阅读说明：本技术 一种在双相体系界面全组分解聚原生生物质制备平台化合物的方法 (A method of at diphasic system interface, full constituent depolymerization protist matter prepares platform chemicals ) 是由 欧阳新平 马观凤 邱学青 谢心怡 郭岳 饶睿恒 于 2019-08-20 设计创作，主要内容包括：本发明属于生物炼制技术领域,公开了一种在双相体系界面全组分解聚原生生物质制备平台化合物的方法。本发明方法包括以下步骤：将木粉、催化剂加入到水/有机溶剂双相溶剂中,分散均匀,通入氢气,加热反应,过滤,分离,得到分解后产物；所述的水/有机溶剂双相溶剂为水/乙酸甲酯、水/正丁醇、水/甲基异丙基甲酮、水/乙酸异丁酯中的一种；所述的催化剂包括氢解催化剂和酸催化剂。本发明在温和条件下一步处理原生生物质材料,原位分离并解聚木质素一步制备单酚类化合物,解聚纤维素和半纤维制备平台化合物,实现生物质的全组分解聚。水相产物收率高达64.81％,单酚类化合物收率高达19.49％,选择性高达65.48％,产物种类简单。(The invention belongs to biorefinery technical fields, disclose a kind of method for preparing platform chemicals in diphasic system interface full constituent depolymerization protist matter.The method of the present invention is uniformly dispersed the following steps are included: wood powder, catalyst are added in water/organic solvent biphasic solvent, is passed through hydrogen, and heating reaction is filtered, separation, product after being decomposed；The water/organic solvent biphasic solvent is one of water/methyl acetate, water/n-butanol, water/methyl isopropyl ketone, water/isobutyl acetate；The catalyst includes hydrogenolysis catalyst and acid catalyst.A step handles protist material to the present invention in a mild condition, and separation in situ and one step of depolymerization lignin prepare single phenolic compound, and depolymerizing cellulose and hemicellulose prepare platform chemicals, realize the full constituent depolymerization of biomass.Water-phase product yield is up to 64.81%, and single phenol class compound yield is up to 19.49%, and selectivity up to 65.48%, product species are simple.)

1. a kind of method for preparing platform chemicals in diphasic system interface full constituent depolymerization protist matter, it is characterised in that packet It includes following steps: wood powder, catalyst being added in water/organic solvent biphasic solvent, are uniformly dispersed, be passed through hydrogen, heating is anti- It answers, filters, separation, product after being decomposed；

The water/organic solvent biphasic solvent is water/methyl acetate, water/n-butanol, water/methyl isopropyl ketone, water/second One of sour isobutyl ester；

The catalyst includes hydrogenolysis catalyst and acid catalyst.

2. the side according to claim 1 for preparing platform chemicals in diphasic system interface full constituent depolymerization protist matter Method, it is characterised in that: in the water/organic solvent biphasic solvent, the volume ratio of water and organic solvent is 1.5:1-1:1.5.

3. the side according to claim 1 for preparing platform chemicals in diphasic system interface full constituent depolymerization protist matter Method, it is characterised in that: the hydrogenolysis catalyst includes at least one of Pd/C, Ru/C and Pt/C.

4. the side according to claim 1 for preparing platform chemicals in diphasic system interface full constituent depolymerization protist matter Method, it is characterised in that: the acid catalyst includes at least one of aryl sulfonic acid, HZSM-5 and HUSY.

5. the side according to claim 1 for preparing platform chemicals in diphasic system interface full constituent depolymerization protist matter Method, it is characterised in that: the hydrogenolysis catalyst is Pd/C.

6. the side according to claim 1 for preparing platform chemicals in diphasic system interface full constituent depolymerization protist matter Method, it is characterised in that: the acid catalyst is HZSM-5.

7. the side according to claim 1 for preparing platform chemicals in diphasic system interface full constituent depolymerization protist matter Method, it is characterised in that: total dosage of the catalyst is the 5-15% of wood powder quality.

8. the side according to claim 1 for preparing platform chemicals in diphasic system interface full constituent depolymerization protist matter Method, it is characterised in that: the mass ratio of the hydrogenolysis catalyst and acid catalyst is 1:4-4:1.

9. the side according to claim 1 for preparing platform chemicals in diphasic system interface full constituent depolymerization protist matter Method, it is characterised in that: the heating reaction is to react 4-6h under the conditions of 160-240 DEG C.

10. according to claim 1 prepare platform chemicals in diphasic system interface full constituent depolymerization protist matter Method, it is characterised in that comprising the following specific steps

(1) wood powder, catalyst and water/organic solvent biphasic solvent are uniformly mixed, are added in high-pressure reactor；

(2) it is passed through the hydrogen of 1-2MPa, stirring is warming up to 160-240 DEG C of reaction 4-6h, Filtration of catalyst and residue, separates Water phase and organic phase, obtain product.

Technical field

The invention belongs to biorefinery technical fields, in particular to one kind is in the primary life of diphasic system interface full constituent depolymerization The method that substance prepares platform chemicals.

Background technique

With getting worse for energy needs aggravation and environmental problem, biomass as a kind of clean renewable energy, Extensive concern has been obtained, the important sources of future source of energy and fine chemicals are considered as.The main component of biomass is Cellulose, hemicellulose, lignin.Cellulose is to pass through linear high score made of β -1,4 glucosides key connection as glucose molecule Sub- compound.And the inside is in addition to glucose molecule in hemicellulose, there are also a lot of other carbohydrates, such as ribose, xylose, gala Sugar, mannose etc..Cellulose and hydrolysis of hemicellulose are prepared into saccharide compound, then a series of important put down can be obtained in conversion Platform compound, such as 5 hydroxymethyl furfural, levulic acid.Different from structurally ordered cellulose, hemicellulose, lignin is one Plant the tridimensional network by being formed by connecting to three kinds of hydroxypropyl (H), guaiacyl (G), lilac base (S) phenylpropyl alcohol alkyl structures Aromatic high polymer, the fields such as preparing in high-quality liquid fuel and high valuable chemicals has great application potential. But lignin structure is complicated, and property is stablized, and generally requires to extract it from biological material to the utilization of lignin, In During lignin extraction, increase its depolymerization difficulty along with the polycondensation of lignin.Cellulose, hemicellulose with it is wooden The architectural difference of element makes it be difficult to convert simultaneously, and the conversion of cellulose and hemicellulose can also inhibit the solution of lignin simultaneously Poly-, current technology needs for each component to be first fractionated mostly, and lignin is often become due to its structural stability A kind of industrial by-products.Therefore, developing efficient, clean new bio refining technology is to realize that the industrialization of biomass full constituent is answered Key.

Realize that the full constituent of biomass utilizes, difficult point is the depolymerization of lignin.Currently, the method for lignin depolymerization has It very much, mainly include the degradation techniques such as hydrogenolysis, oxidation, thermal cracking, enzymatic, base catalysis, acid catalysis, photocatalysis and microwave.Its Middle hydrogenolysis high conversion rate, product oxygen content are low, it is considered to be realize one of the most potential approach of lignin higher value application. But the hydrogenolysis under high temperature and pressure is easy to cause the excessive hydrogenation and reunion of coking and product, is to solve this by solvent regulation The available strategy of problem.The dicyandiamide solution of lignin hydrogenolysis mainly have water, methanol, ethyl alcohol, isopropanol, ethylene glycol, dioxane, The homogeneous system of tetrahydrofuran etc. and their mixed solvent composition.Zhang (Acs Catalysis, 2014,4 (5): A series of Ni bimetallic component catalysts 1574-1583) etc. are prepared for, using water as solvent hydrogenolysis dimerization body Model object, are obtained Highest monomer yield 58% was obtained, then, which is used for the hydrogenolysis of organic solvent lignin by they again, obtains 6.8% Highest monomer yield.Since solubility is lower in pure water for lignin, it is easy to cause coking phenomenon, product yield is low, and alcohol Class favorable solubility is most common hydrogenolysis solvent.Parsell(Green Chemistry,2015,17(3):1492-1499) It,, will be complete to biomass processes 12h at 225 DEG C using methanol as solvent Deng using bimetallic Zn/Pd/C as catalyst Lignin in lignocellulose biomass is converted into two kinds of metoxyphenol products, leaves carbohydrate as solid Residue.However methanol is easy to cause reunion and the formation of coke, a degree of solution also occurs for cellulose and hemicellulose Poly-, so that contain more glucide in product, there is also inhibiting effect for this depolymerization to lignin.Huang (ChemSusChem, 2014,7 (8): 2051-2051) etc. using Supercritical Ethanol as solvent, hydrogenolysis alkali is wooden at 300 DEG C Element obtains the monomer yield of 23wt%, and wherein aromatic hydrocarbons is the primary product of reaction, they, which study, thinks and use methanol phase Than ethyl alcohol has advantage in terms of generating monomer and inhibiting reunion reaction and coke formation.But small molecule alcohol can adsorb On a catalyst, active catalyst sites are occupied, to influence the activity of catalyst.And the alkoxy that alcohols generates is being catalyzed The coverage rate on agent surface can shortening and increase with alcohol chain.In homogeneous solvent system, catalyst, reactant, product, by-product Object is easy to happen reunion reaction and excessive hydrogenation, inhibits catalyst activity, greatly affected wooden all in same system The depolymerization efficiency of element.And for homogeneous mixed solvent system, the recovery processing of solvent, the separation of product also increase it The cost and difficulty of industrial application.

Chinese patent CN109370633A discloses a kind of method that lignin adds hydrogen degradation to prepare bio oil.Made with ethyl alcohol For solvent, MoSe is used₂Lignin hydrogenolysis is prepared bio oil at 250-300 DEG C by base catalyst, and the ingredient of bio oil is main For a series of small molecule phenols, esters and acid compounds.In homogeneous system, product distribution is complex, and degradation obtains Small molecule contain active side-chain structure, be easy to happen aldol condensation polymerization and generate high-molecular compound or be adsorbed on catalysis It is further hydrogenated in agent.In recent years, biphasic solvent system has gradually attracted the concern of scholar, is applied to biomass by more and more The related fields of processing.Chinese patent CN106536496A discloses a kind of biological material production furfural by containing pentosan Method, with the solution processing biomass comprising at least one Alpha-hydroxy sulfonic acid come hydrolyzing biomass, to generate comprising at least one The product stream of C5- carbohydrate in the form of monomer and/or oligomer, and in the presence of heterogeneous solid acid catalyst, it is wrapping In the biphasic reaction medium of aqueous phase and the unmixing organic phase of water, furfural is produced with high yield.Chinese patent CN109280039A A kind of method that 5 hydroxymethyl furfural is prepared based on cellulose conversion is disclosed, using microcrystalline cellulose as raw material, by transition gold Belong to salting liquid and organic solvent forms biphasic solvent system, carries out high-pressure catalytic reaction, the in-situ transesterification to product of organic solvent The efficient preparation for realizing 5 hydroxymethyl furfural is moved, 83.6% yield is obtained.

Traditional biomass refining technology is using lignin as single raw material, in biomass pretreatment separation process, by Phenyl ring and oxygen-containing functional group rich in lignin, the knot under high temperature or acid condition after hydroxyls dehydrate protonation Structure is easy to generate stable C-C key with the carbon generation electrophilic reaction of electron rich on benzene ring building blocks, and depolymerization difficulty is caused to increase Greatly.And the direct depolymerization biological material in homogeneous system, product complicated difficult is to separate, due to cellulose and hemicellulose solution Poly- inhibiting effect, lignin depolymerization low efficiency, product molecule are also readily adsorbed on catalyst and further hydrogenate or meet again, suppression Catalyst activity processed.Lignin depolymerization low efficiency, product separation process is complicated, be easy to meet again and excessive hydrogenation is to restrict biomass The main problem of higher value application.Therefore, the biomass full constituent depolymerization process route of exploitation efficiently, green, environmentally friendly is to realize The key that lignin, cellulose, hemicellulose industrialization comprehensively utilize.

Summary of the invention

In order to overcome the shortcomings and deficiencies of the prior art described above, simplification of flowsheet, the primary purpose of the present invention is that mentioning For a kind of method for preparing platform chemicals in diphasic system interface full constituent depolymerization protist matter.

The method of the present invention handles protist material using one-step method, in a mild condition separating lignin in situ and straight Connecing becomes single phenolic compound for the lignin conversion in biomass, avoids the polycondensation during lignin extraction, Yi Jigao The coking phenomenon of the lower hydrogenolysis of temperature, simplifies process flow.And the cellulose and hemicellulose in biological material then pass through acid and urge Agent depolymerization generates glucose.Reaction completes the subprocess of extraction while end, single phenol substance is primarily present in organic Phase, and water-soluble saccharides are then present in water phase.Organic phase solvent is recyclable to be recycled, and technique is environmentally protective.Biphasic solvent body System inhibits the reunion and excessive hydrogenation of product to the transfer in situ of product during the reaction, promotes reaction forward mobile, together When significantly improve the selectivity of product.

The purpose of the present invention is realized by following proposal:

A method of at diphasic system interface, full constituent depolymerization protist matter prepares platform chemicals, including following step It is rapid: wood powder, catalyst are added in water/organic solvent biphasic solvent, are uniformly dispersed, hydrogen is passed through, heating reaction is filtered, Separation, product after being decomposed.

The water/organic solvent biphasic solvent is preferably water/methyl acetate, water/n-butanol, water/isopropyl methyl first One of ketone, water/isobutyl acetate.

In the water/organic solvent biphasic solvent, the volume ratio of water and organic solvent is preferably 1.5:1-1:1.5.

The catalyst includes hydrogenolysis catalyst and acid catalyst.

The hydrogenolysis catalyst may include at least one of Pd/C, Ru/C and Pt/C etc., preferably Pd/C.

The acid catalyst may include at least one in the Conventional solids acid catalyst such as aryl sulfonic acid, HZSM-5 and HUSY Kind, preferably HZSM-5.

Total dosage of the catalyst is preferably the 5-15% of wood powder quality, wherein hydrogenolysis catalyst and acid catalyst Mass ratio is preferably 1:4-4:1.

The wood powder can be at least one of conventional poplar, birch etc..

The mass volume ratio of the wood powder and biphasic solvent is 1:20-1:30, g, mL.

The pressure for being passed through hydrogen is preferably 1-2MPa.

The heating reaction preferably reacts 4-6h under the conditions of 160-240 DEG C.

The filtering is for removing catalyst and residue.

The separation finger separation water phase and organic phase, isolated organic phase can obtain after solvent is recovered by distillation Obtain the oily liquids product comprising highly selective single phenolic compound；Water-soluble sugar is then retained in water phase.

Further, the method for preparing platform chemicals in diphasic system interface full constituent depolymerization protist matter, Comprising the following specific steps

(1) wood powder, catalyst and water/organic solvent biphasic solvent are uniformly mixed, are added in high-pressure reactor；

(2) it is passed through the hydrogen of 1-2MPa, stirring is warming up to 160-240 DEG C of reaction 4-6h, Filtration of catalyst and residue, Water phase and organic phase are separated, product is obtained.

The method of the present invention participates in reacting jointly using hydrogenolysis catalyst and acid catalyst, preferably business Pd/C and HZSM-5 As catalyst, water/organic solvent biphasic solvent reaction interface is constructed, a step handles protist material in a mild condition Material, separation in situ and depolymerization lignin, a step hydrogenolysis prepare single phenolic compound, avoid lignin during the extraction process again Condensation, and solve the coking problem of lignin high temperature hydrogenolysis；It is flat to prepare glucosyl group for depolymerizing cellulose and hemicellulose simultaneously Platform compound realizes the full constituent depolymerization of biomass.The separation that product is completed while reaction terminates, simplifies technique Step, organic solvent is Ke Xunhuanliyong, environmentally protective.Diphasic system shifts the original position of product simultaneously, turns during the reaction Lignin depolymerization product is moved to organic phase, which not only improves the efficiency of reaction and selectivity, also inhibit the reunion of product And excessive hydrogenation, and the glucose etc. that cellulose and hemicellulose depolymerization generate then is retained in water phase.Using product not With the dissolubility difference in solvent, it can be achieved that the Efficient Conversion of biomass, and highly selective product is obtained, liquid obtained Product is to single phenolic compound especially ihydro naphthyl alcohol selectivity with higher.Low-temp reaction avoids the coking of hydrogenolysis, The transfer separation of product inhibits excessive hydrogenation and reaction of meeting again, and avoids sugar product and makees to the inhibition of lignin depolymerization With, promote the conversion of biological material, obtain 19.49% single phenol class compound yield and 64.81% water phase produce Object yield is up to 65.48% to the selectivity of single phenolic compound in product liquid, has environmentally protective, simple process excellent Point.

The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that

1, the method for the present invention one-step method full constituent depolymerization biological material in a mild condition, avoids lignin and is extracting The structure changes such as the fracture of C-O key, polycondensation, low-temperature treatment inhibit the formation of coke in the process, while converting cellulose and half Cellulose simplifies technique.

2, the method for the present invention is in biphasic solvent interface processing biological material, and transfer lignin depolymerization produces organic solvent in situ Object is to inhibit reunion and excessive hydrogenation phenomenon, and then depolymerization generation glucose is retained in water phase for cellulose and hemicellulose, solves Determined influence and inhibiting effect of the carbohydrate present in product to lignin hydrogenolysis the problem of, choosing of the organic solvent to product molecule Selecting property extracts so that the product liquid selectivity with higher obtained, the separation depolymerization in situ of protolignin at low temperature make Its product structure selectively increases, and is conducive to process downstream.

3, the method for the present invention completes the separation to product while reacting terminates, and technique is simplified, between being suitable for It has a rest, continuous production, organic solvent can be environmentally protective by being simply distilled to recover utilization, has huge industrial application latent Power.

Detailed description of the invention

Fig. 1 is the mixed reaction solution figure obtained in embodiment 1.

Fig. 2 is the product liquid GC-MS spectrogram obtained in embodiment 1.

Fig. 3 is the product liquid GC-MS spectrogram obtained in embodiment 2.

Specific embodiment

Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.

Material involved in the following example can be obtained from commercial channel.Dosage of each component in terms of quality parts by volume, g, mL。

The conversion ratio of biomass, single phenol yield and single phenol selectivity calculation formula are as follows.

The conversion ratio (wt%) of biomass=(wood powder additional amount-(solid residue quality-addition catalytic amount after reaction))/ Wood powder additional amount × 100%；

Single phenol yield (wt%)=mono- phenolic compound gross mass/wood powder additional amount × 100%；

Single phenol selectivity (%)=mono- phenolic compound gross mass/product liquid quality × 100%.