CN115709088A - Preparation method of piperidine deoxidation catalyst - Google Patents
Preparation method of piperidine deoxidation catalyst Download PDFInfo
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- CN115709088A CN115709088A CN202210701397.1A CN202210701397A CN115709088A CN 115709088 A CN115709088 A CN 115709088A CN 202210701397 A CN202210701397 A CN 202210701397A CN 115709088 A CN115709088 A CN 115709088A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002028 Biomass Substances 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000005416 organic matter Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000006392 deoxygenation reaction Methods 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 238000002161 passivation Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 3
- 241001122767 Theaceae Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010438 heat treatment 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention relates to the technical field of oxidant preparation, and discloses a preparation method of a piperidine deoxygenation catalyst, which comprises the steps of dissolving iron-containing inorganic salt in water to obtain a solution A, adding a dispersing agent into deionized water, stirring and treating for 30-60min at 50-90 ℃, then cooling to room temperature, filtering to obtain an extracting solution, adding 0.1-2moL/L potassium hydroxide aqueous solution, treating for 30-60min at 60-80 ℃, filtering and washing until the pH of filtrate is neutral to obtain an activated biomass material, adding a prepared biomass material into a nitrogen-containing organic matter and adding the mixture into the extracting solution to obtain a precursor mixed solution, and carrying out high-temperature roasting and passivation treatment to obtain a Fe-based catalyst.
Description
Technical Field
The invention relates to the technical field of oxidant preparation, in particular to a preparation method of a piperidine deoxidation catalyst.
Background
The piperidine is an organic matter, and has various derived products, part of the products need to be dehydrogenated and deoxidized in the production process, and as a chemical reaction process, the dehydrogenation and deoxidation need a proper catalyst, in the prior art, the catalyst is mostly metal catalyst, the catalytic effect is good, but the pollution of metal ions is easily caused, therefore, the invention provides a preparation method of the piperidine deoxidation catalyst.
Disclosure of Invention
In order to solve the technical problems: in the prior art, the catalyst is mostly metal catalyst, the catalytic effect is good, but the pollution of metal ions is easily caused.
The invention provides a preparation method of a piperidine deoxidation catalyst, which comprises the steps of dissolving iron-containing inorganic salt in water to obtain a solution A, adding a dispersing agent into deionized water, stirring and treating for 30-60min at the temperature of 50-90 ℃, then cooling to room temperature, filtering to obtain an extracting solution, adding 0.1-2moL/L potassium hydroxide aqueous solution, treating for 30-60min at the temperature of 60-80 ℃, filtering and washing until the pH of filtrate is neutral to obtain an activated biomass material, adding the prepared biomass material into a nitrogen-containing organic matter and adding the nitrogen-containing organic matter into the extracting solution to obtain a precursor mixed solution, performing ultrasonic treatment to obtain an iron-containing suspension, removing an iron-containing suspension solvent, and performing high-temperature roasting and passivation treatment to obtain the Fe-based catalyst.
As a further improvement of the technical scheme, the water in the S1 is deionized water.
As a further improvement of the technical scheme, the dispersant is an alkaline reagent.
As a further improvement of the technical scheme, the ratio of the potassium hydroxide added in the S3 to the solution is 1 to 100.
The invention has the technical effects and advantages that: the organic part is added into the Fe catalyst to adsorb metal ions which play a role in the catalysis process, so that a new catalyst is formed, and the metal ions are bound in a calcined product, thereby reducing the environmental pollution caused by the metal ions in the production process.
Drawings
FIG. 1 shows the molecular formula of the product of the present invention after phenol is used as a dispersant.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. The embodiments of the present invention have been presented for purposes of illustration and description, and are not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used only for convenience of description and simplicity of description, and do not indicate or imply that the equipment or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be considered as limiting the present invention.
Examples
The embodiment provides a preparation method of a piperidine deoxygenation catalyst, which comprises the steps of dissolving an iron-containing inorganic salt in water to obtain a solution A, adding a dispersing agent into deionized water, stirring and treating for 30-60min at 50-90 ℃, cooling to room temperature, filtering to obtain an extracting solution, adding 0.1-2moL/L potassium hydroxide aqueous solution, treating for 30-60min at 60-80 ℃, filtering and washing until the pH of a filtrate is neutral to obtain an activated biomass material, adding a nitrogen-containing organic substance into the prepared biomass material, adding the nitrogen-containing organic substance and the nitrogen-containing organic substance into the extracting solution to obtain a precursor mixed solution, performing ultrasonic treatment to obtain an iron-containing suspension, removing an iron-containing suspension solvent, and performing high-temperature roasting and passivation treatment to obtain an Fe-based catalyst, wherein 10.10g of Fe (NO 3). Sub.9H 2O is weighed as an example, and is dissolved in 250mL of deionized water at room temperature to obtain a 0.1moL/L Fe (III) solution. Weighing 3.00g of dry tea (40-60 meshes), adding into 55mL of deionized water, stirring and heating for 1h under the condition of 80 ℃ water bath, and then filtering to obtain 50mL of tea extract for later use. 50ml of KOH solution with the concentration of 2mol/L is prepared, 3.00g of dried tea leaves (40-60 meshes) are added, and the mixture is stirred and dipped for 1 hour under the condition of 80 ℃ water bath. And then, carrying out suction filtration on the impregnation liquid, and washing for multiple times until the pH of the filtrate is approximately equal to 7. Adding the treated folium Camelliae sinensis into the above 50ml folium Camelliae sinensis extractive solution, adding 2.00g melamine, and stirring under heating in 80 deg.C water bath for 15min. After it was cooled to room temperature, 5ml PEG-400 was added to the solution. A25 mLFe (NO 3) 3.9H 2O solution (0.1 mol/L) was added dropwise to the above solution to form a black suspension. After 100W ultrasonic treatment for 10min, the solvent was evaporated at 98 ℃ to obtain a black precursor sample. The black precursor was calcined in a tube furnace at 600 ℃ for 4h in a high purity nitrogen atmosphere of 99.999%. After the temperature is reduced to room temperature, 1 percent of O2/N2 gas is added for passivation for 1h to obtain the Fe-C-K-2.0 catalyst. XRD characterization shows that Fe0, fe3C and graphite carbon crystal forms exist in the catalyst. The particle size of the iron-containing particles in the catalyst was estimated to be about 13.8nm by the scherrer equation. The N2 adsorption characterization test result shows that the specific surface area of the catalyst is 207.4m2 g-1, and the pore diameter is about 4.4nm.
In addition, water was deionized water, and 25ml of absolute ethanol, 0.3 g of p-chloronitrobenzene, and 0.3 g of catalyst were first added to the autoclave. Before the reaction, the reactor system was first hermetically cleaned 6 times with high purity H2 (99.999%) and then subjected to hydrogenation under magnetic stirring (1000 rpm), 423K and 1.1 MPa. The reaction was sampled at intervals and analyzed by gas chromatography (Agilent GC 7890B) equipped with a flame ionization detector.
Furthermore, the dispersing agent is an alkaline reagent, and the test result of the catalytic hydrogenation reaction performance shows that under the reaction experiment conditions, the conversion rate of the p-chloronitrobenzene can exceed 99 percent after the catalysts of Fe-C-K-0.1, fe-C-K-0.5 and Fe-C-K-2.0 are subjected to about 10 hours, 5 hours and 7 hours. Meanwhile, when the conversion rate of p-chloronitrobenzene of the Fe-C-K-0.5 catalyst is 100 percent, the selectivity of p-chloroaniline is 100 percent, and the selectivity of the p-chloroaniline of the Fe-C-K-0.1 catalyst and the Fe-C-K-2.0 catalyst is less than 90 percent.
Further, the ratio of potassium hydroxide to solution was 1 to 100.
It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by one of ordinary skill in the art and related arts based on the embodiments of the present invention without any creative effort, shall fall within the protection scope of the present invention. Structures, devices, and methods of operation not specifically described or illustrated herein are generally practiced in the art without specific recitation or limitation.
Claims (4)
1. A preparation method of the piperidine deoxidation catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1, dissolving iron-containing inorganic salt in water to obtain a solution A;
s2, adding a dispersing agent into deionized water, stirring at 50-90 ℃ for 30-60min, cooling to room temperature, and filtering to obtain an extracting solution;
s3, adding 0.1-2moL/L potassium hydroxide aqueous solution, treating at 60-80 ℃ for 30-60min, and then filtering and washing until the pH value of the filtrate is neutral to obtain the activated biomass material;
s4, adding the prepared biomass material into a nitrogenous organic matter and adding the nitrogenous organic matter and the nitrogenous organic matter into the extracting solution to obtain a precursor mixed solution;
s5, obtaining an iron-containing suspension after ultrasonic treatment;
and S6, removing the iron-containing suspension solvent, and carrying out high-temperature roasting and passivation treatment to obtain the Fe-based catalyst.
2. The method for preparing a piperidine deoxygenation catalyst according to claim 1, comprising the steps of: and water in the S1 is deionized water.
3. The method for preparing a piperidine deoxygenation catalyst according to claim 1, wherein: the dispersant is an alkaline agent.
4. The method for preparing a piperidine deoxygenation catalyst according to claim 3, comprising the steps of: the ratio of potassium hydroxide to solution added in S3 was 1 to 100.
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| CN202210701397.1A CN115709088A (en) | 2022-06-21 | 2022-06-21 | Preparation method of piperidine deoxidation catalyst |
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| CN202210701397.1A CN115709088A (en) | 2022-06-21 | 2022-06-21 | Preparation method of piperidine deoxidation catalyst |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108816275A (en) * | 2018-04-19 | 2018-11-16 | 南京红太阳生物化学有限责任公司 | A kind of catalyst and preparation method and application for synthesis gas pyridine base |
| CN109174168A (en) * | 2018-10-26 | 2019-01-11 | 南京红太阳生物化学有限责任公司 | A kind of catalyst and preparation method and application preparing 2- picoline for pyridine alkylation |
| CN110813296A (en) * | 2019-10-08 | 2020-02-21 | 中国科学院兰州化学物理研究所 | Preparation method of nano-porous Ni-Fe alloy catalyst |
| CN113617354A (en) * | 2021-07-08 | 2021-11-09 | 南京红太阳生物化学有限责任公司 | 3-methylpiperidine dehydrogenation catalyst, and preparation method and application thereof |
| CN114042456A (en) * | 2021-12-03 | 2022-02-15 | 浙江工业大学 | Method for preparing Fe-based catalyst by using biomass as raw material and application of Fe-based catalyst |
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2022
- 2022-06-21 CN CN202210701397.1A patent/CN115709088A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108816275A (en) * | 2018-04-19 | 2018-11-16 | 南京红太阳生物化学有限责任公司 | A kind of catalyst and preparation method and application for synthesis gas pyridine base |
| CN109174168A (en) * | 2018-10-26 | 2019-01-11 | 南京红太阳生物化学有限责任公司 | A kind of catalyst and preparation method and application preparing 2- picoline for pyridine alkylation |
| CN110813296A (en) * | 2019-10-08 | 2020-02-21 | 中国科学院兰州化学物理研究所 | Preparation method of nano-porous Ni-Fe alloy catalyst |
| CN113617354A (en) * | 2021-07-08 | 2021-11-09 | 南京红太阳生物化学有限责任公司 | 3-methylpiperidine dehydrogenation catalyst, and preparation method and application thereof |
| CN114042456A (en) * | 2021-12-03 | 2022-02-15 | 浙江工业大学 | Method for preparing Fe-based catalyst by using biomass as raw material and application of Fe-based catalyst |
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