CN102476980A - Application of tungsten-based catalyst in lignin catalytic hydrogenation for producing aromatic compound - Google Patents
Application of tungsten-based catalyst in lignin catalytic hydrogenation for producing aromatic compound Download PDFInfo
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Abstract
The invention relates to hydrocracking of lignin, and specifically relates to a method for applying a tungsten-based catalyst to catalyze lignin hydrocracking for producing an aromatic compound. The catalyst comprises a main active component of non-zero-valent tungsten, and a second metal component of a small amount of one or more transition metals selected from zero-valent nickel, cobalt, ruthenium, iridium, palladium, platinum, iron, and copper. According to the method, raw materials such as lignin, biomass hydrolysis residue, lignosulfonate, and alkaline lignin are subject to catalytic hydrogenation under a hydrothermal condition with a temperature of 120 to 450 DEG C and a hydrogen pressure of 1 to 20MPa; the raw materials are cracked into C6-C9 phenolic compounds with high selectivity. A maximal phenol yield reaches 55.6%. Compared to existing technologies, according to the invention, renewable natural biomasses are adopted as raw materials, such that the raw materials are cheap, and have wide sources; inorganic acid and alkali are not required, such the production of a large amount of alkaline solution in traditional lignin catalysis is avoided; the tungsten-based catalyst is cheap; the reaction process is green, and has atom economical characteristics.
Description
Technical field
The present invention relates to the preparation of aromatics, the hydrocracking of specifically a kind of loading type carbonization tungsten catalyst catalysis xylogen resource prepares the method for single phenols aromatics.
Background technology
The high speed development of world economy has benefited from fossil energy, like the widespread use of oil, Sweet natural gas, coal.Along with can not constantly consuming by the round-robin fossil resource, it is increasingly serious that energy dilemma and environmental problem have become.Develop renewable new forms of energy and replace the inexorable trend that fossil resource becomes social development.
Biomass resource is present in nature in a large number, is the abundantest on the earth, the most cheap and meets the renewable resources of Sustainable development requirement.In biomass, the content of xylogen is only second to Mierocrystalline cellulose, is the abundantest natural aromatic compound resource of occurring in nature, and all regenerate with 50,000,000,000 tons speed every year.Pulp and paper industry will be isolated about 1.4 hundred million tons of Mierocrystalline celluloses every year from plant, obtain the xylogen sub product about 5,000 ten thousand tons simultaneously.But up to now; The trans-utilization of xylogen still lacks effective way; Surpass 95% xylogen and enter rivers with " black liquor " form or burn, not only wasted biomass resource, and severe contamination environment; Consequent waste water accounts for 30% of national amount of industrial wastewater, is first object of China's trade effluent control.
Aromatics has very important use in chemical industry; For example phenol and terephthalic acid and verivate thereof are not only widely used bulk chemical, also are simultaneously the important source material of producing resin, rubber, medicine intermediate and other fine chemicals.See that from structure xylogen is to be the three-dimensional netted polymkeric substance of main structure body with the aromatic ring, mainly comprises three kinds of structural units: guaiacyl, Syringa oblata Lindl. base, para hydroxybenzene based structures.Link to each other through ehter bond or carbon-carbon bond between the structural unit.Through the design appropriate catalyst; Selectivity is to the xylogen hydrogenating reduction; Cut off the link between the structural unit, can realize preparing the aromatic series phenolic cpd, thereby be applied to every field as the substitute of fossil resource by the xylogen resource; Alleviate the awkward situation of world energy sources crisis to a certain extent, also avoided the discharging of discarded " black liquor " simultaneously.
But,, there is greatly difficulty in its catalytic pyrolysis because of xylogen complicated structure and obstinate physicochemical property.USP (US 4,900,873) uses biphenyl or naphthalene to prepare aromatics as the solvent pyrolysis lignin at 300-400 ℃, but productive rate less than 20%.USP (US5,807,952) prepares phenolic cpd 400-600 ℃ of highly basic catalysis xylogen pyrolysis under air atmosphere such as following KOH, and the phenol maximum output can reach 60%, but severe reaction conditions, and produce a large amount of waste lyes.World patent (WO99/10450) 260-310 ℃ in nitrogen atmosphere with base catalysis xylogen hydrogenation preparing gasoline component, but the complete hydrogenation of phenyl ring needs more hydrogen sources, and alkaline catalysts produces a large amount of waste liquids, contaminate environment.Canadian Patent adopts metallic sulfide be catalyzer in 250-450 ℃ with 15-45MPa under the catalysis lignin degradation obtain phenolic cpd, the highest 40% phenol productive rate that obtains.It is the bimetallic catalyst catalysis xylogen hydrogenation of main active component that Chinese patent (CN 101768052A) has been described with zeroth order Ni, and the raw material peak rate of conversion reaches 53%.See from the finding of document; The xylogen hydrogenation catalyst of report is many at present is main with precious metals such as Pd, Pt; It is to be raw material with the xylogen that any report is not arranged as yet, and, highly selective catalyzed degradation efficient under non-alkaline condition through cheap non-zero valence tungsten-based catalyst produced aromatics.
Summary of the invention
The object of the present invention is to provide a kind of method of tungsten-based catalyst catalysis xylogen raw material degraded system aromatics; It can be implemented under the reaction conditions of hydro-thermal hydrogenation, and the high yield of catalysis xylogen, highly selective are converted into single phenols aromatics.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is:
The xylogen hydrocracking catalyst that is used for according to the invention is the non-zero valence tungsten-based catalyst, is described below:
Said tungsten-based catalyst can be loading type carbonization tungsten catalyst, is made up of active ingredient wolfram varbide and carrier.Carrier is one or more in gac, aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve, the phosphate aluminium molecular sieve; The loading of tungsten in carrier is 5-80wt%, and preferred loading is 10-50wt%, and more preferably loading is 15-40wt%;
Said loading type carbonization tungsten catalyst also can be made up of main active component, carrier and second metal component, three parts.Said main active component is a wolfram varbide, and the loading of tungsten in carrier is 5-80wt%, and preferred loading is 10-50wt%, and more preferably loading is 15-40wt%; Said carrier is one or more in gac, aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve, the phosphate aluminium molecular sieve; In the nickel that said second metal component is a metallic state, iridium, platinum, ruthenium, rhodium, palladium, iron, cobalt, copper, aluminium, tin, molybdenum, chromium, the strontium one or more, one or more in preferred nickel, iridium, ruthenium, palladium, the platinum; The loading of second metal component in carrier is 0.05-30wt%, and preferred loading is 0.1-15wt%, and more preferably loading is 0.2-5wt%.
Said tungsten-based catalyst can be composite catalyst; Comprise catalyst A and catalyst B; The activeconstituents of catalyst A is one or more in the transition metal iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum of the 8th, 9,10 families, and the activeconstituents of catalyst B is one or more in the oxyhydroxide, tungsten bronze(s), wolframic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, para-tungstate, peroxide wolframic acid, peroxide tungstate, heteropoly tungstic acid of muriate, the tungsten of sulfide, the tungsten of oxide compound, the tungsten of tungsten; The metal active composition of catalyst A and the activeconstituents of catalyst B (in tungsten weight) weight ratio are between 0.02-3000 times of scope.
Said catalyst A can be loaded catalyst, and carrier is gac, aluminum oxide, silicon oxide, silit, zirconium white, zinc oxide, titanium oxide is a kind of or the complex carrier more than two kinds; The content of activity component metal on catalyzer is 0.05-50wt%, preferably at 1-30wt%.
Said catalyst A also can be unsupported, with the skeleton metal catalyst of active ingredient as catalyst backbone.
Said loaded catalyst adopts the load method preparation, and the active ingredient salts solution is supported on the carrier, obtains catalyst precursor.After 100-160 ℃ of drying, carry out the temperature programmed reduction(TPR) reaction at hydrogen or methane/hydrogen (methane content is 10-100%v/v).
The reduction temperature of said loading type carbonization tungsten catalyst is between 600-900 ℃, and preferred reduction temperature is 700-800 ℃, and reducing atmosphere is hydrogen or methane/hydrogen (methane content is 20%v/v), and carbonization time is no less than 0.5 hour.
The reduction temperature of said loaded catalyst A is between 250-800 ℃, and preferred reduction temperature is 300-500 ℃, and reducing atmosphere is hydrogen or methane/hydrogen (methane content is 20%v/v), and carbonization time is no less than 0.5 hour.
The reaction process that realizes xylogen shortening cracking system phenolic cpd is following: said xylogen raw material hydrogenation DeR is carried out in airtight autoclave, and the mass ratio of reaction raw materials and solvent is 1: 500-1: 1, preferred 1: 100-1: 5; Catalyst levels is getting final product of catalytic amount, is fast reaction speed, and the mass ratio of xylogen and catalyzer is generally 1: 2-100: 1, and preferred proportion is 2: 1-20: 1; The original pressure of filling hydrogen under the room temperature in the reaction kettle is 1-20MPa, preferred 3-10MPa; Temperature of reaction is 120-450 ℃, preferred 150-300 ℃; Reaction times is 10min-24h.
Compared with prior art, the present invention has following advantage:
1. raw material wood element of the present invention is the abundantest natural reproducible aromatic compound resource of occurring in nature, and wide material sources are with low cost.Prepare aromatic compound with existing petroleum base industry synthetic route and compare, the present invention does not consume fossil resource, has the advantage of regenerated raw materials, meets the requirement of Sustainable development.
2. the present invention has reduced the pollution because of industrial lignin discharges and burning is caused for the utilization of industrial lignin provides new way.
3. catalyzer is main active component with non-zero valence tungsten, and is with low cost, and active high, single phenolic cpd productive rate is up to 55.6%.
4. the reaction system environmental friendliness is pollution-free when being solvent with water; Do not use mineral acid, alkali in the reaction process, avoided common problem of environmental pollution in the lignin degradation technology.
Further specify through specific embodiment below.
Embodiment
Embodiment 1
Activated carbon supported nickel-tungsten carbide catalyzer (Ni-W
2C/AC) preparation: is that 15: 1 ratio is processed mixing solutions with metatungstic acid ammonia and nickelous nitrate according to tungsten/nickel weight ratio, and wherein, the mass concentration of metatungstic acid ammonia is 0.4g/ml.Then, with the method for incipient impregnation with mixing solutions Immesion active carbon carrier (AC).Behind 120 ℃ of oven drying 12h; Place H2 atmosphere to carry out temperature programming carbon thermal response catalyst precursor; Concrete reaction process is: the 1.0g precursor is warming up to 400 ℃ by room temperature 1h in crystal reaction tube; Then be warming up to 700 ℃ and keep 1h to carry out carbonization with 1 ℃/min, hydrogen flow rate is 60ml/min.Obtaining the tungsten loading is that 30wt%, nickel loading are the Ni-W of 2wt%
2The C/AC catalyzer is expressed as Ni-W
2C/AC (2wt%Ni-30wt%W
2C).
Other condition is constant, only changes the concentration of metatungstic acid ammonia and nickelous nitrate in the steeping fluid, perhaps through dipping repeatedly, can obtain active ingredient loading different catalyst; It is formed as follows: the Ni loading is 2wt%, and the tungsten loading is respectively 5wt%, 10wt%, 15wt%, 60wt%, the Ni-W of 80wt%
2The C/AC catalyzer, and the tungsten loading is 30wt%, the nickel loading is respectively 0.05wt%, 0.2wt%, 5wt%, 10wt%, the Ni-W of 30wt%
2The C/AC catalyzer.
Embodiment 2
The Ni-WxC/AC Preparation of catalysts: the preparation process is similar to embodiment 1, and difference is that carbonization temperature is 850 ℃, and obtaining the tungsten loading is that 30wt%, nickel loading are the Ni-WxC/AC catalyzer of 2wt%, and wherein, WxC is W
2The crystalline phase of mixing of C and WC, 1＜x＜2.Be expressed as Ni-WxC/AC (2wt%Ni-30wt%WxC).
Embodiment 3
The WxC/AC Preparation of catalysts: the preparation process is similar to embodiment 1, and difference is only to have used metatungstic acid ammonia in the precursor and does not add nickelous nitrate, and carbonization temperature is 800 ℃, obtains W thus
2The C/AC catalyzer; Or, obtain the WxC/AC catalyzer 850 ℃ of following carbonizations, be W
2The crystalline phase of mixing of C and WC, 1＜x＜2.
Embodiment 4-9
Co-W
2C/AC, Fe-W
2C/AC, Pt-W
2C/AC, Ru-W
2C/AC, Ir-W
2C/AC, Pd-W
2The C/AC Preparation of catalysts: the preparation process is similar to embodiment 1; Difference is to have used Xiao Suangu, iron nitrate, Platinic chloride, ruthenium chloride, chloro-iridic acid and Palladous chloride in the precursor respectively but not nickelous nitrate; The W loading is 30wt% in the catalyzer; Co, Fe, Pt, Ru, Ir, Pd loading are respectively 2wt%, 2wt%, 1wt%, 1wt%, 1wt% and 1wt%, obtain Co-W thus
2C/A, Fe-W
2C/AC, Pt-W
2C/AC, Ru-W
2C/AC, Ir-W
2C/AC and Pd-W
2The C/AC catalyzer.
Embodiment 10-15
Ni-WC supports preparation loading type Ni-WC catalyzer on aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve respectively: the preparation process is similar to embodiment 1; Difference is that carrier uses respectively is aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve and charcoal non activated; Simultaneously, carbonization gas is changed to CH by hydrogen
4/ H
2(volume ratio 1: 4); The W loading is 30wt% in the catalyzer; The Ni loading is 2wt%, and the wolfram varbide crystalline phase is WC, obtains Ni-WC thus and supports on aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve, phosphate aluminium molecular sieve totally seven kinds of catalyzer.
Embodiment 16
The preparation of loaded catalyst Pt/AC: the 0.279g Platinic chloride is dissolved in the 4ml water, and incipient impregnation behind 120 ℃ of dry 12h, obtains catalyst precursor on the 2g absorbent charcoal carrier.Catalyst precursor carries out the temperature programmed reduction(TPR) reaction in nitrogen atmosphere.Concrete reaction process is: precursor is warming up to 350 ℃ by room temperature 1h in crystal reaction tube, and keeps 2h, hydrogen flow rate is 120ml/min, obtains the Pt/AC catalyzer of 5wt%.
The preparation process of said other loaded catalyst A is similar.Xiao Suangu, nickelous nitrate, ruthenium chloride, chloro-iridic acid and Palladous chloride with different mass is carried on the porous support respectively, in nitrogen atmosphere, makes Co/AC, Ni/AC, Ru/AC, Ir/AC, Pd/AC in 450 ℃ of temperature programmed reduction(TPR)s.
Embodiment 17
Different tungsten carbide catalyst catalysis natural lignins hydrogenation reaction in the aqueous solution: the 1.0g white birch wood powder that will contain natural lignin; 0.4g catalyzer and 100ml water join in the 300ml reaction kettle; After feeding three gases of hydrogen exchange; Fill hydrogen to 6MPa, stir, be warming up to 235 ℃ of reaction 4h with the speed of 1000 commentaries on classics/min.Reaction is reduced to room temperature after finishing, the centrifugal back of supernatant liquid sampling analysis.The catalyzer that uses corresponds in table 1 successively: (1) 30wt%W
2C/AC, (2) 30wt%WxC/AC (1＜x＜2), (3) Ni-W
2C/AC (4wt%Ni-30wt%W
2C), (4) Ni-WxC/AC (4wt%Ni-30wt%WxC, 1＜x＜2), (5) Pt-W
2C/AC (1wt%Pt-30wt%W
2C), (6) Ru-W
2C/AC (1wt%Ru-30wt%W
2C), (7) Ir-W
2C/AC (1wt%Ir-30wt%W
2C), (8) Pd-W
2C/AC (1wt%Pd-30wt%W
2C), (9) Ni-W
2C/Al
2O
3, (10) Ni-W
2C/SiO
2, (11) Pd-W
2C/Al
2O
3, (12) 0.05wt%Ni-80wt%W
2C/AC, (13) 20wt%Ni-5wt%W
2C/AC.The product qualitative analysis is through GC-MS coupling technique and standard specimen contrast, and quantitative analysis realizes through the gc marker method.The result sees table 1.Product also comprises the phenolic cpd of C6-C9 such as phenol, 2-methylphenol, 4-ethylphenol except guaiacyl propane, Syringa oblata Lindl. base propane, guaiacyl propyl alcohol and the Syringa oblata Lindl. base propyl alcohol, in table, classifies as other phenol.
The different tungsten carbide catalysts of table 1 are attend natural lignin's Catalytic Hydrogenation Properties relatively
From table, can find out that the promoted tungsten carbide catalyst of different metal can both obtain fragrant phenolic compound by catalysis xylogen hydrogenation, different carrier loaded tungsten carbide catalysts all have excellent catalytic activity.
Embodiment 18
Different composite type catalyst A-B (A and B mass ratio are 1: 3) catalysis natural lignin hydrogenation reaction in the aqueous solution: the 1.0g white birch wood powder that will contain natural lignin; 0.4g catalyzer and 100ml water join in the 300ml reaction kettle; After feeding three gases of hydrogen exchange; Fill hydrogen to 6MPa, stir, be warming up to 235 ℃ of reaction 4h with the speed of 1000 commentaries on classics/min.Reaction is reduced to room temperature after finishing, the centrifugal back of supernatant liquid sampling analysis.Product analysis method is with embodiment 17.The result sees table 2.
Table 2 composite catalyst A-B catalysis natural lignin hydrogenation performance relatively
Embodiment 19
Natural lignin is catalytic conversion reaction in small molecules solution: will contain the 1.0g white birch wood powder of natural lignin, 0.4g Ni-W
2C/AC (4wt%Ni-30wt%W
2C) catalyzer and 100ml small molecules solvent join in the 300ml reaction kettle, feed three gases of hydrogen exchange after, fill hydrogen to 6MPa, stir with the speed of 1000 commentariess on classics/min, be warming up to 235 ℃ simultaneously and react 4h.Reaction is reduced to room temperature after finishing, the centrifugal back of supernatant liquid sampling analysis.Product analysis method is with embodiment 17.The result sees table 3.
From table, can find out that in forming the small molecules solvent of hydrogen bond, the hydrogenation reaction of xylogen is carried out more easily, when wherein being solvent with terepthaloyl moietie, Ni-W
2Fragrant phenol yield is up to 50.6% on the C/AC catalyzer.Its reason is that through the hydrogen bond action between xylogen and small molecules solvent the lignin dissolution degree increases, thereby has increased the surface in contact of xylogen and catalyzer, makes catalyzed reaction more be prone to carry out.
Ni-W in table 3 different solvents
2The hydrogenation result of C/AC catalysis natural lignin
Embodiment 20
Different xylogen catalytic material hydrogenation reactions: with the xylogen raw material (40 order particle) of 1.0g different sources, 0.4g Ni-W
2C/AC (4wt%Ni-30wt%W
2C) catalyzer and 100ml water join in the 300ml reaction kettle, feed three gases of hydrogen exchange after, fill hydrogen to 6MPa, stir with the speed of 1000 commentariess on classics/min, be warming up to 235 ℃ simultaneously and react 4h.Reaction is reduced to room temperature after finishing, the centrifugal back of supernatant liquid sampling analysis.Product analysis method is with embodiment 17.The result sees table 4.
Table 4Ni-W
2The different xylogen raw material of C/AC catalysis hydrogenation result
Embodiment 21
The catalytic hydrogenation reaction of natural lignin under the differential responses condition: with the white birch wood powder (40 order) and the catalyzer (4wt%Ni-30wt%W of different mass
2C/AC) mix with 100ml water, join in the 300ml reaction kettle, feed three gases of hydrogen exchange after, fill hydrogen to formulating pressure, stir with the speed of 1000 commentariess on classics/min, be warming up to formulation thermotonus certain hour simultaneously.Other process is with embodiment 17.The result sees table 5.
The shortening cracking result of table 5 natural lignin under the differential responses condition
Claims (13)
1. the application of tungsten-based catalyst in xylogen shortening system aromatics; It is characterized in that: tungsten-based catalyst with have under the polar solvent effect that forms the hydrogen bond ability, xylogen highly effective hydrogenation cracking in airtight autoclave prepares phenylol, Syringa oblata Lindl. base and pockwood phenolic group aromatics.
2. according to the described application of claim 1, it is characterized in that: said xylogen is one or more in biomass, biomass by hydrolyzation residue and the industrial lignin that contains xylogen.
3. according to the described application of claim 2, it is characterized in that: the said biomass that contain xylogen are one or more in birch, poplar, toothed oak wood, linden, beech, maple, dragon spruce, pine, Eucalyptus, bamboo, the agricultural crop straw, but are not limited to this; Said industrial lignin is one or more in sulfonated lignin, alkali lignin or the dealkalize xylogen.
4. according to the described application of claim 1; It is characterized in that: said have a polar solvent that forms the hydrogen bond ability, can be water, dioxane, THF, phenol and short chain saturated fatty alcohol like one or more in methyl alcohol, ethanol, terepthaloyl moietie, butanols, the butyleneglycol.
5. according to the described application of claim 1; It is characterized in that: said tungsten-based catalyst is a loading type carbonization tungsten catalyst, and carrier is one or more in gac, aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve, the phosphate aluminium molecular sieve.
6. according to the described application of claim 5, it is characterized in that: the loading of tungsten in carrier is 5-80 wt%, and preferred loading is 10-50 wt%, and more preferably loading is 15-40 wt%.
7. according to the described application of claim 1, it is characterized in that: tungsten-based catalyst is a loading type carbonization tungsten catalyst, is made up of main active component, carrier and second metal component, three parts;
Said main active component is a wolfram varbide; Said carrier is one or more in gac, aluminum oxide, silicon oxide, titanium oxide, zirconium white, titanium oxide, Si-Al molecular sieve, the phosphate aluminium molecular sieve; In the nickel that said second metal component is a metallic state, iridium, platinum, ruthenium, rhodium, palladium, iron, cobalt, copper, aluminium, tin, molybdenum, chromium, the strontium one or more.
8. according to the described application of claim 7, it is characterized in that:
The loading of tungsten in carrier is 5-80 wt%, and preferred loading is 10-50 wt%, and more preferably loading is 15-40 wt%;
In the preferred nickel of said second metal component, iridium, ruthenium, palladium, the platinum one or more;
The loading of second metal component in carrier is 0.05-30 wt%, and preferred loading is 0.1-15 wt%, and more preferably loading is 0.2-5 wt%.
9. according to the described application of claim 1; It is characterized in that: said tungsten-based catalyst is a composite catalyst; Comprise catalyst A and catalyst B; The activeconstituents of catalyst A is one or more in the transition metal iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum of the 8th, 9,10 families, and the activeconstituents of catalyst B is one or more in the oxyhydroxide, tungsten bronze(s), wolframic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, para-tungstate, peroxide wolframic acid, peroxide tungstate, heteropoly tungstic acid of muriate, the tungsten of sulfide, the tungsten of oxide compound, the tungsten of tungsten;
The metal active composition of catalyst A and the activeconstituents of catalyst B (in tungsten weight) weight ratio are between 0.02-3000 times of scope.
10. according to the described application of claim 9, it is characterized in that: said catalyst A is a loaded catalyst, and said carrier is gac, aluminum oxide, silicon oxide, silit, zirconium white, zinc oxide, titanium oxide is a kind of or the complex carrier more than two kinds; The content of activity component metal on catalyzer is 0.05-50 wt%, preferably at 1-30 wt%.
11., it is characterized in that according to the described application of claim 9: said catalyst A also can be unsupported, with the skeleton metal catalyst of active ingredient as catalyst backbone.
12. according to the described application of claim 1, it is characterized in that: the mass ratio of said xylogen raw material and solvent is 1:500-1:1; Catalyst levels is getting final product of catalytic amount; The original pressure of filling hydrogen under the room temperature in the reaction kettle is 1-20 MPa; Temperature of reaction is 120-450
oC; Reaction times is 10 min –, 24 h.
13. according to the described application of claim 12, it is characterized in that: the mass ratio of said xylogen raw material and solvent is 1:100-1:5; For adding fast response, the mass ratio of xylogen and catalyzer is generally 1:2-100:1, and preferred proportion is 2:1-20:1; The original pressure of filling hydrogen under the room temperature in the reaction kettle is 3-10 MPa; Temperature of reaction is 150-300
oC.
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