CN115261146A - Method for preparing novel biodiesel by coupling lignin with animal/vegetable oil - Google Patents
Method for preparing novel biodiesel by coupling lignin with animal/vegetable oil Download PDFInfo
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- CN115261146A CN115261146A CN202210773332.8A CN202210773332A CN115261146A CN 115261146 A CN115261146 A CN 115261146A CN 202210773332 A CN202210773332 A CN 202210773332A CN 115261146 A CN115261146 A CN 115261146A
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- lignin
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- vegetable oil
- biodiesel
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- 229920005610 lignin Polymers 0.000 title claims abstract description 62
- 235000015112 vegetable and seed oil Nutrition 0.000 title claims abstract description 40
- 239000008158 vegetable oil Substances 0.000 title claims abstract description 40
- 239000010775 animal oil Substances 0.000 title claims abstract description 38
- 239000003225 biodiesel Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000008878 coupling Effects 0.000 title claims abstract description 17
- 238000010168 coupling process Methods 0.000 title claims abstract description 17
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 150000002989 phenols Chemical class 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 21
- 238000005886 esterification reaction Methods 0.000 abstract description 16
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 10
- 239000000194 fatty acid Substances 0.000 abstract description 10
- 229930195729 fatty acid Natural products 0.000 abstract description 10
- 150000004665 fatty acids Chemical class 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 8
- 125000003118 aryl group Chemical group 0.000 abstract description 7
- 230000032050 esterification Effects 0.000 abstract description 7
- -1 cyclic alcohols Chemical class 0.000 abstract description 6
- 239000012075 bio-oil Substances 0.000 abstract description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 abstract description 2
- 230000001360 synchronised effect Effects 0.000 abstract description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 29
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 24
- 229960001867 guaiacol Drugs 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 13
- 239000005639 Lauric acid Substances 0.000 description 12
- 239000000446 fuel Substances 0.000 description 12
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 235000013824 polyphenols Nutrition 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 7
- PJPLDEHITPGDLR-UHFFFAOYSA-N cyclohexyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC1CCCCC1 PJPLDEHITPGDLR-UHFFFAOYSA-N 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- JKSGBCQEHZWHHL-UHFFFAOYSA-N 2-phenoxyethylbenzene Chemical compound C=1C=CC=CC=1OCCC1=CC=CC=C1 JKSGBCQEHZWHHL-UHFFFAOYSA-N 0.000 description 5
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical compound COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IOZFUGDROBQPNP-UHFFFAOYSA-N 1-methylcyclohexane-1,2-diol Chemical compound CC1(O)CCCCC1O IOZFUGDROBQPNP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical class O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing novel biodiesel by lignin coupling animal/vegetable oil, which comprises the steps of uniformly mixing lignin derived phenols, animal/vegetable oil and a solvent, and carrying out catalytic reaction on a catalyst at high temperature in a hydrogen atmosphere to obtain a product, namely the biodiesel. The invention provides a new strategy for producing novel biodiesel by carrying out hydrodeoxygenation coupling in-situ esterification on lignin pyrolysis bio-oil and animal/vegetable oil, efficiently utilizes aromatic ring units and methoxy functional groups of lignin, and realizes efficient preparation of the biodiesel through selective conversion of the lignin and the animal/vegetable oil. Specifically, lignin-derived phenols can be effectively converted into cyclic alcohols through hydrodeoxygenation, and then the cyclic alcohols are esterified with fatty acids in situ to prepare fatty acid cyclohexyl, namely biodiesel; and methanol generated in the demethoxylation process of phenols can be converted into fatty acid methyl ester, so that the synchronous increment of aromatic ring units and methoxy functional groups in phenols is realized.
Description
[ technical field ] A
The invention relates to the technical field of organic synthesis, in particular to a method for preparing novel biodiesel by lignin coupling animal/vegetable oil.
[ background ] A method for producing a semiconductor device
In order to solve the problems of petroleum shortage and environmental pollution caused by the use of petroleum, the development of renewable liquid fuels is urgently needed. Compared with gasoline, diesel oil is widely used in the field of long-distance transportation, such as large-scale vehicle transportation, ocean transportation and the like, and the fields are not suitable for being driven by electric power in a short period, so that the demand for replacing liquid fuel is more urgent. Biodiesel is considered a sustainable, environmentally friendly fuel due to its clean, renewable, and carbon neutral properties. The main component of biodiesel is a monoalkyl ester of a long chain fatty acid, traditionally prepared by transesterification of vegetable oils and short chain alcohols. In the above-mentioned techniques, animal/vegetable oils, waste oils and fats, or microbial oils and fats are generally used as raw materials.
Lignin is one of the main components of lignocellulosic biomass, and accounts for about 15 to 30% by weight of biomass and 40% by energy. The industries of papermaking, cellulosic ethanol preparation and the like can generate a large amount of waste lignin, and due to the complex and stubborn structure, most of lignin is used as low-grade fuel to supply heat or generate electricity through direct combustion at present. Lignin has unique aromatic ring structures and oxygen-containing functional groups, and can be used for preparing advanced liquid fuels and high-value chemicals by adopting a proper method. In recent years, some researchers have developed a variety of advanced conversion techniques, such as pyrolysis and liquefaction, to depolymerize lignin into various phenolic derivatives. The phenols are usually used for preparing lower hydrocarbons such as aromatic hydrocarbon, naphthenic hydrocarbon and the like and cyclohexanol derivatives by Hydrodeoxygenation (HDO), however, the cetane number of the products is low, and the products cannot be directly used instead of diesel oil. Therefore, there is a need to develop new utilization techniques to achieve efficient conversion of lignin to biodiesel.
[ summary of the invention ]
The invention aims to solve the problems in the prior art and provides a method for preparing novel biodiesel by lignin-coupled animal/vegetable oil, wherein the conversion rate of raw materials can reach 100%, the yield of esters is high, and the fuel characteristics basically meet the standard of biodiesel.
In order to realize the purpose, the invention provides a method for preparing novel biodiesel by lignin coupling animal/vegetable oil, which comprises the steps of uniformly mixing lignin derived phenols, animal/vegetable oil and a solvent, and carrying out catalytic reaction on a catalyst at high temperature in a hydrogen atmosphere to obtain a product, namely the biodiesel.
The invention provides a novel strategy for producing novel biodiesel by coupling Hydrodeoxygenation (HDO) and in-situ esterification of lignin pyrolysis bio-oil and animal/vegetable oil, which efficiently utilizes aromatic ring units and methoxy functional groups of lignin and realizes the efficient preparation of the biodiesel by the selective conversion of the lignin and the animal/vegetable oil. Specifically, lignin-derived phenols can be effectively converted into cyclic alcohols through HDO, and then esterified with fatty acids in situ to prepare fatty acid cyclohexyl (i.e., biodiesel) without adding an external alcohol source; and methanol generated in the demethoxylation process of phenols can be converted into fatty acid methyl ester, so that the synchronous increment of aromatic ring units and methoxy functional groups in phenols is realized.
In the method, phenols are subjected to aromatic ring hydrogenation and demethoxylation to generate cyclohexanol and methanol, and then are esterified with long-chain fatty acid to obtain high-carbon esters, and proper temperature and pressure are required to ensure good aromatic ring hydrogenation, demethoxylation and esterification activities. In addition, the esterification reaction is a reversible reaction, and has high sensitivity to temperature. Preferably, the catalytic reaction temperature is 100-350 ℃, and the reaction pressure is 0.1-5 MPa. Further, the catalytic reaction temperature is preferably 200 to 300 ℃ and the reaction pressure is preferably 2 to 4MPa.
Preferably, the lignin-derived phenols are phenol-rich products obtained by thermally depolymerizing lignin, wherein the lignin is common industrial lignin or lignin extracted from lignocellulose, and common kraft lignin, alkali lignin, ground wood lignin, cellulosic ethanol lignin and the like can be selected. The thermal depolymerization is pyrolysis and liquid-phase depolymerization, and the liquid-phase depolymerization comprises acid-base depolymerization, reductive depolymerization, oxidative depolymerization and the like.
Preferably, the main components of the lignin-derived phenols comprise phenolic monomers and phenolic oligomers. Among these, phenolic monomers generally have a structure similar to that of the original lignin monomers, consisting of a phenolic nucleus, substituted with one or two ortho-methoxy groups and a para-side chain, and mainly include (alkyl) phenols, (alkyl) guaiacols and (alkyl) syringols. The phenolic oligomers include mainly beta-O-4 dimer (e.g., phenoxyethylbenzene), alpha-O-4 dimer (benzylphenyl ether), 4-O-5 dimer (4-phenoxyphenol), and the like.
When the amount of the catalyst, the volume of the solvent and the pressure of hydrogen are fixed, the proper concentration of the phenols can ensure the effect of generating the cyclic alcohol and the methanol by the HDO, and simultaneously, the economical efficiency of the process is considered. The molar ratio of the lignin-derived phenol to the solvent is preferably 1.
Preferably, said animal/vegetable oils are rich in long chain fatty acids. The esterification reaction requires the participation of fatty acid, so animal/vegetable oil rich in fatty acid (such as lauric acid, palmitic acid and the like) is suitable as reactant; meanwhile, in order to ensure that the produced esters have a high cetane number, the carbon number of the fatty acid should not be too low, and preferably 10 or more.
Preferably, the molar ratio of the animal/vegetable oil to the lignin-derived phenols is 1. The excessive animal/vegetable oil is kept, so that the degree of esterification reaction can be obviously improved; however, if the amount of the animal/vegetable oil is too large, the active sites of the catalyst are preempted, which is not favorable for the esterification reaction, and further, the molar ratio of the animal/vegetable oil to the lignin-derived phenol is preferably 3.
Preferably, the solvent is long-chain liquid alkane, and the carbon number is preferably between 8 and 18. During the esterification reaction, alcohol and water are not suitable to be used as solvents, and meanwhile, oxygen-containing solvents are easy to adsorb on the surface of the catalyst to hinder the esterification reaction, so that liquid hydrocarbons are the best choice of the solvents in the reaction.
Preferably, the catalyst is supported on a neutral carrierThe noble metal catalyst is Ru, rh, pt, pd, etc., and the neutral carrier is active carbon or SiO2And SBA-15. The conversion of phenol HDO into cyclic alcohol requires the participation of metal hydrogenation sites and oxophilic sites, and in addition, requires that active metals and carriers can maintain high stability in a fatty acid solution under a hydrogen atmosphere, so that common noble metals and the carriers are selected as catalysts. Wherein the loading amount of the noble metal accounts for 1.0-6.0 percent of the total mass of the catalyst, and preferably 2.0-5.0 percent; the mass ratio of the catalyst to the phenols is 1. The proper noble metal loading and catalyst amount can ensure good conversion effect and improve the process economy.
Preferably, the lignin-derived phenols, the animal/vegetable oils and the solvent are homogeneously mixed in a high pressure reaction vessel. Phenols have high boiling points and high viscosities, and gas phase reactions in fixed beds are difficult to atomize, and coking and even reactor plugging are easily caused. Meanwhile, most of the long-chain fatty acid is in a solid state at normal temperature, and the gas phase reaction is difficult to feed, so that a high-pressure reaction kettle is adopted.
The invention has the beneficial effects that:
(1) The invention develops a new technical route for preparing high-grade liquid fuel by the synergistic conversion of the lignin and the animal/vegetable oil for the first time, can directly convert lignin-derived phenols and the animal/vegetable oil into the biodiesel by a one-pot method, and has the advantages of simple process flow, strong operability and great industrial popularization potential.
(2) The invention realizes the efficient and stable conversion of lignin-derived phenols and animal/vegetable oil to high-carbon esters, the fuel characteristics of the obtained high-carbon esters conform to the standard of biodiesel, and the esters have the potential of replacing the traditional petroleum diesel and have positive effects on relieving the situation of shortage of petroleum resources.
(3) The invention combines two industrial/agricultural wastes of lignin and animal/vegetable oil, changes waste into valuable, realizes high-value utilization of the lignin and has wide application prospect.
The features and advantages of the present invention will be described in detail by embodiments in conjunction with the accompanying drawings.
[ description of the drawings ]
FIG. 1 is an in situ esterification of typical lignin-derived phenolics with lauric acid HDO-to produce biodiesel in accordance with the present invention.
[ detailed description ] embodiments
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
In the following embodiments, guaiacol, 2, 6-dimethoxyphenol, 1, 2-dimethoxybenzene, phenoxyethylbenzene, benzylphenyl ether and 4-phenoxyphenol are typical lignin-derived phenols having various functional groups and linkages, and lauric acid is a representative fatty acid in vegetable oils. With Ru/nano-SiO2Dodecane is the solvent.
Catalyst preparation
Ruthenium chloride (RuCl)3·xH238 to 42 weight percent of O and Ru) aqueous solution is dipped in nano-SiO2Prepared by 5wt% Ru/nano-SiO2. After 24h of impregnation, infrared drying at 70 ℃, drying in air at 110 ℃ for 12h, and then calcining in air at 350 ℃ for 4h (5 ℃/min). Subsequently, the prepared catalyst was ground and subjected to H at 280 deg.C2Reducing for 3h in atmosphere to obtain Ru/nano-SiO2。
Performance testing
HDO-in situ esterification experiments were conducted in a 100mL reaction kettle. Adding phenols, lauric acid, dodecane solvent and catalyst into a reaction kettle, and reacting with H at room temperature2After purging for 5 times, the pressure is increased to 3MPa. The reaction was carried out at 250 ℃ for 3h with a stirring speed of 800rpm. After the reaction, ethyl acetate was used to facilitate the dissolution of unconverted reactants and products. The product was qualitatively and quantitatively analyzed by gas chromatography mass spectrometry (GC-MS, traceDSQ II) and gas chromatography (GC, agilent 7890A), respectively. Wherein the conversion of reactants and the yield of esters areThe calculation formulas are respectively as follows:
reactant conversion = (moles reactant consumed/moles reactant before reaction) × 100 mol%;
ester yield = (moles of ester produced/moles of reactants before reaction) × 100mol%.
Examples 1 to 3
Examples 1 to 3 three phenolic monomers of guaiacol, 2, 6-dimethoxyphenol and 1, 2-dimethoxybenzene were used as reactants, respectively, and the three phenolic monomers were 10mmol of phenols, 40mL of dodecane solvent, 40mmol of lauric acid and 0.1g of catalyst.
Examples 4 to 7
Example 4, example 6 and example 7 were carried out under the same conditions as in example 1 except that phenoxyethylbenzene, benzylphenyl ether and 4-phenoxyphenol dimers were used as reactants, respectively, and 5mmol of phenols were used.
The catalyst used in example 5 was 0.2g, and the other conditions were the same as in example 4.
Examples 8 to 13
Examples 8 to 13 all used guaiacol as a reactant, the amounts of substances were 35.4, 17.7, 11.8, 8.8, 7.1 and 5.9mmol, respectively, and the amount of lauric acid substances was 4 times that of guaiacol, and the rest conditions were the same as in example 1.
Examples 14 to 18
Examples 14 to 18 all use guaiacol as a reactant, lauric acid in amounts of 10, 30, 50, 70 and 90mmol, respectively, and the rest conditions were the same as in example 1.
Examples 19 to 22
The reaction temperatures of examples 19 to 22 were 100 ℃, 200 ℃, 300 ℃ and 350 ℃, respectively, and the remaining conditions were the same as in example 1.
Examples 23 to 27
The reaction pressures in examples 23 to 27 were 0.1MPa, 1MPa, 2MPa, 4MPa and 5MPa, respectively, and the other conditions were the same as in example 1.
TABLE 1 Properties of phenol coupled lauric acid HDO-in situ esterification for biodiesel production in examples 1-18
From the results of examples 1 to 7, it can be seen that good conversion of the phenols was achieved with the exception of phenoxyethylbenzene. Despite the weaker activity of phenoxyethylbenzene, high yields of esters were obtained with increased catalyst usage (example 5). Thus, the disclosed methods can efficiently convert various lignin-derived phenolic monomers and dimers to higher carbon esters under mild conditions.
Comparing examples 8 to 13, it can be seen that the conversion of the reactants and the yield of biodiesel gradually increase as the concentration of guaiacol is continuously decreased. However, the cost of the whole process is gradually increased because the factors such as the amount of catalyst used, the volume of solvent and the power consumption at elevated temperature are constant.
According to examples 14 to 18, as the molar ratio of lauric acid/guaiacol is increased from 1 to 1 by 5 (example 14 to example 16), guaiacol is always completely converted, the addition of lauric acid promotes the demethoxylation of 1-methyl-1, 2-cyclohexanediol (guaiacol hydrogenation product) to generate cyclohexanol and methanol, and the increase of the alcohol yield also promotes the subsequent esterification reaction and the gradual increase of the ester yield; however, as the molar ratio of lauric acid/guaiacol increases (examples 17 and 18), a large amount of lauric acid covers the active sites of the catalyst, which gradually decreases the conversion of guaiacol, and is not favorable for the formation of higher esters.
According to examples 19 to 22, the temperature increase favours the guaiacol hydrogenation, demethoxylation and esterification reactions, leading to an increase in the yield of the various esters; however, when the temperature was too high (350 ℃, example 22), the esterification reaction was weakened and accompanied by coke formation.
According to examples 23 to 27, the increase in pressure favours the hydrogenation of guaiacol, while also promoting the transmethylation to 1-methyl-1, 2-cyclohexanediol rather than the demethoxylation to methanol, so that when the guaiacol is completely converted (examples 1, 26 to 27), the increase in pressure is continued and the yields of cyclohexyl laurate and methyl laurate gradually decrease.
Fuel characteristics of high carbon esters
TABLE 2 Fuel characteristics of methyl laurate and cyclohexyl laurate
aNational standard of the people's republic of China (GB 25199-2017)
bThe freezing point and cold filter plugging point of No. 0 diesel oil are-20 DEG C
cCetane number determination using an automatic Diesel cetane number tester (LAB 131)
dThe cetane number of No. 0 diesel oil is 53.8
To verify the utility of the novel biodiesel prepared according to the present invention, the fuel properties of methyl laurate and cyclohexyl laurate were tested and the results are summarized in table 2 above. The results show that the calorific value of the methyl laurate and the cyclohexyl laurate is as high as 38MJ/kg, which is lower than that of petroleum diesel oil (46-48 MJ/kg). Besides the slightly higher viscosity of the cyclohexyl laurate, various key indicators such as flash point and cetane number meet the BD100 standard (GB 25199-2017). Methyl laurate and cyclohexyl laurate (1 v/v) were blended at 5% volume fraction in diesel fuel No. 0 based on the product distribution, and the addition of esters increased the cetane number of the diesel fuel from 53.8 to 55.8. It is clear that the blended diesel meets the B5 standard.
The invention adopts a Hydrodeoxygenation (HDO) -in-situ esterification strategy, takes lignin-based bio-oil and animal/vegetable oil as raw materials, and produces the biodiesel by utilizing specific oxygen-containing functional groups. The lignin-based bio-oil is subjected to HDO to produce cyclohexanol and methanol, and then is esterified with fatty acid to produce esters with high cetane number, and the fuel characteristics of the produced cyclohexyl laurate and methyl laurate are proved to meet the standard of biodiesel.
Claims (10)
1. A method for preparing novel biodiesel by lignin coupling animal/vegetable oil is characterized in that: uniformly mixing lignin derived phenols, animal/vegetable oil and a solvent, and carrying out catalytic reaction on a catalyst at high temperature in a hydrogen atmosphere to obtain the biodiesel.
2. The method for preparing the novel biodiesel by coupling the lignin with the animal/vegetable oil, which is disclosed by claim 1, is characterized in that: the catalytic reaction temperature is 100-350 ℃, and the reaction pressure is 0.1-5 MPa.
3. The method for preparing the novel biodiesel by coupling the lignin with the animal/vegetable oil, which is disclosed by claim 1, is characterized in that: the lignin derived phenols are phenol-rich products obtained by thermally depolymerizing lignin, and the thermal depolymerization comprises pyrolysis and liquid-phase depolymerization.
4. The method for preparing the novel biodiesel by coupling the lignin with the animal/vegetable oil, which is disclosed by claim 3, is characterized in that: the liquid phase depolymerization includes acid-base depolymerization, reduction depolymerization and oxidation depolymerization.
5. The method for preparing the novel biodiesel by coupling the lignin with the animal/vegetable oil, which is disclosed by claim 1, is characterized in that: the lignin-derived phenolic component comprises phenolic monomers and phenolic oligomers.
6. The method for preparing the novel biodiesel by coupling the lignin with the animal/vegetable oil, which is disclosed by claim 1, is characterized in that: the molar ratio of the lignin-derived phenols to the solvent is 1.
7. The method for preparing the novel biodiesel by coupling the lignin with the animal/vegetable oil, which is disclosed by claim 1, is characterized in that: the animal/vegetable oil is rich in long chain fatty acids.
8. The method for preparing the novel biodiesel by coupling the lignin with the animal/vegetable oil, which is disclosed by claim 1, is characterized in that: the molar ratio of the animal/vegetable oil to the lignin-derived phenols is 1.
9. The method for preparing the novel biodiesel by coupling the lignin with the animal/vegetable oil, which is disclosed by claim 1, is characterized in that: the solvent is long-chain liquid alkane.
10. The method for preparing the novel biodiesel by coupling the lignin with the animal/vegetable oil, which is disclosed by claim 1, is characterized in that: the catalyst is a noble metal catalyst loaded by a neutral carrier.
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