CN114308093A - High-load nickel-based carbide catalyst and preparation method and application thereof - Google Patents
High-load nickel-based carbide catalyst and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 55
- 239000002243 precursor Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 229910052593 corundum Inorganic materials 0.000 claims description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 11
- 239000012702 metal oxide precursor Substances 0.000 claims description 11
- 238000002407 reforming Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000013110 organic ligand Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000008021 deposition Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 4
- 150000001721 carbon Chemical group 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 25
- 238000012360 testing method Methods 0.000 description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000001569 carbon dioxide Substances 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000013112 stability test Methods 0.000 description 7
- 229910001092 metal group alloy Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- 238000010586 diagram Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
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- 150000001247 metal acetylides Chemical class 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000012430 stability testing Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal carbides Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 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
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a high-load nickel-based carbide catalyst, which is a coated interstitial carbide alloy catalyst; the molecular formula of the nickel-based catalyst is Ni3MCx/NyOzWherein M is metal, x is more than 0 and less than or equal to 1, and metal oxide NyOzIs a carrier; the metal M is alloyed with the metal Ni, C is an interstitial carbon atom, Ni3MCxThe carrier is a gap carbide alloy, and the gap carbide alloy is coated by the carrier. The high-load nickel-based carbide catalyst has good activity, stability and anti-carbon deposition performance. The invention also provides a preparation method and application of the high-load nickel-based carbide catalyst.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a high-load nickel-based carbide catalyst and a preparation method and application thereof.
Background
In the face of the energy and environmental problems faced by the world at present, new energy is vigorously developed, and the reduction of carbon emission is the direction of effort in our country in the aspects of environmental protection and energy application.
Methane (CH)4) And carbon dioxide (CO)2) The recycling and conversion of two main greenhouse gases and carbon-containing resources have received wide social attention in recent years. On the one hand, the natural gas, coal bed gas and biogas which can be directly obtained contain CH4In addition, it also contains a relatively high proportion of CO2. The traditional process removes CO through a pre-decarbonization step before methane enrichment2The process steps are complex, and the economic cost is high. On the other hand, with the development of modern industry, the concentration of carbon dioxide in the atmosphere is continuously increased, and the carbon dioxide breaks through 400ppm from 280ppm before the industrial revolution to 2013, and reaches 415ppm even in 2019, and CO is generated2Global climate change due to the continuous increase in concentration has become one of the problems facing mankind. Taking the steel industry as an example, the carbon emission accounts for 7-9% of the direct global carbon emission, wherein the carbon emission accounts for CH in tail gases of coke oven gas, blast furnace gas, basic oxygen furnace gas and the like4And CO2The content difference is large, and how to compound and utilize the gases becomes a key for reducing the carbon emission of the steel industry (Angew. chem. int. Ed.,2021,60: 11852-11857).
Methane Dry Reforming (DRM) technology can simultaneously utilize CH4And CO2These two gases, and the ability to convert these two typical greenhouse gases into the ideal raw gas syngas for fischer-tropsch synthesis, have been widely studied. DRM is a strong endothermic reaction, which needs to be carried out at a higher temperature, while CH is at a higher temperature4The progress of side reactions such as cracking and carbon monoxide (CO) disproportionation often leads to deactivation of the catalyst. On the other hand, rich in CO2Especially CO2/CH4When the content exceeds the stoichiometric ratio of 1/1, the metal catalyst is easily exposed to CO2Oxidation, leading to a reduction in catalyst activity and even deactivation.
Nickel-based catalysts have been widely studied due to their higher catalytic activity and low price, compared to noble metal catalysts. However, the nickel-based catalyst is prone to carbon deposition under the reaction conditions, which results in the reduction of the catalyst activity and the blockage of the reactor, thereby causing the increase of the production cost and increasing the potential safety hazard (appl.Catal.A: Gen.,2015,495: 141-151; J.Am.chem.Soc.,017,139: 1937-1949; appl.Catal.B: environ.,2019,246: 221-231). Studies have shown that transition metal carbides, such as Mo2The transition metal carbide catalyst such as C has good anti-carbon deposition performance in methane dry reforming because the electronic and geometric properties of metal atoms are changed by doping carbon atoms. However, in the presence of CO2In the reaction gas of (2), these metal carbides are rapidly oxidized to thereby deactivate the catalyst (Nat. Commun.,2020,11: 4072; Phys. chem. Phys.,2020,4: 4549-. Thus, the use of metal carbides for dry reforming of methane often requires either higher pressures or the addition of CO gas to the reaction gas. On the other hand, like raney nickel, high-loading nickel-based catalysts have unique advantages in industrial applications, whereas for conventional supported catalysts, the loading is generally controlled to be less than 20 wt% in order to ensure the dispersibility of the active metal of the catalyst to maintain its catalytic performance. Thus, a catalyst useful for CO enrichment was synthesized2Raw material gas, high-load Ni-based catalyst with good anti-carbon deposition performance and oxidation resistance in CH4And CO2The direct conversion and utilization field has very important significance.
Disclosure of Invention
Therefore, the present invention aims to solve the above problems and provide a high-loading nickel-based carbide catalyst, and a preparation method and applications thereof.
The invention provides a high-load nickel-based carbide catalyst, which is a coated interstitial carbide alloy catalyst;
the molecular formula of the high-load nickel-based carbide catalyst is Ni3MCx/NyOzWherein M is metal, x is more than 0 and less than or equal to 1, and metal oxide NyOzIs a carrier;
the metal M is alloyed with the metal Ni, C is an interstitial carbon atom, Ni3MCxThe carrier is a gap carbide alloy, and the gap carbide alloy is coated by the carrier.
Further, x is more than or equal to 0.25 and less than or equal to 0.8.
Further, the Ni content is 40-60 wt%.
Further, M is at least one of Al, Zn, In, Ga, Mg and Ca;
the metal oxide NyOzIs Al2O3、ZrO2、Fe2O3、CeO2At least one of (1).
Further, the carrier fully or partially coats the interstitial carbide alloy.
The invention also provides a preparation method of the high-load nickel-based carbide catalyst, which comprises the following steps:
preparing a metal M precursor: mixing soluble salt containing metal element M, solvent and organic ligand, and then stirring and centrifuging to obtain a metal M precursor;
synthesizing a metal oxide precursor: will contain Ni2+Mixing the soluble salt and the soluble salt containing the metal element N to obtain a solution A, dissolving the metal M precursor to obtain a solution B, mixing the solution A and the solution B, carrying out hydrothermal reaction to obtain a hydrothermal product, and washing and roasting the hydrothermal product to obtain the metal oxide precursor;
reduction: reducing the oxide precursor by using hydrogen to obtain a reduction product; and
carbonizing: the reduction product is treated with CH4And CO2The mixed gas is carbonized to obtain the needed catalyst.
Further, the M is Al, the solvent is at least one of methanol solution, urea solution and ammonia water solution, and the organic ligand is at least one of 2-methylimidazole, ethylenediamine tetraacetic acid, 2-mercaptosuccinic acid and terephthalic acid.
Further, the temperature of the hydrothermal reaction is 100-150 ℃, and the time is 12-36 h.
Further, the reduction temperature is 400-600 ℃, and the carbonization temperature is 450-650 ℃.
The invention also provides an application of the high-load nickel-based carbide catalyst, and the high-load nickel-based carbide catalyst is applied to dry reforming of methane.
The technical scheme of the invention can synthesize the high-load core-shell nickel-based carbide catalyst, which not only solves the problem that the catalyst is rich in CO2The problem of easy oxidation inactivation in gas is solved, the stability and the practicability of the catalyst are improved, higher methane and carbon dioxide activation capability is ensured, and the catalyst can well adapt to various proportions of rich CO2The reaction environment of the methane-carbon dioxide mixed gas atmosphere and the high-temperature reaction environment are particularly suitable for being applied to methane dry reforming. In addition, the C atoms generated by methane cracking are stored in the metal alloy interstitial sites, and carbon monoxide is generated through the reaction with carbon dioxide, so that the coupling of carbon-carbon bonds is avoided, the carbon deposition path of the dry reforming reaction of methane is avoided, and the catalyst has good carbon deposition resistance.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
Fig. 1 is an XRD pattern of Al precursor in experimental group 1.
Fig. 2 is an SEM image of the Al precursor in experimental group 1.
FIG. 3 shows NiO/Al in Experimental group 22O3XRD pattern of (a).
FIG. 4 shows NiO/Al in Experimental group 22O3BET diagram (b).
FIG. 5 shows Ni in Experimental group 33AlC0.5/Al2O3XRD pattern of (a).
FIG. 6 shows Ni in Experimental group 33AlC0.5/Al2O3A TEM image of (a).
Fig. 7 is a catalyst stability test chart of the test groups 1,6, and 7.
Figure 8 is an XRD pattern of the catalyst after the stability test of test group 1.
Fig. 9 is a graph of air TG of the catalyst after the stability test of test group 1.
Detailed Description
The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example one
The preparation method of the high-load nickel-based carbide catalyst comprises the following steps:
step S1: preparing a metal M precursor: mixing soluble salt containing metal element M, solvent and organic ligand, and then stirring and centrifuging to obtain a metal M precursor;
step S2: synthesizing a metal oxide precursor: will contain Ni2+Mixing the soluble salt and the soluble salt containing the metal element N to obtain a solution A, dissolving the metal M precursor to obtain a solution B, mixing the solution A and the solution B, carrying out hydrothermal reaction to obtain a hydrothermal product, and washing and roasting the hydrothermal product to obtain the metal oxide precursor;
step S3: reduction: reducing the oxide precursor by using hydrogen to obtain a reduction product; and
step S4: carbonizing: the reduction product is treated with CH4And CO2The mixed gas is carbonized to obtain the needed catalyst.
The preparation method of the nickel-based catalyst realizes that C atoms generated by methane cracking are stored in metal alloy interstitial sites and react with carbon dioxide to generate carbon monoxideThereby avoiding the coupling of carbon-carbon bonds and avoiding the carbon deposition path of the dry reforming reaction of methane, and leading the prepared nickel-based catalyst to have good carbon deposition resistance. And well solves the problem that the catalyst is rich in CO2The problem of easy oxidation inactivation in gas is solved, the stability and the practicability of the catalyst are improved, higher methane and carbon dioxide activation capability is ensured, and the catalyst can well adapt to various proportions of rich CO2The methane-carbon dioxide mixed gas atmosphere and the high-temperature reaction environment.
In step S1, the metal element M may be at least one of Al, Zn, In, Ga, Mg, Ca, preferably Al.
The soluble salt containing the metal element M can be at least one of a nitrate solution, an acetate solution and a sulfate solution, namely when the M is Al, the soluble salt can be one or a mixture of more of aluminum nitrate, aluminum acetate and aluminum sulfate; the solubility of the soluble salt is preferably 0.1 to 0.5 mol/L.
The solvent may be at least one of methanol solution, urea solution, and ammonia solution. The organic ligand can be at least one of 2-methylimidazole, ethylenediamine tetraacetic acid, 2-mercaptosuccinic acid and terephthalic acid. When M is Al, the solvent is preferably methanol solution and the organic ligand is preferably terephthalic acid.
Step S1 may specifically be mixing the aluminum nitrate solution, the methanol solution, and the phthalic acid, stirring for 12 hours, and then obtaining the metal Al precursor by centrifugation and filtration.
In step S2, Ni2+The soluble salt can be at least one of nitrate solution, acetate solution and sulfate solution, the metal element N can be at least one of Al, Zr, Fe and Ce, and the soluble salt of the metal element N can be at least one of nitrate solution, acetate solution and sulfate solution. It is understood that when M is Al, N is preferably Al, which not only can reduce the kinds of raw materials and ensure the stability of the final catalyst, but also the molar ratio of nickel ions to aluminum ions is 1 to 5:1, the total concentration is preferably 0.5 to 1.5 mol/L.
The metal M precursor is preferably dissolved with a sodium carbonate solution, further with a concentration of 0.5-1.5 mol/L.
The temperature of the hydrothermal reaction is preferably 100-150 ℃, and the hydrothermal time is preferably 12-36 h.
The roasting temperature is preferably 400-800 ℃, and the time is preferably 3-8 h.
Step S2 may specifically be mixing a nickel nitrate solution and an aluminum nitrate solution to obtain a solution a, dissolving the metal Al precursor to obtain a solution B, then uniformly mixing the solution a and the solution B, stirring for 30min, performing a hydrothermal reaction at 120 ℃ for 12h to obtain a hydrothermal product, centrifuging and washing the obtained hydrothermal product, and calcining at 600 ℃ for 5h to obtain a metal oxide precursor NiO/Al2O3。
In step S3, the reduction temperature is preferably 400-600 ℃, and the reduction time is preferably 1-5 h. Further, the reduction temperature is 550 ℃, and the reduction time is 2 hours. The hydrogen concentration in the reducing environment is preferably 10% to 100%.
In step S4, the carbonization temperature is preferably 450-650 ℃, and the carbonization time is preferably 1-5 h. Further, the carbonization temperature is 500 ℃, and the carbonization time is preferably 2 h.
Example two
A nickel-based catalyst, which can be prepared by the preparation method of the nickel-based catalyst provided in the first embodiment, wherein the nickel-based catalyst is a coated interstitial carbide alloy catalyst;
the molecular formula of the high-load nickel-based carbide catalyst is Ni3MCx/NyOzWherein M is metal, x is more than 0 and less than or equal to 1, and metal oxide NyOzIs a carrier;
the metal M is alloyed with the metal Ni, C is an interstitial carbon atom, Ni3MCxThe carrier is a gap carbide alloy, and the gap carbide alloy is coated by the carrier.
As a coated catalyst, the coating form of the catalyst may be fully coated or partially coated, that is, the carrier fully coats or partially coats the interstitial carbide alloy, and preferably, the coating form of the nickel-based catalyst is fully coated. Preferably, the coating thickness is 2-10nm, and the grain size of the interstitial carbide alloy is 5-100 nm.
Preferably, x is more than or equal to 0.25 and less than or equal to 0.8, and the Ni content is 40-60 wt%.
The M may be at least one of Al, Zn, In, Ga, Mg, and Ca, and is more preferably Al. The metal oxide NyOzMay be Al2O3、ZrO2、Fe2O3、CeO2More preferably Al2O3。
In some embodiments, the nickel-based catalyst has the formula Ni3AlC0.5/Al2O3。
EXAMPLE III
The application of the high-load nickel-based carbide catalyst provided in the second embodiment is applied to the dry reforming of methane.
Example four
Under the condition of preparing the synthesis gas by dry reforming of methane, the methane and the carbon dioxide are in contact reaction with the high-load nickel-based carbide catalyst provided in the second embodiment.
Preferably, the contacting reaction is carried out in a fixed bed reactor. The reaction condition is CH4With CO2The ratio of (1): 1-4, the reaction temperature is 450-650 ℃, and the reaction pressure is normal pressure. Atmospheric pressure here means one atmosphere, i.e. 1 bar.
Some specific experimental groups and test/characterization results are provided below
1.02g of terephthalic acid and 1.20g of Al (NO) were taken3)3·9H2Dissolving O in 40mL of methanol solution, washing the wall of the beaker by 32mL of terephthalic acid solution, stirring at room temperature for 12h, and then obtaining the Al precursor by centrifuging and washing.
Mixing 5.81g Ni (NO)3)2·6H2O and 1.88g Al (NO)3)3·9H2Dissolving O in 20mL of distilled water and stirring for 20 min; dissolving 2g of Al precursor prepared in the experimental group 1 in 0.75M sodium carbonate solution; and the two solutions were mixed well and stirred at room temperature for 30 min. Subsequently, the above solution was transferred to a 100mL autoclave and reacted at 120 ℃ for 12 hours to obtain a product. Centrifuging and washing the product, and roasting at 600 ℃ for 5h to obtain a metal oxide precursor NiO/Al2O3。
Experimental group 3
NiO/Al obtained from experiment group 22O3Reduction with hydrogen at 550 ℃ for 2h and CH at 500 ℃4/CO2The mixed gas is carbonized for 2 hours to obtain the metal alloy interstitial carbide catalyst Ni3AlC0.5/Al2O3。
The following tests/characterizations were performed for the above experimental groups
1. Al precursor obtained for Experimental group 1
Fig. 1 is an XRD pattern of Al precursor in experimental group 1. This indicates that Al has reacted with the organic framework and that a precursor to Al was successfully prepared.
Fig. 2 is an SEM image of the Al precursor in experimental group 1. This indicates the morphological characteristics of the Al precursor.
2. NiO/Al metal oxide precursor obtained by aiming at experimental group 22O3。
FIG. 3 shows NiO/Al in Experimental group 22O3XRD pattern of (a). The figure illustrates NiO/Al after firing2O3The catalyst mainly comprises NiO and amorphous Al2O3。
FIG. 4 shows NiO/Al in Experimental group 22O3BET diagram (b). The figure illustrates the channel structure and specific surface area of the catalyst. The pore size distribution diagram shows that the catalyst has rich mesoporous structure.
Table 1 shows the specific surface area, average pore diameter, and pore volume of the metal oxide precursors in experimental group 2.
TABLE 1
Table 2 shows the metal contents of the metal oxide precursors in experimental group 2.
TABLE 2
3. Metal alloy interstitial carbide catalyst Ni obtained by aiming at experimental group 33AlC0.5/Al2O3
FIG. 5 shows Ni in Experimental group 33AlC0.5/Al2O3XRD pattern of (a). As can be seen in this figure, Ni appears at 43.3 °, 50.4 ° and 74.0 ° 2 θ3AlC0.5Characteristic diffraction peak of (A) indicates that the catalyst Ni is successfully prepared3AlC0.5/Al2O3. Al is not obtained2O3The characteristic diffraction peak of (2) is due to the low crystallinity of the oxide, which cannot be detected by XRD.
FIG. 6 shows Ni in Experimental group 33AlC0.5/Al2O3A TEM image of (a). As can be seen from the figure, the catalysis is of a core-shell structure, i.e., about 2nm of Al2O3The shell is wrapped with about 80nm of Ni3AlC0.5。
Stability testing was performed on the catalysts:
test set 1
The performance of the catalyst prepared in experimental group 3 was investigated using a fixed bed reactor. The fixed bed reactor had an outer diameter of 12mm, an inner diameter of 8mm and a length of 450 mm. The reactants and products were detected by gas chromatography with a TCD detector and a soap bubble flow meter.
Reaction conditions are as follows: 0.1g of catalyst mixed with 1g of quartz sand is filled in a constant temperature area of a fixed bed reactor, and after the temperature is raised to 500 ℃ under Ar, the constant temperature area is switched to CH4/CO2The flow rate of the mixed gas was 60mL/min, and the reaction pressure was normal pressure, 1/1. Atmospheric pressure here means one atmosphere, i.e. 1 bar.
The differences from test set 1 are: the temperature is raised to 450 ℃, 550 ℃, 600 ℃ and 650 ℃ under Ar.
Test set 6
The difference from test set 1 is: CH (CH)4/CO2=1/2。
Test group 7
The difference from test set 1 is: CH (CH)4/CO2=1/4。
Test groups 8 to 11
The difference from test group 7 is: the temperature is raised to 450 ℃, 550 ℃, 600 ℃ and 650 ℃ under Ar.
Fig. 7 is a catalyst stability test chart of the test groups 1,6, and 7. The catalyst did not significantly deactivate in the 100h test, indicating that the catalyst is in CH4/CO2The stability of the product is good in 1/1, 1/2 and 1/4 atmosphere.
The test data from test groups 1 to 5 were collated to give Table 3:
TABLE 3CH4/CO 21/1 time difference in reaction temperature versus Ni3AlC0.5/Al2O3Effect of Metal alloy interstitial carbide catalyst on methane Dry reforming
As can be seen from Table 3, the catalyst synthesized by the present invention has good conversion of methane and carbon dioxide at a relatively low temperature. The methane conversion and carbon dioxide conversion can reach 57.1% and 69.2% conversion respectively at 650 ℃.
Table 4 was obtained by collating the test data from test groups 7-11:
TABLE 4 CH4/CO 21/4 time difference in reaction temperature versus Ni3AlC0.5/Al2O3Effect of Metal alloy interstitial carbide catalyst on methane Dry reforming
As can be seen from table 4, the catalysts synthesized in the examples of the present invention have good conversion rates of methane and carbon dioxide at lower temperatures. The methane conversion and carbon dioxide conversion can reach 91.6% and 42.5% conversion respectively at 650 ℃.
Further characterization was performed for the catalysts after stability testing in test group 1
FIG. 8 is an XRD pattern of the catalyst after stability test of test group 1, Al2O3Is an amorphous substance. The spectrum shows that no diffraction peak of carbon species appears, which indicates that the catalyst has good anti-carbon deposition performance. And the comparison with the XRD pattern (figure 6) of the catalyst before the stability test shows that the two are consistent, which indicates that the catalyst has high stability.
Fig. 9 is a graph of air TG of the catalyst after the stability test of test group 1. The atlas shows that the catalyst has obvious weight loss peak at the temperature of less than 200 ℃, which is because the water absorbed by the catalyst is removed; the increase in mass at 200-400 ℃ is attributed to the oxidation of the carbide metal in the catalyst; the weight loss above 400 ℃ is due to mass loss caused by oxidation of the liberated carbon species in the alloy catalyst. Thus, the data also show that the catalyst has good resistance to carbon deposition.
In conclusion, the nickel-based metal carbide interstitial catalyst prepared by the method can be well suitable for dry reforming reaction of methane, and can adapt to different reactant proportions, namely CH4/CO2The range is 1: 1-1: 4. The catalyst has good activity, stability and anti-carbon deposition performance. In addition, the catalyst is rich in CO compared to other carbide catalysts2Has good oxidation resistance in the reaction gas. In addition, the catalyst of the invention has simple production and lower cost, and is easy to realize industrialization.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A high-load nickel-based carbide catalyst is characterized in that: it is a coated interstitial carbide alloy catalyst;
the molecular formula of the high-load nickel-based carbide catalyst is Ni3MCx/NyOzWherein M is metal, x is more than 0 and less than or equal to 1, and metal oxide NyOzIs a carrier;
the metal M is alloyed with the metal Ni, C is an interstitial carbon atom, Ni3MCxThe carrier is a gap carbide alloy, and the gap carbide alloy is coated by the carrier.
2. The high loading nickel-based carbide catalyst of claim 1, wherein: x is more than or equal to 0.25 and less than or equal to 0.8.
3. The high loading nickel-based carbide catalyst of claim 1, wherein: the Ni content is 40-60 wt%.
4. The high loading nickel-based carbide catalyst of claim 1, wherein: the M is at least one of Al, Zn, In, Ga, Mg and Ca;
the metal oxide NyOzIs Al2O3、ZrO2、Fe2O3、CeO2At least one of (1).
5. A high loading nickel based carbide catalyst according to any of claims 1 to 4, wherein: the carrier fully or partially coats the interstitial carbide alloy.
6. A preparation method of a high-load nickel-based carbide catalyst is characterized by comprising the following steps: the method comprises the following steps:
preparing a metal M precursor: mixing soluble salt containing metal element M, solvent and organic ligand, and then stirring and centrifuging to obtain a metal M precursor;
synthesizing a metal oxide precursor: will contain Ni2+Mixing the soluble salt and the soluble salt containing the metal element N to obtain a solution A, dissolving the metal M precursor to obtain a solution B, mixing the solution A and the solution B, carrying out hydrothermal reaction to obtain a hydrothermal product, and washing and roasting the hydrothermal product to obtain the metal oxide precursor;
reduction: reducing the oxide precursor by using hydrogen to obtain a reduction product; and
carbonizing: the reduction product is treated with CH4And CO2The mixed gas is carbonized to obtain the needed catalyst.
7. The method of preparing the high loading nickel-based carbide catalyst of claim 6, wherein: the M is Al, the solvent is at least one of methanol solution, urea solution and ammonia water solution, and the organic ligand is at least one of 2-methylimidazole, ethylenediamine tetraacetic acid, 2-mercaptosuccinic acid and terephthalic acid.
8. The method of preparing the high loading nickel-based carbide catalyst of claim 6, wherein: the temperature of the hydrothermal reaction is 100-150 ℃, and the time is 12-36 h.
9. A method of preparing a high loading nickel-based carbide catalyst according to any of claims 6 to 8, wherein: the reduction temperature is 400-600 ℃, and the carbonization temperature is 450-650 ℃.
10. The application of the high-load nickel-based carbide catalyst is characterized in that: use of the high loading nickel-based carbide catalyst as claimed in any of claims 1 to 5 in dry reforming of methane.
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