CN117024238A - Method for synthesizing polycyclic alkane from lignin-derived phenols through one-pot two-step method - Google Patents
Method for synthesizing polycyclic alkane from lignin-derived phenols through one-pot two-step method Download PDFInfo
- Publication number
- CN117024238A CN117024238A CN202310432340.0A CN202310432340A CN117024238A CN 117024238 A CN117024238 A CN 117024238A CN 202310432340 A CN202310432340 A CN 202310432340A CN 117024238 A CN117024238 A CN 117024238A
- Authority
- CN
- China
- Prior art keywords
- reaction
- lignin
- catalyst
- solid acid
- aviation kerosene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229920005610 lignin Polymers 0.000 title claims abstract description 23
- 150000002989 phenols Chemical class 0.000 title claims abstract description 23
- -1 polycyclic alkane Chemical class 0.000 title claims abstract description 17
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 33
- 239000011973 solid acid Substances 0.000 claims abstract description 23
- 239000003350 kerosene Substances 0.000 claims abstract description 17
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 150000002576 ketones Chemical class 0.000 claims description 6
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims 2
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 claims 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims 1
- 229960001867 guaiacol Drugs 0.000 claims 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 13
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000006012 monoammonium phosphate Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a method for synthesizing polycyclic alkane from lignin-derived phenols by a one-pot two-step method. 1) In the first step of reaction, lignin-derived phenolic compounds are firstly converted into ketone compounds under the action of a hydrogenation catalyst, and then the ketone compounds are rapidly subjected to aldol condensation under the action of solid acid to generate aviation kerosene precursors; 2) In the second reaction step, the reaction condition is directly enhanced without separating the product in the first step, and the aviation kerosene precursor directly realizes complete hydrodeoxygenation to generate polycyclic alkane under the action of a hydrogenation catalyst and solid acid in the first step; lignin-derived phenolic compounds are synthesized into multi-ring aviation kerosene in a reaction vessel by changing reaction conditions. Compared with the traditional chain aviation kerosene, the density and the heat value of the aviation kerosene are high, and the aviation kerosene can be used as a substitute of the traditional aviation fuel. The catalyst and the raw materials used in the application have rich sources, low price and easy separation; the whole production process is simple and convenient to operate.
Description
Technical Field
A method for synthesizing polycyclic alkane from lignin-derived phenolic compound by a one-pot two-step method. The method of the application relates to two processes of one pot, wherein the first process is that lignin-derived phenolic compounds are hydrogenated to generate ketone compounds, then the ketone compounds undergo aldol condensation under the action of solid acid, and simultaneously carbon-carbon double bonds are saturated; the second process is a complete hydrodeoxygenation reaction.
Background
Biomass energy has rich reserves, can be regenerated and is CO 2 Neutral, and the like, so that the biomass resources are utilized to produce aviation fuel components or chemicals to replace fuel or chemicals obtained by traditional oil refining, the external dependence of petroleum in China can be reduced, and the current green development concept is met. Lignin is the second largest biomass resource in nature, except cellulose, and is the only clean non-petroleum resource in nature that can provide renewable aromatic compounds. The biomass oil obtained by pyrolysis of lignin has more benzene ring structural units, is a cheap and clean resource capable of being converted into high-energy aromatic hydrocarbon and naphthenic hydrocarbon, and is one of the most potential petroleum supplementary energy sources.
Cyclohexanone and its derivatives are important biomass platform compounds that can be obtained by hydrogenation of lignin-derived phenols ([ CN103724174B ]; shaping, X.; wang, C.; wang, W.organic Process Research & Development 2021,25 (11), 2425-2431; xu, G.Y.; guo, J.H.; zhang, Y.; fu, Y.; chen, J.Z.; ma, L.L.; guo, Q.X.Chemcatchem 2015,7 (16), 2485-2492.). While cyclohexanone and its derivatives may undergo aldol condensation followed by hydrodeoxygenation to obtain a multicycloalkane. However, the process involves a plurality of reaction courses, has more separation steps and consumes more energy; the direct conversion of lignin-derived phenols to polycycloalkanes by single pot tandem reactions is therefore attractive compared to stepwise synthesis strategies.
Disclosure of Invention
The application converts lignin-derived phenols into oxygen-containing aviation kerosene precursors under mild conditions by using a solid acid catalyst and a hydrogenation catalyst which are easy to separate, and then the catalyst and the solvent used in the last step are continuously used, and the liquid fuel is obtained in high yield through a two-step process after simply raising the temperature and the reaction pressure; the catalyst has the characteristics of no solvent, easy separation, simple operation process, low energy consumption, low cost and the like, and provides a new route for synthesizing high-density multi-ring aviation kerosene by using lignin-derived phenolic compounds.
The application is realized by the following technical scheme:
the reaction process is realized by a one-pot two-step reaction process.
In the first step of reaction, lignin-derived phenolic compounds are firstly subjected to selective hydrogenation to ketone under the action of a hydrogenation catalyst in a hydrogen atmosphere, and then the ketone compounds are rapidly subjected to aldol condensation under the action of a solid acid catalyst to generate aviation kerosene precursors, namely unsaturated organic matters containing multiple carbon numbers;
the reaction is carried out in a batch kettle reactor, and the molar ratio of lignin-derived phenols to active components in the hydrogenation catalyst is 1: 0.0002-0.005, the mass ratio of the solid acid catalyst to the reaction substrate is 0.2-1, the reaction temperature is 80-120 ℃, the reaction time is 2-12 h, and the reaction pressure is 0.5-2 MPa.
The second process continues with the catalyst and solvent of the first step. After the step 1 is completed, the hydrogen reaction pressure is directly flushed to 3 MPa-5 MPa without opening a kettle, the temperature is increased to 180-240 ℃, and the reaction time is 4-12 h. The aviation kerosene precursor directly realizes complete hydrodeoxygenation to generate polycyclic alkane under the action of a hydrogenation catalyst and solid acid in the first step.
Further, in the above technical scheme, the above two steps of reactions are both carried out in a hydrogen atmosphere.
Further, in the above technical scheme, in the first step, the hydrogenation catalyst is a supported catalyst a/X, and includes two parts of a metal active site a and a support X supported on a support. The carrier X is SiO 2 、TiO 2 、CeO 2 、Al 2 O 3 At least one of MgAl-HT, mgO, liAl-HT; the load metal is Pt, pd, ru, ir, rh, ni,Fe. One or more than two of Cu, wherein the loading of the catalyst is between 0.1wt% and 15 wt%.
Further, in the above technical scheme, the solid acid catalyst in the first step is Nafion-212, amberlyst-15, amberlyst-36, tiP 2 ，CeP 2 ，AlP 2 ，ZrP 0.5 ，ZrP 1 ，ZrP 2 ，ZrP 3 At least one of; wherein, the solid acid Nafion-212, amberlyst-15 and amberlyst-36 are commercially available, and other solid acids are prepared by adopting a coprecipitation method. TiP (TiP) 2 ，CeP 2 ，AlP 2 The metal precursor nitrate solution and the ammonium dihydrogen phosphate solution are mixed and stirred at 50 ℃ according to a certain molar ratio, then concentrated ammonia water is added dropwise to adjust the PH value to 8-10, stirring is continued for 4-8 h, filtering and washing are carried out, drying is carried out at 80 ℃ overnight, and calcination is carried out at 350-650 ℃ for 5-8 h. Zirconium phosphate (ZrP) x ) The preparation method comprises the steps of preparing basic zirconia solution and monoammonium phosphate solution with different molar ratios, then dropwise adding the monoammonium phosphate solution into the basic zirconia solution, continuously stirring for 4 hours after the addition, filtering and washing to be neutral, then drying at 120 ℃ overnight, and roasting at 400 ℃ for 4 hours.
Through the steps, the high-density aviation fuel with the multi-ring structure is successfully synthesized.
The product polycycloalkane has the structure:
the method for combining the solid acid catalyst and the noble metal hydrogenation catalyst, which are cheap and easy to obtain, can realize the expected series process. The process can be carried out in two steps, under the condition of unchanged catalyst and solvent, the hydrogenation and subsequent aldol condensation of the phenolic compound are realized in the first step to obtain the oxygen-containing aviation kerosene precursor, and the complete hydrodeoxygenation of the oxygen-containing aviation kerosene precursor is realized in the second step by strengthening the reaction condition, so as to finally obtain the polycyclic alkane.
Drawings
FIG. 1 is a mass spectrum of the product of example 64;
FIG. 2 is a mass spectrum of the product of example 67;
FIG. 3 is a mass spectrum of the product of example 68;
FIG. 4 is a mass spectrum of the product of example 69;
FIG. 5 is a mass spectrum of the product distribution of the raw material phenol of example 64 during the first reaction step;
FIG. 6 is a mass spectrum of the target product of the phenol feed of example 64 during the first reaction step.
Detailed Description
The present application will be described with reference to specific examples, but the scope of the present application is not limited to these examples.
The sources of catalyst in the examples below: the hydrogenation catalyst in the first step is a supported catalyst A/X, and comprises a metal active site A and a carrier X which are supported on a carrier. The carrier X is SiO 2 、TiO 2 、CeO 2 、Al 2 O 3 At least one of MgAl-HT, mgO, liAl-HT; the load metal is one or more than two of Pt, pd, ru, ir, rh, ni, fe, cu, wherein the load of the catalyst is between 0.1 and 15 percent.
The solid acid catalyst is Nafion-212, amberlyst-15, amberlyst-36, tiP 2 ，CeP 2 ，AlP 2 ，ZrP 0.5 ，ZrP 1 ，ZrP 2 ，ZrP 3 At least one of; wherein, the solid acid Nafion-212, amberlyst-15 and amberlyst-36 are commercially available, and other solid acids are prepared by adopting a coprecipitation method. TiP (TiP) 2 ，CeP 2 ，AlP 2 The metal precursor nitrate solution and the ammonium dihydrogen phosphate solution are mixed and stirred at 50 ℃ according to a certain molar ratio, then concentrated ammonia water is added dropwise to adjust the PH value to 8-10, stirring is continued for 4-8 h, filtering and washing are carried out, drying is carried out at 80 ℃ overnight, and calcination is carried out at 350-650 ℃ for 5-8 h. Zirconium phosphate (ZrP) x ) Preparing basic zirconia solution and monoammonium phosphate solution with different molar ratios, then dropwise adding the monoammonium phosphate solution into the basic zirconia solution, continuously stirring for 4 hours after the addition is finished, filtering and washing to be neutral,and then drying at 120 ℃ overnight, and roasting at 400 ℃ for 4 hours.
Example 1:
the following reaction scheme is the reaction scheme of the present application, and the reaction conditions in example 2 are employed.
Examples 2 to 10:
1) In the first reaction step, 0.4g of phenol (or other phenols) and a certain amount of catalyst were added to the reaction vessel, 40ML of cyclohexane was added as a solvent, and the reaction was carried out at a certain temperature and pressure for a certain period of time, and the detailed reaction results are shown in table 1.
Table 1 reaction conditions and results for the hydrogenation and aldol condensation of phenol and its derivatives.
It can be seen from Table 1 that the conversion activity of different lignin-derived phenols is related to its structure, wherein phenol is easily hydrogenated and aldolised, the conversion activity of para-substituted alkylphenols is not much different from that of phenol, followed by meta-substituted alkylphenols and ortho-substituted alkylphenols; at the same time, the type of substituent also affects the conversion activity of the phenolic derivative.
2) Effect of different combinations of catalysts on the first step reaction.
Adding 0.4g of phenol and a catalyst (comprising a hydrogenation catalyst and a solid acid) into a batch reaction kettle of 100ML, adding 40ML of cyclohexane as a solvent, and reacting under certain conditions; the detailed reaction results are shown in Table 2.
Table 2 reaction results of phenol in the first step reaction using different catalyst combinations.
As can be seen from table 2, phenol has different conversion activities with different catalyst combinations, and catalytic properties affect the hydrogenation of phenol to ketone and further to aldol condensation products. Overall, noble metals have better hydrogenation performance, but the selective hydrogenation effect of different noble metals on phenol is different, and some noble metals are catalyzed by excessive hydrogenation, which affects the subsequent aldol condensation reaction. Meanwhile, different solid acids also show aldol condensation capability with different effects, and the solid acid aldol condensation capability is strong, so that the excessive hydrogenation of cyclohexanone into alcohol can be inhibited to a certain extent. The metal loading is also a significant effect on the selective hydrogenation catalysis of phenol.
3) Influence of reaction conditions on the selective hydrogenation of phenol and aldol condensation reaction.
Adding 0.4g of phenol and 40ML of cyclohexane into a 100ML batch reactor, entering a certain amount of combined catalyst, and reacting for a period of time under different conditions; the results are shown in Table 3.
TABLE 3 reaction results of phenol under different reaction conditions
As can be seen from Table 3, the reaction conditions have a certain effect on the distribution of the product. The metal hydrogenation catalyst mainly acts on the process of forming ketone or alcohol by the hydrogenation of phenol, the too low dosage of the hydrogenation catalyst can cause incomplete reaction of phenol, and the too high dosage can cause the reduction of ketone selectivity; the temperature and pressure have the same effect on the hydrogenation process; the solid acid catalyst acts mainly on aldol condensation of ketones, however, excessive acid may lead to a decrease in carbon balance, possibly excessive acid resulting in hydrogenation of alcohols to alkanes. By optimizing the reaction conditions, 89% of oxygen-containing aviation kerosene precursors can be obtained, and the oxygen-containing aviation kerosene precursors are directly subjected to hydrogen addition and deoxidation to form alkane in the second step.
4) One-pot two-step synthesis of polycyclic alkane from lignin-derived phenols
The first reaction step was carried out by mixing 0.4g of the substrate of examples 2-10 with 1wt% Pd/MgAl-HT catalyst and ZrP in the amounts indicated in Table 4 2 Adding the catalyst into a reaction kettle, and simultaneously adding 40ML cyclohexane to prepare the catalystThe solvent was reacted at 120℃under a hydrogen pressure of 100Psi for 12 hours.
The different oxygen-containing aviation kerosene precursors are fully hydrodeoxygenated.
After the first step of reaction is finished, the temperature is reduced to room temperature, then hydrogen is flushed to 4MPa, the temperature is increased for reaction, and the reaction conditions are shown in Table 4. Wherein the starting materials of examples 64-72 correspond to the target products of the substrates of examples 2-10 in step 1 after 12 hours of reaction in the first step, respectively, and the target products are directly hydrodeoxygenated in the second step to obtain the corresponding bicycloalkane fuel.
Both reactions were carried out in a hydrogen atmosphere.
TABLE 4 final Synthesis of different lignin-derived phenols into bicycloalkanes in a one pot two step process
As can be seen from Table 4, after the series reaction, we can directly obtain the polycyclic alkane in one pot, the process is simple, separation is not needed, and the chemical production is facilitated.
Claims (8)
1. A method for synthesizing polycyclic alkane from lignin-derived phenols by a one-pot two-step method is characterized in that:
1) In the first step of reaction, lignin-derived phenolic compounds are firstly subjected to selective hydrogenation to ketone under the action of a hydrogenation catalyst in a hydrogen atmosphere, and then the ketone compounds are rapidly subjected to aldol condensation under the action of a solid acid catalyst to generate unsaturated organic matters with multiple carbon numbers from aviation kerosene precursors;
2) In the second reaction step, the reaction condition is directly enhanced without separating the product in the first step, the hydrogen pressure is increased to 3 MPa-5 MPa, the temperature is increased to 180-240 ℃, and the reaction time is 4-12 h; the aviation kerosene precursor directly realizes complete hydrodeoxygenation to generate polycyclic alkane under the action of a hydrogenation catalyst and solid acid in the first step.
2. The method according to claim 1, characterized in that:
the lignin-derived phenolic compounds in step 1) are phenol, o-cresol, m-cresol, p-ethylphenol, p-propylphenol, guaiacol, methylguaiacol, o-diphenol lignin-derived phenolic compounds.
3. The method according to claim 1, characterized in that:
the hydrogenation catalyst in the steps 1 and 2) is a supported catalyst A/X, and comprises a metal active component A and a carrier X which are supported on a carrier; the carrier X is SiO 2 、TiO 2 、CeO 2 、Al 2 O 3 At least one of MgAl-HT, mgO, liAl-HT; the metal active component A is one or more than two of Pt, pd, ru, ir, rh, ni, fe, cu, wherein the metal active component loading of the catalyst is between 0.1wt% and 15 wt%.
4. The method according to claim 1, characterized in that:
the solid acid catalyst in step 1 and 2) is Nafion-212, amberlyst-15, amberlyst-36, tiP, ceP, alP, zrP 0.5 ，ZrP 1 ，ZrP 2 ，ZrP 3 At least one kind.
5. The method according to claim 1, characterized in that:
the molar ratio of lignin-derived phenols to active component on the hydrogenation catalyst support is 1:0.0002 to 0.005, the mass ratio of the solid acid catalyst to the reaction substrate is between 0.2 and 1.
6. The method according to claim 1 or 2, characterized in that:
in the step 1), the hydrogenation and aldol condensation reaction are carried out in a batch kettle type reactor, the reaction temperature is between 80 and 180 ℃, the reaction time is between 2 and 12 hours, the reaction pressure is between 0.5 and 2MPa, and the hydrogenation catalyst and the solid acid are required to be added simultaneously in the reaction process.
7. The method according to claim 1 or 2, characterized in that:
the hydrodeoxygenation in step 2) is performed on the basis of step 1. After the step 1 is completed, the reaction pressure is directly flushed to 3 MPa-5 MPa without opening a kettle, the temperature is increased to 180-240 ℃, and the reaction time is 4-12 h.
8. The process according to claim 1 or 2, characterized in that the product polycycloalkane has the structure
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310432340.0A CN117024238A (en) | 2023-04-20 | 2023-04-20 | Method for synthesizing polycyclic alkane from lignin-derived phenols through one-pot two-step method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310432340.0A CN117024238A (en) | 2023-04-20 | 2023-04-20 | Method for synthesizing polycyclic alkane from lignin-derived phenols through one-pot two-step method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117024238A true CN117024238A (en) | 2023-11-10 |
Family
ID=88600996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310432340.0A Pending CN117024238A (en) | 2023-04-20 | 2023-04-20 | Method for synthesizing polycyclic alkane from lignin-derived phenols through one-pot two-step method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117024238A (en) |
-
2023
- 2023-04-20 CN CN202310432340.0A patent/CN117024238A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109382104B (en) | Method and catalyst for preparing ethanol from lignocellulose biomass in one step | |
| CN103159606B (en) | A kind of take furfural as the method that cyclopentanone prepared by raw material | |
| CN103977796B (en) | Catalyst used in preparation of long-chain alkane through catalytic hydrodeoxygenation of biomass | |
| US20140150332A1 (en) | Metal phosphorus compound for preparing biodiesel and method for preparing biodiesel using the same | |
| CN107235829B (en) | Method for preparing 4-ethylphenol by selective hydrogenolysis of lignin | |
| CN107304367B (en) | Preparation method of branched alkane in range of gasoline, aviation kerosene or diesel oil | |
| US11578023B2 (en) | Method and catalyst for producing methylbenzyl alcohol from ethanol by catalytic conversion | |
| CN111218308B (en) | Method for preparing high-density fuel from biomass raw material | |
| CN110117499B (en) | Method for preparing alkane by hydrodeoxygenation of oxygen-containing organic compound | |
| EP3789373A1 (en) | Method for producing methylbenzyl alcohol by catalytic conversion of ethanol and catalyst therefor | |
| CN114522716B (en) | Bimetal supported catalyst, preparation method thereof and application thereof in palm oil hydroconversion preparation of biological aviation kerosene | |
| CN111217679B (en) | Method for depolymerizing lignin to phenol by one-step method through bifunctional catalyst | |
| CN111215090A (en) | Application of oxygen-rich vacancy tungsten oxide supported catalyst in lignin depolymerization | |
| CN110935473B (en) | Hydrodeoxygenation catalyst and preparation method and application thereof | |
| CN117024238A (en) | Method for synthesizing polycyclic alkane from lignin-derived phenols through one-pot two-step method | |
| CN114920632B (en) | Method for preparing p-methylbenzaldehyde by utilizing wood chips | |
| CN117019147A (en) | Synthesis method of high-dispersity supported catalyst and method for preparing furfuryl alcohol by catalyzing furfural by using high-dispersity supported catalyst | |
| CN114931971B (en) | Nickel nanocluster loaded intergranular mesoporous zeolite catalyst and preparation method and application thereof | |
| CN113813991A (en) | Preparation method and application of phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst | |
| CN115894177B (en) | Method for selectively preparing phenol compounds by catalyzing guaiacol | |
| CN115779980B (en) | Ni/CeO 2 Application of Rh catalyst in selective hydrogenation of guaiacol to preparation of cyclohexanol | |
| CN113444543B (en) | Biological aviation kerosene component oil and preparation method thereof | |
| CN109772332B (en) | Supported metal catalyst directly prepared from solid and application thereof | |
| CN113444541B (en) | Biodiesel component oil and preparation method thereof | |
| KR101551399B1 (en) | The method for preparation of catalysts for the production of oxygenated carbon compound and production method of oxygenated carbon compound using thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |