CN108218718B - Method for efficiently preparing N, N-dibenzyl ethylenediamine through catalytic hydrogenation - Google Patents
Method for efficiently preparing N, N-dibenzyl ethylenediamine through catalytic hydrogenation Download PDFInfo
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- CN108218718B CN108218718B CN201810287219.2A CN201810287219A CN108218718B CN 108218718 B CN108218718 B CN 108218718B CN 201810287219 A CN201810287219 A CN 201810287219A CN 108218718 B CN108218718 B CN 108218718B
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- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 21
- ACTNHJDHMQSOGL-UHFFFAOYSA-N n',n'-dibenzylethane-1,2-diamine Chemical compound C=1C=CC=CC=1CN(CCN)CC1=CC=CC=C1 ACTNHJDHMQSOGL-UHFFFAOYSA-N 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 114
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 81
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 75
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 51
- 239000011593 sulfur Substances 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 23
- 239000007791 liquid phase Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 27
- 239000012065 filter cake Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 230000007935 neutral effect Effects 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 238000005121 nitriding Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 3
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims description 3
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 description 3
- -1 nitrile compound Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- ACYBVNYNIZTUIL-UHFFFAOYSA-N n'-benzylethane-1,2-diamine Chemical compound NCCNCC1=CC=CC=C1 ACYBVNYNIZTUIL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 229930186147 Cephalosporin Natural products 0.000 description 1
- 241000228143 Penicillium Species 0.000 description 1
- 229960000723 ampicillin Drugs 0.000 description 1
- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940124587 cephalosporin Drugs 0.000 description 1
- 150000001780 cephalosporins Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229940056360 penicillin g Drugs 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
-
- 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
-
- B01J35/60—
Abstract
The invention discloses a method for efficiently preparing N, N-dibenzyl ethylenediamine by catalytic hydrogenation, which comprises the following steps: in a reaction kettle, N, N-dibenzylidene ethylenediamine is subjected to liquid-phase catalytic hydrogenation reaction under the action of a nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalyst to prepare N, N-dibenzylidene ethylenediamine; the invention provides a method for efficiently preparing N, N-dibenzyl ethylenediamine by catalytic hydrogenation of N, N-dibenzylidene ethylenediamine through liquid-phase catalytic hydrogenation.
Description
Technical Field
The invention relates to a method for efficiently preparing N, N-dibenzyl ethylenediamine by catalytic hydrogenation.
Background
N, N-dibenzylethylenediamine is a medical intermediate, and is mainly used for producing long-acting penicillin G, long-acting penicillium V, long-acting ampicillin, long-acting cephalosporins and other medicines. Currently, N-dibenzylidene ethylenediamine is mainly prepared industrially by catalytic hydrogenation of N, N-dibenzylidene ethylenediamine. Wherein the hydrogenation catalyst is the key technology of the process.
The catalyst for preparing N, N-dibenzylidene ethylenediamine by hydrogenating N, N-dibenzylidene ethylenediamine in industry is mainly Pd/C and Pt/C. However, the common Pd/C or Pt/C catalyst has the problem that the activity and the selectivity are difficult to be compatible. This is mainly because when the activity of the Pd/C or Pt/C catalyst is too low, polymerization reaction easily occurs to generate by-products such as poly-benzyl ethylenediamine; if the Pd/C or Pt/C catalyst activity is too high, a more severe C-N hydrogenolysis reaction is caused to generate by-products such as monobenzylethylenediamine and the like. Therefore, a hydrogenation catalyst with proper activity must be designed to obtain high yield of N, N-dibenzylethylenediamine.
Currently, the commercial Pd/C and Pt/C catalysts generally use activated carbon as a carrier, and although the activated carbon has the advantages of low price, large specific surface area and the like, the pore structure of the activated carbon is mainly microporous, and the surface of the activated carbon is neutral. When the Pd/C or Pt/C catalyst with activated carbon as a carrier is applied to the preparation of N, N-dibenzylidene ethylene diamine by hydrogenation of N, N-dibenzylidene ethylene diamine, raw materials and products have serious diffusion resistance in micropores of the activated carbon, so that the reaction speed is slowed down, side reactions such as C-N hydrogenolysis and polymerization are easily caused, and the smooth reaction is not facilitated. In addition, an imine or nitrile compound is likely to undergo a polymerization reaction when subjected to a hydrogenation reaction in a neutral environment, but is effectively inhibited in an alkaline environment.
Therefore, it is very meaningful to find a method for preparing N, N-dibenzyl ethylenediamine with high selectivity and high efficiency by catalytic hydrogenation.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for efficiently preparing N, N-dibenzylidene ethylenediamine by catalytic hydrogenation of N, N-dibenzylidene ethylenediamine through liquid-phase catalytic hydrogenation.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for efficiently preparing N, N-dibenzyl ethylenediamine by catalytic hydrogenation comprises the following steps: in a reaction kettle, N, N-dibenzylidene ethylenediamine is subjected to liquid phase catalytic hydrogenation reaction under the action of a nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalyst to prepare the N, N-dibenzylidene ethylenediamine.
Further, the preparation method of the nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalyst comprises the following steps:
1) weighing nitrogen/sulfur co-doped mesoporous carbon for preparing the catalyst, preparing the nitrogen/sulfur co-doped mesoporous carbon into slurry at the temperature of 20-90 ℃, slowly dropwise adding a solution of a soluble precious metal compound according to the loading amount of the precious metal, and fully and uniformly stirring;
2) after dipping for 0.5-8 h, adding an alkaline solution to adjust the pH value of the solution to 7.5-10.0, cooling the temperature to room temperature, filtering, and washing a filter cake to be neutral by deionized water;
3) and preparing the filter cake into slurry at the temperature of 20-90 ℃, dropwise adding a liquid-phase reducing agent, stirring, filtering, washing the filter cake to be neutral by using deionized water, and performing vacuum drying at the temperature of 70-120 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalyst.
Further, the noble metal is one or more of Pd or Pt; the soluble precious metal compound is one or more of H2PdCl4, K2PdCl4, Na2PdCl4, Pd (NO3)2, H2PtCl6, K2PtCl6, Na2PtCl6 or Pt (NO3) 2; the alkaline solution is one or more of NaOH, KOH, NaHCO3, Na2CO3, KHCO3, K2CO3 or ammonia water and the like; the liquid phase reducing agent is one or more of hydrazine hydrate, formic acid, formaldehyde, potassium formate or sodium formate; the loading amount of the noble metal in the nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalyst is 2-10 wt%, and preferably 3-8 wt%.
Further, the nitrogen/sulfur co-doped mesoporous carbon is prepared by the following method: under inert atmosphere, nitrogen-containing compounds are used for high-temperature nitridation treatment of mesoporous carbon, and then H2S is used for high-temperature vulcanization treatment, so that nitrogen/sulfur doped mesoporous carbon is obtained.
Further, the inert atmosphere is one or more of nitrogen, argon and helium; the granularity of the mesoporous carbon is 100-1000 meshes, preferably 150-800 meshes; the specific surface area is 600-2000 m2/g, preferably 1000-1800 m 2/g; the average pore diameter is 2 to 20nm, preferably 2 to 10 nm.
Further, the nitrogen-containing compound is one or more of ammonia gas and urea; the mass ratio of the nitrogen-containing compound to the mesoporous carbon is 0.05-10: 1, preferably 0.1 to 5: 1; the mass ratio of the H2S to the mesoporous carbon is (0.5-50): 1, preferably 1 to 20: 1; the high-temperature nitriding treatment temperature is 400-1500 ℃, and preferably 600-1200 ℃; the nitriding treatment time is 0.5-50 h, preferably 1-20 h; the high-temperature vulcanization treatment temperature is 500-1200 ℃, and preferably 600-1000 ℃; the vulcanization treatment time is 1-30 h, preferably 2-20 h.
Furthermore, in the liquid-phase catalytic hydrogenation reaction, the dosage of the nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalyst is 0.5-3.0 wt% of the mass of the N, N-dibenzylidene ethylenediamine.
Further, the liquid-phase catalytic hydrogenation reaction takes ethyl acetate as a reaction solvent, and the addition amount of the reaction solvent is 0.5-3.0 ml/g based on the mass of the N, N-dibenzylidene ethylenediamine.
Further, the reaction temperature of the liquid phase catalytic hydrogenation reaction is 50-120 ℃, and preferably 60-110 ℃.
Further, in the liquid phase catalytic hydrogenation reaction, the hydrogen pressure is controlled to be 0.2-3.0 MPa, and preferably 0.3-1.0 MPa.
The liquid phase catalytic hydrogenation reaction of the present invention can obtain the target product through conventional post-treatment after the reaction is completed, for example, the following post-treatment method can be adopted: after the reaction is finished, cooling the temperature to room temperature, taking out the reaction mixture, filtering to remove the catalyst, and distilling or rectifying the filtrate to obtain the target compound.
Compared with the prior art, the invention has the following advantages:
1) the nitrogen element in the nitrogen/sulfur co-doped mesoporous carbon carrier adopted by the invention can provide proper alkalinity, and N, N-dibenzylidene ethylenediamine and other polymerization reactions; the sulfur element in the carrier can form an electronic effect with the loaded metal atoms, so that the activity of the noble metal catalyst is properly reduced, the inhibition of C-N hydrogenolysis reaction is facilitated, and the selectivity of a target product N, N-dibenzyl ethylenediamine is facilitated to be improved.
2) The nitrogen and sulfur elements are directly doped into the carbon skeleton or connected with the carbon material through N-C or S-C bonds, so that the nitrogen elements are not easy to lose in the hydrogenation reaction, therefore, the nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalyst has good stability in the hydrogenation reaction, and the catalyst is continuously applied for 40 times without obvious inactivation.
3) The nitrogen/sulfur co-doped mesoporous carbon carrier adopted by the invention has larger aperture, is beneficial to the transmission of raw materials and products in a catalyst pore channel, not only accelerates the reaction speed, but also is beneficial to improving the selectivity of N, N-dibenzylethylenediamine.
4) The selectivity of the catalytic hydrogenation method for preparing the N, N-dibenzyl ethylenediamine is more than 96.0 wt%, and the imine conversion rate reaches 100 wt%.
5) The catalyst adopted by the invention does not contain other metal elements except the noble metal active component, and the difficulty of recycling the noble metal catalyst is not increased.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example one
Weighing 10g of mesoporous carbon, wherein the granularity of the mesoporous carbon is 800 meshes, and the specific surface area of the mesoporous carbon is 1400m2Per gram, the average pore diameter is 4nm, the mixture is evenly mixed with 0.8g of urea and treated for 5 hours at 1000 ℃ in the nitrogen atmosphere; then 1L/H of H is introduced into the reactor under the nitrogen atmosphere2And S, treating for 5 hours at 1000 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon. Then preparing the nitrogen/sulfur co-doped mesoporous carbon into slurry with the temperature of 80 ℃ in 100ml of deionized water, and slowly dropwise adding 10ml of H2PdCl4The solution (Pd content is 0.1g/ml) is stirred for 2.5 h; adjusting the pH value of the solution to 8 by using 10 wt% NaOH solution, reducing the temperature to room temperature, filtering, and washing a filter cake to be neutral by using deionized water; and preparing the filter cake into slurry at 80 ℃, dropwise adding 10ml of 85% hydrazine hydrate solution, stirring for 2h, filtering, washing the filter cake to be neutral by using deionized water, and performing vacuum drying at 100 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon supported palladium catalyst.
Example two
Weighing 10g of mesoporous carbon, wherein the granularity of the mesoporous carbon is 400 meshes, and the specific surface area of the mesoporous carbon is 1200m2Per g, mean pore diameter of 4nm, placing it in NH3Treating at 800 deg.C for 10 hr at a gas flow rate of 2L/H, and introducing 2L/H of H under nitrogen atmosphere2And S, treating for 5 hours at 1000 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon. Preparing the nitrogen/sulfur co-doped mesoporous carbon into slurry with the temperature of 60 ℃ in 100ml of deionized water, and slowingSlowly dropwise adding 6ml of H2PtCl6Stirring the solution (the Pt content is 0.1g/ml) for 2 hours; adjusting the pH value of the solution to 8.5 by using 10 wt% KOH solution, reducing the temperature to room temperature, filtering, and washing a filter cake to be neutral by using deionized water; and preparing the filter cake into slurry at 60 ℃, dropwise adding 10ml of formaldehyde, stirring for 2h, filtering, washing the filter cake to be neutral by using deionized water, and drying in vacuum at 90 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon supported platinum catalyst.
EXAMPLE III
Weighing 10g of mesoporous carbon, wherein the granularity of the mesoporous carbon is 150 meshes, and the specific surface area of the mesoporous carbon is 1000m2G, average pore diameter of 10nm, mixing with 4g urea, treating at 1200 deg.C for 3 hr under helium atmosphere, and introducing 3L/hr of H under nitrogen atmosphere2And S, treating for 5 hours at 600 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon. Preparing the nitrogen/sulfur co-doped mesoporous carbon into slurry at the temperature of 40 ℃ in 100ml of deionized water, and slowly dropwise adding 10ml of Pd (NO)3)2Stirring the solution (Pd content is 0.005g/ml) for 4 h; adjusting the pH value of the solution to 9 by using ammonia water, reducing the temperature to room temperature, filtering, and washing a filter cake to be neutral by using deionized water; and preparing the filter cake into slurry at 40 ℃, dropwise adding 30ml of formic acid, stirring for 4 hours, filtering, washing the filter cake to be neutral by using deionized water, and drying in vacuum at 80 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon supported palladium catalyst.
Example four
Weighing 10g of mesoporous carbon, wherein the granularity of the mesoporous carbon is 200 meshes, and the specific surface area of the mesoporous carbon is 1000m2G, average pore diameter of 20nm, mixing with 8g urea, treating at 500 deg.C for 13 hr under nitrogen atmosphere, and introducing 1L/hr of H under nitrogen atmosphere2And S, treating for 15 hours at 900 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon. Preparing the nitrogen/sulfur co-doped mesoporous carbon into slurry with the temperature of 90 ℃ in 100ml of deionized water, and slowly dropwise adding 10ml of K2PtCl6Stirring the solution (the Pt content is 0.03g/ml) for 1 h; adjusting the pH value of the solution to 9.5 by using 10 wt% KOH solution, reducing the temperature to room temperature, filtering, and washing a filter cake to be neutral by using deionized water; preparing the filter cake into slurry at 30 ℃, dropwise adding 15ml formic acid, stirring for 4h, filtering, washing the filter cake with deionized water tillAnd (4) neutralizing, and drying in vacuum at 100 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon supported platinum catalyst.
EXAMPLE five
Weighing 10g of mesoporous carbon, wherein the granularity of the mesoporous carbon is 600 meshes, and the specific surface area of the mesoporous carbon is 1100m2G, average pore diameter of 15nm, mixing with 10g urea, treating at 600 deg.C for 10 hr under nitrogen atmosphere, and introducing 5L/hr of H under nitrogen atmosphere2And S, treating for 2 hours at 1000 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon. Preparing the nitrogen/sulfur co-doped mesoporous carbon into slurry at the temperature of 70 ℃ in 100ml of deionized water, and slowly dropwise adding 10ml of Na2PdCl4Stirring the solution (the Pd content is 0.02g/ml) for 2 hours; adjusting the pH value of the solution to 8.5 by using 10 wt% NaOH solution, reducing the temperature to room temperature, filtering, and washing a filter cake to be neutral by using deionized water; and preparing the filter cake into slurry at 30 ℃, dropwise adding 3ml of 85 wt% hydrazine hydrate, stirring for 4 hours, filtering, washing the filter cake to be neutral by using deionized water, and performing vacuum drying at 110 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon supported palladium catalyst.
EXAMPLE six
Weighing 10g of mesoporous carbon, wherein the granularity of the mesoporous carbon is 400 meshes, and the specific surface area of the mesoporous carbon is 1300m2G, average pore diameter of 8nm, mixing with 10g urea, treating at 650 deg.C for 6 hr under nitrogen atmosphere, and introducing 1L/hr of H under nitrogen atmosphere2And S, treating at 1000 ℃ for 20h to obtain the nitrogen/sulfur co-doped mesoporous carbon. Preparing the nitrogen/sulfur co-doped mesoporous carbon into slurry with the temperature of 70 ℃ in 100ml of deionized water, and slowly dropwise adding 10ml of H2PtCl6Stirring the solution (the Pt content is 0.015g/ml) for 2 hours; adjusting the pH value of the solution to 8.5 by using 10 wt% NaOH solution, reducing the temperature to room temperature, filtering, and washing a filter cake to be neutral by using deionized water; and preparing the filter cake into slurry at 30 ℃, dropwise adding 3ml of 85 wt% hydrazine hydrate, stirring for 4h, filtering, washing the filter cake to be neutral by using deionized water, and performing vacuum drying at 110 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon supported platinum catalyst.
Examples seven to twelve
Examples seven to twelve examined the performance of different nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalysts prepared in examples one to six in the reaction for preparing N, N-dibenzylethylenediamine by hydrogenation.
Adding 100g of N, N-dibenzylidene ethylenediamine, 100ml of ethyl acetate and 0.8g of nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalyst into a 500ml stainless steel reaction kettle, closing the reaction kettle, replacing air in the reaction kettle with nitrogen for three times, and then replacing with hydrogen for three times; heating to 90 ℃ and hydrogen pressure of 0.8MPa, starting stirring at the stirring speed of 900r/min, and reacting for 1 h; stopping the reaction, cooling to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by gas chromatography. The results of the experiment are shown in table 1.
TABLE 1 catalytic hydrogenation performance of different nitrogen/sulfur co-doped mesoporous carbon supported noble metals
Examples thirteen to seventeen
The thirteen to seventeen examples investigate the reaction performance of the nitrogen/sulfur co-doped mesoporous carbon supported palladium catalyst in the preparation of N, N-dibenzylethylenediamine by catalytic hydrogenation under different hydrogenation reaction conditions. Adding 100g of N, N-dibenzylidene ethylenediamine, 150ml of ethyl acetate and 1.0g of the nitrogen/sulfur co-doped mesoporous carbon supported palladium catalyst prepared in the first embodiment into a 500ml stainless steel reaction kettle, closing the reaction kettle, replacing air in the reaction kettle with nitrogen for three times, and replacing with hydrogen for three times; after the temperature and the hydrogen pressure are increased to the range required by the reaction, stirring is started, the stirring speed is 1200r/min, and the reaction is carried out for 2 hours; stopping the reaction, cooling to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by gas chromatography. The results of the experiment are shown in table 2.
TABLE 2 catalytic performance of nitrogen/sulfur co-doped mesoporous carbon supported palladium catalyst under different hydrogenation reaction conditions
EXAMPLE eighteen
In the eighteenth embodiment, the application performance of the nitrogen/sulfur co-doped mesoporous carbon supported platinum catalyst prepared in the second embodiment in the reaction of preparing N, N-dibenzylethylenediamine by hydrogenation is examined. Adding 100g of N, N-dibenzylidene ethylenediamine, 200ml of ethyl acetate and 1.0g of the nitrogen/sulfur co-doped mesoporous carbon supported palladium catalyst prepared in the first embodiment into a 500ml stainless steel reaction kettle, closing the reaction kettle, replacing air in the reaction kettle with nitrogen for three times, and replacing with hydrogen for three times; heating to 80 deg.C and hydrogen pressure of 0.6MPa, stirring at 900r/min, and reacting for 2 hr; stopping the reaction, cooling to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by gas chromatography. The reaction was continued after the completion of the reaction by adding 0.01g of fresh catalyst of example one each time, and the conditions of the completion were the same, and the results are shown in Table 3.
TABLE 3 application performance of nitrogen/sulfur co-doped mesoporous carbon supported palladium catalyst
Of course, the above is only a typical example of the present application, and besides, the present application may have other embodiments, and all technical solutions formed by using equivalent substitutions or equivalent transformations fall within the scope of the present application.
Claims (8)
1. A method for efficiently preparing N, N-dibenzyl ethylenediamine by catalytic hydrogenation is characterized by comprising the following steps: in a reaction kettle, N, N-dibenzylidene ethylenediamine is subjected to liquid-phase catalytic hydrogenation reaction under the action of a nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalyst to prepare the N, N-dibenzylidene ethylenediamine, and the preparation method of the nitrogen/sulfur co-doped mesoporous carbon comprises the following steps: under an inert atmosphere, firstly, nitrogen-containing compounds are used for high-temperature nitridation treatment of mesoporous carbon, then H2S is used for high-temperature vulcanization treatment, and nitrogen/sulfur doped mesoporous carbon is obtained, wherein the nitrogen-containing compounds are one or more of ammonia gas and urea, and the mass ratio of the nitrogen-containing compounds to the mesoporous carbon is 0.05-10: 1, the mass ratio of the H2S to the mesoporous carbon is (0.5-50): 1, the high-temperature nitriding treatment temperature is 400-1500 ℃, the nitriding treatment time is 0.5-50 h, the high-temperature vulcanizing treatment temperature is 500-1200 ℃, and the vulcanizing treatment time is 1-30 h.
2. The method for efficiently preparing N, N-dibenzylethylenediamine by catalytic hydrogenation according to claim 1, wherein the method for preparing the nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalyst comprises the following steps:
1) weighing nitrogen/sulfur co-doped mesoporous carbon for preparing the catalyst, preparing the nitrogen/sulfur co-doped mesoporous carbon into slurry at the temperature of 20-90 ℃, slowly dropwise adding a solution of a soluble precious metal compound according to the loading amount of the precious metal, and fully and uniformly stirring;
2) after dipping for 0.5-8 h, adding an alkaline solution to adjust the pH value of the solution to 7.5-10.0, cooling the temperature to room temperature, filtering, and washing a filter cake to be neutral by deionized water;
3) and preparing the filter cake into slurry at the temperature of 20-90 ℃, dropwise adding a liquid-phase reducing agent, stirring, filtering, washing the filter cake to be neutral by using deionized water, and performing vacuum drying at the temperature of 70-120 ℃ to obtain the nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalyst.
3. The method for efficiently preparing N, N-dibenzylethylenediamine through catalytic hydrogenation according to claim 2, wherein the noble metal is one or more of Pd and Pt, the soluble noble metal compound is one or more of H2PdCl4, K2PdCl4, Na2PdCl4, Pd (NO3)2, H2PtCl6, K2PtCl6, Na2PtCl6 or Pt (NO3)2, the alkaline solution is one or more of NaOH, KOH, NaHCO3, Na2CO3, KHCO3, K2CO3 or an ammonia solution, the liquid phase reducing agent is one or more of hydrazine hydrate, formic acid, formaldehyde, potassium formate or sodium formate, and the loading amount of the noble metal in the nitrogen/sulfur mesoporous carbon supported noble metal catalyst is 2-10 wt%.
4. The method for efficiently preparing N, N-dibenzylethylenediamine through catalytic hydrogenation according to claim 1, wherein the inert atmosphere is one or more of nitrogen, argon and helium, the particle size of the mesoporous carbon is 100-1000 meshes, the specific surface area is 600-2000 m2/g, and the average pore diameter is 2-20 nm.
5. The method for efficiently preparing N, N-dibenzylidene ethylenediamine through catalytic hydrogenation according to claim 1, wherein the amount of the nitrogen/sulfur co-doped mesoporous carbon supported noble metal catalyst in the liquid-phase catalytic hydrogenation reaction is 0.5-3.0 wt% of the mass of N, N-dibenzylidene ethylenediamine.
6. The method for efficiently preparing N, N-dibenzylidene ethylenediamine through catalytic hydrogenation according to claim 1, wherein ethyl acetate is used as a reaction solvent in the liquid-phase catalytic hydrogenation reaction, and the addition amount of the reaction solvent is 0.5-3.0 ml/g based on the mass of N, N-dibenzylidene ethylenediamine.
7. The method for efficiently preparing N, N-dibenzylethylenediamine through catalytic hydrogenation according to claim 1, wherein the reaction temperature of the liquid-phase catalytic hydrogenation reaction is 50-120 ℃.
8. The method for efficiently preparing N, N-dibenzylethylenediamine through catalytic hydrogenation according to claim 1, wherein the hydrogen pressure is controlled to be 0.2-3.0 MPa in the liquid-phase catalytic hydrogenation reaction.
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| CN112206800B (en) * | 2020-08-31 | 2023-05-23 | 浙江工业大学 | Nitrogen-sulfur doped carbon material supported palladium catalyst, preparation method thereof and application thereof in tetrahydrophthalic anhydride hydrogenation reaction |
| CN112191243A (en) * | 2020-08-31 | 2021-01-08 | 浙江工业大学 | High-dispersion nitrogen-sulfur co-doped catalyst, preparation thereof and application of catalyst in synthesizing N, N-dibenzylethylenediamine |
| CN112403504B (en) * | 2020-12-07 | 2022-04-19 | 厦门大学 | Nitrogen-sulfur co-doped catalyst and preparation method and application thereof |
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