CN115400780B - KOH activated nitrogen-doped carbon material supported catalyst and preparation method thereof - Google Patents
KOH activated nitrogen-doped carbon material supported catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN115400780B CN115400780B CN202211049315.6A CN202211049315A CN115400780B CN 115400780 B CN115400780 B CN 115400780B CN 202211049315 A CN202211049315 A CN 202211049315A CN 115400780 B CN115400780 B CN 115400780B
- Authority
- CN
- China
- Prior art keywords
- carbon material
- nitrogen
- doped carbon
- koh
- activated nitrogen
- 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.)
- Active
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 125
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 25
- 238000003786 synthesis reaction Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 23
- 239000011261 inert gas Substances 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 230000004913 activation Effects 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 13
- 230000003213 activating effect Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- 239000013110 organic ligand Substances 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 8
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- -1 carbon olefin Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 3
- 230000001976 improved effect Effects 0.000 abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- 238000010494 dissociation reaction Methods 0.000 abstract description 8
- 230000005593 dissociations Effects 0.000 abstract description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 5
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 5
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 9
- 229960004642 ferric ammonium citrate Drugs 0.000 description 9
- 235000000011 iron ammonium citrate Nutrition 0.000 description 9
- 239000004313 iron ammonium citrate Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229960002413 ferric citrate Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/643—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
Abstract
The application discloses a KOH activated nitrogen-doped carbon material supported catalyst and a preparation method thereof. The KOH activated nitrogen-doped carbon material supported catalyst effectively improves the specific surface area and the nitrogen doping degree of the carrier, changes the percentage of different types of nitrogen, changes the carbon-nitrogen configuration, promotes the generation of pyrrole nitrogen, exposes more electron-rich sites, improves the electron cloud density of Fe, promotes the dissociation of CO and the generation of active components, and thus remarkably improves the reactivity; effectively improves the ratio of the low-carbon olefin in the product, is helpful for directionally producing the low-carbon olefin, and has the O/P (2-4) value which is compared with that of the active carbon and the SiO 2 And gamma-Al 2 O 3 The traditional catalyst used as a carrier is respectively improved by 0.40 times, 1.63 times and 1.33 times.
Description
Technical Field
The application belongs to the technical field of catalytic conversion of synthesis gas, and particularly relates to a KOH activated nitrogen-doped carbon material supported catalyst and a preparation method thereof.
Background
Synthesis gas is an important chemical feed gas that can be used to produce a variety of hydrocarbon chemicals, including long-carbon hydrocarbons (e.g., gasoline, kerosene, diesel, wax, etc.) and short-carbon hydrocarbons (e.g., ethylene, propylene, butene). The synthetic gas has wide sources and can be obtained by converting coal, petroleum, natural gas, biomass and the like. In consideration of the current situations of rich coal resources and over-high dependence of crude oil in China, a chemical route for efficiently utilizing coal-based synthesis gas is developed, and the method has important strategic significance for stabilizing national energy safety and promoting energy diversification.
Fischer-Tropsch synthesis is the synthesis of gas (CO and H 2 ) Converted to clean liquid fuel or other hydrocarbon chemicals under the action of a catalyst. The specific reaction process is that CO is dissociated, carbon-carbon coupled and hydrogenated on the surface of the metal catalyst, and the like, and finally the mixture of alkane, alkene, and the like is generated. The products of the current commercial fischer-tropsch synthesis process are mainly concentrated in oils and lower olefins (C 2 -C 4 =) commonly used catalysts include metals such as Fe, co, etc., wherein Fe-based catalysts are often used in the reaction field of synthesis gas to make light olefins due to their wide process operating range and weak carbon chain growth capability.
Currently, supports for Fischer-Tropsch based Fe-based catalysts are formed as oxides (e.g., siO 2 、Al 2 O 3 Etc.), but the interaction force between the metal and the carrier is strong, so that the metal is difficult to be reduced and carbonized further to generate an active phase state, and the activity of the catalyst is affected.
Disclosure of Invention
The invention aims to provide a KOH activated nitrogen-doped carbon material supported catalyst and a preparation method thereof, which are used for solving the technical problems that in the prior art, a carrier of a Fischer-Tropsch synthesis Fe-based catalyst is mainly oxide, but interaction force between metal and the carrier is strong, so that the metal is difficult to reduce and further carbonize to generate an active phase state, and the activity of the catalyst is influenced.
In order to achieve the above purpose, a technical scheme adopted in the application is as follows: a KOH activated nitrogen-doped carbon material supported catalyst is provided that includes a support including a KOH activated nitrogen-doped carbon material and a metal active component.
In one or more embodiments, the metal active component is one or more combinations of Fe, co, and Ni.
In one or more embodiments, the KOH activated nitrogen-doped carbon material has a residual K element content of 0 to 1.8%.
Preferably, the residual K element content in the KOH activated nitrogen-doped carbon material is 0.6%.
In one or more embodiments, the nitrogen-doped carbon material is an organometallic framework ZIF-8 derived nitrogen-doped carbon material.
In order to achieve the above purpose, another technical scheme adopted in the application is as follows: the preparation method of the KOH activated nitrogen-doped carbon material supported catalyst comprises the following steps:
preparing a nitrogen-doped carbon material;
uniformly dispersing the nitrogen-doped carbon material in KOH solution, evaporating, drying, activating and roasting in an inert gas atmosphere, and washing to obtain a KOH-activated nitrogen-doped carbon material;
immersing the metal active component solution into the KOH activated nitrogen-doped carbon material, uniformly dispersing, drying and roasting to obtain the KOH activated nitrogen-doped carbon material.
In one or more embodiments, the step of preparing a nitrogen-doped carbon material specifically includes:
dissolving metal zinc salt and nitrogen-containing organic ligand in deionized water, and stirring to obtain white solid precipitate;
and washing and drying the white solid precipitate, and roasting in an inert gas atmosphere to obtain the nitrogen-doped carbon material.
In one or more embodiments, the metal zinc salt is zinc nitrate hexahydrate, the nitrogen-containing organic ligand is 2-methylimidazole, the weight ratio of the metal zinc salt to the nitrogen-containing organic ligand to deionized water is 0.11 (0.33-0.40): 60-70%, the white solid precipitate is washed and dried, and then baked under an inert gas atmosphere to obtain the nitrogen-doped carbon material, wherein the baking temperature is 900-1100 ℃.
In one or more embodiments, in the step of uniformly dispersing the nitrogen-doped carbon material in a KOH solution, evaporating, drying, activating and roasting in an inert gas atmosphere, washing, and obtaining a KOH-activated nitrogen-doped carbon material,
the mass ratio of KOH in the KOH solution to the nitrogen-doped carbon material is (1-3): 1, the activating and roasting temperature is 600-800 ℃, and the activating and roasting time is 1-3 h.
In one or more embodiments, in the step of uniformly dispersing the nitrogen-doped carbon material in a KOH solution, evaporating, drying, activating and roasting in an inert gas atmosphere, washing, and obtaining a KOH-activated nitrogen-doped carbon material,
the washing is specifically to firstly wash by dilute hydrochloric acid, and then wash by deionized water until the pH value is=7 so as to completely remove KOH; or directly washing with deionized water to make the content of the residual K element be 0.6% -1.8%.
Preferably, the washing is specifically direct washing with deionized water, so that the content of residual K element is 0.6%.
In one or more embodiments, the steps of immersing the metal active component solution into the KOH-activated nitrogen-doped carbon material, uniformly dispersing, drying and roasting are performed,
the metal active component solution comprises one or more of Fe, co and Ni ion solutions, the drying temperature is 50-80 ℃, the drying time is 8-24 h, the roasting temperature is 400-600 ℃, and the roasting time is 2-4 h.
In order to achieve the above object, another technical solution adopted in the present application is: the application of the KOH activated nitrogen-doped carbon material supported catalyst in any embodiment in the Fischer-Tropsch synthesis reaction for improving the conversion rate of synthesis gas and the ratio of low-carbon olefin in the product.
The beneficial effect of this application is, in contrast to prior art:
the KOH activated nitrogen-doped carbon material supported catalyst adopts the KOH activated nitrogen-doped carbon material as the carrier, so that the specific surface area and the nitrogen doping degree of the carrier are effectively improved, the percentage of different types of nitrogen is changed, the carbon-nitrogen configuration is changed, the generation of pyrrole nitrogen is promoted, more electron-rich sites are exposed, the electron cloud density of Fe is improved, the CO dissociation and the generation of active components are promoted, and the reaction activity is remarkably improved; compared with the method adopting active carbon and SiO 2 And gamma-Al 2 O 3 Conventional catalysts as supports for the conversion of synthesis gasThe CO conversion rate is respectively improved by 9.96 times, 5.30 times and 3.49 times.
The KOH activated nitrogen-doped carbon material supported catalyst adopts the KOH activated nitrogen-doped carbon material as the carrier, so that the catalytic activity is obviously improved compared with the nitrogen-doped carbon material which is not subjected to KOH activation, and the CO conversion rate is improved by 84% when the synthesis gas is converted for 15 hours.
The KOH activated nitrogen-doped carbon material supported catalyst effectively improves the ratio of the low-carbon olefin in the product, is favorable for directionally producing the low-carbon olefin, and has the O/P (2-4) value which is compared with that of the catalyst adopting activated carbon and SiO 2 And gamma-Al 2 O 3 The traditional catalyst used as a carrier is respectively improved by 0.40 times, 1.63 times and 1.33 times.
According to the preparation method of the KOH activated nitrogen-doped carbon material supported catalyst, different residual content of K elements in the KOH activated nitrogen-doped carbon material can be realized through different washing means, and the residual K elements can further promote adsorption and dissociation of CO, so that the reaction activity is further improved.
Drawings
FIG. 1 is a transmission electron micrograph and a particle size distribution chart of effect example 1;
FIG. 2 is a graph showing the CO conversion rate change during the synthesis gas conversion reaction of example 5 and comparative example 2 in effect example 3.
Detailed Description
At present, the carrier of the Fischer-Tropsch synthesis catalyst is SiO 2 、Al 2 O 3 The equal oxide is taken as the main material, and the interaction force between the carrier oxide and the metal is strong, so that the metal is difficult to reduce and further carbonize to generate an active phase state, and the activity of the catalyst is correspondingly influenced.
To solve this problem, the applicant developed a catalyst using a KOH-activated nitrogen-doped carbon material as a support to avoid the problems of the conventional support.
Specifically, referring to fig. 1, fig. 1 is a preparation method of a KOH activated nitrogen-doped carbon material supported catalyst provided in the present application, where the preparation method includes:
s100, preparing a nitrogen-doped carbon material.
In one embodiment, the nitrogen-doped carbon material is a nitrogen-doped carbon material derived from an organometallic framework ZIF-8, and the organometallic framework ZIF-8 has the advantages of porosity, high chemical stability and thermal stability, low cost, easy obtainment and the like, and is beneficial to improving the loading rate and the catalytic activity of the catalyst.
Specifically, referring to fig. 2, fig. 2 is a flow chart of an embodiment corresponding to step S100 in fig. 1.
The step of preparing the nitrogen-doped carbon material includes:
s101, dissolving metal zinc salt and nitrogen-containing organic ligand in deionized water, and stirring to obtain white solid precipitate.
S102, washing and drying the white solid precipitate, and roasting the white solid precipitate in an inert gas atmosphere to obtain the nitrogen-doped carbon material.
The metal zinc salt can be zinc nitrate hexahydrate, the nitrogen-containing organic ligand can be 2-methylimidazole, the weight ratio of the metal zinc salt to the nitrogen-containing organic ligand to deionized water can be 0.11 (0.33-0.40) (60-70), and the roasting temperature can be 900-1100 ℃.
The nitrogen-doped carbon material derived from the organometallic framework ZIF-8 can be obtained by stirring, mixing and precipitating zinc nitrate hexahydrate and 2-methylimidazole at room temperature and then roasting under an inert gas atmosphere.
In this embodiment, the room temperature is 25.+ -. 5 ℃. In other embodiments, the nitrogen-doped carbon material may be a nitrogen-doped carbon material with other configurations, and may be prepared by other preparation methods, which can achieve the effects of the present embodiment.
And S200, uniformly dispersing the nitrogen-doped carbon material in a KOH solution, evaporating, drying, activating and roasting in an inert gas atmosphere, and washing to obtain the KOH-activated nitrogen-doped carbon material.
The nitrogen-doped carbon material is dispersed in KOH, evaporated, dried and baked, so that the nitrogen-doped carbon material can be effectively activated, the specific surface area and the nitrogen doping degree of the nitrogen-doped carbon material are improved, the percentage of different types of nitrogen is changed, the carbon-nitrogen configuration is changed, the generation of pyrrole nitrogen is promoted, and more electron-rich sites are exposed.
By introducing more electron-rich sites, the CO dissociation and metal carbonization processes in the Fischer-Tropsch synthesis reaction are facilitated, and the activity of the catalyst is improved.
The mass ratio of KOH in the KOH solution to the nitrogen-doped carbon material can be (1-3): 1; the temperature of the activation roasting can be 600-800 ℃, and the time of the activation roasting can be 1-3 hours, so that the nitrogen-doped carbon material has rich pore structures and proper nitrogen configuration.
When the temperature of the activation roasting is gradually increased from 600 ℃ to 800 ℃, more carbon reacts with KOH, so that more pore structures are generated, and the specific surface area of the corresponding nitrogen-doped carbon material is gradually increased.
The carbon-nitrogen configuration gradually changes with the increase of the activation roasting temperature, and the generated KOH activated nitrogen-doped carbon material has the optimal configuration and can expose the most electron-rich sites when the activation roasting temperature is 700 ℃.
The washing may be performed with dilute hydrochloric acid followed by deionized water to ph=7 to completely remove KOH.
The washing can also be directly performed by deionized water, so that part of KOH remains on the nitrogen-doped carbon material, the content of the residual K element is controlled to be 0.6% -1.8%, and the content of the residual K element is preferably controlled to be 0.6%.
The proper residual K can further promote the adsorption and dissociation of CO and improve the catalytic performance; however, when the content of the residual K element is too high, carbon deposition is serious, resulting in a decrease in the catalyst activity.
S300, dipping the metal active component solution into the KOH activated nitrogen-doped carbon material, uniformly dispersing, drying and roasting to obtain the catalyst.
The metal active component solution may be one or a combination of Fe, co and Ni ion solutions. The active metal component solution is immersed on the KOH activated nitrogen-doped carbon material, and then dried and roasted, so that the active metal component is effectively loaded in the pore structure of the nitrogen-doped carbon material.
Due to the high specific surface area, the electron-rich sites and the weak interaction force between the KOH activated nitrogen-doped carbon material and the metal, the metal can participate in the reaction more efficiently in the Fischer-Tropsch synthesis reaction, the adsorption and dissociation of CO are promoted, and the catalytic performance is improved.
The application also provides a KOH activated nitrogen-doped carbon material supported catalyst prepared by adopting any one of the embodiments, which comprises a carrier and a metal active component, wherein the carrier comprises a KOH activated nitrogen-doped carbon material, the metal active component is one or a combination of more of Fe, co and Ni, and the weight ratio of the carrier to the metal active component is (80-95): (5-20), and the content of the residual K element in the KOH activated nitrogen-doped carbon material is 0-1.8%.
The present application will be described in detail with reference to the following examples. The examples are not intended to limit the present application and structural, methodological, or functional modifications from the embodiments described herein are intended to be included within the scope of the present application.
In the following examples and effect examples, transmission electron patterns of samples were tested using a JEM-2100F field emission transmission electron microscope; the specific surface area and pore structure parameters of the samples were measured by ASAP2460 physical adsorption instrument from Micromeritics company, USA; the K element content analysis of the samples was tested using an inductively coupled plasma emission spectrometer model Vista-MPX from Varian company, USA.
Example 1:
a KOH activated nitrogen doped carbon material supported catalyst is prepared by the following steps:
(1) Will be 0.33gZn (NO 3 ) 2 ·6H 2 O and 0.99g of 2-methylimidazole are respectively dissolved in 90mL of deionized water, then the two solutions are uniformly mixed and magnetically stirred for 24 hours at room temperature, centrifugally separated and washed, and then dried for 12 hours at 50 ℃ to obtain white solid powder, namely the metal organic framework ZIF-8;
(2) Roasting the white solid powder under inert gas Ar, wherein the roasting temperature is 1000 ℃, and the roasting time is set to be 2 ℃ and min -1 Is heated to the target temperature and maintained for 2 hours, and the Ar flow rate is 120 mL-min -1 Obtaining a nitrogen-doped carbon material;
(3) Mixing 0.72g of nitrogen-doped carbon material with 1.44g of KOH and dispersing in 30mL of deionized water, stirring uniformly, putting into an oil bath at 80 ℃ and stirring to evaporate water until the mixed solution becomes smooth viscous liquid, vacuum drying at 80 ℃ for 12h, activating and roasting under inert gas Ar, wherein the activating and roasting temperature is 600 ℃, and setting the temperature to be 1 ℃ and min -1 Is heated to the target temperature and maintained for 1h, and the Ar flow rate is 100 mL-min -1 The method comprises the steps of carrying out a first treatment on the surface of the Fully grinding the activated and roasted sample, adding 250mL of 1mol/L dilute hydrochloric acid, uniformly mixing, stirring for 4 hours in a water bath at 80 ℃, washing with deionized water to be neutral, and drying to obtain the KOH activated nitrogen-doped carbon material;
(4) Weighing 0.214g of ferric ammonium citrate, dissolving in 1mL of deionized water, dropwise adding a ferric citrate solution onto the prepared KOH activated nitrogen-doped carbon material, performing ultrasonic treatment for 30min, vacuum drying the immersed sample at 50 ℃ for 12h, and roasting in a tube furnace at a heating rate of 5 ℃/min for 2h at 500 ℃ under inert gas Ar; after the roasting is finished and cooled to room temperature, introducing 1%O volume fraction into a tube furnace 2 And passivating the Ar mixed gas for 1h to obtain the catalyst.
Example 2:
a KOH activated nitrogen-doped carbon material supported catalyst prepared in substantially the same manner as in example 1, except that:
the activation baking temperature in step (3) of this example was 700 ℃.
Example 3:
a KOH activated nitrogen-doped carbon material supported catalyst prepared in substantially the same manner as in example 1, except that:
the activation baking temperature in step (3) of this example was 750 ℃.
Example 4:
a KOH activated nitrogen-doped carbon material supported catalyst prepared in substantially the same manner as in example 1, except that:
the temperature of the activation baking in step (3) of this example was 800 ℃.
Example 5:
a KOH activated nitrogen-doped carbon material supported catalyst prepared in substantially the same manner as in example 2, except that:
in the step (3) of the embodiment, after the activated and roasted sample is sufficiently ground, the sample is directly washed by deionized water, and the dosage of the deionized water is 3L, so that the KOH activated nitrogen-doped carbon material has the K element content of 0.6 percent by mass.
Example 6:
a KOH activated nitrogen-doped carbon material supported catalyst prepared in substantially the same manner as in example 2, except that:
in the step (3) of the embodiment, after the activated and roasted sample is sufficiently ground, the sample is directly washed by deionized water, and the dosage of the deionized water is 2L, so that the KOH activated nitrogen-doped carbon material has the K element content of 1.1 percent by mass.
Example 7:
a KOH activated nitrogen-doped carbon material supported catalyst prepared in substantially the same manner as in example 4, except that:
in the step (3) of the embodiment, after the activated and roasted sample is sufficiently ground, the sample is directly washed by deionized water, and the dosage of the deionized water is 1L, so that the KOH activated nitrogen-doped carbon material has the K element content of 1.8% by mass.
Example 8:
a KOH activated nitrogen-doped carbon material supported catalyst prepared in substantially the same manner as in example 1, except that:
in this example, in step (4), 0.127g of nickel nitrate was used in place of 0.214g of ferric ammonium citrate, and dissolved in 1ml of deionized water.
Example 9:
a KOH activated nitrogen-doped carbon material supported catalyst prepared in substantially the same manner as in example 1, except that:
in this example, in step (4), 0.128g of cobalt nitrate hexahydrate was used in place of 0.214g of ferric ammonium citrate, and dissolved in 1ml of deionized water.
Comparative example 1:
a catalyst, the preparation method includes:
weighing 0.214g of ferric ammonium citrate, dissolving in 1mL of deionized water, dropwise adding a ferric ammonium citrate solution onto active carbon, performing ultrasonic treatment for 30min, vacuum drying the immersed sample at 50 ℃ for 12h, and roasting in a tube furnace at a heating rate of 5 ℃/min for 2h at 500 ℃ under inert gas Ar; after the roasting is finished and cooled to room temperature, introducing 1%O volume fraction into a tube furnace 2 And passivating the Ar mixed gas for 1h to obtain the catalyst.
Wherein the activated carbon is commercial activated carbon provided by Fujian Xinsen carbon Co.
Comparative example 2:
a catalyst, the preparation method includes:
(1) Will be 0.33gZn (NO 3 ) 2 ·6H 2 O and 0.99g of 2-methylimidazole are respectively dissolved in 90mL of deionized water, then the two solutions are uniformly mixed and magnetically stirred for 24 hours at room temperature, centrifugally separated and washed, and then dried for 12 hours at 50 ℃ to obtain white solid powder, namely the metal organic framework ZIF-8;
(2) Roasting the white solid powder under inert gas Ar, wherein the roasting temperature is 1000 ℃, and the roasting time is set to be 2 ℃ and min -1 Is heated to the target temperature and maintained for 2 hours, and the Ar flow rate is 120 mL-min -1 Obtaining a nitrogen-doped carbon material;
(3) Weighing 0.214g of ferric ammonium citrate, dissolving in 1mL of deionized water, dropwise adding a ferric citrate water solution onto a nitrogen-doped carbon material, performing ultrasonic treatment for 30min, vacuum drying the immersed sample at 50 ℃ for 12h, and roasting in a tube furnace at a heating rate of 5 ℃/min for 2h at 500 ℃, wherein the roasting atmosphere is inert gas Ar; after the roasting is finished and cooled to room temperature, introducing 1%O volume fraction into a tube furnace 2 And passivating the Ar mixed gas for 1h to obtain the catalyst.
Comparative example 3:
a catalyst, the preparation method includes:
weighing 0.214g of ferric ammonium citrate, dissolving in 1mL of deionized water, dropwise adding the ferric ammonium citrate solution onto silicon dioxide, performing ultrasonic treatment for 30min, and soakingVacuum drying the sample at 50 ℃ for 12 hours, and roasting in a tube furnace at a heating rate of 5 ℃/min for 2 hours at 500 ℃, wherein the roasting atmosphere is inert gas Ar; after the roasting is finished and cooled to room temperature, introducing 1%O volume fraction into a tube furnace 2 And passivating the Ar mixed gas for 1h to obtain the catalyst.
Comparative example 4:
a catalyst, the preparation method includes:
0.214g of ferric ammonium citrate is weighed and dissolved in 1mL of deionized water, and the gamma-Al is added dropwise into the molten iron citrate solution 2 O 3 Then carrying out ultrasonic treatment for 30min, drying the immersed sample in vacuum at 50 ℃ for 12h, and roasting in a tube furnace at 500 ℃ for 2h at a heating rate of 5 ℃/min, wherein the roasting atmosphere is inert gas Ar; after the roasting is finished and cooled to room temperature, introducing 1%O volume fraction into a tube furnace 2 And passivating the Ar mixed gas for 1h to obtain the catalyst.
Effect example 1: catalyst characterization analysis
Transmission electron microscopy analysis was performed on the KOH activated nitrogen-doped carbon material supported catalysts prepared in examples 1 to 4 to obtain a transmission electron micrograph and a particle size distribution curve as shown in fig. 1, wherein a, b, c, d corresponds to examples 1, 2, 3, and 4, respectively.
As shown in FIG. 1, in the catalysts prepared in examples 1 to 4, fe nanoparticles were small in size and uniformly dispersed, and their average particle diameters were 5.0nm, 4.7nm, 4.6nm and 4.9nm, respectively. Thus, the catalysts prepared in examples 1 to 4 are all capable of uniformly supporting small-sized metal nanoparticles, contributing to improved catalytic performance in fischer-tropsch synthesis.
Effect example 2: carrier characterization analysis
Specific surface area and pore structure parameters were measured for the KOH activated nitrogen-doped carbon materials prepared in examples 1 to 4, and the following table data was obtained.
From the above table, as the activation roasting temperature of KOH activation increases, the specific surface area and pore volume of the obtained KOH activated nitrogen-doped carbon material gradually increase, while the average pore diameter remains small.
This is mainly due to the fact that when the temperature of the activation bake is gradually increased from 600 ℃ to 800 ℃, more carbon will react with KOH, so that more pore structures are created, and the specific surface area of the corresponding nitrogen-doped carbon material gradually increases.
Effect example 3: analysis of catalytic Performance
The catalysts prepared in examples 1 to 9 and comparative examples 1 to 4 were separately tabletted and sieved to 40-60 mesh, 0.1g of the catalyst was taken and mixed with 1.9g of quartz sand, and catalyst reaction evaluation was performed in a pressurized micro reaction system.
Specifically, under 340 ℃ and 1.0MPa, introducing reaction gas CO, H2 and internal standard gas Ar, ensuring that the feed flow ratio is CO/H2/Ar=4.5/4.5/1.0, and the ratio (airspeed) of the reaction gas flow rate to the catalyst dosage is 9000 mL.g -1 ·h -1 The reaction is carried out. Before the reaction, the catalyst is in situ high-purity H 2 Reducing for 4h at 350 ℃. And (3) preserving the temperature of the reaction tail gas, and analyzing the reaction tail gas by adopting online chromatography.
At 50h of synthesis gas conversion, the CO conversions, CO, of examples 1 to 9 were recorded 2 Selectivity, product distribution and O/P (2-4), wherein: O/P (2-4) represents the ratio of alkene to alkane in the C2-C4 hydrocarbon compound. The following table data were obtained:
as can be seen from the above table, the CO conversion rate is highest in example 2 among examples 1 to 4, and the CO is correspondingly 2 The selectivity also peaks, mainly due to the gradual change in configuration of the nitrogen-doped carbon material when the activation temperature is gradually increased from 600 ℃ to 800 ℃, and the optimum configuration of the KOH-activated nitrogen-doped carbon material when the activation roasting temperature is 700 ℃ to maximize exposureRich in electron sites, thereby contributing to enhanced catalytic activity.
In comparative examples 2, 5 and 6, when K element remains in the KOH activated nitrogen-doped carbon material, the activity of the catalyst is significantly improved, mainly because the K element can further promote adsorption and dissociation of CO, and catalytic performance is improved.
Meanwhile, the catalytic activity of example 6 is lower than that of example 5, mainly because carbon deposition is generated when the content of K element is too high, and the catalyst activity is affected. Accordingly, in comparative examples 4 and 7, when K element remains in the KOH activated nitrogen-doped carbon material, the activity of the catalyst is also improved.
In addition, when K element is remained in the KOH activated nitrogen doped carbon material, the ratio of alkene to alkane in the product can be effectively improved, and the selectivity of alkene in the product can be improved.
With example 5 as the best example, the catalytic performance was compared with the catalysts of comparative examples 1 to 4, and at 15 hours of the synthesis gas conversion reaction, the CO conversion, CO, were recorded for example 5 and comparative examples 1 to 4 2 Selectivity, product distribution and O/P (2-4), wherein: O/P (2-4) represents the ratio of alkene to alkane in the C2-C4 hydrocarbon compound. The following table data were obtained:
from the above table, the catalyst of example 5 has greatly improved catalytic activity over the conventional catalysts of comparative examples 1, 3 and 4. Specifically, when the synthesis gas is converted for 15 hours, the catalyst adopting KOH activated nitrogen-doped carbon material as a carrier is compared with the catalyst adopting active carbon and SiO 2 And gamma-Al 2 O 3 As the catalyst of the carrier, the CO conversion rate is respectively improved by 9.96 times, 5.30 times and 3.49 times.
Meanwhile, the O/P (2-4) value of the catalyst of the example 5 is respectively increased by 0.40 times, 1.63 times and 1.33 times compared with that of the catalysts of the comparative examples 1, 3 and 4, and the catalyst of the example 5 effectively improves the ratio of the low-carbon olefin in the product.
The catalyst of example 5 has a greatly improved catalytic activity over the catalyst of comparative example 2 which was not activated by KOH. Specifically, when the synthesis gas is converted for 15 hours, the catalyst adopting KOH activated nitrogen-doped carbon material as a carrier has the advantage that the CO conversion rate is improved by 84% compared with the catalyst adopting the nitrogen-doped carbon material as the carrier, so that the KOH activation can effectively activate the nitrogen-doped carbon material, improve the specific surface area and the nitrogen doping degree of the material, change the percentage of different types of nitrogen, change the carbon-nitrogen configuration, promote the generation of pyrrole nitrogen, expose more electron-rich sites and improve the catalytic activity.
The CO conversion during the synthesis gas conversion reaction was recorded every 1h for the catalysts of example 5 and comparative example 2, and a curve was drawn to give fig. 2.
As shown in the figure, the catalyst of the embodiment 5 has the obvious performance advantage that the CO conversion rate is far higher than that of the comparative example 2 in the whole synthesis gas conversion reaction process, and the KOH activated nitrogen-carbon material supported Fe-based catalyst has more electron-rich sites, improves the electron cloud density of Fe, promotes CO dissociation and the generation of active components, thereby remarkably improving the reaction activity.
The previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure. Various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the scope of the disclosure. Thus, the disclosure is not limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (11)
1. A KOH activated nitrogen-doped carbon material supported catalyst comprising a support and a metal active component, the support comprising a KOH activated nitrogen-doped carbon material; the content of residual K element in the KOH activated nitrogen-doped carbon material is 0.6-1.8%, the preparation method of the KOH activated nitrogen-doped carbon material comprises the steps of uniformly dispersing the KOH activated nitrogen-doped carbon material in a KOH solution, evaporating, drying, activating and roasting in an inert gas atmosphere, and washing to obtain the KOH activated nitrogen-doped carbon material, wherein the washing is specifically and directly carried out by deionized water so that the content of residual K element is 0.6% -1.8%;
the nitrogen-doped carbon material is an organic metal framework ZIF-8 derived nitrogen-doped carbon material, and the activation roasting temperature is 600-800 ℃.
2. The KOH activated nitrogen-doped carbon material supported catalyst of claim 1, wherein the metal active component is one or more combinations of Fe, co, and Ni.
3. The KOH activated nitrogen-doped carbon material supported catalyst of claim 1, wherein the weight ratio of the support to the metal active component is (80-95): (5-20).
4. The KOH activated nitrogen-doped carbon material supported catalyst of claim 1, wherein the residual K element content of the KOH activated nitrogen-doped carbon material is 0.6%.
5. The preparation method of the KOH activated nitrogen-doped carbon material supported catalyst is characterized by comprising the following steps of:
preparing a nitrogen-doped carbon material, wherein the nitrogen-doped carbon material is derived from an organic metal framework ZIF-8;
uniformly dispersing the nitrogen-doped carbon material in KOH solution, evaporating, drying, activating and roasting in inert gas atmosphere, washing to obtain KOH-activated nitrogen-doped carbon material, wherein the washing is specific
Directly washing with deionized water to ensure that the content of residual K element is 0.6-1.8%, wherein the temperature of activation roasting is 600-800 ℃;
immersing the metal active component solution into the KOH activated nitrogen-doped carbon material, uniformly dispersing, drying and roasting to obtain the KOH activated nitrogen-doped carbon material.
6. The method according to claim 5, wherein the step of preparing the nitrogen-doped carbon material specifically comprises:
dissolving metal zinc salt and nitrogen-containing organic ligand in deionized water, and stirring to obtain white solid precipitate;
and washing and drying the white solid precipitate, and roasting in an inert gas atmosphere to obtain the nitrogen-doped carbon material.
7. The method according to claim 6, wherein the metal zinc salt is zinc nitrate hexahydrate, the nitrogen-containing organic ligand is 2-methylimidazole, the weight ratio of the metal zinc salt to the nitrogen-containing organic ligand to deionized water is 0.11 (0.33-0.40): (60-70), the white solid precipitate is washed and dried, and then baked in an inert gas atmosphere to obtain the nitrogen-doped carbon material, wherein the baking temperature is 900-1100 ℃.
8. The method according to claim 5, wherein in the step of uniformly dispersing the nitrogen-doped carbon material in KOH solution, evaporating, drying, activating and calcining under an inert gas atmosphere, washing to obtain KOH-activated nitrogen-doped carbon material,
the mass ratio of KOH in the KOH solution to the nitrogen-doped carbon material is (1-3): 1, and the activation and roasting time is 1-3 hours.
9. The method according to claim 5, wherein in the step of uniformly dispersing the nitrogen-doped carbon material in KOH solution, evaporating, drying, activating and calcining under an inert gas atmosphere, washing to obtain KOH-activated nitrogen-doped carbon material,
the washing is specifically to directly wash with deionized water so that the content of residual K element is 0.6%.
10. The method according to claim 5, wherein the steps of immersing the metal active component solution into the KOH-activated nitrogen-doped carbon material, dispersing uniformly, drying, and calcining,
the metal active component solution comprises one or more of Fe, co and Ni ion solutions, the drying temperature is 50-80 ℃, the drying time is 8-24 hours, the roasting temperature is 400-600 ℃, and the roasting time is 2-4 hours.
11. Use of a KOH activated nitrogen-doped carbon material supported catalyst according to any one of claims 1 to 4 or a KOH activated nitrogen-doped carbon material supported catalyst prepared according to any one of claims 5 to 10 in a fischer-tropsch synthesis reaction to increase the conversion of synthesis gas and increase the low carbon olefin ratio in the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211049315.6A CN115400780B (en) | 2022-08-30 | 2022-08-30 | KOH activated nitrogen-doped carbon material supported catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211049315.6A CN115400780B (en) | 2022-08-30 | 2022-08-30 | KOH activated nitrogen-doped carbon material supported catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115400780A CN115400780A (en) | 2022-11-29 |
| CN115400780B true CN115400780B (en) | 2024-03-05 |
Family
ID=84164449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211049315.6A Active CN115400780B (en) | 2022-08-30 | 2022-08-30 | KOH activated nitrogen-doped carbon material supported catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115400780B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109346732A (en) * | 2018-09-20 | 2019-02-15 | 上海理工大学 | A kind of porous C catalyst of N doping and its preparation and application using potato preparation |
| CN110026228A (en) * | 2019-05-22 | 2019-07-19 | 福州大学 | A kind of preparation of nitrogenous porous carbon materials and its H2S selective catalytic oxidation application |
| CN110371973A (en) * | 2019-08-07 | 2019-10-25 | 中国石油化工股份有限公司 | A kind of poly- p-phenylenediamine/graphene-based nitrogen-doped porous carbon material preparation method |
| CN111530409A (en) * | 2020-05-12 | 2020-08-14 | 湖南垚恒环境科技有限公司 | Nitrogen-doped porous carbon material derived from zeolite imidazole framework material and preparation method thereof |
| CN112264074A (en) * | 2020-11-04 | 2021-01-26 | 天津大学 | Nitrogen-doped carbon nanosheet-loaded Fe-based catalyst and preparation method and application thereof |
| WO2021027100A1 (en) * | 2019-08-12 | 2021-02-18 | 山东大学 | Nitrogen-doped porous carbon material, preparation method therefor and use thereof |
| CN113106491A (en) * | 2021-04-30 | 2021-07-13 | 佛山仙湖实验室 | Preparation method of nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material, product and application thereof |
| WO2022036878A1 (en) * | 2020-08-20 | 2022-02-24 | 浙江大学 | High-nitrogen biochar composite material, preparation method therefor, and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10201802B2 (en) * | 2016-07-12 | 2019-02-12 | Farad Power, Inc. | Method of making hetero-atom doped activated carbon |
-
2022
- 2022-08-30 CN CN202211049315.6A patent/CN115400780B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109346732A (en) * | 2018-09-20 | 2019-02-15 | 上海理工大学 | A kind of porous C catalyst of N doping and its preparation and application using potato preparation |
| CN110026228A (en) * | 2019-05-22 | 2019-07-19 | 福州大学 | A kind of preparation of nitrogenous porous carbon materials and its H2S selective catalytic oxidation application |
| CN110371973A (en) * | 2019-08-07 | 2019-10-25 | 中国石油化工股份有限公司 | A kind of poly- p-phenylenediamine/graphene-based nitrogen-doped porous carbon material preparation method |
| WO2021027100A1 (en) * | 2019-08-12 | 2021-02-18 | 山东大学 | Nitrogen-doped porous carbon material, preparation method therefor and use thereof |
| CN111530409A (en) * | 2020-05-12 | 2020-08-14 | 湖南垚恒环境科技有限公司 | Nitrogen-doped porous carbon material derived from zeolite imidazole framework material and preparation method thereof |
| WO2022036878A1 (en) * | 2020-08-20 | 2022-02-24 | 浙江大学 | High-nitrogen biochar composite material, preparation method therefor, and application thereof |
| CN112264074A (en) * | 2020-11-04 | 2021-01-26 | 天津大学 | Nitrogen-doped carbon nanosheet-loaded Fe-based catalyst and preparation method and application thereof |
| CN113106491A (en) * | 2021-04-30 | 2021-07-13 | 佛山仙湖实验室 | Preparation method of nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material, product and application thereof |
Non-Patent Citations (10)
| Title |
|---|
| Activating nitrogen-doped carbon nanosheets by KOH treatment to promote the Fischer-Tropsch synthesis performance;Zhao Q等;CHEMICAL ENGINEERING JOURNAL;第455卷;140810 * |
| Highly active and controllable MOF-derived carbon nanosheets supported iron catalysts for Fischer-Tropsch synthesis;Qiao Zhao等;Carbon;20210331;第173卷;364-375 * |
| Mechanistic and structure investigation of the KOH activation ZIF-8 derived porous carbon as metal-free for unprecedented peroxymonosulfate activation degradation of bisphenol A;Peng Zhan等;Chemosphere;20220810;第307卷;135961 * |
| Nitrogen-doped hierarchically porous carbon derived from ZIF-8 and its improved effect on the dehydrogenation of LiBH4;Zhao Y等;INTERNATIONAL JOURNAL OF HYDROGEN ENERGY;20161019;第41卷(第39期);17175-17182 * |
| Nitrogen-doped porous carbons through KOH activation with superior performance in supercapacitors;Min Zhou等;Carbon;20140331;第68卷;185-194 * |
| Recent progress in the development of biomass-derived nitrogen-doped porous carbon;Matsagar B M等;Journal of Materials Chemistry A;20211231;第9卷(第7期);3703-3728 * |
| Understanding the KOH activation mechanism of zeolitic imidazolate framework-derived porous carbon and their corresponding furfural/acetic acid adsorption separation performance;Yuan M等;CHEMICAL ENGINEERING JOURNAL;20210930;第428卷;全文 * |
| 上官文峰等.能源材料 原理与应用.上海：上海交通大学出版社,2017,148-149. * |
| 基于聚多巴胺的氮掺杂碳材料的制备及其电化学性能;冷爽等;应用化学;20180410;第35卷(第4期);477-483 * |
| 氮掺杂生物质碳材料催化剂的制备及其催化CH_4-CO_2重整性能;马晓等;洁净煤技术;20220515;第28卷(第5期);5全文9-70 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115400780A (en) | 2022-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Advanced strategies for stabilizing single-atom catalysts for energy storage and conversion | |
| CN107308951B (en) | Preparation method of wide-temperature catalyst for preferentially oxidizing CO in hydrogen-rich atmosphere, product and application thereof | |
| CN109759064B (en) | Co @ C/biomass catalyst and preparation method and application thereof | |
| CN105536811A (en) | A core-shell type catalyst for lower-alkene preparation from synthetic gas, a preparing method thereof and applications of the catalyst | |
| CN110813320B (en) | Carbon-supported palladium-based alloy catalyst, preparation method thereof and application of catalyst in preparation of styrene | |
| CN112264074B (en) | Nitrogen-doped carbon nano-sheet-loaded Fe-based catalyst and preparation method and application thereof | |
| CN109718852A (en) | The preparation method of one pot process spherical shell type stable metal nanocatalyst | |
| CN110787789A (en) | Preparation and application of catalyst for preparing methanol by carbon dioxide hydrogenation | |
| CN104841442A (en) | Preparation method of anti-carbon deposition mesoporous confinement methane dry reforming catalyst | |
| CN108084449B (en) | Controllable preparation of monatomic and cluster iron catalyst by taking Fe-MOFs as precursor | |
| CN113398975B (en) | Preparation method of NiCu catalyst for selective hydrogenation of acetylene or butadiene in monoolefin-rich atmosphere, product and application | |
| CN115400780B (en) | KOH activated nitrogen-doped carbon material supported catalyst and preparation method thereof | |
| CN114768859B (en) | Nickel-silicon catalyst suitable for methane dry reforming and preparation method thereof | |
| CN107185525B (en) | Octahedral Pt nanoparticle loaded gamma-Al2O3Process for preparing form catalyst | |
| CN114054065A (en) | Preparation method of organic-inorganic hybrid material coated nickel silicate nanotube catalyst | |
| CN116116426B (en) | Iron-based catalyst for Fischer-Tropsch synthesis and preparation method and application thereof | |
| CN113083306A (en) | Preparation method and application of catalyst for improving content of phenolic compounds in low-rank coal microwave pyrolysis tar | |
| CN113368870B (en) | Sulfur ligand modified monoatomic catalyst and preparation method and application thereof | |
| CN112403466A (en) | Preparation method of core-shell catalyst for dry reforming of methane and carbon dioxide | |
| CN113856721A (en) | Iron-carbon skeleton catalyst for directly preparing low-carbon hydrocarbon from synthesis gas, preparation method of iron-carbon skeleton catalyst, method for preparing low-carbon hydrocarbon from synthesis gas and application of iron-carbon skeleton catalyst | |
| Zhang et al. | Highly activated Ag-doped Fe-based catalysts designed for Fischer–Tropsch synthesis | |
| CN115475637B (en) | Catalyst for preparing olefin by Fischer-Tropsch synthesis, and preparation method and application thereof | |
| CN115591550B (en) | Diatomic quantum dot catalyst and preparation method thereof | |
| CN114308061B (en) | NiAu bimetallic alloy nano-catalyst and synthesis and application thereof | |
| CN113663714B (en) | Aluminum nitride-based catalyst and preparation method and application thereof |
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 |