CN111215129A - ReOxMethod for catalytically cracking carbon-carbon bond of lignin by HZSM-5 - Google Patents
ReOxMethod for catalytically cracking carbon-carbon bond of lignin by HZSM-5 Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
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- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
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- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
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Abstract
The invention provides a ReOxA process for preparing aromatic compound by catalyzing the carbon-carbon bond breaking of lignin model compound with 5-5, β -1, β - β, β -5 structure by HZSM-5 includes reaction on xylene solvent and ReOxThe catalyst is/HZSM-5, and the catalyst catalyzes and cracks the carbon-carbon bond of the lignin model compound to convert the lignin model compound into small-molecule aromatic chemicals, and the yield reaches over 80 percent. Compared with the traditional lignin depolymerization method, the method has the following distinctive characteristics: inorganic acid and alkali are not needed in the reaction process, so that the generation of a large amount of acid liquor in the traditional lignin catalysis is avoided; the catalyst has longer service life and higher reaction activity; the monophenol product has high selectivity; the invention realizes the selective breakage of the carbon-carbon bond of the lignin, opens up a new depolymerization strategy for preparing aromatic chemicals from renewable lignin resources, and simultaneously opens up a new way for producing aromatic compounds by non-petroleum routes.
Description
Technical Field
The invention provides a method for preparing a compound with ReOxthe method is a new method for generating corresponding aromatic compounds by breaking carbon-carbon bonds of dimers of various lignin model compounds 5-5, β -1, β - β, β -5 by using/HZSM-5 as a catalyst and xylene as a solvent.
Background
The lignin is a complex phenolic polymer consisting of a plurality of phenylpropane structural units (i.e. a guaiacyl structure, a syringyl structure, a p-hydroxyphenyl structure and the like), and is the only renewable resource capable of directly providing aromatic rings in nature. Lignin is abundant in nature (next to cellulose) and widely available (chem. Currently, only the paper industry worldwide produces over 5000 million tons of lignin per year, however, less than 2% of the lignin is used for industrial production, and the rest is mostly burned directly, which causes serious waste of resources while putting a great pressure on the environment (j. Meanwhile, lignin molecules have a plurality of functional groups such as aromatic groups, methoxy groups, phenolic (alcoholic) hydroxyl groups, carbonyl groups, carboxyl groups and the like, active sites such as unsaturated double bonds and the like, and a C/H content ratio (chem. Rev.2010,110,3552) similar to that of petroleum, so that the lignin is expected to be a main renewable raw material for producing high-grade bio-fuel oil such as aromatic hydrocarbon, naphthenic hydrocarbon, alkane and the like and high-value-added aromatic fine chemicals such as phenols and the like based on a special chemical structure and a carbon-hydrogen ratio of the lignin. Therefore, the method has important significance for efficient comprehensive utilization of lignin by analyzing the internal structure of the lignin, knowing the internal chemical bonding mode of the lignin and determining the activation and breaking paths of main chemical bonds of the lignin so as to guide directional depolymerization of the lignin.
At present, three ways of lignin degradation and utilization mainly comprise thermal cracking, catalytic oxidation and catalytic hydrogenolysis. Thermal cracking generally requires higher temperatures and has the problem of high energy consumption, and the cracked bio-oil has a lower thermal value and generally needs further upgrading for use as transportation fuel. Catalytic hydrogenolysis and catalytic oxidation are the two main strategies for selectively cleaving lignin aryl ether bonds to obtain aromatic compounds, but in most systems, fragments of carbon-carbon bonds remain. The bond energy of carbon-carbon bonds in lignin is higher than that of carbon-oxygen bonds, and carbon-carbon bonds are more tenacious than carbon-oxygen bonds, so that effective depolymerization is difficult. In conclusion, the development of a method for effectively depolymerizing carbon-carbon bonds of lignin to obtain aromatic chemicals has a distinctive characteristic, and is particularly important for the efficient utilization of lignin.
The invention provides a method for preparing a compound with ReOxthe method is a new method for generating corresponding aromatic compounds by breaking carbon-carbon bonds of multiple lignin 5-5, β -1, β - β, β -5 model compounds by using dimethylbenzene as a catalyst and using dimethylbenzene as a solvent.
Disclosure of Invention
The invention aims to provide a method for reducing the content of carbon monoxide in a fuel cell by ReOxThe method for catalyzing and cracking carbon-carbon bonds of lignin by HZSM-5. The carbon-carbon bond of the lignin model compound is efficiently depolymerized by taking the lignin model compound as a substrate and one or more than one of dimethylbenzene as a reaction solvent.
In order to achieve the purpose, the invention adopts the technical scheme that: one or more than two of lignin model compounds are used as substrates, xylene is used as reaction solvent, and the reaction is carried out in ReOxIn the presence of/HZSM-5, reacting for 12-24 hours at 100-350 ℃ in a closed high-pressure reaction kettle under the hydrogen pressure of 1-10MPa and x is 6-7, and catalytically cracking carbon-carbon bond of the lignin model compoundPreparing the aromatic compound.
Filling hydrogen into the reaction kettle before reaction, wherein the initial pressure of the hydrogen at room temperature is 1MPa-10MPa, and the optimal initial pressure is 3MPa-8 MPa; the preferred reaction temperature is 120 ℃ to 280 ℃; the reaction time is preferably 14h to 20 h.
The catalyst ReOxActive component ReO of HZSM-5xThe loading on the HZSM-5 carrier is 0.1 wt% to 10 wt%, preferably the loading is 5 wt% to 8 wt%.
The xylene solvent is one or two or three of p-xylene, o-xylene and m-xylene, and the volume ratio of the two combined solvents is preferably 0.1-10.
the lignin model compound is one or more than two of 2, 2' -dihydroxy biphenyl (5-5), 1, 4-biphenyl butane (β - β), benzyl-4-hydroxybenzophenone (β -1) and dehydrodiisobutyrol (β -5).
The aromatic compound is: one or more of phenol, guaiacol, toluene, ethylbenzene, propylbenzene, 1-phenethyl alcohol and o-diphenol.
The reaction solvent amount is 5mL-10mL, the substrate amount is 100mg-500mg, and the catalyst amount is 50mg-200 mg.
The invention has the following advantages:
1) in the hydrogenolysis or oxidation reaction of lignin, an acidic or alkaline environment is often needed, and liquid acid or alkali is not needed to be added in the method, so that the generation of a large amount of waste liquid in the traditional lignin catalysis is avoided.
2) The aromatic product generated by the method has high selectivity, the aromatic ring is not damaged, and the atom economy is higher; while the traditional hydrogenolysis of lignin is difficult to avoid the hydrogenation reaction of benzene ring to obtain the mixture of phenols and alkanes, and the oxidative depolymerization is difficult to avoid excessive oxidation.
3) The catalyst of the present invention has longer service life and higher reaction activity.
In summary, this patent provides ReOxThe method for catalytically cracking the carbon-carbon bond of lignin by HZSM-5 is a very practical and inventive method for depolymerizing lignin.
The invention will now be illustrated by means of specific examples.
Detailed Description
Example 1:
100mg of a model lignin compound, 2' -dihydroxybiphenyl, 100mg of catalyst ReOx/HZSM-5(5wt％ReOxX is 7), 15ml of p-xylene is added into a 75 ml reaction kettle, hydrogen is introduced to replace gas for three times, then the hydrogen is filled to 5MPa, the temperature is raised to 280 ℃, and the reaction is carried out for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the centrifuged supernatant was subjected to chromatography, whereby the conversion was 90.9% and the yield of phenol was 83.4% (the yield was calculated by the following equation: phenol yield (%): phenol yield true/2).
Example 2:
100mg of a lignin model compound 2, 2' -dihydroxybiphenyl and 15ml of p-xylene are added into a 75 ml reaction kettle, hydrogen is introduced to replace the gas for three times, the hydrogen is filled to 5MPa, the temperature is increased to 280 ℃, and the reaction is carried out for 24 hours. After the reaction is finished, the reaction solution is cooled to room temperature, the centrifuged supernatant is taken for chromatographic analysis, the conversion rate is 0%, the yield of phenol is 0%, and blank experiments show that the reaction can not be carried out when no catalyst is added.
Examples 3 to 7:
other process conditions and experimental procedures were the same as in example 1, but different hydrogen initiation pressures were used, and the results are shown in Table 1, ReO among the different hydrogen initiation pressuresx/HZSM-5(5wt％ReOxX ═ 7) results of experiments for catalytic conversion of lignin
. As shown in Table 1, the phenol yield increased with increasing initial pressure.
Examples 8 to 14
The other process conditions and experimental procedures were the same as in example 1, but different reaction temperatures were used, and the results are shown in Table 2.
TABLE 2 ReO at different reaction temperaturesx/HZSM-5(5wt％ReOxX ═ 7) catalytic conversionResults of lignin experiments
. As shown in Table 2, as the reaction temperature increased, the phenol yield increased and the conversion increased.
Examples 15 to 18
The other process conditions and experimental procedures were the same as in example 1, but with different reaction times, the results are shown in Table 3.
TABLE 3 ReO at different reaction timesx/HZSM-5(5wt％ReOxX ═ 7) results of experiments for catalytic conversion of lignin
. As shown in Table 3, the phenol yield increased with the increase of the reaction time, and the conversion increased.
Examples 19 to 23
The other process conditions and experimental procedures were the same as in example 1, but with different loadings of catalyst, the results are shown in table 4.
TABLE 4 different loadings of ReOxExperimental result of/HZSM-5 (x is 7) catalytic conversion lignin
Examples 24 to 25
The other process conditions and experimental procedures were the same as in example 1, but different reaction solvents were used, and the results are shown in Table 5. TABLE 5 different reaction solvents ReOx/HZSM-5(5wt％ReOxX ═ 7) results of experiments for catalytic conversion of lignin
Examples 26 to 31
The other process conditions and experimental procedures were the same as in example 1, but different combinations of solvents were used, and the results are shown in Table 6.
TABLE 6 different combination solvents ReOx/HZSM-5(5wt％ReOxX ═ 7) results of experiments for catalytic conversion of lignin
Examples 32 to 40
100mg of a model lignin compound, 2' -dihydroxybiphenyl, 100mg of catalyst ReOx/HZSM-5(5wt％ReOx) And 15ml of p-xylene are added into a 75 ml reaction kettle, hydrogen is introduced to replace the gas for three times, the hydrogen is filled to 5MPa, the temperature is raised to 300 ℃, and the reaction is carried out for 24 hours. After the reaction is finished, cooling to room temperature, taking the centrifuged supernatant, performing chromatographic analysis, and then filtering to obtain the catalyst, drying the catalyst at 50 ℃ for 10 hours, and directly putting the catalyst into the next cycle for use, wherein the results of the catalyst cycle experiment are shown in Table 7.
TABLE 7 ReOx/HZSM-5(5wt％ReOxX ═ 7) cycle use test results
Examples 41 to 42
The other process conditions and experimental procedures were the same as in example 1, but with different substrate amounts, the results are shown in Table 8.
TABLE 8 ReO at different substrate dosagesx/HZSM-5(5wt％ReOxX ═ 7) results of experiments for catalytic conversion of lignin
Examples 43 to 44
The other process conditions and experimental procedures were the same as in example 1, but with different amounts of catalyst, the results are shown in Table 9.
TABLE 9 ReO at different catalyst base loadingsx/HZSM-5(5wt％ReOxX ═ 7) results of experiments for catalytic conversion of lignin
Example 45
The other experimental procedures were the same as in example 1 except that 100mg of 1, 4-diphenylbutane was dissolved in 15mL of p-xylene and reacted at 300 ℃ for 24 hours with a conversion of 88.2% to obtain 82.4% yield of ethylbenzene, 30.5% yield of toluene and 45.6% yield of propylbenzene.
Example 46
The other experimental procedures were the same as in example 1 except that 100mg of benzyl-4-hydroxybenzophenone was dissolved in 15mL of p-xylene and reacted at 300 ℃ for 24 hours with a conversion of 95.4% to give a toluene yield of 90.8%, a phenol yield of 45.8% and a 1-phenylethyl alcohol yield of 20.2%.
Example 47
The other experimental procedures were the same as in example 1 except that 100mg of dehydrodiisobutyronitrile was dissolved in 15mL of p-xylene and reacted at 300 ℃ for 24 hours to obtain 85.4% conversion, 77.5% yield of guaiacol, 55.6% yield of o-diphenol and 24.2% yield of propylbenzene.
As can be seen from the above examples: the invention provides a ReOxThe method for efficiently depolymerizing the carbon-carbon bond of the lignin model compound by the HZSM-5 has high selectivity of the aromatic compound, provides theoretical basis and scientific basis for high-valued conversion of lignin, and opens up a new way for producing the aromatic compound by a non-petroleum route.
Claims (8)
1.ReOxThe method for catalyzing and cracking the carbon-carbon bond of the lignin by the HZSM-5 is characterized by comprising the following steps: one or more than two of lignin model compounds are used as substrates, xylene is used as reaction solvent, and the reaction is carried out in ReOxIn the presence of HZSM-5, reacting for 12-24 hours at 100-350 ℃ in a closed high-pressure reaction kettle under the hydrogen pressure of 1-10MPa and x is 6-7, and catalytically cracking carbon-carbon bonds of the lignin model compound to prepare the aromatic compound.
2. The method of claim 1, wherein: filling hydrogen into the reaction kettle before reaction, wherein the initial pressure of the hydrogen at room temperature is 1MPa-10MPa, and the optimal initial pressure is 3MPa-8 MPa.
3. The method of claim 1, wherein: the preferred reaction temperature is 120 ℃ to 280 ℃; the reaction time is preferably 14h to 20 h.
4. The method of claim 1, wherein: the catalyst ReOxActive component ReO of HZSM-5xThe loading on the HZSM-5 carrier is 0.1 wt% to 10 wt%, preferably the loading is 5 wt% to 8 wt%.
5. The method of claim 1, wherein: the xylene solvent is one or two or three of p-xylene, o-xylene and m-xylene, and the volume ratio of the two combined solvents is preferably 0.1-10.
6. the method according to claim 1, wherein the lignin model compound is one or more of 2, 2' -dihydroxybiphenyl (5-5), 1, 4-biphenylbutane (β -beta.), benzyl-4-hydroxybenzophenone (β -1), and dehydrodiisobutylaminol (β -5).
7. The method of claim 1, wherein: the aromatic compound is: one or more of phenol, guaiacol, toluene, ethylbenzene, propylbenzene, 1-phenethyl alcohol and o-diphenol.
8. The method of claim 1, wherein: the reaction solvent amount is 5mL-10mL, the substrate amount is 100mg-500mg, and the catalyst amount is 50mg-200 mg.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011003029A2 (en) * | 2009-07-01 | 2011-01-06 | The Regents Of The University Of California | Catalytic disproportionation and catalytic reduction of carbon-carbon and carbon-oxygen bonds of lignin and other organic substrates |
| US20150224485A1 (en) * | 2014-02-07 | 2015-08-13 | Basf Corporation | Catalyst for pyrolysis of feedstock |
| US20170152200A1 (en) * | 2015-11-30 | 2017-06-01 | Sabic Global Technologies, B.V. | Zeolite Catalyst for Lignin to Phenol Conversion |
| CN107473944A (en) * | 2016-06-08 | 2017-12-15 | 中国科学院大连化学物理研究所 | ReOxThe method of/AC catalytic pyrolysis lignin aryl oxide keys |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011003029A2 (en) * | 2009-07-01 | 2011-01-06 | The Regents Of The University Of California | Catalytic disproportionation and catalytic reduction of carbon-carbon and carbon-oxygen bonds of lignin and other organic substrates |
| US20150224485A1 (en) * | 2014-02-07 | 2015-08-13 | Basf Corporation | Catalyst for pyrolysis of feedstock |
| CN106163655A (en) * | 2014-02-07 | 2016-11-23 | 巴斯夫公司 | Catalyst for raw material pyrolysis |
| US20170152200A1 (en) * | 2015-11-30 | 2017-06-01 | Sabic Global Technologies, B.V. | Zeolite Catalyst for Lignin to Phenol Conversion |
| CN107473944A (en) * | 2016-06-08 | 2017-12-15 | 中国科学院大连化学物理研究所 | ReOxThe method of/AC catalytic pyrolysis lignin aryl oxide keys |
Non-Patent Citations (1)
| Title |
|---|
| 赵岩等: "HZSM-5分子筛催化热裂解生物质制备芳烃化合物", 《化工新型材料》 * |
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