CN110624551B - Preparation method of lotus seedpod-based carbon-supported nickel catalyst - Google Patents
Preparation method of lotus seedpod-based carbon-supported nickel catalyst Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 240000002853 Nelumbo nucifera Species 0.000 title claims abstract description 78
- 235000006508 Nelumbo nucifera Nutrition 0.000 title claims abstract description 78
- 235000006510 Nelumbo pentapetala Nutrition 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 45
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 39
- 238000005406 washing Methods 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 238000002791 soaking Methods 0.000 claims abstract description 22
- AQIOEJQXNRLGFZ-UHFFFAOYSA-L potassium zinc dichloride Chemical compound [Cl-].[Zn+2].[Cl-].[K+] AQIOEJQXNRLGFZ-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000012153 distilled water Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000007873 sieving Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000009835 boiling Methods 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 abstract description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 abstract 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 230000009467 reduction Effects 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000011592 zinc chloride Substances 0.000 description 9
- 235000005074 zinc chloride Nutrition 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000007868 Raney catalyst Substances 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010796 biological waste Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B01J35/398—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method of a lotus seedpod-based carbon-supported nickel catalyst, which comprises the following steps: washing, drying, crushing and sieving the lotus seedpod shells to obtain lotus seedpod shell powder; mixing and soaking the lotus seedpod shell powder with a nickel acetate solution, stirring and heating until the mixture is boiling, and then carrying out vacuum freeze drying to obtain nickel acetate-loaded lotus seedpod shell powder; mixing and grinding the nickel acetate-loaded lotus seedpod housing powder, zinc powder and zinc chloride-potassium chloride mixed salt to obtain a mixture, heating the mixture to 700-800 ℃ in an inert gas atmosphere, preserving heat for 2-6 h, and then cooling to room temperature to obtain a crude catalyst product; and sequentially carrying out distilled water soaking, acid washing, water washing and drying on the crude catalyst product to prepare the lotus seedpod shell-based carbon-supported nickel catalyst. The method is simple and convenient to operate, can improve the catalytic activity of the prepared lotus seedpod-based carbon-supported nickel catalyst, and can be used for preparing p-aminophenol by hydrogenating p-nitrophenol.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method of a catalyst with carbon-supported nickel on a shower-shell base.
Background
The existing catalytic hydrogenation catalysts used in petroleum refining process mainly include Fe, Co, Ni, W, Mo, Cr, Ru, Rh, Pd, Pt, etc., among which Ni is widely used. Since the 20 th century, Raney nickel has the advantages of simple preparation, high catalytic activity, strong stability and the like, and is widely applied to hydrogenation, dehydrogenation and many other chemical fields, however, Raney nickel is easy to combust in air, has poor heat resistance, is easy to form local overheating, is easy to lose activity and cannot be regenerated, and the production capacity and the service life of a catalyst are limited. It is known that the catalytic reaction occurring in industry is mainly heterogeneous catalysis, the heterogeneous catalytic reaction is often carried out on an interface, the activity of the catalyst is increased along with the increase of the specific surface area, and in order to obtain higher activity, an active component is often supported on a carrier with large specific surface area. Compared with Raney nickel, the supported nickel catalyst uses less nickel and is more stable. Therefore, Raney nickel is gradually replaced by a nickel-supported catalyst and becomes one of the research focuses on the preparation of transition metal catalysts.
China is a big agricultural country, and a lot of waste biomass is directly combusted every year, so that resources are wasted, and the environment is polluted. The method has the advantages that the biological waste with low price is prepared into the carbon material with high specific surface area and then the nickel is loaded, so that the cost of the carrier is reduced, and the environmental problem caused by the combustion of the waste biomass is solved. The lotus seed pod shell is a by-product of the lotus seed and is also a usable biomass, has the characteristics of light weight, large internal pore diameter, large specific surface area after carbon formation, high chemical stability and the like, is nontoxic, cannot cause environmental pollution, and has wide application prospect.
At present, the preparation method of the nickel-supported catalyst mainly comprises an isometric immersion reduction method, a sol-gel method, a hydrothermal reduction method and the like, and the sol-gel and hydrothermal reduction have the defects of long preparation process period, high reduction temperature of active component nickel and high cost of the prepared nickel-supported catalyst. The isovolumetric impregnation reduction method has simple process, but the active component nickel of the prepared nickel catalyst is unevenly distributed and is easy to sinter and agglomerate together in the temperature rise process of the catalytic reaction, thereby reducing the surface active sites and lowering the catalytic performance of the catalyst.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a lotus seed shell-based carbon-supported nickel catalyst, and aims to provide a lotus seed shell-based carbon-supported nickel catalyst which is simple in preparation process and capable of improving catalytic activity.
In order to realize the purpose, the invention provides a preparation method of a shower-shell-based carbon-supported nickel catalyst, which comprises the following steps:
washing, drying, crushing and sieving the lotus seedpod shells to obtain lotus seedpod shell powder;
mixing and soaking the lotus seedpod shell powder with a nickel acetate solution, stirring and heating until the mixture is boiled, and then carrying out vacuum freeze drying to obtain the lotus seedpod shell powder loaded with nickel acetate;
mixing and grinding the nickel acetate-loaded lotus seed pod powder, zinc powder and zinc chloride-potassium chloride mixed salt to obtain a mixture, heating the mixture to 700-800 ℃ in an inert gas atmosphere, preserving heat for 2-6 hours, and then cooling to room temperature to obtain a crude catalyst product;
and sequentially carrying out distilled water soaking, acid washing, water washing and drying on the crude catalyst product to prepare the lotus seedpod shell-based carbon-supported nickel catalyst.
Optionally, in the step of washing, drying, crushing and sieving the lotus seedpod shells to obtain lotus seedpod shell powder, the drying temperature is 80-100 ℃, and the drying time is 10-12 hours; and/or the presence of a gas in the gas,
and sequentially carrying out distilled water soaking, acid washing, water washing and drying on the crude catalyst product to prepare the lotus seedpod shell-based carbon-supported nickel catalyst, wherein the drying temperature is 80-100 ℃, and the drying time is 10-12 hours.
Optionally, in the step of washing, drying, crushing and sieving the lotus seedpod shells to obtain the lotus seedpod shell powder,
and the sieving is to sieve through a 100-200 mesh sieve.
Optionally, the lotus seedpod shell powder is taken to be mixed with nickel acetate solution for soaking, stirred and heated to boiling, and then is subjected to vacuum freeze drying to obtain the nickel acetate-loaded lotus seedpod shell powder,
the solid-liquid ratio of the lotus seed pod powder to the nickel acetate solution is 1 g: (10-20) ml.
Optionally, the concentration of the nickel acetate solution is 0.01-0.20 mol/L.
Optionally, the lotus seedpod shell powder is taken to be mixed with nickel acetate solution for soaking, stirred and heated to boiling, and then is subjected to vacuum freeze drying to obtain the nickel acetate-loaded lotus seedpod shell powder,
the vacuum freeze drying step comprises pre-freezing for 3-4 h at-40 to-25 ℃, and then placing the mixture in a cold trap at-40 to-30 ℃ and under the working pressure of 30-50 Pa, and carrying out vacuum freeze drying for 8-10 h.
Optionally, in the step of mixing and grinding the nickel acetate-loaded shower shell powder, zinc powder and zinc chloride-potassium chloride mixed salt to obtain a mixture, heating the mixture to 700-800 ℃ in an inert gas atmosphere, preserving the temperature for 2-6 h, then cooling to room temperature to obtain a crude catalyst product,
the weight ratio of the nickel acetate-loaded lotus seedpod shell powder to the zinc chloride-potassium chloride mixed salt is 1: (0.01-0.1): (3-30).
Optionally, in the zinc chloride-potassium chloride mixed salt, the molar fraction of the zinc chloride is 0.3-0.5.
Optionally, the inert gas comprises any one of argon and nitrogen.
Optionally, in the step of sequentially carrying out distilled water soaking, acid washing, water washing and drying on the crude catalyst product to prepare the lotus seedpod nickel-loaded catalyst,
the acid used for acid cleaning is hydrochloric acid with the mass fraction of 1-10%.
According to the technical scheme provided by the invention, the waste lotus seedpod shells impregnated with nickel acetate are used as raw materials, zinc chloride-potassium chloride mixed salt and zinc powder are added, nickel acetate is decomposed into nickel oxide at high temperature, and then the nickel oxide and the added zinc or newly generated carbon are subjected to oxidation reduction reaction to prepare the lotus seedpod shell-based carbon-supported nickel catalyst; in addition, molten zinc chloride-potassium chloride mixed salt can be coated on the surface of the metal particles to prevent the metal particles from agglomerating and sintering, and zinc oxide existing in nickel are eluted by acid washing to enable the nickel particles to form a porous structure, so that the active sites of the nickel particles are increased, and the catalytic activity of the nickel particles is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic flow chart of an embodiment of a method for preparing a shower-shell-based carbon-supported nickel catalyst provided by the invention.
The implementation, functional features and advantages of the present invention will be further described with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
At present, the preparation method of the nickel-supported catalyst mainly comprises an isometric immersion reduction method, a sol-gel method, a hydrothermal reduction method and the like, and the sol-gel and hydrothermal reduction have the defects of long preparation process period, high reduction temperature of active component nickel and high cost of the prepared nickel-supported catalyst. The isovolumetric impregnation reduction method has simple process, but the active component nickel of the prepared nickel catalyst is unevenly distributed and is easy to sinter and agglomerate together in the temperature rise process of the catalytic reaction, thereby reducing the surface active sites and lowering the catalytic performance of the catalyst.
In view of this, the invention provides a preparation method of a carbon-supported nickel catalyst, which can be used for preparing a carbon-supported nickel catalyst, and the shower-shell-based carbon-supported nickel catalyst has high catalytic activity. The flow chart of an embodiment of the preparation method of the shower-shell-based carbon-supported nickel catalyst is provided by combining the schematic flow chart with the figure 1, and the preparation method of the shower-shell-based carbon-supported nickel catalyst comprises the following steps:
and step S10, washing, drying and crushing the lotus seed pod shells, and sieving to obtain lotus seed pod shell powder.
According to the technical scheme, the lotus seedpod shells which are light in weight, large in internal pore size, large in specific surface area after carbon formation and high in chemical stability are selected as raw materials, the lotus seedpod shells are cleaned firstly, dried for 10-12 hours at the temperature of 80-100 ℃, crushed and then screened through a 100-200-mesh sieve, and uniform lotus seedpod shell powder is prepared.
And step S20, mixing and soaking the lotus seedpod shell powder with a nickel acetate solution, stirring and heating until the mixture is boiled, and then carrying out vacuum freeze drying to obtain the nickel acetate-loaded lotus seedpod shell powder.
The solid-liquid ratio of the lotus seed pod powder to the nickel acetate solution is 1 g: (10-20) ml, wherein the concentration of the nickel acetate solution is 0.01-0.20 mol/L. In addition, the vacuum freeze drying step comprises pre-freezing for 3-4 hours at-40 ℃ to-25 ℃, and then performing vacuum freeze drying for 8-10 hours under the conditions that the temperature of a cold trap is-40 ℃ to-30 ℃ and the working pressure is 30-50 Pa.
And step S30, mixing and grinding the nickel acetate loaded lotus seed pod powder, zinc powder and zinc chloride-potassium chloride mixed salt to obtain a mixture, heating the mixture to 700-800 ℃ in an inert gas atmosphere, preserving heat for 2-6 hours, and then cooling to room temperature to obtain a catalyst crude product.
The weight ratio of the nickel acetate-loaded lotus seedpod shell powder to the zinc chloride-potassium chloride mixed salt is 1: (0.01-0.1): (3-30). In addition, in the zinc chloride-potassium chloride mixed salt, the mole fraction of the zinc chloride is 0.3-0.5, namely the ratio of the quantity of the zinc chloride to the sum of the quantities of the zinc chloride and the potassium chloride in the zinc chloride-potassium chloride mixed salt is 0.3-0.5. Under the conditions of molten salt and high temperature, the biomass material and the nickel acetate can be quickly and uniformly cracked; then the mixed zinc powder and the fresh carbon generated by cracking can reduce the nickel oxide in situ to generate nickel or nickel-zinc alloy and zinc oxide, thus preparing the catalyst of the lotus seedpod-based carbon-supported nickel through one-step cracking. Moreover, molten zinc chloride and potassium chloride can be coated on the surface of the nickel metal particles to prevent the agglomeration and sintering of the nickel metal particles.
Preferably, the heating is performed in a tube furnace to a temperature of 700 ℃ to 800 ℃. Further, the inert gas includes any one of argon and nitrogen.
And step S40, sequentially carrying out distilled water soaking, acid washing, water washing and drying on the catalyst crude product to obtain the lotus seedpod-based carbon-supported nickel catalyst.
The acid washing is to wash off zinc and zinc oxide existing in the nickel, so that the nickel particles form a porous structure, active sites of the nickel particles are enlarged, and the catalytic activity of the nickel particles is improved. The acid used for acid cleaning is hydrochloric acid with the mass fraction of 1-10%. In addition, the drying temperature is 80-100 ℃, and the drying time is 10-12 h.
According to the technical scheme provided by the invention, the waste lotus seedpod shell impregnated with nickel acetate is used as a raw material, zinc chloride-potassium chloride mixed salt and zinc powder are added, nickel acetate is decomposed into nickel oxide at high temperature, and then the nickel oxide and the added zinc or newly generated carbon are subjected to oxidation-reduction reaction to prepare the catalyst of carbon-supported nickel of the lotus seedpod shell base, the process can be completed by only one-step thermal cracking, and the operation is simple; in addition, molten zinc chloride-potassium chloride mixed salt can be coated on the surface of the metal particles to prevent the metal particles from agglomerating and sintering, and zinc oxide existing in nickel are eluted by acid washing to enable the nickel particles to form a porous structure, so that the active sites of the nickel particles are increased, and the catalytic activity of the nickel particles is improved.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
Washing and drying the lotus seedpod shells (the drying temperature is 80 ℃, and the drying time is 12 hours), crushing, and sieving with a 200-mesh sieve; 1g of lotus seedpod shell powder is mixed and soaked with 20ml of nickel acetate solution with the concentration of 0.01mol/L, stirred and heated to be boiled, then pre-frozen for 3h at the temperature of minus 40 ℃, and then placed under the conditions that the temperature of a cold trap is minus 30 ℃ and the working pressure is 50Pa, and vacuum freeze drying is carried out for 8 h. Mixing and grinding 1g of dried powder, 0.1g of zinc powder and 30g of zinc chloride-potassium chloride mixed salt (the mole fraction of zinc chloride is 0.3), pouring the mixture into a crucible, placing the crucible into a tubular furnace, continuously introducing argon, heating to 700 ℃, preserving heat for 6 hours, taking out the product, soaking the product in distilled water after the product is cooled to room temperature, washing with 5% HCl, washing with distilled water, centrifuging, and drying (the drying temperature is 80 ℃ and the drying time is 12 hours) to obtain the lotus-shell-based carbon-supported nickel catalyst. The specific surface area of the prepared sample is 1155m through BET detection2.g-1。
Example 2
Washing and drying the lotus seedpod shells (the drying temperature is 100 ℃, the drying time is 10 hours), crushing, and sieving by using a 170-mesh sieve; 1g of lotus seedpod shell powder is mixed and soaked with 17ml of nickel acetate solution with the concentration of 0.05mol/L, stirred and heated to be boiled, then pre-frozen for 3 hours at the temperature of minus 30 ℃, and then placed under the conditions that the temperature of a cold trap is minus 40 ℃ and the working pressure is 40Pa, and vacuum freeze drying is carried out for 10 hours. Mixing and grinding 1g of dried powder with 0.01g of zinc powder and 3g of zinc chloride-potassium chloride mixed salt (the mole fraction of zinc chloride is 0.5), pouring the mixture into a crucible, placing the crucible into a tubular furnace, continuously introducing argon, heating to 800 ℃, preserving heat for 2 hours, taking out the product after the mixture is cooled to room temperature, soaking the product in distilled water, washing with 1% HCl, washing with distilled water, centrifuging, and drying (the drying temperature is 100 ℃ and the drying time is 10 hours) to obtain the lotus seedpod-based carbon-supported nickel catalyst. The specific surface area of the prepared sample is 983m through BET detection2.g-1。
Example 3
Washing and drying the lotus seedpod shells (the drying temperature is 90 ℃, and the drying time is 11 hours), crushing, and sieving with a 100-mesh sieve; soaking 1g of lotus seedpod shell powder in 12ml of nickel acetate solution with the concentration of 0.13mol/LStirring and heating to boil, pre-freezing at-25 deg.C for 3 hr, and vacuum freeze-drying at-35 deg.C under 30Pa for 9 hr. Mixing and grinding 1g of dried powder, 0.05g of zinc powder and 15g of zinc chloride-potassium chloride mixed salt (the mole fraction of zinc chloride is 0.4), pouring the mixture into a crucible, placing the crucible into a tubular furnace, continuously introducing argon, heating to 750 ℃, preserving heat for 4 hours, taking out the product, soaking the product in distilled water after cooling to room temperature, washing with 10% HCl, washing with distilled water, centrifuging, drying (the drying temperature is 90 ℃, and the drying time is 11 hours), and preparing the lotus seedpod-based carbon-supported nickel catalyst. The sample prepared has a specific surface area of 910m by BET detection2.g-1。
Example 4
Washing and drying the lotus seedpod shells (the drying temperature is 80 ℃, and the drying time is 12 hours), crushing, and sieving with a 200-mesh sieve; 1g of lotus seedpod shell powder is taken to be mixed with 10ml of nickel acetate with the concentration of 0.2mol/L for soaking, stirred and heated to boiling, then pre-frozen for 3h at the temperature of minus 35 ℃, and then placed under the conditions that the temperature of a cold trap is minus 40 ℃ and the working pressure is 50Pa for vacuum freeze drying for 10 h. Mixing and grinding 1g of dried powder, 0.08g of zinc powder and 8g of zinc chloride-potassium chloride mixed salt (the mole fraction of zinc chloride is 0.5), pouring the mixture into a crucible, placing the crucible into a tubular furnace, continuously introducing nitrogen, heating to 780 ℃, preserving heat for 2 hours, taking out a product, soaking the product in distilled water, washing the product with 10% HCl, washing the product with the distilled water, centrifuging, and drying (the drying temperature is 80 ℃ and the drying time is 12 hours) to obtain the lotus seedpod shell-based carbon-supported nickel catalyst. The specific surface area of the prepared sample is 875m through BET detection2.g-1。
Comparative example 1
The procedure was as in example 2, except that the argon gas was continuously introduced and the temperature was increased to 500 ℃.
Comparative example 2
The procedure was the same as in example 1, except that the nickel acetate-loaded lotus seedpod powder was not charged with zinc powder and the zinc chloride-potassium chloride mixed salt.
0.15g of the catalyst prepared in examples 1 to 4 and comparative examples 1 and 2 was added to an autoclave, 0.02mmol of p-nitrophenol and 150ml of ethanol were sequentially added, after sealing, the air in the autoclave was replaced with hydrogen, and the process was repeated 3 times, followed by introduction of 2.0MPa hydrogen, and the reaction was carried out at a stirring speed of 1000rpm and a reaction temperature of 100 ℃ for 1 hour. The results of the activity evaluation are shown in Table 1.
TABLE 1 Activity evaluation results
| Conversion rate | Selectivity is selected | |
| Example 1 | 93％ | 99.8％ |
| Example 2 | 86％ | 99.1％ |
| Example 3 | 85％ | 99.0％ |
| Example 4 | 89％ | 99.4％ |
| Comparative example 1 | 65％ | 76.1％ |
| Comparative example 2 | 79％ | 94.1％ |
As can be seen from table 1, the conversion of the carbon-supported nickel catalyst prepared by the preparation method of the present invention generally reaches 85% or more, and the selectivity reaches 99% or more, whereas in comparative example 1, the conversion of the prepared carbon-supported nickel catalyst is only 65% and the selectivity is 76.1% under the same conditions as in example 2 except that argon is continuously introduced and the temperature is increased to 500 ℃. Meanwhile, the catalyst prepared in comparative example 2 also had significantly lower conversion and selectivity than the examples.
In conclusion, the lotus-pod-based carbon-supported nickel catalyst prepared by the preparation method has better catalytic activity.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (9)
1. A preparation method of a shower-shell-based carbon-supported nickel catalyst is characterized by comprising the following steps:
washing, drying, crushing and sieving the lotus seedpod shells to obtain lotus seedpod shell powder;
mixing and soaking the lotus seedpod shell powder with a nickel acetate solution, stirring and heating until the mixture is boiled, and then carrying out vacuum freeze drying to obtain the lotus seedpod shell powder loaded with nickel acetate;
mixing and grinding the nickel acetate-loaded lotus seedpod housing powder, zinc powder and zinc chloride-potassium chloride mixed salt to obtain a mixture, heating the mixture to 700-800 ℃ in an inert gas atmosphere, preserving heat for 2-6 hours, and then cooling to room temperature to obtain a crude catalyst product; the weight ratio of the nickel acetate-loaded lotus seedpod shell powder to the zinc chloride-potassium chloride mixed salt is 1: (0.01-0.1): (3-30);
and sequentially carrying out distilled water soaking, acid washing, water washing and drying on the crude catalyst product to prepare the lotus seedpod shell-based carbon-supported nickel catalyst.
2. The method for preparing the lotus seedpod shell-based carbon-supported nickel catalyst as claimed in claim 1, wherein in the step of washing, drying, crushing and sieving the lotus seedpod shell to obtain lotus seedpod shell powder, the drying temperature is 80-100 ℃, and the drying time is 10-12 h; and/or the presence of a gas in the gas,
and sequentially carrying out distilled water soaking, acid washing, water washing and drying on the crude catalyst product to prepare the lotus seedpod shell-based carbon-supported nickel catalyst, wherein the drying temperature is 80-100 ℃, and the drying time is 10-12 hours.
3. The method for preparing a lotus seedpod-based carbon-supported nickel catalyst as claimed in claim 1, wherein in the step of washing, drying, crushing and sieving the lotus seedpod to obtain the lotus seedpod powder,
and the sieving is to sieve through a 100-200 mesh sieve.
4. The method for preparing the lotus seedpod carbon-supported nickel catalyst as claimed in claim 1, wherein the step of mixing and soaking the lotus seedpod powder with nickel acetate solution, stirring and heating to boil, then vacuum freeze-drying to obtain the nickel acetate-supported lotus seedpod powder,
the solid-to-liquid ratio of the lotus seedpod powder to the nickel acetate solution is 1 g: (10-20) ml.
5. The method for preparing a shower-shell-based carbon-supported nickel catalyst as claimed in claim 4, wherein the concentration of the nickel acetate solution is 0.01-0.20 mol/L.
6. The preparation method of the shower nozzle shell-based carbon-supported nickel catalyst as claimed in claim 1, wherein in the step of mixing and soaking the shower nozzle shell powder with nickel acetate solution, stirring and heating to boiling, and then vacuum freeze-drying to obtain the shower nozzle shell powder loaded with nickel acetate,
the vacuum freeze drying step comprises the steps of pre-freezing for 3-4 hours at-40 to-25 ℃, and then, vacuum freeze drying for 8-10 hours under the conditions that the temperature of a cold trap is-40 to-30 ℃ and the working pressure is 30-50 Pa.
7. The method for preparing a shower-shell-based carbon-supported nickel catalyst as claimed in claim 1, wherein the zinc chloride-potassium chloride mixed salt has a molar fraction of 0.3 to 0.5.
8. The method of preparing a showerhead housing-based carbon-supported nickel catalyst according to claim 1, wherein the inert gas atmosphere comprises any one of argon and nitrogen.
9. The method of claim 1, wherein the step of sequentially soaking the crude catalyst in distilled water, washing with acid, washing with water, and drying to obtain the showerhead housing-based carbon-supported nickel catalyst,
the acid used for pickling is hydrochloric acid with the mass fraction of 1% -10%.
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