gas chromatographic analysis products distribution, steaming instrument removing ethyl acetate with revolving, being weighed as total product weight.
The calculation formula of transformation efficiency is as described in formula 1, and reaction conditions and reaction result refer to table 3.
Table 3
As table 3 result shows, the acetylcholine response medium used, between the interval and hydrogen pressure 1MPa-4MPa of temperature of reaction 180 DEG C-200 DEG C, all serves promoter action to hydrogenolysis.The transformation efficiency of the mixed solvent remarkably influenced alkali lignin adopting ethanol and methylsulphonic acid choline to form, alkali lignin peak rate of conversion can reach 40%.In addition under nickel catalyzator effect, alkali lignin highly selective can generate benzene ring phenolic compound, phenolic compound overall selectivity can reach more than 98%, particularly the mass ratio of mixed solvent methylsulphonic acid choline and water be 8:2, hydrogen pressure be 4MPa time, the selectivity of phenol and 4-ethylphenol is best, can reach more than 75%.
Claims (9)
1. prepare a method for benzene ring phenolic compound with alkali lignin, it is characterized in that:
Temperature of reaction be 150 DEG C-300 DEG C, under hydrogen pressure is 0.1MPa-13MPa condition, under the effect of metal catalyst, in the solvent containing cholinium ion liquid, take alkali lignin as reaction raw materials, carry out hydrogenation degraded alkali lignin and prepare benzene ring phenolic compound;
Wherein can be the one in mixed solvent or cholinium ion liquid that the solvent, cholinium ion liquid and the inorganic solvent that only contain cholinium ion liquid form and the mixed solvent that organic solvent forms containing the solvent of cholinium ion liquid.
2. in accordance with the method for claim 1, it is characterized in that:
In reaction system, the mass concentration of alkali lignin is 0.1-200%, and preferred mass concentration is 10-100%.
3. in accordance with the method for claim 1, it is characterized in that:
Reaction is carried out in high-pressure reactor, and the reaction times is 0.5h-24h, and the preferred reaction time is 3h-12h;
Preferable reaction temperature is 180 DEG C-250 DEG C; Preferred hydrogen pressure is 1MPa-4MPa.
4. in accordance with the method for claim 1, it is characterized in that:
Metal catalyst is Raney's nickel and/or load type metal catalyst;
Load type metal catalyst is that active constituent loading is on carrier with one or two or more kinds in metallic iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, tungsten, copper, silver or gold; Carrier is one or two or more kinds in silicon oxide, silicon carbide, gac, aluminum oxide, zinc oxide, ferric oxide, titanium oxide or zirconium white; In load type metal catalyst, the mass content of metal active constituent is 0.5-40%, is preferably 10-20%;
The mass concentration of metal catalyst in reaction system is 0.001-5%, is preferably 0.1-1%.
5. in accordance with the method for claim 4, it is characterized in that:
Preferred load type metal catalyst is for active constituent loading is on carrier with one or more in metallic nickel, rhodium, gold or palladium; Preferred vector is one or two or more kinds of titanium oxide, gac or ferric oxide.
6. in accordance with the method for claim 4, it is characterized in that:
Metal catalyst is more preferably the one in Raney's nickel and loaded catalyst palladium carbon.
7. in accordance with the method for claim 1, it is characterized in that:
Described cholinium ion liquid is choline chloride 60, bursine, trifluoroacetic acid choline, levulinic acid choline, trifluoromethanesulfonic acid choline, methylsulphonic acid choline, Phenylsulfonic acid choline, phosphorylcholine or choline sulfate;
Inorganic solvent is water;
Organic solvent is one or two or more kinds in ethyl acetate, methylene dichloride, methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, propylene glycol, toluene, dimethylbenzene, tetrahydrofuran (THF), methyltetrahydrofuran or ether;
When described solvent is mixed solvent, cholinium ion liquid is 100:1 to 1:100 with inorganic solvent or organic solvent volume ratio.
8. in accordance with the method for claim 1, it is characterized in that:
Cholinium ion liquid is methylsulphonic acid choline or phosphorylcholine;
Inorganic solvent is water;
Organic solvent is one or both in ethyl acetate or ethanol;
When described solvent is mixed solvent, cholinium ion liquid is 10:1 to 1:10 with inorganic solvent or organic solvent volume ratio.
9. in accordance with the method for claim 1, it is characterized in that: described benzene ring phenolic compound is mainly phenol, pyrocatechol, p-ethyl phenol, methyl catechol, 4-ethyl guaiacol and 4-ethyl pyrocatechol.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517190A (en) * | 2016-10-27 | 2017-03-22 | 陕西科技大学 | Co-production method of monophenol compound and activated carbon by lignin catalytic pyrolysis |
| CN107051582A (en) * | 2017-05-19 | 2017-08-18 | 青岛科技大学 | The Benzylation reaction new method of one kind catalysis |
| CN107235829A (en) * | 2017-06-20 | 2017-10-10 | 华南理工大学 | The method that a kind of selective hydrogenolysis of lignin prepares 4 ethyl -phenols |
| CN107286006A (en) * | 2017-06-09 | 2017-10-24 | 东南大学 | A kind of method that catalyzed alcoholysis lignin prepares Acetovanillone and acetosyringone |
| CN109967072A (en) * | 2019-03-06 | 2019-07-05 | 华南理工大学 | A kind of lignin-base nano flower porous carbon support load Ru base catalyst and preparation method thereof and the application in lignin depolymerization |
| CN110128247A (en) * | 2019-05-23 | 2019-08-16 | 南京林业大学 | A kind of method of catalytic lignin depolymerization |
| CN110229049A (en) * | 2019-07-15 | 2019-09-13 | 中国林业科学研究院林产化学工业研究所 | A kind of method of microwave cooperating double solvents Catalytic lignin hydrogenolysis preparation phenolic substances |
| CN111302906A (en) * | 2020-03-31 | 2020-06-19 | 河北工业大学 | Method for preparing guaiacol by catalyzing lignin with binuclear sulfonic acid type ionic liquid |
| CN112657512A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Silver-fluorine supported catalyst, preparation method and application |
| CN114713232A (en) * | 2022-04-25 | 2022-07-08 | 中国科学院生态环境研究中心 | Non-noble metal catalyst and preparation method and application thereof |
| CN115120521A (en) * | 2022-06-16 | 2022-09-30 | 广东省科学院化工研究所 | Polyphenol active composition and preparation method and application thereof |
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Cited By (18)
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|---|---|---|---|---|
| CN106517190B (en) * | 2016-10-27 | 2018-05-04 | 陕西科技大学 | A kind of method of catalytic lignin thermal cracking coproduction list phenolic compound and activated carbon |
| CN106517190A (en) * | 2016-10-27 | 2017-03-22 | 陕西科技大学 | Co-production method of monophenol compound and activated carbon by lignin catalytic pyrolysis |
| CN107051582A (en) * | 2017-05-19 | 2017-08-18 | 青岛科技大学 | The Benzylation reaction new method of one kind catalysis |
| CN107051582B (en) * | 2017-05-19 | 2019-08-13 | 青岛科技大学 | A kind of Benzylation reaction new method of catalysis |
| CN107286006B (en) * | 2017-06-09 | 2021-05-04 | 东南大学 | Method for preparing vanillone and acetosyringone by catalytic alcoholysis of lignin |
| CN107286006A (en) * | 2017-06-09 | 2017-10-24 | 东南大学 | A kind of method that catalyzed alcoholysis lignin prepares Acetovanillone and acetosyringone |
| CN107235829A (en) * | 2017-06-20 | 2017-10-10 | 华南理工大学 | The method that a kind of selective hydrogenolysis of lignin prepares 4 ethyl -phenols |
| CN107235829B (en) * | 2017-06-20 | 2020-05-22 | 华南理工大学 | Method for preparing 4-ethylphenol by selective hydrogenolysis of lignin |
| CN109967072A (en) * | 2019-03-06 | 2019-07-05 | 华南理工大学 | A kind of lignin-base nano flower porous carbon support load Ru base catalyst and preparation method thereof and the application in lignin depolymerization |
| CN110128247A (en) * | 2019-05-23 | 2019-08-16 | 南京林业大学 | A kind of method of catalytic lignin depolymerization |
| CN110128247B (en) * | 2019-05-23 | 2022-05-06 | 南京林业大学 | Method for catalytic depolymerization of lignin |
| CN110229049A (en) * | 2019-07-15 | 2019-09-13 | 中国林业科学研究院林产化学工业研究所 | A kind of method of microwave cooperating double solvents Catalytic lignin hydrogenolysis preparation phenolic substances |
| CN112657512A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Silver-fluorine supported catalyst, preparation method and application |
| CN111302906A (en) * | 2020-03-31 | 2020-06-19 | 河北工业大学 | Method for preparing guaiacol by catalyzing lignin with binuclear sulfonic acid type ionic liquid |
| CN111302906B (en) * | 2020-03-31 | 2022-09-13 | 河北工业大学 | Method for preparing guaiacol by catalyzing lignin with binuclear sulfonic acid type ionic liquid |
| CN114713232A (en) * | 2022-04-25 | 2022-07-08 | 中国科学院生态环境研究中心 | Non-noble metal catalyst and preparation method and application thereof |
| CN115120521A (en) * | 2022-06-16 | 2022-09-30 | 广东省科学院化工研究所 | Polyphenol active composition and preparation method and application thereof |
| CN115120521B (en) * | 2022-06-16 | 2024-05-28 | 广东省科学院化工研究所 | Polyphenol active composition and preparation method and application thereof |
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