CN111068784A - Preparation method and application of lignin ligand hexahedral iron-based catalyst - Google Patents
Preparation method and application of lignin ligand hexahedral iron-based catalyst Download PDFInfo
- Publication number
- CN111068784A CN111068784A CN201911322634.8A CN201911322634A CN111068784A CN 111068784 A CN111068784 A CN 111068784A CN 201911322634 A CN201911322634 A CN 201911322634A CN 111068784 A CN111068784 A CN 111068784A
- Authority
- CN
- China
- Prior art keywords
- lignin
- ligand
- based catalyst
- iron
- temperature
- 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.)
- Granted
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229920005610 lignin Polymers 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 31
- 239000003446 ligand Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000013067 intermediate product Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- -1 4-bromobutyrate amide Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- CQZIEDXCLQOOEH-UHFFFAOYSA-N 3-bromopropanenitrile Chemical compound BrCCC#N CQZIEDXCLQOOEH-UHFFFAOYSA-N 0.000 claims description 3
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000013384 organic framework Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- XYHHQIWETDSNOP-UHFFFAOYSA-N 4-bromobutanamide Chemical compound NC(=O)CCCBr XYHHQIWETDSNOP-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- 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
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0269—Complexes comprising ligands derived from the natural chiral pool or otherwise having a characteristic structure or geometry
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method and application of a lignin ligand hexahedral iron-based catalyst. Under the alkaline condition, the lignin ligand hexahedron iron-based catalyst can be obtained after three steps of surface functional group modification, metal coordination and carbonization. The material has a metalloid-organic framework (MOF) structure, is a hexahedral iron-based catalyst, has a large specific surface area, and has high stability and high reaction activity. The lignin which is the main raw material for preparing the material has rich sources, can obviously reduce the production cost and has excellent social and economic benefits; the material has better catalytic hydrogenation capability and better application prospect in the fields of water electrolysis, catalytic hydrogenation and the like.
Description
Technical Field
The invention relates to the field of catalyst preparation, in particular to a preparation method and application of a lignin ligand hexahedral iron-based catalyst.
Background
Lignin is an amorphous, three-dimensional network phenolic natural polymer biomass, and the content of components in woody plants is second to that of cellulose and chitin. The industrial lignin is mainly derived from black liquor of a pulp mill and waste residue of a biomass ethanol refinery, and the lignin is difficult to be effectively utilized due to amorphous structure and complex fine components. Currently, most of the lignin can only be used as low-grade fuel to obtain energy, and only a small amount of lignin is made into fine chemicals and carbon materials through biorefinery and carbonization technologies to obtain more valuable utilization.
The ligands for preparing the metal-organic framework structure (MOF) material comprise cyanide, organic nitrile, pyridine-based donor and the like, the ligands are difficult to synthesize and have high price, part of reagents are toxic, and the ligands can be used only by post treatment.
With the continuous and deep understanding of human beings on the problems of environmental pollution, resource crisis and the like, the properties of reproducibility, degradability and the like of natural polymers are increasingly regarded. If the MOF-like structure can be prepared by taking lignin as a raw material, the production cost can be greatly reduced, the negative influence of the transitional exploitation of petroleum products on the earth ecology can be reduced, and the method has excellent social and economic benefits.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a preparation method and application of a lignin ligand hexahedral iron-based catalyst.
The technical scheme of the invention is as follows: a preparation method of a lignin ligand hexahedral iron-based catalyst comprises the following steps:
(1) preparation of intermediate product: adding lignin into tetrahydrofuran solution, heating and ultrasonically treating, then slowly adding sodium hydride, raising the temperature to 70-105 ℃, reacting for 90 min, then adding a substituting agent, reacting for 12 h, cooling, pouring into ethanol solution, and performing rotary evaporation to obtain an intermediate product;
(2) preparation of carboxylated lignin: hydrolyzing the intermediate product prepared in the step 1 in a methanol solution of sodium carbonate at constant temperature for 24h to obtain carboxylated lignin;
(3) preparation of lignin-iron complex: putting the modified lignin prepared in the step 2 into a mixed solvent system, adding ferric salt, stirring until the ferric salt is fully dissolved, performing ultrasonic treatment, transferring the solution into a hydrothermal kettle, performing hydrothermal reaction in a high-pressure reaction kettle, centrifuging, washing, and performing freeze drying to obtain a lignin-iron complex;
(4) preparation of a lignin ligand hexahedral iron-based catalyst: the lignin-iron complex was placed in a glass tube furnace in N2Then carrying out carbonization reaction to obtain the lignin ligand hexahedral iron-based catalyst.
In step 1, the substituting agent can be selected from 3-bromopropionitrile, ethyl 5-bromobutyrate or 4-bromobutyrate amide.
In step 2, the mixed solvent system refers to: the volume ratio is 15-25: 1: 1 of Dimethylacetamide (DMA), methanol and deionized water, or a mixture of 15-25: 1: 1 of Diethoxymethane (DEF), ethanol and deionized water, or a mixture of ethanol and deionized water in a volume ratio of 15-25: 1: 1 dimethyl sulfoxide (DMSO), methanol, and deionized water.
In step 3, the conditions of the hydrothermal reaction are as follows: the hydrothermal pressure is 1-3MPa, the hydrothermal temperature is set at 100-150 ℃, and the hydrothermal time is 24 h.
In step 4, the carbonization reaction conditions are as follows: firstly, the furnace temperature is increased to 400 ℃ at the speed of 1 ℃/min, the temperature is kept for 2 h, then the furnace temperature is increased to 700 ℃ at the speed of 3 ℃/min, the temperature is kept for 3 h, and finally the temperature is cooled to the room temperature.
The hexahedral iron-based catalyst with the lignin ligand prepared by the method can be applied to catalytic hydrogenation reaction.
The invention has the beneficial effects that:
1. the lignin ligand hexahedral iron-based catalyst prepared by the invention is prepared by firstly performing surface modification on lignin to prepare carboxylated lignin and then coordinating ferric nitrate and the lignin through hydrothermal reaction, has an MOF-like structure, is a hexahedral iron-based catalyst, has a large specific surface area, is enhanced in chelating force, and has strong stability and high reaction activity;
2. the method disclosed by the invention has the advantages that the source of the main raw material lignin is rich, the production cost can be obviously reduced, the negative influence of the transitional exploitation of petroleum products on the earth ecology can be reduced, and the method has excellent social and economic benefits;
3. the lignin ligand hexahedral iron-based catalyst prepared by the method disclosed by the invention has better catalytic hydrogenation capacity.
Drawings
FIG. 1 is an SEM photograph of a lignin ligand hexahedral iron-based catalyst prepared according to the first embodiment;
FIG. 2 shows N of carboxylated lignin and hexahedral iron-based lignin catalyst prepared in the first embodiment2Adsorption and desorption isotherms.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1
1 g of lignin and 200 mL of tetrahydrofuran are added into a round bottom flask, ultrasonic heating is carried out for 30 min, then 2g of sodium hydride is slowly added for reaction for 90 min, finally 5 mL of 3-bromopropionitrile is added, the temperature is raised to 100 ℃, and the mixture is condensed, refluxed and stirred for 24 h. After cooling, pouring the mixture into a beaker filled with 200 mL of ethanol for rotary evaporation to obtain an intermediate product, adding 10 mL of tetrahydrofuran, 50 mL of ethanol and 25 mL of 2mol/L sodium hydroxide solution into the intermediate product, hydrolyzing in an oil bath at 100 ℃ for 6-7 h, then adding 30 mL of methanol and 25 mL of 2mol/L sodium carbonate solution, and continuing to hydrolyze for 24 h. And then carrying out rotary evaporation on the cooled product, adjusting the pH value to 2, and freeze-drying to obtain the carboxylated modified lignin, wherein the carboxyl functional group in the lignin is favorable for the coordination of iron ions with the lignin.
0.7 g of modified lignin is added into a mixture of DMA, methanol and deionized water, wherein the volume ratio of the DMA to the methanol to the deionized water is 20: 1: 1, adding 0.1 g of ferric nitrate after fully stirring, carrying out ultrasonic treatment for 20 min, transferring the mixture into a hydrothermal kettle, placing the hydrothermal kettle into a high-pressure reaction kettle for hydrothermal reaction, wherein the hydrothermal pressure is 1.5 MPa, the hydrothermal reaction temperature is 150 ℃, the hydrothermal time is 24h, and finally washing and drying the mixture to obtain the lignin-iron complex;
finally, the lignin-iron complex is placed in a tube furnace in N2Then carrying out carbonization reaction, firstly raising the furnace temperature to 400 ℃ at the speed of 1 ℃/min, preserving the temperature for 2 h, then raising the furnace temperature to 700 ℃ at the speed of 3 ℃/min, preserving the temperature for 3 h, and finally cooling to room temperature to obtain the lignin ligand hexahedron iron-based catalyst.
FIG. 1 is SEM photograph of the prepared hexahedral iron-based catalyst with lignin ligands, from which it can be seen that the hexahedral iron-based catalyst with lignin ligands of regular shape and uniform size is obtained from N in FIG. 22The adsorption and desorption isotherm shows that the surface area of the carboxylated lignin is 28.6 m/g, while the specific area of the lignin ligand hexahedral iron-based catalyst is as high as 500.9 m/g, and the larger specific area is favorable for the adsorption of hydrogen on the surface of the catalyst, the reaction and the dissociation of products.
The catalyst is applied to the hydrogenation reaction of carbon monoxide, the pressure is 2.0 Mpa, the temperature is 330 ℃, and the space velocity is 6000 mL/h.g, because the hexahedral structure catalyst with high specific surface can provide more active sites, the adsorption performance to gas is enhanced, and the mass transfer rate is improved, one of the catalyst isConversion rate of carbon oxide 86.5%, low carbon olefin (C)2-C4) Selectivity of (2) is 51.2%, C2-C4The selectivity of the alkane was 21.2%, the long-chain hydrocarbon compound C5+The selectivity was 12.4% and the methane selectivity was 15.2%.
Example 2
1 g of lignin and 200 mL of tetrahydrofuran are added into a round bottom flask, ultrasonic heating is carried out for 30 min, then 2g of sodium hydride is slowly added for reaction for 90 min, finally 6 mL of 5-bromobutyric acid ethyl ester is added, the temperature is raised to 90 ℃, and the mixture is condensed, refluxed and stirred for 24 h. After cooling, pouring the mixture into a beaker filled with 200 mL of ethanol for rotary evaporation to obtain an intermediate product, adding 10 mL of tetrahydrofuran, 50 mL of ethanol and 25 mL of 2mol/L sodium hydroxide solution into the intermediate product, hydrolyzing in an oil bath at 100 ℃ for 6-7 h, then adding 30 mL of methanol and 25 mL of 2mol/L sodium carbonate solution, and continuing to hydrolyze for 24 h. Then rotationally evaporating the cooled product, adjusting the pH value to 2, and freeze-drying to obtain carboxylated modified lignin;
0.5 g of modified lignin is put into DEF, ethanol and deionized water according to the volume ratio of 15: 1: 1, adding 0.2 g of ferric chloride after fully stirring, carrying out ultrasonic treatment for 20 min, transferring the mixture into a hydrothermal kettle, placing the hydrothermal kettle into a high-pressure reaction kettle for hydrothermal reaction, wherein the hydrothermal pressure is 2 MPa, the hydrothermal reaction temperature is 130 ℃, the hydrothermal time is 24h, and finally washing and drying the mixture to obtain a lignin-iron complex;
finally, the lignin-iron complex is placed in a tube furnace in N2Then carrying out carbonization reaction, raising the furnace temperature to 400 ℃ at the speed of 1 ℃/min, preserving the temperature for 2 h, then raising the furnace temperature to 700 ℃ at the speed of 3 ℃/min, preserving the temperature for 3 h, and finally cooling to room temperature to obtain the lignin ligand hexahedral iron-based catalyst.
The catalyst is applied to the hydrogenation reaction of carbon monoxide, the conversion rate of carbon monoxide is 89.1 percent under the conditions that the pressure is 2.0 Mpa, the temperature is 340 ℃, and the space velocity is 6000 mL/h.g, and the low-carbon olefin (C)2-C4) Selectivity of (3) is 53.4%, C2-C4The selectivity to alkanes was 17.2%, long-chain hydrocarbon compound C5+The selectivity was 11.1% and the methane selectivity was 18.3%.
Example 3
1 g of lignin and 200 mL of tetrahydrofuran are added into a round bottom flask, ultrasonic heating is carried out for 30 min, then 2g of sodium hydride is slowly added for reaction for 90 min, finally 4 mL of 4-bromobutyramide is added, the temperature is raised to 80 ℃, and the mixture is condensed, refluxed and stirred for 24 h. After cooling, pouring the mixture into a beaker filled with 200 mL of ethanol for rotary evaporation to obtain an intermediate product, adding 10 mL of tetrahydrofuran, 50 mL of methanol and 25 mL of 2mol/L sodium carbonate solution into the intermediate product, hydrolyzing in an oil bath at 100 ℃ for 6-7 h, then adding 30 mL of ethanol and 25 mL of 2mol/L sodium hydroxide solution, and continuing to hydrolyze for 24 h. Then rotationally evaporating the cooled product, adjusting the pH value to 3, and freeze-drying to obtain carboxylated modified lignin;
1.0 g of modified lignin is added into DMSO, methanol and deionized water in a volume ratio of 25: 1: 1, adding 0.4 g of ferric sulfate after fully stirring, carrying out ultrasonic treatment for 20 min, transferring the mixture into a hydrothermal kettle, placing the hydrothermal kettle into a high-pressure reaction kettle for hydrothermal reaction, wherein the hydrothermal pressure is 1.3 MPa, the hydrothermal reaction temperature is 110 ℃, the hydrothermal time is 24h, and finally washing and drying the mixture to obtain the lignin-iron complex;
finally, the lignin-iron complex is placed in a tube furnace in N2Then carrying out carbonization reaction, raising the furnace temperature to 400 ℃ at the speed of 1 ℃/min, preserving the temperature for 2 h, then raising the furnace temperature to 700 ℃ at the speed of 3 ℃/min, preserving the temperature for 3 h, and finally cooling to room temperature to obtain the lignin ligand hexahedral iron-based catalyst.
The catalyst is applied to the hydrogenation reaction of carbon monoxide, the conversion rate of carbon monoxide is 79.6 percent under the conditions that the pressure is 2.0 Mpa, the temperature is 330 ℃, and the space velocity is 5000 mL/h.g, and the low-carbon olefin (C)2-C4) Selectivity of (2) was 52.9%, C2-C4The selectivity of the alkane was 15.3%, the long-chain hydrocarbon compound C5+The selectivity was 15.3% and the methane selectivity was 16.5%.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (6)
1. The preparation method of the lignin ligand hexahedral iron-based catalyst is characterized by comprising the following steps of:
(1) preparation of intermediate product: adding lignin into tetrahydrofuran solution, heating and ultrasonically treating, then slowly adding sodium hydride, raising the temperature to 70-105 ℃, reacting for 90 min, then adding a substituting agent, reacting for 12 h, cooling, pouring into ethanol solution, and performing rotary evaporation to obtain an intermediate product;
(2) preparation of carboxylated lignin: hydrolyzing the intermediate product prepared in the step 1 in a methanol solution of sodium carbonate at constant temperature for 24h to obtain carboxylated lignin;
(3) preparation of lignin-iron complex: putting the modified lignin prepared in the step 2 into a mixed solvent system, adding ferric salt, stirring until the ferric salt is fully dissolved, performing ultrasonic treatment, transferring the solution into a hydrothermal kettle, performing hydrothermal reaction in a high-pressure reaction kettle, centrifuging, washing, and performing freeze drying to obtain a lignin-iron complex;
(4) preparation of a lignin ligand hexahedral iron-based catalyst: the lignin-iron complex was placed in a glass tube furnace in N2Then carrying out carbonization reaction to obtain the lignin ligand hexahedral iron-based catalyst.
2. The method of claim 1, wherein in step 1, the substitution agent is selected from the group consisting of 3-bromopropionitrile, ethyl 5-bromobutyrate and 4-bromobutyrate amide.
3. The method for preparing a lignin ligand hexahedral iron-based catalyst according to claim 1, wherein in the step 2, the mixed solvent system is: the volume ratio is 15-25: 1: 1 of a mixture of dimethylacetamide, methanol and deionized water, or a mixture of dimethylacetamide, methanol and deionized water in a volume ratio of 15-25: 1: 1 of diethoxymethane, ethanol and deionized water, or a mixture of diethoxymethane, ethanol and deionized water in a volume ratio of 15-25: 1: 1, dimethyl sulfoxide, methanol and deionized water.
4. The method for preparing a lignin ligand hexahedral iron-based catalyst according to claim 1, wherein in the step 3, the hydrothermal reaction conditions are: the hydrothermal pressure is 1-3MPa, the hydrothermal temperature is set at 100-150 ℃, and the hydrothermal time is 24 h.
5. The method for preparing a lignin ligand hexahedral iron-based catalyst according to claim 1, wherein in the step 4, the carbonization reaction conditions are as follows: firstly, the furnace temperature is increased to 400 ℃ at the speed of 1 ℃/min, the temperature is kept for 2 h, then the furnace temperature is increased to 700 ℃ at the speed of 3 ℃/min, the temperature is kept for 3 h, and finally the temperature is cooled to the room temperature.
6. The use of the lignin-ligand hexahedral iron-based catalyst prepared by the method for preparing the lignin-ligand hexahedral iron-based catalyst according to any one of claims 1 to 5 in catalytic hydrogenation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911322634.8A CN111068784B (en) | 2019-12-20 | 2019-12-20 | Preparation method and application of lignin ligand hexahedral iron-based catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911322634.8A CN111068784B (en) | 2019-12-20 | 2019-12-20 | Preparation method and application of lignin ligand hexahedral iron-based catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111068784A true CN111068784A (en) | 2020-04-28 |
| CN111068784B CN111068784B (en) | 2021-09-21 |
Family
ID=70316058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911322634.8A Active CN111068784B (en) | 2019-12-20 | 2019-12-20 | Preparation method and application of lignin ligand hexahedral iron-based catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111068784B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113527703A (en) * | 2021-07-16 | 2021-10-22 | 淮阴师范学院 | Metal carbon-based coordination polymer, preparation method and application thereof in synthesis of 2, 5-furandimethanol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786923A (en) * | 2018-05-08 | 2018-11-13 | 上海应用技术大学 | A kind of preparation method of kernel-shell structure, visible light catalyst |
| CN108822312A (en) * | 2018-05-15 | 2018-11-16 | 江苏理工学院 | A kind of preparation method and application of high-specific surface area carboxylated globular lignin |
| CN108993409A (en) * | 2018-07-13 | 2018-12-14 | 江西康清环保科技有限公司 | A kind of preparation method of the sewage treatment porous adsorbing material based on biomass |
| CN109794245A (en) * | 2019-01-11 | 2019-05-24 | 江苏理工学院 | A kind of iron-based hydrogenation catalyst (Fe of honeycomb3O4@C)/C and its preparation method and application |
-
2019
- 2019-12-20 CN CN201911322634.8A patent/CN111068784B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786923A (en) * | 2018-05-08 | 2018-11-13 | 上海应用技术大学 | A kind of preparation method of kernel-shell structure, visible light catalyst |
| CN108822312A (en) * | 2018-05-15 | 2018-11-16 | 江苏理工学院 | A kind of preparation method and application of high-specific surface area carboxylated globular lignin |
| CN108993409A (en) * | 2018-07-13 | 2018-12-14 | 江西康清环保科技有限公司 | A kind of preparation method of the sewage treatment porous adsorbing material based on biomass |
| CN109794245A (en) * | 2019-01-11 | 2019-05-24 | 江苏理工学院 | A kind of iron-based hydrogenation catalyst (Fe of honeycomb3O4@C)/C and its preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113527703A (en) * | 2021-07-16 | 2021-10-22 | 淮阴师范学院 | Metal carbon-based coordination polymer, preparation method and application thereof in synthesis of 2, 5-furandimethanol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111068784B (en) | 2021-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104557801B (en) | Method for preparing gamma-valerolactone from furfural on metal/solid acid catalyst | |
| CN101428795B (en) | Carbon preparation material based on coke modification and sulphur-applying activated char, and production process thereof | |
| CN108273536B (en) | Preparation method of nitrogen-doped three-dimensional porous nano iron-based catalyst | |
| CN110228797B (en) | Method for preparing two-dimensional molybdenum nitride or tungsten nitride nanosheets at low cost | |
| CN112044450B (en) | Acid-base bifunctional biomass carbon-based catalyst and preparation method thereof | |
| CN112844422B (en) | Gas/solid two-phase interface photocatalytic system for preparing hydrogen from seawater and preparation and use method | |
| CN113522333A (en) | Preparation method and application of carbon-nitrogen co-doped iron-cobalt-based catalyst | |
| CN113117688A (en) | MOF precursor molybdenum-nickel catalyst, preparation method thereof and application thereof in lignin degradation | |
| CN102114413A (en) | Macroporous spherical polyacrylonitrile chelatesorbent and microwave radiating preparation process thereof | |
| CN108671960A (en) | A kind of high hydrothermal stability MOFs catalyst, the method for preparing and preparing chemicals for cellulose conversion | |
| CN111068784B (en) | Preparation method and application of lignin ligand hexahedral iron-based catalyst | |
| Hemalatha et al. | Catalytic hydrolysis of fruit waste using magnetic carbon acid catalyst for bioethanol production | |
| CN111097448B (en) | Preparation method of composite carbon-based solid acid catalyst and application of composite carbon-based solid acid catalyst in lignocellulose liquefaction | |
| CN102733230A (en) | Process for producing high-purity ammonium lignin by taking papermaking black liquid as material | |
| CN113402485A (en) | Method for preparing 5-hydroxymethylfurfural by converting cellulose in composite molten salt hydrate | |
| CN113546664B (en) | Cobalt-nitrogen co-doped fish scale biochar catalyst and preparation method and application thereof | |
| Wang et al. | Efficient hydrolysis of bagasse cellulose to glucose by mesoporous carbon solid acid derived from industrial lignin | |
| CN109721485A (en) | A kind of method that oxycellulose prepares formic acid and acetic acid | |
| CN114950447B (en) | Vanillin hydrodeoxygenation method based on alkali lignin carbon-stabilized cobalt-based catalyst | |
| CN113908856B (en) | Method for preparing sulfur-doped bimetallic catalyst by using MOF as carrier and application | |
| CN113441115B (en) | Preparation method and application of lignin-based heavy metal adsorption and soil improvement repairing agent | |
| Feng et al. | A Hybrid Catalytic Conversion of Corncob to Furfurylamine in Tandem Reaction with Aluminium-Based Alkaline-Treated Graphite and ω-Transaminase Biocatalyst in γ-Valerolactone–Water | |
| CN115138392A (en) | Multifunctional biochar catalyst rich in oxygen-containing functional groups and preparation method thereof | |
| CN103113949B (en) | Method for preparing briquette binder | |
| CN113713771A (en) | Method for preparing adsorbing material and pentosan through biomass catalysis hydrothermal method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |