CN109174132A - The catalyst and preparation method of aromatic hydrocarbon are prepared for Catalytic lignin model compound reaction - Google Patents
The catalyst and preparation method of aromatic hydrocarbon are prepared for Catalytic lignin model compound reaction Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
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- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
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Abstract
The present invention relates to a kind of catalyst and preparation method that aromatic hydrocarbon is prepared for Catalytic lignin model compound reaction；Lignin model compound hydrogenation deoxidation to be catalyzed a variety of representative structures prepares aromatic product as target, has synthesized the sulfide catalyst using CoAl houghite oxide as carrier, using the method load molybdenum disulfide of hydration as active component.With MoS2/Co9S8‑Al2O3It indicates, MoS2It is dispersed in catalyst surface, Co forms Co through over cure9S8Phase, with carrier Al2O3Stable veneer structure is formed, the cyclical stability of catalyst is conducive to.The raw materials used in the present invention price is more cheap, and preparation is simple, in the catalytically active assessment of catalyst, for different lignin model compounds, almost realizes and very converts, reaches 85% or more to the yield of aromatic product.Also, catalyst is recycled through 10 times, and catalytic activity remains unchanged.
Description
Technical field
The invention belongs to Industrial Catalysis and bioenergy transformation technology field, are related specifically to a kind of for Catalytic lignin
Model compound reaction prepares the catalyst and preparation method of aromatic hydrocarbon.
Background technique
Lignin is one of important composition ingredient of Wooden Biomass, is widely present in nature with the second largest storage.Wood
Quality is primarily present in xylophyta and herbaceous plant, is the main ingredient for constituting plant skeleton.Lignin is by a large amount of fragrance
Structure connects to form complicated reticular structure by C-C and C-O, has the characteristics that be difficult to degrade, therefore is usually added by catalysis
The higher value application that hydrogen carries out lignin.But the processing of its raw material is still a difficult point, it is main by studying its mould at present
The conversion of type compound (representing monomer or dimer that C-O in lignin structure is keyed mode) and further to disclose its wooden
The transformation rule of plain raw material.According to the difference of product, the catalytic conversion reaction of lignin model compound is mainly divided at present
For two classes.First is that realizing that the complete hydrogenation of aromatic structure generates cycloalkane, the preparation for bio oil；Second is that carrying out deoxidation to it
And retain aromatic structure, the preparation for high valuable chemicals.The refining techniques of bio oil is developed so far, and is had been achieved for very
The achievement more attracted attention.Noble metal Rh, Pt, Pd of such as support type, transition metal Ni, Cu, Co etc. all have good cycloalkane
Selectivity.But it is directed to aromatic product, research at present includes transition metal nitride, phosphide and sulfide etc..Wherein,
Sulfide catalyst is cheap, and preparation is simple.The conventional vulcanized object catalyst of prior art document report petrochemical industry is (as vulcanized
NiMo, CoMo be carried on the carriers such as aluminium oxide, active carbon, silica, alumina silicate) be applied to lignin plus hydrogen it is de-
Oxygen shows good aromatic product selectivity.
Document (CoMo sulfide-catalyzed hydrodeoxygenation of lignin model
compounds:An extended reaction network for the conversion of monomeric and
Dimeric substrates, Journal of Catalysis 285 (2012) 315-323) investigate commercialization CoMoS/
Al2O3Hydrogenation of the catalyst to all kinds of lignin model compounds.Catalyst can be realized Most models as the result is shown
The conversion of conjunction object, but product complex distribution, and the yield of aromatic hydrocarbon is lower.Document (Iron (II) Disulfides as
Precursors of Highly Selective Catalysts for Hydrodeoxygenation of Dibenzyl
Ether into Toluene, ChemCatChem 2015,7,960-966) have studied FeS2It is supported on different carriers to two
The Hydrogenation of benzyl oxide.The results show that catalyst reaches 98% or more to the yield of toluene, still, catalyst is recycled through 3 times
Afterwards, catalytic activity is decreased obviously.
Therefore, although sulfide catalyst lignin conversion field application potential, with deoxygenation into
Row, often generates a small amount of water, so that there is the problems such as coking, partial oxidation, sulphur loss in sulfide catalyst, so as to cause
Catalytic activity decline.How to design and take into account efficient and stable sulfide catalyst, is about lignin on sulfide catalyst
Catalyzed conversion research is still an extremely challenging project, and this technology, which is designed to provide one kind and overcomes, to be existed in the prior art
Deficiency and disadvantage catalyst preparation method.
Summary of the invention
The present invention provides it is a kind of applied to lignin model compound hydrogenation deoxidation prepare aromatic hydrocarbon catalyst and its
Preparation method.
The present invention prepares aromatic hydrocarbon production to be catalyzed the lignin model compound hydrogenation deoxidation of a variety of representative structures
Object is target, has been synthesized using CoAl houghite oxide as carrier, using the method load molybdenum disulfide of hydration as activity
The sulfide catalyst of component.
Catalyst prepared by the present invention, with MoS2/Co9S8-Al2O3It indicates, wherein MoS2It is dispersed in catalyst table
Face, Co form Co through over cure9S8Phase, with carrier Al2O3Stable veneer structure is formed, the stable circulation of catalyst is conducive to
Property.Meanwhile the synergistic effect between Co and Mo sulfide, be conducive to the hydrogenation deoxidation activity for improving catalyst.
In order to achieve the goal above, the technical scheme adopted by the invention is as follows:
A kind of catalyst preparing aromatic hydrocarbon applied to lignin model compound hydrogenation deoxidation；Its structural formula is MoS2/
Co9S8-Al2O3, wherein MoS2It is dispersed in catalyst surface, Co forms Co through over cure9S8Phase, with carrier Al2O3It is formed
Stable veneer structure.
The method for preparing catalyst for being applied to lignin model compound hydrogenation deoxidation and preparing aromatic hydrocarbon of the invention, tool
Steps are as follows for body:
(1) taking Co:Al molar ratio range is the houghite hydroxide precursor of 1:1-5:1, roasts and Co is made3O4-
Al2O3Houghite oxide carrier；
(2) by (NH4)2Mo7O24Aqueous solution carries out hydration load with houghite oxide under conditions of closed, then
It is dried and obtains (NH4)2Mo7O24/Co3O4-Al2O3Solid；
(3) above-mentioned solid passes through elevated temperature cure, wherein (NH4)2Mo7O24Vulcanization forms MoS2, Co3O4Form Co9S8, Al2O3
Stablize constant to get to MoS2/Co9S8-Al2O3Hydrogenation deoxidation catalyst.
Roasting condition is roasted 4-6 hours under the conditions of 300-500 DEG C in the step (1).
Hydration load 6-20h, ((NH in the step (2)4)2Mo7O24):(Co3O4-Al2O3) mass ratio be 1:4-1:1.
Step (2) drying temperature is 50-100 DEG C, drying time 6-20h.
Catalyst of the present invention is applied to the method that lignin model compound hydrogenation deoxidation prepares aromatic hydrocarbon, by lignin mould
Type compound and internal standard compound dodecane are dissolved in methyl cyclohexane alkane solvents, are added in batch reactor together with catalyst, are led to
Enter hydrogen, heating is stirred to react.
Preferred catalyst and lignin model compound mass ratio are 1:4~1, reaction condition are as follows: reaction temperature 250-270
℃,H2Initial pressure 2-3Mpa, reaction time 5-10h.
The present invention prepares aromatic hydrocarbon production to be catalyzed the lignin model compound hydrogenation deoxidation of a variety of representative structures
Object is target, has been synthesized using CoAl houghite oxide as carrier, using the method load molybdenum disulfide of hydration as activity
The sulfide catalyst of component.It is indicated with MoS2/Co9S8-Al2O3, MoS2 is dispersed in catalyst surface, and Co is through over cure
Co9S8 phase is formed, stable veneer structure is formed with carrier Al2O3, is conducive to the cyclical stability of catalyst.
The analysis method of final product in the present invention: with gas chromatograph-mass spectrometer (GC-MS) and gas chromatograph respectively to
The product liquid arrived carries out qualitative and quantitative detection.
The model compound includes: dimer (diphenyl ether, benzyl ether, benzyl phenyl ether, m-phenoxy toluene), monomer
(phenol, 4- methylphenol, 4- ethyl -phenol, 4- propylphenol, benzylalcohol, methyl phenyl ethers anisole).Wherein, it is visited first with diphenyl ether for reaction
Needle molecule excavates the optimal ratio of the catalyst and optimum reaction condition, is catalyst: substrate=1:2 in mass ratio, instead
265 DEG C of temperature are answered, H2Initial pressure 3Mpa, under the addition of reaction time 10h, diphenyl ether conversion ratio reaches 99.8%, the receipts of benzene
Rate reaches 86.9%.And catalyst circulation stability is evaluated, catalyst is recycled through 10 times, and catalyst activity maintains
Stablize.Then using the lignin model compound of other different structures as substrate, the application universality of the catalyst is investigated.
The raw materials used price of prepared catalyst of the present invention is more cheap, and preparation method is simple, and reactivity is high, and circulation makes
It is good with property.In the catalytically active assessment of catalyst, for different lignin model compounds, almost realizes and very converts,
85% or more is reached to the yield of aromatic product, catalyst is recycled through 10 times, and catalyst activity maintains to stablize.
Detailed description of the invention
Fig. 1 is CoAl houghite oxide carrier XRD diagram.
Fig. 2 is catalyst MoS2/Co9S8-Al2O3XRD diagram.
Catalyst TEM schemes in Fig. 3 embodiment 2.
Specific embodiment
It is further described in detail below by specific embodiment:
A kind of Catalytic lignin model compound reaction prepares the preparation method of the catalyst of aromatic hydrocarbon, and specific steps are such as
Under:
1) taking Co:Al molar ratio range is the houghite hydroxide precursor of 1:1-5:1, in 300-500 DEG C of condition
Co is made in lower roasting 4-6 hours3O4-Al2O3Houghite oxide carrier；
2) by (NH4)2Mo7O24Aqueous solution carries out hydration load 6- under conditions of closed with CoAl houghite oxide
20h, mass ratio m ((NH4)2Mo7O24):m(Co3O4-Al2O3) it is 1:4-1:1, it is then dried, drying temperature 50-100
DEG C, drying time be 6-20h to get arrive (NH4)2Mo7O24/Co3O4-Al2O3Solid；
3) above-mentioned solid vulcanizes by temperature programming, wherein (NH4)2Mo7O24Vulcanization forms MoS2, Co3O4Form Co9S8,
Al2O3Stablize constant to get to MoS2/Co9S8-Al2O3Hydrogenation deoxidation catalyst.
The reaction that aromatic hydrocarbon is prepared applied to lignin model compound hydrogenation deoxidation, by lignin model compound and interior
Mark object dodecane is dissolved in methyl cyclohexane alkane solvents, is added in batch reactor together with catalyst, is passed through hydrogen, heating is stirred
Mix reaction；Catalyst and lignin model compound mass ratio are 1:4~1, reaction condition are as follows: 250-270 DEG C of reaction temperature, H2
Initial pressure 2-3Mpa, reaction time 5-10h.
Embodiment 1, MoS2/Co9S8-Al2O3The preparation of catalyst
(1) the houghite hydroxide precursor for being 1:1 by Co:Al molar ratio, roasts 6 hours under the conditions of 300 DEG C,
Co is made3O4-Al2O3Houghite oxide carrier；
(2) 0.247g ammonium molybdate is dissolved in 40ml deionized water, is stirred to clarify；After degassing, by the above-mentioned Co of 2.0g3O4-
Al2O3Carrier is added into solution, the closed storage 20h of room temperature.
(3) deionized water and dehydrated alcohol filtering and washing 2-3 times are used, 50 DEG C of dry 20h obtain (NH4)2Mo7O24/
Co3O4-Al2O3Solid.
(4) above-mentioned solid is under 400 DEG C, the heating rate of 5 °/min, H2S/H2(H2S volume fraction is 10%) gaseous mixture
Vulcanize 4h in atmosphere.In sulfidation, (NH4)2Mo7O24Vulcanization forms MoS2, Co3O4Form Co9S8, Al2O3Stablize it is constant, i.e.,
Obtaining Co:Al molar ratio is 1:1, has loaded MoS2MoS2/Co9S8-Al2O3Catalyst.
Embodiment 2, MoS2/Co9S8-Al2O3The preparation of catalyst
(1) the houghite hydroxide precursor for being 3:1 by Co:Al molar ratio, roasts 5 hours under the conditions of 400 DEG C,
Co is made3O4-Al2O3Houghite oxide carrier；Carrier XRD diagram is as shown in Figure 1, it can be observed that typical Co3O4Crystal phase
Diffraction maximum；
(2) 1.235g ammonium molybdate is dissolved in 40ml deionized water, is stirred to clarify；After degassing, 2.0g Co:Al is rubbed
You are than the Co for 1:13O4-Al2O3Carrier is added into solution, the closed storage 12h of room temperature.
(3) deionized water and dehydrated alcohol filtering and washing 2-3 times are used, 70 DEG C of dry 12h obtain (NH4)2Mo7O24/
Co3O4-Al2O3Solid.
(4) above-mentioned solid is under 400 DEG C, the heating rate of 5 °/min, H2S/H2(H2S volume fraction is 10%) gaseous mixture
Vulcanize 4h in atmosphere.In sulfidation, (NH4)2Mo7O24Vulcanization forms MoS2, Co3O4Form Co9S8, Al2O3Stablize it is constant, i.e.,
Obtaining Co:Al molar ratio is 3:1, has loaded MoS2MoS2/Co9S8-Al2O3Catalyst.
Catalyst XRD diagram is as shown in Fig. 2, it can be observed that typical Co9S8Crystal phase diffraction maximum, MoS2Since content is lower
And dispersion degree is high, therefore does not observe MoS2Characteristic diffraction peak.Catalyst TEM is as shown in figure 3, it can be observed that intensive
Co9S8(311) crystal face lattice fringeCo9S8With Al2O3Form the veneer structure of catalyst；It simultaneously can be with
Observe the MoS of part2(002) lattice fringe of crystal facePresentation is uniformly distributed.
Embodiment 3, MoS2/Co9S8-Al2O3The preparation of catalyst
(1) the houghite hydroxide precursor for being 5:1 by Co:Al molar ratio, roasts 3 hours under the conditions of 500 DEG C,
Co is made3O4-Al2O3Houghite oxide carrier；
(2) 2.47g ammonium molybdate is dissolved in 40ml deionized water, is stirred to clarify；After degassing, by 2.0g Co:Al mole
Than the Co for 1:13O4-Al2O3Carrier is added into solution, the closed storage 6h of room temperature.
(3) deionized water and dehydrated alcohol filtering and washing 2-3 times are used, 100 DEG C of dry 6h obtain (NH4)2Mo7O24/
Co3O4-Al2O3Solid.
(4) above-mentioned solid is under 400 DEG C, the heating rate of 5 °/min, H2S/H2(H2S volume fraction is 10%) gaseous mixture
Vulcanize 4h in atmosphere.In sulfidation, (NH4)2Mo7O24Vulcanization forms MoS2, Co3O4Form Co9S8, Al2O3Stablize it is constant, i.e.,
Obtaining Co:Al molar ratio is 5:1, has loaded MoS2MoS2/Co9S8-Al2O3Catalyst.
This technology comments the hydrogenation deoxidation performance of catalyst using a variety of lignin model compounds as reaction substrate
Valence.Concrete activity test condition are as follows: in 2.5mmol lignin model compound and 2.5mmol dodecane dissolution hexahydrotoluene
It is 20ml, catalyst amount 106mg-426mg to volume.The batch reactor of the 50ml size of use is reacted, instead
Answer condition are as follows: 250-270 DEG C, H2Initial pressure 2-3Mpa, 5-10h.Embodiment 4-18 is the evaluation of catalyst reaction performance.
Conversion ratio calculation formula are as follows:
Calculation of yield formula are as follows:
Embodiment 4, the evaluation of diphenyl ether hydrogenation deoxidation reactivity worth
The MoS that Example 1,2,3 obtains respectively2/Co9S8-Al2O3Catalyst represents 4- in lignin structure to contain
The model compound diphenyl ether of O-5 key is substrate, carries out reaction evaluating, reaction condition are as follows: diphenyl ether 426mg, catalyst amount
213mg (catalyst: substrate=1:2), 265 DEG C, H2Initial pressure 3Mpa, 10h.The results are shown in Table 1:
1 difference CoAl molar ratio catalyst of table is to diphenyl ether hydrogenation deoxidation reaction result
Embodiment 5, the evaluation of diphenyl ether hydrogenation deoxidation reactivity worth
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst, using diphenyl ether as substrate, at a temperature of investigation differential responses
The performance of catalyst, reaction condition are as follows: diphenyl ether 426mg, catalyst amount 213mg (catalyst: substrate=1:2), 250-270
℃,H2Initial pressure 3Mpa, 10h.The results are shown in Table 1:
Influence of 2 reaction temperature of table to diphenyl ether hydrogenation deoxidation reaction result
Embodiment 6, the evaluation of diphenyl ether hydrogenation deoxidation reactivity worth
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst is investigated under differential responses pressure using diphenyl ether as substrate
The performance of catalyst, reaction condition are as follows: diphenyl ether 426mg, catalyst amount 213mg (catalyst: substrate=1:2), 265 DEG C,
H2Initial pressure 2-3Mpa, 10h.The results are shown in Table 1:
Influence of 3 reaction pressure of table to diphenyl ether hydrogenation deoxidation reaction result
Embodiment 7, the evaluation of diphenyl ether hydrogenation deoxidation reactivity worth
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst is investigated under the differential responses time using diphenyl ether as substrate
The performance of catalyst, reaction condition are as follows: diphenyl ether 426mg, catalyst amount 213mg (catalyst: substrate=1:2), 265 DEG C,
H2Initial pressure 3Mpa, 5-10h.The results are shown in Table 1:
Influence of 4 reaction time of table to diphenyl ether hydrogenation deoxidation reaction result
Embodiment 8, the evaluation of diphenyl ether hydrogenation deoxidation reactivity worth
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst investigates different catalysts dosage using diphenyl ether as substrate
The performance of lower catalyst, reaction condition are as follows: diphenyl ether 426mg, catalyst amount 106-426mg (catalyst: substrate=1:4-1:
1), 265 DEG C, H2Initial pressure 3Mpa, 10h.The results are shown in Table 1:
Influence of 5 catalyst amount of table to diphenyl ether hydrogenation deoxidation reaction result
Embodiment 9, phenol hydrogenation deoxygenation performance evaluation
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst carries out reaction evaluating using phenol as substrate, reacts item
Part are as follows: phenol 235mg, catalyst amount 213mg, 265 DEG C, H2Initial pressure 3Mpa, 10h.The results are shown in Table 2:
6 MoS of table2/Co9S8-Al2O3Catalyst Pyrogentisinic Acid's hydrogenation deoxidation reaction result
Embodiment 10, the evaluation of 4- methylphenol hydrogenation deoxidation reactivity worth
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst carries out reaction evaluating using 4- methylphenol as substrate,
Reaction condition are as follows: 4- methylphenol 270mg, catalyst amount 213mg, 265 DEG C, H2Initial pressure 3Mpa, 10h.As a result such as table 3
It is shown:
7 MoS of table2/Co9S8-Al2O3Catalyst is to 4- methylphenol hydrogenation deoxidation reaction result
Embodiment 11, the evaluation of 4- ethyl -phenol hydrogenation deoxidation reactivity worth
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst carries out reaction evaluating using 4- ethyl -phenol as substrate,
Reaction condition are as follows: 4- ethyl -phenol 305mg, catalyst amount 213mg, 265 DEG C, H2Initial pressure 3Mpa, 10h.As a result such as table 4
It is shown:
8 MoS of table2/Co9S8-Al2O3Catalyst is to 4- ethyl -phenol hydrogenation deoxidation reaction result
Embodiment 12, the evaluation of 4- propylphenol hydrogenation deoxidation reactivity worth
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst carries out reaction evaluating using 4- propylphenol as substrate,
Reaction condition are as follows: 4- propylphenol 340mg, catalyst amount 213mg, 265 DEG C, H2Initial pressure 3Mpa, 10h.As a result such as table 5
It is shown:
9 MoS of table2/Co9S8-Al2O3Catalyst is to 4- propylphenol hydrogenation deoxidation reaction result
Embodiment 13, the evaluation of methyl phenyl ethers anisole hydrogenation deoxidation reactivity worth
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst carries out reaction evaluating, reaction using methyl phenyl ethers anisole as substrate
Condition are as follows: methyl phenyl ethers anisole 270mg, catalyst amount 213mg, 265 DEG C, H2Initial pressure 3Mpa, 10h.The results are shown in Table 6:
10 MoS of table2/Co9S8-Al2O3Catalyst is to methyl phenyl ethers anisole hydrogenation deoxidation reaction result
Embodiment 14, the evaluation of benzylalcohol hydrogenation deoxidation reactivity worth
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst carries out reaction evaluating using benzylalcohol as substrate, reacts item
Part are as follows: benzylalcohol 270mg, catalyst amount 213mg, 265 DEG C, H2Initial pressure 3Mpa, 10h.The results are shown in Table 7:
11 MoS of table2/Co9S8-Al2O3Catalyst is to benzylalcohol hydrogenation deoxidation reaction result
Embodiment 15, the evaluation of benzyl phenyl ether hydrogenation deoxidation reactivity worth
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst, using benzyl phenyl ether as substrate, reaction condition are as follows: benzyl
Base phenyl ether 460mg, catalyst amount 213mg, 265 DEG C, H2Initial pressure 3Mpa, 10h.Reaction evaluating is carried out, as a result such as table 8
It is shown:
12 MoS of table2/Co9S8-Al2O3Catalyst is to benzyl phenyl ether hydrogenation deoxidation reaction result
Embodiment 16, the evaluation of benzyl ether hydrogenation deoxidation reactivity worth
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst, using benzyl ether as substrate, reaction condition are as follows: benzyl ether
495mg, catalyst amount 213mg, 265 DEG C, H2Initial pressure 3Mpa, 10h.Reaction evaluating is carried out, the results are shown in Table 9:
13 MoS of table2/Co9S8-Al2O3Catalyst is to benzyl ether hydrogenation deoxidation reaction result
Embodiment 17, the evaluation of m-phenoxy toluene hydrogenation deoxidation reactivity worth
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst, using m-phenoxy toluene as substrate, reaction condition are as follows:
M-phenoxy toluene 465mg, catalyst amount 213mg, 265 DEG C, H2Initial pressure 3Mpa, 10h.Reaction evaluating is carried out, as a result
It is as shown in table 10:
14 MoS of table2/Co9S8-Al2O3Catalyst is to m-phenoxy toluene hydrogenation deoxidation reaction result
Embodiment 18, catalyst circulation stability test
The MoS that Example 2 obtains2/Co9S8-Al2O3Catalyst carries out cyclical stability survey using diphenyl ether as substrate
Examination.Circulation rear catalyst carries out recycling washing drying every time, for recycling next time.Reaction condition are as follows: catalyst amount 213mg
(catalyst: substrate=1:2), 265 DEG C, H2Initial pressure 3Mpa, 10h.Reaction result is as shown in table 5:
15 MoS of table2/Co9S8-Al2O3Catalyst is to diphenyl ether hydrogenation deoxidation reaction cycle steady testing result
Claims (7)
1. a kind of catalyst for preparing aromatic hydrocarbon for Catalytic lignin model compound reaction；It is characterized in that structural formula is MoS2/
Co9S8-Al2O3, wherein MoS2It is dispersed in catalyst surface, Co forms Co through over cure9S8Phase, with carrier Al2O3It is formed
Stable veneer structure.
2. the preparation method of the catalyst that aromatic hydrocarbon is prepared for the reaction of Catalytic lignin model compound of claim 1,
It is characterized in that specific step is as follows:
(1) taking Co:Al molar ratio range is the houghite hydroxide precursor of 1:1-5:1, roasts and Co is made3O4-Al2O3Class
Hydrotalcite oxide carrier；
(2) by (NH4)2Mo7O24Aqueous solution carries out hydration load with houghite oxide under conditions of closed, then carries out
Drying to obtain (NH4)2Mo7O24/Co3O4-Al2O3Solid；
(3) above-mentioned solid passes through elevated temperature cure, wherein (NH4)2Mo7O24Vulcanization forms MoS2, Co3O4Form Co9S8, Al2O3Stablize
It is constant to get arrive MoS2/Co9S8-Al2O3Hydrogenation deoxidation catalyst.
3. method according to claim 2, it is characterized in that roasting condition is roasted under the conditions of 300-500 DEG C in step (1)
4-6 hours.
4. method according to claim 2, it is characterized in that hydration load 6-20h, ((NH in step (2)4)2Mo7O24):
(Co3O4-Al2O3) mass ratio be 1:4-1:1.
5. method according to claim 2, it is characterized in that step (2) drying temperature is 50-100 DEG C, drying time 6-
20h。
6. claim 1 catalyst is applied to the method that lignin model compound hydrogenation deoxidation prepares aromatic hydrocarbon, characterized in that
Lignin model compound and internal standard compound dodecane are dissolved in methyl cyclohexane alkane solvents, are added together with catalyst intermittent anti-
It answers in kettle, is passed through hydrogen, heating is stirred to react.
7. method as claimed in claim 6, it is characterized in that catalyst and lignin model compound mass ratio are 1:4~1, instead
Answer condition are as follows: 250-270 DEG C of reaction temperature, H2Initial pressure 2-3Mpa, reaction time 5-10h.
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