CN113663675A - Preparation of nickel-based catalyst for lignin reductive depolymerization by EDTA-assisted impregnation method - Google Patents

Preparation of nickel-based catalyst for lignin reductive depolymerization by EDTA-assisted impregnation method Download PDF

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CN113663675A
CN113663675A CN202111029523.5A CN202111029523A CN113663675A CN 113663675 A CN113663675 A CN 113663675A CN 202111029523 A CN202111029523 A CN 202111029523A CN 113663675 A CN113663675 A CN 113663675A
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catalyst
nickel
edta
lignin
catalytic reduction
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侯美岩
毕亚东
王海军
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Tianjin Golden Eagle Technology Co ltd
Tianjin University of Technology
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Tianjin Golden Eagle Technology Co ltd
Tianjin University of Technology
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B01J23/755—Nickel
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    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers

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Abstract

The invention relates to a nickel-based catalyst suitable for catalytic reduction conversion of lignin and a preparation method thereof. The catalyst takes metal Ni as an active component and mesoporous gamma-Al2O4Is a carrier. The active component Ni accounts for 5-35% of the mass of the catalyst. By mixing Ni (EDTA)2‑The NiE/MA catalyst is prepared by impregnating an anionic complex onto a Mesoporous Alumina (MA) support having a positive surface charge. Compared with Ni/MA catalyst prepared by conventional impregnation method, the reduced NiE/MA catalyst has higher nickel crystal grain dispersity, and the surface of catalyst particle forms very thin microporous carbon shell. The introduction of EDTA ligand during the preparation process has a significant effect on the product distribution of 4-propylguaiacol hydrogenation. The catalyst still keeps better stability after five times of circulation. For the catalytic reduction depolymerization of real biomass poplar wood chips, the total yield of phenolic monomer products on NiE/MA reaches 34.5 percent, while the yield on Ni/MA is only 26.0 percent.

Description

Preparation of nickel-based catalyst for lignin reductive depolymerization by EDTA-assisted impregnation method
The technical field is as follows:
the invention belongs to the technical field of preparation of lignin reduction conversion catalysts, and particularly relates to mesoporous gamma-Al2O3A nickel-based catalyst used for the catalytic reduction conversion of lignin and a preparation method thereof.
Background art:
lignocellulose has a global yield of up to 100 million tons and is the most abundant biomass resource. Lignocellulose is the major component of plant cells, and its composition and structure depend on the species of the plant. Lignocellulose consists of three parts, cellulose, hemicellulose and lignin. The lignin consists of various methoxylated phenylpropane units, is the only renewable aromatic resource, but has a very complex structure; furthermore, lignin is often insufficiently used because it has aromaticity, which is resistant to modification by biological and chemical techniques, as compared with cellulose and hemicellulose. In order to fully utilize lignocellulose, methods for increasing the value of lignin products are continuously sought. Catalytic reduction is one of effective methods for depolymerizing lignocellulose into monomer compounds, however, at present, the catalytic reduction depolymerization research of lignin mainly adopts expensive noble metal catalysts such as Ru/C and the like, and the development of a substituted non-noble metal catalyst can make the process more practical. The lignin has a firm structure and a complex network structure, and C-O-C and a small amount of C-C bonds in the lignin are mainly broken in the depolymerization process of the lignin, so that the catalyst is required to have an excellent hydrogenation function and a remarkable depolymerization effect on the lignin; meanwhile, the stability of the catalyst in the catalytic process, the catalyst recovery and the like are considered while the activity of the catalyst is considered. Only by comprehensively considering the factors, the practicability of the catalyst can be greatly improved.
The invention content is as follows:
the invention aims to provide a nickel-based catalyst for catalytic reduction and conversion of lignin and a preparation method thereof, which are used for replacing a noble metal catalyst used in the catalytic process of the lignin, solving the problem of poor thermal stability of the catalyst and preparing the nickel-based catalyst which has high activity and high stability and can be subjected to magnetic separation.
In order to achieve the purpose, the invention adopts the following technical scheme:
mesoporous gamma-Al2O3The nickel-based catalyst used for the catalytic reduction conversion of lignin and used as a carrier is characterized in that: the nickel-based catalyst comprises Ni-EDTA/Al2O3-T; wherein Ni represents an active component introduced by nickel nitrate hexahydrate; EDTA refers to an auxiliary impregnating agent, namely ethylenediaminetetraacetic acid (EDTA); al (Al)2O3Represents mesoporous gamma-Al of carrier2O3(ii) a T represents the reduction temperature of the catalyst under a hydrogen atmosphere. The content of nickel in the calcined catalyst is 5-35 wt% of the mass of the catalyst.
Ni of nickel nitrate hexahydrate dissolved in water2+With EDTA, form a blue, water-soluble anionic complex Ni (EDTA)2-。
Ni in EDTA and nickel nitrate hexahydrate2+The molar ratio of (A) to (B) is 0 to 2.
Firstly, mesoporous gamma-Al is added2O3Heat treatment, reloading of water-soluble Ni (EDTA)2-A complex compound.
(1) Mesoporous gamma-Al2O3Pretreatment of a carrier: the purchased nano-scale mesoporous gamma-Al2O3Carrying out heat treatment on the carrier, wherein the treatment atmosphere is air, the treatment temperature is 550 ℃, and the treatment time is 5 h;
(2) water-soluble Ni (EDTA)2-Preparation of a complex precursor: respectively dissolving nickel nitrate hexahydrate (A) and ethylenediamine tetraacetic acid (B) in deionized water, adding ammonia water into the solution (B), and keeping the pH value of the solution (B) at 8.0 (C); dropwise adding A to C, maintaining pH at 8 to obtain blue Ni-EDTA solution (D), and adding nitre hexahydrateAdjusting the mass of EDTA by the molar weight of nickel acid, and preparing a catalyst with the molar ratio of EDTA to Ni of 0-2;
(3) preparation of the catalyst: adding a certain amount of pretreated mesoporous alumina into distilled water (E), controlling the theoretical loading amount to be 5-35 wt%, and dropwise adding nitric acid into the mixture E until the pH is 4 (less than the pH)ZPC7.5) (F); d was slowly added dropwise to F (G); stirring the G at normal temperature overnight, removing water by rotary evaporation at a certain temperature, and drying in an oven overnight; and calcining the dried product in a tubular furnace at the temperature of 500 ℃ for 5h in an argon atmosphere, and reducing the calcined product at the temperature of 450-550 ℃ for 4h to obtain the catalyst.
The specific surface area of the catalyst prepared in the step (3) is 120-300 m2And/g, the active component is simple substance nickel.
Based on the technical scheme, a reaction substrate (lignocellulose or lignin model molecules) and a catalyst take methanol or normal hexane as a solvent, and the initial pressure of filling hydrogen in a reaction kettle at room temperature is 0.8-1.0 MPa; the reaction temperature is 160-240 ℃; the reaction time is 3-4 h.
The invention has the beneficial effects that:
(1) the invention adopts an EDTA auxiliary impregnation method to form Ni (EDTA)2-The complex hinders the sintering and agglomeration of nickel particles and improves the dispersibility of active components, and the preparation method has simple equipment structure and is convenient and easy to implement;
(2) according to the catalyst particles prepared by the method, due to the addition of EDTA, a thin-layer carbon shell formed on the surface of the calcined catalyst can stabilize nickel particles in the reaction process;
(3) the catalyst prepared by the method has hydrogenation reaction for 4 hours under the conditions of 0.8MPa and 240 ℃, can be repeatedly used for 5 times, has no reduction in activity, has good stability and can be used for a long time.
Description of the drawings:
FIG. 1 shows Ru/C and Ni-EDTA/Al2O3The catalysts are used for gas phase spectrograms of the propyl guaiacol hydrogenation products.
FIG. 2 shows Ru/C and Ni-EDTA/Al2O3Gas phase spectrogram for wood chip hydrogenation monomer product。
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
2g of nickel nitrate hexahydrate and 2g of EDTA with 1g of gamma-Al were used2O3Preparing to obtain a catalyst; 0.2g of reaction substrate 4-n-propylguaiacol, 0.1g of internal standard substance n-decane, 0.05g of the catalyst and 20mL of solvent n-hexane are respectively added into a stainless steel reaction kettle and filled with the required reaction initiation H2The pressure was 0.8MPa, the stirring speed of the stirring paddle was set to 500rpm, the reaction temperature was set to 240 ℃ and the reaction temperature was maintained for 4 hours, and the pressure was about 3.6MPa when the temperature reached 240 ℃. After the reaction is finished, 1/4 which is the total mass of the reaction product solution is weighed and added into a 10mL volumetric flask for uniform dilution. 0.4 mu L of solution to be detected is extracted by a micro-sampling needle and enters a gas chromatograph for detection, and the conversion rate of the reaction substrate 4-propyl guaiacol, the selectivity and the yield of each product and the whole carbon balance of the reaction are calculated according to a standard curve and the integrated peak area of the gas chromatograph.
When the catalyst is calcined, the yield of the direct reaction is 47.8 percent, the conversion rate is 54 percent, and the carbon balance is 94 percent; when the catalyst is used for wood chip hydrogenation after being reduced at 500 ℃, the yield is increased by 88.8 percent, the conversion rate is 100 percent, the carbon balance is 88.8 percent, the time chart of the product peak detected by a gas phase is shown in figure 1, and the detailed quantitative result of the product is shown in table 1.
Example 2
Example 1 was repeated, and a catalyst circulation experiment was performed using the above-described reduced catalyst. After each reaction, the used catalyst is collected into a 10ml disposable plastic centrifuge tube, the tube is washed by absolute ethyl alcohol, then the centrifuge is used for removing the absolute ethyl alcohol, the operation of washing the catalyst is repeated for 3 times, and the recovered catalyst is put into a vacuum drying oven for drying at 40 ℃ for 12h and then is used for the hydrogenation catalytic conversion of 4-propylguaiacol.
The conversion rates of the catalysts after five recovery and re-reaction were all 100%, the monomer yields were 90.5, 88.1, 89.6, 91.2, and 92.4%, respectively, and the detailed results are shown in table 1.
TABLE 1 results of catalytic hydrogenation of model compound 4-propylguaiacol
Figure BSA0000251611160000051
Example 3
2g of the treated poplar wood chips, 0.3g of the catalyst of example 1 and 40ml of methanol as solvents are respectively added into a 100ml autoclave, the autoclave is installed, 1MPa of hydrogen (at room temperature) is filled after gas replacement, the stirring speed of a stirring paddle is adjusted to 450-rpm (revolutions per minute) and 500rpm (revolutions per minute), and then the pressure is maintained for more than 5min to check whether the air leakage phenomenon occurs in the autoclave. If the sealing performance is good, the temperature is raised to 240 ℃ (10 ℃/min) and maintained for 3h at 240 ℃. The reacted reaction product is filtered by a vacuum filter (0.2 mu m filter membrane) in a suction way, and the lower layer liquid is steamed for 1h in a rotary way at 33 ℃ to obtain the brown raw lignin oil. The mixture was extracted with dichloromethane and water to give an aqueous phase containing sugars as the upper layer and a dichloromethane phase containing "DCM lignin" as the lower layer. And the monomer yield in DCM lignin was checked using the gas phase.
The yield of the monomer directly reacted after the catalyst was calcined was 24.9%; when the catalyst is used for wood chip hydrogenation after being reduced at 500 ℃, the monomer yield is increased to 34.5%, the peak time chart of the monomer product detected by gas phase is shown in figure 2, the detailed results are shown in table 2, and the product arrangement sequence in the table is the same as the peak sequence of the gas phase chart.
Example 4
Example 3 was repeated except that the reduction temperatures of the catalysts were 450, 475, 525, 550 ℃ respectively. The yields of monomers catalyzed by the catalyst under the above hydrogenation conditions were 22.1, 32.2, 30.8 and 29.8%, respectively, and the detailed results are shown in table 2.
Example 5
Example 3 was repeated except that the mass of nickel nitrate hexahydrate was maintained at 2g during the catalyst preparation, and 0g, 1g and 4g of EDTA were added to make the ratio of EDTA to Ni in the catalyst2+The molar ratio is respectively 0, 0.5 and 2, and the wood chips are processedThe hydrogenation reaction gave monomer yields of 24.2, 26.2 and 18.4%, respectively, and the detailed results are shown in table 2.
TABLE 2 hydrogenation of poplar wood chips with different catalysts
Figure BSA0000251611160000061

Claims (8)

1. Mesoporous gamma-Al2O3The nickel-based catalyst used for the catalytic reduction conversion of lignin and used as a carrier is characterized in that: the nickel-based catalyst comprises Ni-EDTA/Al2O3-T; wherein Ni represents an active component introduced by nickel nitrate hexahydrate; EDTA refers to an auxiliary impregnating agent, namely ethylenediaminetetraacetic acid (EDTA); al (Al)2O3Represents mesoporous gamma-Al of carrier2O3(ii) a T represents the reduction temperature of the catalyst under a hydrogen atmosphere.
2. The mesoporous gamma-Al of claim 12O3The nickel-based catalyst used for the catalytic reduction conversion of lignin and used as a carrier is characterized in that: the content of nickel in the calcined catalyst is 5-35 wt% of the mass of the catalyst.
3. The mesoporous gamma-Al of claim 12O3The nickel-based catalyst used for the catalytic reduction conversion of lignin and used as a carrier is characterized in that: ni of nickel nitrate hexahydrate dissolved in water2+Water-soluble anionic complexes Ni (EDTA) forming a blue color with EDTA2-。
4. The mesoporous gamma-Al of claim 12O3The nickel-based catalyst used for the catalytic reduction conversion of lignin and used as a carrier is characterized in that: ni in EDTA and nickel nitrate hexahydrate2+The molar ratio of (A) to (B) is between 0 and 2.
5. A process for preparing a compound according to claim 1With mesoporous gamma-Al2O3A method for preparing a nickel-based catalyst for catalytic reduction conversion of lignin, which is supported, characterized by comprising: firstly, mesoporous gamma-Al is added2O3Calcining, and loading water-soluble Ni (EDTA)2-A complex compound.
6. The mesoporous gamma-Al of claim 52O3A method for preparing a nickel-based catalyst for catalytic reduction conversion of lignin, which is supported, characterized by comprising: the method comprises the following specific steps:
(1) mesoporous gamma-Al2O3Pretreatment of a carrier: the purchased nano-scale mesoporous gamma-Al2O3Carrying out heat treatment on the carrier, wherein the treatment atmosphere is air, the treatment temperature is 550 ℃, and the treatment time is 5 h;
(2) water-soluble Ni (EDTA)2-Preparation of a complex precursor: respectively dissolving nickel nitrate hexahydrate (A) and ethylenediamine tetraacetic acid (B) in deionized water, adding ammonia water into the solution (B), and keeping the pH value of the solution (B) at 8.0 (C); dropwise adding the A into the C, maintaining the pH value at 8 to obtain a blue Ni-EDTA solution (D), and adjusting the mass of EDTA according to the molar weight of nickel nitrate hexahydrate to prepare a catalyst with the molar ratio of EDTA to Ni being 0-2;
(3) preparation of the catalyst: adding a certain amount of pretreated mesoporous alumina into distilled water (E), controlling the theoretical loading amount to be 5-35 wt%, and dropwise adding nitric acid into the mixture E until the pH is 4 (less than the pH)ZPC7.5) (F); d was slowly added dropwise to F (G); stirring the G at normal temperature overnight, removing water by rotary evaporation at a certain temperature, and drying in an oven overnight; and calcining the dried product in a tubular furnace at the temperature of 500 ℃ for 5h in an argon atmosphere, and reducing the calcined product at the temperature of 450-550 ℃ for 4h to obtain the catalyst.
7. The mesoporous gamma-Al of claim 62O3A method for preparing a nickel-based catalyst for catalytic reduction conversion of lignin, which is supported, characterized by comprising: the specific surface area of the catalyst prepared in the step (3) is 120-300 m2/g。
8. According to the claimsThe mesoporous gamma-Al of claim 62O3A method for preparing a nickel-based catalyst for catalytic reduction conversion of lignin, which is supported, characterized by comprising: the active component of the catalyst prepared in the step (3) is simple substance nickel.
CN202111029523.5A 2021-09-07 2021-09-07 Preparation of nickel-based catalyst for lignin reductive depolymerization by EDTA-assisted impregnation method Pending CN113663675A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116371451A (en) * 2023-04-14 2023-07-04 西安交通大学 Cerium doped nickel-based catalyst suitable for methane dry reforming and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116371451A (en) * 2023-04-14 2023-07-04 西安交通大学 Cerium doped nickel-based catalyst suitable for methane dry reforming and preparation method thereof
CN116371451B (en) * 2023-04-14 2024-05-17 西安交通大学 Cerium doped nickel-based catalyst suitable for methane dry reforming and preparation method thereof

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