CN110639567B - Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof - Google Patents
Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN110639567B CN110639567B CN201910960532.2A CN201910960532A CN110639567B CN 110639567 B CN110639567 B CN 110639567B CN 201910960532 A CN201910960532 A CN 201910960532A CN 110639567 B CN110639567 B CN 110639567B
- Authority
- CN
- China
- Prior art keywords
- carbon
- nanocluster
- bifunctional catalyst
- reaction
- supported
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 70
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 94
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 38
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- BPEVHDGLPIIAGH-UHFFFAOYSA-N ruthenium(3+) Chemical compound [Ru+3] BPEVHDGLPIIAGH-UHFFFAOYSA-N 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 239000003814 drug Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 208000030507 AIDS Diseases 0.000 description 1
- 108010020056 Hydrogenase Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
- 239000003430 antimalarial agent Substances 0.000 description 1
- 239000003907 antipyretic analgesic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003589 local anesthetic agent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B01J35/394—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
Abstract
The invention discloses a carbon-supported ruthenium phosphide nanocluster bifunctional catalyst, a preparation method and application thereof, wherein the preparation method of the catalyst comprises the following steps: dispersing activated carbon powder and a Ru precursor in water, stirring to enable the Ru precursor to be fully adsorbed on the surface of the activated carbon, then evaporating to remove moisture, mixing and grinding the obtained solid powder and sodium hypophosphite, placing the mixture in a tubular furnace to carry out high-temperature calcination in an inert atmosphere, enabling the Ru precursor loaded on the activated carbon to react with the sodium hypophosphite at high temperature to convert the mixture into a ruthenium phosphide active component, washing the calcined product with water, and drying to obtain the carbon-loaded ruthenium phosphide nanocluster bifunctional catalyst. The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst can be used for catalyzing the reaction of quinoline hydrogenation and the dehydrogenation of 1,2,3, 4-tetrahydroquinoline, and is high in catalytic activity, good in stability, simple in preparation method and easy for industrial mass production.
Description
Technical Field
The invention discloses a carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and a preparation method and application thereof.
Background
Quinoline and 1,2,3, 4-tetrahydroquinoline and derivatives thereof are important intermediates for the synthesis of drugs, pesticides, dye alkaloids and many other bioactive molecules, and have very important application values. Secondly, quinoline and derivatives thereof are important raw materials for synthesizing and preparing some medical medicines. The quinoline compounds are mainly used for synthesizing antimalarial drugs, antipyretic analgesic drugs, local anesthetic drugs and the like, and besides being used for drug synthesis, quinoline and derivatives thereof are also used for researching and treating AIDS. Therefore, the development of the bifunctional catalyst for quinoline hydrogenation and dehydrogenation of 1,2,3, 4-tetrahydroquinoline and derivatives thereof is important in the industrial production of the hydrogenation and dehydrogenation reactions and has important industrial value. At present, the hydrogenation of quinoline and the dehydrogenation of 1,2,3, 4-tetrahydroquinoline mainly focus on developing a bifunctional catalyst which has high selectivity, high activity, high stability and can effectively complete the hydrogenation and dehydrogenation reactions. Although Pd, pt, rh and Co based Catalysts (Danhua Ge, lei Hu, jianying Wang, xingming Li, fenqiang Qi, jianmei Lu, xueqin Cao, hongwei Gu; reproducible Hydrogenation-Oxidative Dehydrogenation of microorganisms over a Highly Active Pt Nanowire Catalyst under Mill Conditions; chemCat chem, 2013, 5, 2183-2186, christophe Draredet, rong Ye, walter T. Ralston, F. Dean Toste, gabor A. Somorjai, dendrimer-Stabilized methods as effective Catalysts for reproducible Dehydrogenation/Hydrogenation of N-Heterocycles, J. Am. Chem. Soc., 2017, 139, 18084-18092, jinlei Li, guolang Liu, xiagangding Long, guang Gao, jun Wu, fuwei Li, differential activity in a functional Co. N-doped graphene series for catalytic Dehydrogenation and catalytic series for catalytic Hydrogenation, 20153, journal 3, 355, quatern series for catalytic Hydrogenation, and similar series for catalytic Hydrogenation, 2013, 53, journal 53, for catalytic series, for catalytic Hydrogenation, and catalytic series for catalytic Hydrogenation, and for catalytic Hydrogenation, for bifunctional quinoline, for Dehydrogenation, 2013, 355, 3, and 53, for Dehydrogenation, and for catalytic Hydrogenation. However, the noble metal-based catalysts Pd, pt and Rh have limited their catalytic applications due to their rarity and high cost, and the Co catalysts are too complicated in preparation process and expensive in support, and thus are not suitable for industrial catalytic applications. Therefore, the development of the supported bifunctional catalyst which is efficient, recyclable and simple to prepare is very important in the aspects of quinoline hydrogenation and tetrahydroquinoline dehydrogenation. The transition metal is expected to replace noble metal to become a novel catalyst because the transition metal contains unfilled d orbitals and unpaired d orbital electrons. To date, researchers have conducted some research into the catalytic activity of transition metals and their compounds (sulfides, nitrides, carbides, phosphides, etc.) in hydrogenation. Among them, transition metal phosphides are particularly spotlighted because of their high catalytic activity as a mechanism of catalysis like hydrogenase.
Disclosure of Invention
The invention aims to provide a carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and a preparation method and application thereof. The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst can be used for catalyzing the reaction of quinoline hydrogenation and the dehydrogenation of 1,2,3, 4-tetrahydroquinoline, and is high in catalytic activity, good in stability, simple in preparation method and easy for industrial mass production.
The preparation method of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is characterized by comprising the following steps of:
1) Uniformly dispersing activated carbon powder in water at room temperature, adding a Ru precursor into the obtained suspension, and stirring to ensure that the Ru precursor is fully adsorbed on the surface of the activated carbon to obtain suspension A;
2) Evaporating the suspension A obtained in the step 1) to remove water to obtain solid powder;
3) Mixing the solid powder obtained in the step 2) with sodium hypophosphite, fully grinding, transferring the obtained mixed powder into a tubular furnace, carrying out high-temperature calcination in an inert atmosphere, reacting a Ru precursor loaded on active carbon with the sodium hypophosphite at high temperature to convert the Ru precursor into a ruthenium phosphide active component, washing the calcined solid product with deionized water, and drying to obtain the carbon-loaded ruthenium phosphide nanocluster bifunctional catalyst.
The preparation method of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is characterized in that in the step 1), a Ru precursor is ruthenium trichloride, ruthenium (III) tris (acetylacetonate) or ruthenium (III) acetate, preferably ruthenium trichloride; the mass ratio of the active carbon powder to the Ru precursor is 20-60: 1.
The preparation method of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is characterized in that in the step 2), the evaporation temperature of the suspension A is 75-90 ℃.
The preparation method of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is characterized in that in the step 3), the gas in the inert atmosphere is nitrogen; the high-temperature calcination temperature is 400-700 ℃, and the high-temperature calcination time is 3-7 h.
The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst prepared by the method.
The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in the catalytic quinoline hydrogenation reaction is characterized in that the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is added into a high-pressure reactor, quinoline and a solvent are added into the high-pressure reactor, and H is used 2 After the air in the high-pressure reactor is replaced and exhausted, the high-pressure reactor is filled with H with a certain pressure 2 Heating and stirring for several hours, and reacting after the reaction is finishedFiltering the solution, concentrating the filtrate and removing the solvent to obtain the product of the quinoline hydrogenation reaction.
The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in catalyzing quinoline hydrogenation reaction is characterized in that the mass ratio of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst to quinoline is 1: 4 to 7, preferably 1: 5; the solvent is ethanol or water, and the dosage of the solvent is 5-8 times of the mass of quinoline.
The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in the catalytic quinoline hydrogenation reaction is characterized in that H filled in a high-pressure reactor during thermal stirring reaction 2 The pressure is 0.3-1Mpa, the heating reaction temperature is 50-80 ℃, the heating reaction time is 3-10h, and the stirring speed is 800-1200 rpm.
The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in catalyzing tetrahydroquinoline dehydrogenation reaction is characterized in that the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is added into a high-pressure reactor, tetrahydroquinoline and a solvent are added into the high-pressure reactor, and N is used 2 Displacing and exhausting air in the high-pressure reactor and leading N to be 2 And (3) after the internal space of the high-pressure reactor is filled, heating and stirring for reaction, filtering the reaction liquid after the reaction is finished, and concentrating the filtrate to remove the solvent to obtain the tetrahydroquinoline dehydrogenation reaction product.
The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in catalyzing dehydrogenation reaction of tetrahydroquinoline is characterized in that the mass ratio of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst to the tetrahydroquinoline is 1 (1.5-2); the solvent is benzene solvent, and the benzene solvent is p-xylene, o-xylene, m-xylene, xylene or mesitylene; the dosage of the solvent is 10-12 times of the mass of the tetrahydroquinoline; the reaction temperature is 135-145 ℃, and the reaction time is 20-24 h; the stirring speed is 250-450 rpm.
Compared with the prior art, the invention has the beneficial effects that:
1) According to the preparation method of the carbon-supported ruthenium phosphide nanocluster catalyst, the impregnation method is utilized, ru (III) in the Ru precursor solution is successfully supported on the surface of the active carbon, then the active carbon and sodium hypophosphite are fully ground and then the active carbon is calcined at high temperature in the inert atmosphere, so that the Ru precursor supported on the surface of the active carbon is decomposed and subjected to phosphorization, the prepared catalyst is good in stability, and the active component of the ruthenium phosphide nanoparticles, which has good dispersity and is in the shape of a nanocluster, is supported on the surface of the active carbon. Compared with the catalyst in the prior art, the catalyst has the advantages that the surface of the active carbon carrier is rich in active species of high-valence Ru (I) and Ru (II) (under the action of phosphorus, a ruthenium component in the phosphorized ruthenium dioxide can show a high valence state relative to zero), so that the application of the bifunctional catalyst for catalyzing the quinoline hydrogenation reaction and the 1,2,3, 4-tetrahydroquinoline dehydrogenation reaction is realized, and the catalyst shows excellent activity and stability for both the hydrogenation reaction and the dehydrogenation reaction.
2) The active component of the catalyst is unique Ru 2 The catalyst has a structure of P, has good dehydrogenation effect on 1,2,3, 4-tetrahydroquinoline, and is a bifunctional catalyst (because hydrogenation and dehydrogenation are a pair of reversible reactions, the conversion between reactants and products can be realized by changing reaction conditions by using one catalyst). In the active component of the catalyst of the present invention, the phosphorus atom bonded to the metallic ruthenium generates an electron-deficient metal by extracting electrons from the metallic ruthenium, and the change of the electron density of the 3d layer of the metallic ruthenium is also a main reason for having both catalytic quinoline hydrogenation and 1,2,3, 4-tetrahydroquinoline dehydrogenation as a bifunctional catalyst.
Drawings
Fig. 1 is a TEM image of the carbon-supported ruthenium phosphide nanocluster catalyst prepared in example 1;
FIG. 2 is a graph of the results of a statistical analysis of the particle size of the black dots of FIG. 1;
fig. 3 is an XPS plot of the carbon-supported ruthenium phosphide nanocluster catalyst prepared in example 1;
FIG. 4 is a graph showing the reaction results of the continuous hydrogenation reaction of quinoline;
FIG. 5 is a comparison graph of reaction results of quinoline hydrogenation reaction for 5 hours under different application times of the catalyst;
FIG. 6 is a graph showing the results of the continuous dehydrogenation of 1,2,3, 4-tetrahydroquinoline;
FIG. 7 is a graph showing the reaction results of 1,2,3, 4-tetrahydroquinoline continuous dehydrogenation reaction for 23h under different application times of the catalyst.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
The starting reagents used in the following examples were all of analytical grade, were purchased directly from the market and did not require further processing.
Example 1
Adding 0.5 g of activated carbon powder (with the particle size of 170-220 meshes) into 50 mL of water at room temperature, and performing ultrasonic treatment to uniformly disperse the activated carbon to obtain a first suspension; 1 mL of 10mg/mL RuCl 3 The aqueous solution was added dropwise to the first suspension, and stirred at room temperature for 3 hours to allow RuCl 3 Fully adsorbing the suspension on the surface of the activated carbon to obtain second suspension.
The second suspension was stirred continuously at a temperature of 80 ℃ until the water was totally evaporated, yielding a first solid powder. Fully grinding the first solid powder and 100 mg of sodium hypophosphite in a mortar, transferring the ground mixed powder into a porcelain boat, and calcining the porcelain boat in a tube furnace under the nitrogen atmosphere, wherein the calcining process comprises the following steps: heating from room temperature to 600 deg.C at a heating rate of 5 deg.C/min, maintaining at 600 deg.C for 5h, and naturally cooling to room temperature to obtain a second solid powder. And (3) washing the second solid powder with deionized water for 3 times (the volume of the deionized water adopted in each washing is 30 mL), and then drying in a vacuum drying oven at 60 ℃ for 10h to obtain the carbon-supported ruthenium phosphide nanocluster catalyst.
A TEM image of the carbon-supported ruthenium phosphide nanocluster catalyst prepared in example 1 is shown in fig. 1, and it can be seen from fig. 1 that: the active component of the ruthenium phosphide is uniformly dispersed on the active carbon carrier in the form of nanocluster, and the particle size distribution of the active component of the ruthenium phosphide is basically in the range of 1.2-4.0 nm (the particle size distribution of the active component of the ruthenium phosphide is concentrated and is uniformly distributed on the surface of the active carbon). According to the graph result of fig. 1, the analysis is performed by using the size distribution statistical software to analyze the size of the black dot part in fig. 1 (i.e., the analysis is performed on the size of the ruthenium phosphide nanoparticles), and the analysis result is shown in fig. 2, and it can be seen from fig. 2 that the average particle size of the ruthenium phosphide active ingredient is 2.6 nm.
The carbon-supported ruthenium phosphide nanocluster catalyst prepared in example 1 was subjected to X-ray analysis, and the XPS analysis result thereof is shown in fig. 3. As can be seen from fig. 3, the Ru component on the catalyst surface is a high-valence Ru component.
Example 2
Adding 1 g of activated carbon powder (with the particle size of 170-220 meshes) into 120 mL of water at room temperature, and performing ultrasonic treatment to uniformly disperse the activated carbon to obtain a first suspension; 2.2 mL of 10mg/mL RuCl 3 The aqueous solution was added dropwise to the first suspension, and stirred at room temperature for 4 hours to allow RuCl 3 Fully adsorbing the suspension on the surface of the activated carbon to obtain second suspension.
The second suspension was stirred continuously at a temperature of 78 ℃ until the water was totally evaporated, yielding a first solid powder. Fully grinding the first solid powder and 500 mg of sodium hypophosphite in a mortar, transferring the ground mixed powder into a porcelain boat, and calcining the porcelain boat in a tube furnace under the nitrogen atmosphere, wherein the calcining process comprises the following steps: heating to 650 deg.C at a heating rate of 7 deg.C/min from room temperature, maintaining at 650 deg.C for 4.5 h, and naturally cooling to room temperature to obtain a second solid powder. And (3) washing the second solid powder with deionized water for 3 times (the volume of the deionized water adopted in each washing is 80 mL), and then drying in a vacuum drying oven at 60 ℃ for 12 h to obtain the carbon-supported ruthenium phosphide nanocluster catalyst.
Example 3
Adding 0.3 g of activated carbon powder (with the particle size of 170-220 meshes) into 50 mL of water at room temperature, and performing ultrasonic treatment to uniformly disperse the activated carbon to obtain a first suspension; 0.7 mL of 10mg/mL aqueous solution of ruthenium (III) tris (acetylacetonate) was added dropwise to the first suspension, and the mixture was stirred at room temperature for 3 hours to allow the ruthenium (III) tris (acetylacetonate) to be sufficiently adsorbed on the surface of the activated carbon, thereby obtaining a second suspension.
The second suspension was stirred continuously at a temperature of 90 ℃ until the water was totally evaporated, yielding a first solid powder. Fully grinding the first solid powder and 60 mg of sodium hypophosphite in a mortar, transferring the ground mixed powder into a porcelain boat, and calcining the porcelain boat in a tube furnace under nitrogen atmosphere, wherein the calcining process comprises the following steps: heating from room temperature to 700 deg.C at a heating rate of 7 deg.C/min, maintaining at 700 deg.C for 6 h, and naturally cooling to room temperature to obtain a second solid powder. And (3) washing the second solid powder with deionized water for 3 times (the volume of the deionized water adopted in each washing is 20 mL), and then drying in a vacuum drying oven at 70 ℃ for 8 h to obtain the carbon-supported ruthenium phosphide nanocluster catalyst.
Example 4 the catalyst of example 1 was used to catalyze the quinoline hydrogenation reaction:
weighing 150 mg of prepared carbon-supported ruthenium phosphide nanocluster catalyst, 600 mu L of quinoline and 20 mL of ethanol, adding into a high-pressure reaction kettle, and reacting with H 2 After the air in the high-pressure reaction kettle is replaced and exhausted, H with the pressure of 0.5 Mpa is filled into the high-pressure reaction kettle 2 . The reaction solution in the autoclave was stirred at 60 ℃ for reaction, and the reaction results were sampled every 1 hour (gas chromatography was used for analysis to calculate the hydrogenation effect of quinoline), and the reaction results of the continuous hydrogenation of quinoline are shown in fig. 4. As can be seen from FIG. 4, the hydrogenation reaction of quinoline tends to be stable after 5 hours of continuous reaction, i.e. the reaction is substantially complete after 5 hours, and the yield of 1,2,3, 4-quinoline, which is the product of the hydrogenation reaction of quinoline, is as high as about 97%.
After the continuous hydrogenation reaction of the quinoline is finished for 5 hours, discharging the reaction liquid in the high-pressure reaction kettle, filtering, repeatedly applying the filtered solid catalyst for the continuous hydrogenation reaction of the quinoline, and applying the experimental conditions unchanged (and the catalyst is applied for each time and is subjected to catalytic reaction for 5 hours). The reaction results of quinoline hydrogenation for 5h under different application times of the catalyst are shown in fig. 5. As can be seen from FIG. 5, the yield of the hydrogenation product 1,2,3, 4-quinoline after 8 times of use of the catalyst was 91.5%. As can be seen from the reaction results, the catalytic activity of the catalyst is not obviously reduced under the condition of repeated application, thereby indicating that the catalyst has higher stability.
Example 5 the catalyst of example 1 was used to catalyze the dehydrogenation of 1,2,3, 4-tetrahydroquinoline:
weighing 300 mg of prepared carbon-supported ruthenium phosphide nanocluster catalyst, 400 mu L of 1,2,3, 4-tetrahydroquinoline and 20 mL of mesitylene, adding the materials into a 100 mL round-bottom flask, and adding N 2 The air in the autoclave was purged (the autoclave was filled with nitrogen atmosphere), the reaction was stirred at 135 ℃, a sample was taken during the reaction (gas chromatography was used for analysis to calculate the effect of dehydrogenation of 1,2,3, 4-tetrahydroquinoline), and the results of the continuous dehydrogenation of 1,2,3, 4-tetrahydroquinoline are shown in FIG. 6. As can be seen from FIG. 6, the dehydrogenation reaction of 1,2,3, 4-tetrahydroquinoline tends to be stable after 23 hours of continuous reaction, i.e., the reaction is substantially complete after 23 hours, and the yield of the dehydrogenation reaction product quinoline of 1,2,3, 4-tetrahydroquinoline is as high as about 98% or more.
After the 1,2,3, 4-tetrahydroquinoline continuous dehydrogenation reaction is finished for 23 hours, discharging the reaction liquid in the round-bottom flask, filtering, repeatedly applying the filtered solid catalyst for the 1,2,3, 4-tetrahydroquinoline continuous dehydrogenation reaction, and applying the experimental conditions unchanged (and the catalyst is applied for each time and is subjected to catalytic reaction for 23 hours). The reaction results of the 1,2,3, 4-tetrahydroquinoline continuous dehydrogenation reaction for 23h under different application times of the catalyst are shown in FIG. 7. As can be seen from FIG. 7, the yield of the dehydrogenation product, quinoline, was 93.0% after the catalyst was used repeatedly 8 times. As can be seen from the reaction results, the catalytic activity of the catalyst is not obviously reduced under the condition of repeated application, thereby indicating that the catalyst has higher stability.
Example 6:
the catalyst of example 2 is used for catalyzing quinoline hydrogenation reaction, the operation steps are repeated in example 4, the reaction time is 5h, sampling analysis is carried out, and the result is that: the yield of 1,2,3, 4-quinoline, which is the product of the quinoline hydrogenation reaction, was 99.0%.
The catalyst of example 2 was used to catalyze the dehydrogenation of 1,2,3, 4-tetrahydroquinoline, example 5 was repeated for the operating procedure, and a sample was taken for 23h for analysis, with the results: the yield of the product quinoline of the dehydrogenation reaction of 1,2,3, 4-tetrahydroquinoline was 99.1%.
Example 7:
the catalyst of the example 3 is used for catalyzing quinoline hydrogenation reaction, the operation steps are repeated in the example 4, the reaction time is 5h, sampling analysis is carried out, and the result is that: the yield of 1,2,3, 4-quinoline, which is the product of the quinoline hydrogenation reaction, was 99.2%.
The catalyst of example 3 was used to catalyze the dehydrogenation of 1,2,3, 4-tetrahydroquinoline, example 5 was repeated for the operating procedure, and a sample was taken for 23h for analysis, with the results: the yield of the product quinoline of the dehydrogenation reaction of 1,2,3, 4-tetrahydroquinoline was 99.1%.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (10)
1. A carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is characterized in that a preparation method of the catalyst comprises the following steps:
1) Uniformly dispersing activated carbon powder in water at room temperature, adding a Ru precursor into the obtained suspension, and stirring to ensure that the Ru precursor is fully adsorbed on the surface of the activated carbon to obtain suspension A; the mass ratio of the active carbon powder to the Ru precursor is 20-60: 1;
2) Evaporating the suspension A obtained in the step 1) to remove water to obtain solid powder;
3) Mixing the solid powder obtained in the step 2) with sodium hypophosphite, fully grinding, transferring the obtained mixed powder into a tubular furnace, carrying out high-temperature calcination in an inert atmosphere, reacting a Ru precursor loaded on activated carbon with the sodium hypophosphite at high temperature to convert the Ru precursor into a ruthenium phosphide active component, washing the calcined solid product with deionized water, and drying to obtain the carbon-loaded ruthenium phosphide nanocluster dual-function catalyst which is rich in active species of Ru (I) and Ru (II) with high valence states, wherein under the action of phosphorus, a ruthenium component in the ruthenium phosphide shows a high valence state relative to zero valence state; in the step 3), the gas of the inert atmosphere is nitrogen; the high-temperature calcination temperature is 400-700 ℃, and the high-temperature calcination time is 3-7 h;
the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is applied to the catalytic quinoline hydrogenation reaction or the catalytic tetrahydroquinoline dehydrogenation reaction.
2. The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst according to claim 1, wherein in the step 1), the Ru precursor is ruthenium trichloride, ruthenium (III) tris (acetylacetonate) or ruthenium (III) acetate.
3. The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst as claimed in claim 2, wherein the Ru precursor is ruthenium trichloride.
4. The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst as claimed in claim 1, wherein in step 2), the temperature for evaporating the suspension a is 75-90 ℃.
5. The carbon-supported di-ruthenium phosphide nanocluster bifunctional catalyst as claimed in claim 1, wherein the carbon-supported di-ruthenium phosphide nanocluster bifunctional catalyst is applied to the catalytic quinoline hydrogenation reaction, and the application method comprises the following steps: adding the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst into a high-pressure reactor, adding quinoline and a solvent into the high-pressure reactor, and adding H 2 After the air in the high-pressure reactor is replaced and exhausted, the high-pressure reactor is filled with H with a certain pressure 2 Heating and stirring for reaction for several hours, filtering the reaction liquid after the reaction is finished, and concentrating the filtrate to remove the solvent to obtain the quinoline hydrogenation reaction product.
6. The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst as claimed in claim 5, wherein the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is applied to the catalytic quinoline hydrogenation reaction, and the mass ratio of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst to quinoline is 1: 4 to 7; the solvent is ethanol or water, and the dosage of the solvent is 5-8 times of the mass of quinoline.
7. The carbon-supported di-ruthenium phosphide nanocluster bifunctional catalyst according to claim 6, wherein the carbon-supported di-ruthenium phosphide nanocluster bifunctional catalyst is applied to the catalytic quinoline hydrogenation reaction, and the mass ratio of the carbon-supported di-ruthenium phosphide nanocluster bifunctional catalyst to quinoline is 1: 5.
8. The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst as claimed in claim 5, wherein the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is applied to catalyzing quinoline hydrogenation reaction, and H filled in a high-pressure reactor is subjected to thermal stirring reaction 2 The pressure is 0.3-1Mpa, the heating reaction temperature is 50-80 ℃, the heating reaction time is 3-10h, and the stirring speed is 800-1200 rpm.
9. The carbon-supported di-ruthenium phosphide nanocluster bifunctional catalyst as claimed in claim 1, wherein the carbon-supported di-ruthenium phosphide nanocluster bifunctional catalyst is applied to catalyzing tetrahydroquinoline dehydrogenation reaction, the carbon-supported di-ruthenium phosphide nanocluster bifunctional catalyst is added into a high-pressure reactor, tetrahydroquinoline and a solvent are added into the high-pressure reactor, and N is used 2 Displacing and exhausting air in the high-pressure reactor and leading N to be 2 After the internal space of the high-pressure reactor is filled, heating and stirring for reaction, filtering the reaction liquid after the reaction is finished, and concentrating the filtrate to remove the solvent to obtain the tetrahydroquinoline dehydrogenation reaction product.
10. The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst as claimed in claim 9, wherein the mass ratio of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst to tetrahydroquinoline is 1 (1.5-2); the solvent is benzene solvent, and the benzene solvent is p-xylene, o-xylene, m-xylene or mesitylene; the dosage of the solvent is 10-12 times of the mass of the tetrahydroquinoline; the reaction temperature is 135-145 ℃, and the reaction time is 20-24 h; the stirring speed is 250-450 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910960532.2A CN110639567B (en) | 2019-10-10 | 2019-10-10 | Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910960532.2A CN110639567B (en) | 2019-10-10 | 2019-10-10 | Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110639567A CN110639567A (en) | 2020-01-03 |
| CN110639567B true CN110639567B (en) | 2022-10-21 |
Family
ID=68993788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910960532.2A Active CN110639567B (en) | 2019-10-10 | 2019-10-10 | Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110639567B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111617785B (en) * | 2020-07-09 | 2021-10-15 | 北京化工大学 | Supported ruthenium-based phosphide catalyst and preparation method thereof |
| CN113410472A (en) * | 2021-06-03 | 2021-09-17 | 扬州大学 | Alcohol fuel cell anode catalyst and preparation method thereof |
| CN113584502B (en) * | 2021-07-28 | 2022-07-01 | 青岛科技大学 | Preparation and application of molybdenum phosphide-ruthenium phosphide bimetal phosphide |
| CN115254158B (en) * | 2022-08-22 | 2023-12-22 | 中国科学院兰州化学物理研究所 | Nanocluster metal phosphide-phosphorus-carbon catalyst and preparation and application thereof |
| CN115487805B (en) * | 2022-09-09 | 2023-10-03 | 清华大学 | Preparation method and application of efficient catalyst for preparing cyclohexanol by hydrogenating aqueous phase phenol |
| CN115518685B (en) * | 2022-09-19 | 2024-03-12 | 浙江工业大学 | Carbon-supported p-toluenesulfonic acid catalyst and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862673B (en) * | 2010-06-28 | 2012-06-27 | 南开大学 | New method for preparing loaded Ru2P under mild condition |
| CN101992109B (en) * | 2010-09-06 | 2013-01-02 | 常州介孔催化材料有限公司 | Transition metal phosphide hydrofined catalyst and preparation method thereof |
| US9636664B1 (en) * | 2015-06-04 | 2017-05-02 | Alliance For Sustainable Energy, Llc | Metal phosphide catalysts and methods for making the same and uses thereof |
| CN107162968B (en) * | 2017-05-25 | 2019-10-25 | 陕西师范大学 | A kind of method of visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound |
| CN107824209B (en) * | 2017-11-09 | 2020-06-12 | 中国科学院上海硅酸盐研究所 | Catalyst for selective hydrogenation of quinoline compounds and preparation method thereof |
-
2019
- 2019-10-10 CN CN201910960532.2A patent/CN110639567B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110639567A (en) | 2020-01-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110639567B (en) | Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof | |
| CN107694592B (en) | Monatomic noble metal catalyst prepared by ultrasonic-assisted displacement reaction and method thereof | |
| US6670300B2 (en) | Textured catalysts, methods of making textured catalysts, and methods of catalyzing reactions conducted in hydrothermal conditions | |
| Burton et al. | Facile, surfactant-free synthesis of Pd nanoparticles for heterogeneous catalysts | |
| JP5715726B2 (en) | Ruthenium fine particles having substantially face-centered cubic structure and method for producing the same | |
| CN107626304B (en) | Supported noble metal catalyst and preparation and application thereof | |
| CN1974083A (en) | Prepn process and application of metal-carbon nanometer composite material | |
| Li et al. | Stable and efficient CuCr catalyst for the solvent-free hydrogenation of biomass derived ethyl levulinate to γ-valerolactone as potential biofuel candidate | |
| CN107159287B (en) | Pt/α-MoC1-xApplication of supported catalyst in catalytic hydrogenation reaction | |
| Can et al. | A facile synthesis of monodisperse cobalt–ruthenium alloy nanoparticles as catalysts for the dehydrogenation of morpholine borane and the hydrogenation of various organic compounds | |
| EP3321249B1 (en) | Method for producing acrylic acid | |
| JP6553804B2 (en) | Heterogeneous catalyst for acrylic acid production and method for producing acrylic acid using the same | |
| EP4025340B1 (en) | Materials comprising carbon-embedded nickel nanoparticles, processes for their manufacture, and use as heterogeneous catalysts | |
| EP4025339B1 (en) | Materials comprising carbon-embedded cobalt nanoparticles, processes for their manufacture, and use as heterogeneous catalysts | |
| Klasovsky et al. | Influence of Preparation Parameters on the Performance of Colloid-derived Oxidic Palladium Catalysts for Selective Hydrogenation of C–C Triple Bonds | |
| JPWO2018225759A1 (en) | Method for producing aliphatic hydrocarbon and carbon monoxide | |
| EP4025338B1 (en) | Materials comprising carbon-embedded iron nanoparticles, processes for their manufacture, and use as heterogeneous catalysts | |
| Xiao et al. | Controllable modification for adjacent circumstance controls cellulose conversion to ketols on Ni CCCs at particle levels | |
| WO2021256061A1 (en) | Platinum-tungsten solid solution particles and catalyst containing same | |
| Wei et al. | Crucial size effect on dicarbonylation of acetylene over Pd/CsHPMo heterogeneous catalysts | |
| Favier et al. | Bimetallic Nanoparticles in Ionic Liquids: Synthesis and Catalytic Applications | |
| CN117399012A (en) | Catalyst for packaging rare alloy nano particles and preparation method and application thereof | |
| CN110773152A (en) | Preparation method of carbon-supported 4-coordinated-oxygen manganese atomic-level dispersed catalyst | |
| García‐Álvarez et al. | Nanocatalysts for Rearrangement Reactions |
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 |