CN113950371A - 过氧化氢合成以及再生催化剂及其制造方法 - Google Patents
过氧化氢合成以及再生催化剂及其制造方法 Download PDFInfo
- Publication number
- CN113950371A CN113950371A CN202080042262.8A CN202080042262A CN113950371A CN 113950371 A CN113950371 A CN 113950371A CN 202080042262 A CN202080042262 A CN 202080042262A CN 113950371 A CN113950371 A CN 113950371A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- magnesium
- cerium
- alumina
- palladium
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 230000008929 regeneration Effects 0.000 title description 18
- 238000011069 regeneration method Methods 0.000 title description 18
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 title description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 35
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011777 magnesium Substances 0.000 claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 33
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 24
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 19
- 239000012224 working solution Substances 0.000 claims abstract description 17
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000001172 regenerating effect Effects 0.000 claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 22
- 238000010304 firing Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- OTBHDFWQZHPNPU-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CCCC2 OTBHDFWQZHPNPU-UHFFFAOYSA-N 0.000 description 5
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- -1 anthraquinone (anthraquinone) series compound Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- RRTQFNGJENAXJJ-UHFFFAOYSA-N cerium magnesium Chemical compound [Mg].[Ce] RRTQFNGJENAXJJ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- KHTIGPKSZNZLNJ-UHFFFAOYSA-N magnesium palladium Chemical compound [Mg].[Pd] KHTIGPKSZNZLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
- B01J2523/22—Magnesium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
- B01J2523/37—Lanthanides
- B01J2523/3712—Cerium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/82—Metals of the platinum group
- B01J2523/824—Palladium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种利用蒽醌法制造过氧化氢以及再生工作溶液的催化剂及其制造方法，公开一种钯、镁以及铈成分被均匀地分布到氧化铝中，或钯成分以环状形态分布到氧化铝球体而镁以及铈成分被均匀地分布到氧化铝中的催化剂及其制造方法。
Description
技术领域
本发明涉及一种利用蒽醌法制造过氧化氢以及再生工作溶液的催化剂及其制造方法。
背景技术
过氧化氢(H202)是在如抛光剂、消毒剂、医药品以及氧化剂等多种领域使用的化学制品。过氧化氢是通过利用氢气以及氧气的直接合成法以及利用蒽醌(anthraquinone)系列化合物连续执行加氢以及氧化工程的蒽醌法进行制造。接下来将对蒽醌法进行简单的描述。
过氧化氢可以通过对向烷基蒽醌(通常被称之为2-乙基-蒽醌、EAQ)溶解到适当的有机溶剂中而获得的工作溶液(working solution)反复执行加氢和氧化的方式进行制造。在重复执行如上所述的加氢以及氧化工程时，作为副产物的四氢蒽醌等将被蓄积在工作溶液中，而且会在催化剂上发生焦炭沉积，从而导致过氧化氢的制造以及再生效率的下降。尤其是，在将作为副产物的四氢蒽醌(THAQ)再生为蒽醌时，可以采用在工作溶液中使用通过在40～150℃的温度下将镁担载到活性氧化铝中并在烧制之前利用氨进行处理而获得的催化剂的技术(公开编号10-2009-0006733)。
发明内容
技术问题
但是，目前仍然需要开发出一种可以在改善再生效率的同时在过氧化氢的制造中促进加氢过程的催化剂。本发明在对蒽醌法进行研究开发的过程中，确认在向含浸有镁以及铈的氧化铝载体担载钯时与未添加铈的催化剂相比，不仅可以提升其再生效率，还可以在蒽醌法中改善加氢效率，从而完成了本发明。此外，还确认在添加铈时其氧气吸附量会增加，因此有利于催化剂的再生。
技术方案
本发明涉及一种不仅可以促进利用蒽醌法的过氧化氢的制造工程中的加氢步骤，还可以改善工作溶液的再生效率的催化剂及其制造方法。
本发明人了解到，当在工作溶液的再生中使用通过将镁以及铈担载到活性氧化铝并烧制之后含浸靶并经过还原而获得的催化剂时，可以有效地实现再生转化。本发明人还惊人地发现，所述催化剂还可以在蒽醌法的过氧化氢的制造工程中作为作为加氢步骤的催化剂使用。
本发明作为利用包括加氢步骤的蒽醌法制造过氧化氢时在加氢步骤中适用的催化剂或用于对利用蒽醌法制造过氧化氢时所使用的工作溶液进行再生的催化剂，提供一种钯、镁以及铈成分被均匀地分布到氧化铝中，或钯成分被分布到氧化铝核心而镁以及铈成分被均匀地分布到氧化铝中的催化剂。此外，本发明作为催化剂的制造方法，提供一种利用镁以及铈水溶液对活性氧化铝进行含浸处理并烧制之后利用钯水溶液进行处理而担载钯成分的催化剂制造方法，非限制性地，在本发明中含浸到所述活性氧化铝中的镁以及铈的含量与含浸有镁以及铈的活性氧化铝的重量相比可以分别为1～10重量％以及0.10～0.25重量％，而所述烧制之后担载的钯含量与担载之后的催化剂的重量相比可以是0.1～10重量％。
有益效果
通过本发明的加氢催化剂，可以改善反应性以及耐久性并借此提升蒽醌法的整体效率，而且可以通过再生催化剂防止蒽醌或有机溶剂发生劣化并将无法生成过氧化氢的副产物选择性地再生为有效的蒽醌。
附图说明
图1对在实施例中制造的催化剂粉末(D90＝150μm)进行了图示。
图2是粉末内的成分分布图，镁以及铈被均匀分布到载体内部，而钯则主要呈现出了与载体外廓相距一定间隔并以10μm至20μm的厚度分布的环状(ring)结构体。
图3是适用实施例的另一结构的粉末成分分布图，镁以及铈被均匀分布到载体内部，且钯也均匀分布到整个催化剂中。
图4是适用本发明的催化剂的蒽醌加氢评估结果。
图5对适用本发明的催化剂中添加铈时的程序升温氧化(TPO)结果进行了图示。
具体实施方式
接下来，将对本发明进行详细的说明。
本发明涉及一种在通过将镁以及铈担载到活性氧化铝并烧制之后含浸靶并经过还原而获得的催化剂及其制造方法，已确认在将其适用于工作溶液的再生以及蒽醌制造工程中的加氢步骤时，可以有效地实现再生转化以及加氢。接下来，将对本发明的特征步骤进行说明。
1)在作为载体的活性氧化铝中担载镁以及铈的步骤
制造相当于载体所具有的总气孔体积的Mg-Ce络合物，并利用担载法将其含浸到载体中。在含浸之后通过在空气(Air)环境下使氧化铝流动而执行均质化过程，从而使得载体内的金属浓度变得相同，接下来在100～150℃下执行24小时的干燥过程。在干燥之后在空气(Air)环境下以200～400℃第一次去除有机物以及氮氧化物之后，在500～700℃执行烧制过程。当在热处理步骤中以500℃以下的温度进行热处理时，则可能会导致担载金属不会转化成金属氧化物质的问题，而当在以700℃以上的温度进行热处理时，则可能会因为金属之间发生凝聚而导致催化剂活性降低的问题。含浸到活性氧化铝中的镁以及铈的含量与烧制之后的含浸有镁以及铈的活性氧化铝的重量相比可以分别为1～10重量％以及0.10～0.25重量％，当镁含量为下限值以下时，可能会导致催化剂的耐久性以及热血稳定性下降的问题，而当镁含量为上限值以上时，可能会导致活性物质即钯的分散度下降的问题。此外，当铈的含量为下限值以下时，可能会导致催化剂再生时的效率下降的问题，而当铈的含量为上限值以上时，反而可能会导致催化剂活性下降的问题。
2)向镁-铈-氧化铝的复合氧化物担载钯活性金属的步骤
将1％重量的饱和钯络合剂水溶液对所述镁-铈-氧化铝的复合氧化物进行处理并借此担载到载体中，接下来通过对其进行还原而获得最终催化剂。利用钯水溶液的担载温度为50～80℃并进行30分钟～20小时的处理为宜，而在还原时以40～70℃的温度进行30分钟～20小时的处理为宜。所担载的钯含量与担载之后的催化剂的重量相比可以是0.1～10重量％。当所担载的钯含量小于0.1重量％时，可能会导致初期性能下降以及耐久性减少的问题，而当所担载的钯含量大于10重量％时，可能会因为钯粒子之间的凝聚现象而导致分散度降低以及活性下降的问题。
接下来，将对具体的示例进行记载。
实施例1
作为在实施例1中使用的载体，使用了γ氧化铝，在以600℃对勃姆石(制造企业：德国BASF，比表面积：250m2/g，气孔体积：0.55cm3/g，平均气孔大小：8.6nm)进行烧制后使用。烧制之后的氧化铝为γ相，其比表面积为180m2/g。
作为镁前驱体使用了硝酸镁(Mg(NO3)2.6H2O)，作为铈的前驱体使用了硝酸铈(Ce(NO3)3.6H2O)，而作为活性金属前驱体使用了四氯合钯酸(H2PdCl4)。
首先，将相当于催化剂整体重量的5.0％的硝酸镁以及相当于0.5％的硝酸铈混合到离子水中。
将所制造的镁-铈复合溶液利用初始润湿法含浸到载体中。将担载有镁-铈的组合物在空气环境下以550℃执行2小时的热处理过程，从而对金属进行固定。
接下来，向200ml的水添加100g的担载有镁-铈的氧化铝组合物，然后添加相当于催化剂整体重量的1.0％的钯前驱体以及相当于3.0％的乙二醇以及盐酸并在搅拌的同时升温至80℃，接下来在所述温度下维持30分钟。
催化还原过程是通过向担载有镁-铈-钯的复合体投入还原剂的方式执行。作为还原剂，使用了甲酸钠(NaCOOH)。
图1对所制造的催化剂粉末(D90＝150μm)进行了图示，镁以及铈被均匀分布到载体内部，而钯则主要呈现出了与载体外廓相距一定间隔并以10μm至20μm的厚度分布的环状(ring)结构体(图2)。如上所述的环状结构体与表面相距5～8μm的间隔并以环状形态存在，在用于制造过氧化氢的流化床反应中将有利于防止因为冲击而导致的物理性损失现象。
实施例2
在实施例2中，利用除铈之外的镁-钯复合体进行制造，而且镁以及钯的组成以与实施例1相同的方式进行制造。
实施例3
在实施例3中，除了以烧制之后的氧化铈的含量与整体重量相比为2.0％的方式进行制造之外，按照与实施例1相同的方法制造催化剂。与实施例1类似，镁以及铈被均匀分布到载体内部，而钯主要是以与载体外廓相距一定间隔的20μm的厚度分布。
实施例4
在实施例4中，按照与实施例1相同的组成进行制造。但是，在担载钯时将乙二醇以及盐酸的浓度增加至2倍。在所述催化剂中，镁以及铈被均匀地分布到载体内部，而钯也被均匀地分布到整个催化剂中(图3)。
比较例1
在比较例1中，除了将在实施例1中使用的载体在850℃下进行烧制后使用之外，按照与实施例1相同的方法制造催化剂。(氧化铝的分析结果为θ相，其比表面积为120m2/g。)
镁以及铈被均匀分布到载体内部，而钯主要是以与载体外廓相距一定间隔的40μm的厚度分布。
比较例2
在比较例2中，除了将载体以850℃进行烧制制造之外，按照与实施例2相同的方法制造催化剂。在所述催化剂中，镁以及铈被均匀分布到载体内部，而钯主要是以与载体外廓相距一定间隔的40μm的厚度分布。
比较例3
在比较例3中，使用与比较例1相同的组成以及载体进行制造。但是，在担载钯时将乙二醇以及盐酸的浓度增加至2倍。在所述催化剂中，镁以及铈被均匀地分布到载体内部，而钯也被均匀地分布到整个催化剂中。
性能评估
在本发明中，催化剂的性能评估方法是通过两种方法执行。
第一种是用于通过氧化工程制造过氧化氢的蒽醌加氢反应，而第二种是对通过加氢反应中的副反应生成的工作溶液进行再生的再生反应。
1)加氢性能评估
为了对催化剂的加氢活性进行测定而执行了加氢反应，而反应器利用水晶材质的搅拌式反应系统进行了评估。工作溶液是通过在1L的将1,3,5-三甲基苯(1,3,5-trimethylbenzene)和磷酸三辛酯(trioctyl phosphate)按照1:1的体积比混合的溶液中溶解90g的2-乙基蒽醌(2-EAQ)的方式进行制造。为了进行评估，向30ml的工作溶液添加0.4g的催化剂并投入到反应器中，并将反应器的温度维持在60℃，而搅拌器维持500rpm。为了执行加氢反应，在通过利用氮气对反应器内部进行吹扫而去除反应器内部的氢气之后注入了氢气。通过填充氢气而使得反应器内部的压力达到0.3MPa。将经过加氢的样本在大气压力以及室温下利用O2进行20分钟的氧化之后，利用去离子水进行5次萃取。将所获得的过氧化氢水溶液移动到气相色谱仪(GC)中，接下来通过火焰离子化检测器(FID，Flameionization detector)执行了定量分析。
对2-乙基氢蒽醌(EAQH2)的选择度是根据过氧化氢与2-乙基四氢氢蒽醌(H4EAQH2，ethyltetrahydroanthrahydroquinone)之外的副产物的量进行计算。
对2-乙基氢蒽醌(EAQH2)的选择度＝[所生成的2-乙基氢蒽醌(EAQH2)的选择度/发生反应的乙基蒽醌(EAQ)]×100％
发生反应的乙基蒽醌(EAQ)＝[2-乙基氢蒽醌(EAQH2)+2-乙基四氢氢蒽醌(H4EAQH2)+副反应物]
2)四氢蒽醌(THAQ，Tetrahydroanthraquinone)再生性能评估
为了对催化剂的再生效率进行测定而执行了再生评估反应，而反应器利用不锈钢(SUS)材质的搅拌式反应系统进行了评估。向圆形搅拌式反应器投入镁条，接下来向50g的在加氢反应时所产生的副产物工作溶液(Working solution)投入10g的催化剂并对其再生效率进行了测定。接下来，利用液相色谱仪(LC)进行测定。其结果如下述表1所示。
【表1】
此外，向催化剂添加铈时的程序升温氧化(TPO)结果如下所示。即，通过向完成还原的催化剂注入O2进行升温的结果可以确认，添加Ce的催化剂的O2吸附量与未添加的催化剂相比相对较高，这表明在催化剂中会因为工作溶液而发生焦炭(Coke)沉积并需要周期性地进行再生，但是在将所沉积的焦炭(Coke)进行再生时，可以通过向催化剂添加Ce而提升再生效率。
Claims (6)
1.一种催化剂，其特征在于：
作为利用包括加氢步骤的蒽醌法制造过氧化氢时在加氢步骤中适用的催化剂，钯、镁以及铈成分被均匀地分布到氧化铝中，或钯成分以环状形态分布到氧化铝球体而镁以及铈成分被均匀地分布到氧化铝中。
2.一种催化剂，其特征在于：
作为用于对利用蒽醌法制造过氧化氢时所使用的工作溶液进行再生的催化剂，钯、镁以及铈成分被均匀地分布到氧化铝中，或钯成分以环状形态分布到氧化铝球体而镁以及铈成分被均匀地分布到氧化铝中。
3.根据权利要求1或权利要求2所述的催化剂，其特征在于：
所述环状形态与氧化铝球体表面相距5～8㎛并以10～20㎛的厚度形成。
4.一种催化剂的制造方法，其特征在于：
作为根据权利要求1或权利要求2所述的催化剂的制造方法，利用镁以及铈水溶液对活性氧化铝进行含浸处理并烧制之后利用钯水溶液进行处理而担载钯成分。
5.根据权利要求4所述的催化剂的制造方法，其特征在于：
含浸到所述活性氧化铝中的镁以及铈的含量与烧制之后的含浸有镁以及铈的活性氧化铝的重量相比分别为1～10重量%以及0.10～0.25重量%。
6.根据权利要求4所述的催化剂的制造方法，其特征在于：
所述烧制之后担载的钯含量与担载之后的催化剂的重量相比为0.1～10重量%。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2019-0074204 | 2019-06-21 | ||
| KR1020190074204A KR102220225B1 (ko) | 2019-06-21 | 2019-06-21 | 과산화수소 합성 및 재생 촉매 및 이의 제조방법 |
| PCT/KR2020/007437 WO2020256328A1 (ko) | 2019-06-21 | 2020-06-09 | 과산화수소 합성 및 재생 촉매 및 이의 제조방법 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113950371A true CN113950371A (zh) | 2022-01-18 |
| CN113950371B CN113950371B (zh) | 2023-12-29 |
Family
ID=74037334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080042262.8A Active CN113950371B (zh) | 2019-06-21 | 2020-06-09 | 过氧化氢合成以及再生催化剂及其制造方法 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20220331789A1 (zh) |
| EP (1) | EP3988210A4 (zh) |
| JP (1) | JP7336539B2 (zh) |
| KR (1) | KR102220225B1 (zh) |
| CN (1) | CN113950371B (zh) |
| WO (1) | WO2020256328A1 (zh) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001170485A (ja) * | 1999-12-16 | 2001-06-26 | Asahi Kasei Corp | アントラキノン類の水素化触媒 |
| JP2001300327A (ja) * | 2000-04-21 | 2001-10-30 | Mitsubishi Gas Chem Co Inc | 担持触媒及びその製造方法 |
| JP2006511334A (ja) * | 2002-12-20 | 2006-04-06 | ハイドロカーボン テクノロジーズ インコーポレイテッド | 使用済の担持された金属触媒の再生 |
| JP2009034663A (ja) * | 2007-07-11 | 2009-02-19 | Mitsubishi Gas Chem Co Inc | 過酸化水素製造に用いる作動溶液の再生触媒の製造方法 |
| CN101497040A (zh) * | 2008-02-03 | 2009-08-05 | 中国科学院大连化学物理研究所 | 一种用于双氧水生产的整体催化剂及其制备和应用 |
| CN102451685A (zh) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | 一种选择性加氢催化剂及其制备方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5853693A (en) * | 1996-04-03 | 1998-12-29 | Mitsubishi Gas Chemical Company, Inc. | Hydrogenation catalyst for production of hydrogen peroxide, and method for preparation of same |
| JPH09271668A (ja) * | 1996-04-03 | 1997-10-21 | Mitsubishi Gas Chem Co Inc | 過酸化水素製造に使用される水素化触媒 |
| TW377306B (en) * | 1996-12-16 | 1999-12-21 | Asahi Chemical Ind | Noble metal support |
| FI108432B (fi) | 2000-03-06 | 2002-01-31 | Kemira Chemicals Oy | Ty÷liuoksen regenerointi vetyperoksidin tuotantoprosessissa |
| TWI383951B (zh) | 2006-05-09 | 2013-02-01 | Mitsubishi Gas Chemical Co | 包含動作溶液之再生步驟的過氧化氫之製造方法 |
| CN101433841B (zh) | 2007-12-13 | 2010-04-14 | 中国石油天然气股份有限公司 | 一种选择性加氢催化剂及其制备方法 |
| CN101406837A (zh) | 2008-10-24 | 2009-04-15 | 傅骐 | 具有抗碱性能的生产过氧化氢用钯催化剂的制备方法及产品 |
| CN107189812B (zh) * | 2017-06-02 | 2019-01-25 | 钦州学院 | 一种裂解c6-c8馏分选择性加氢的方法 |
-
2019
- 2019-06-21 KR KR1020190074204A patent/KR102220225B1/ko active IP Right Grant
-
2020
- 2020-06-09 WO PCT/KR2020/007437 patent/WO2020256328A1/ko active Application Filing
- 2020-06-09 US US17/619,701 patent/US20220331789A1/en active Pending
- 2020-06-09 CN CN202080042262.8A patent/CN113950371B/zh active Active
- 2020-06-09 JP JP2021571400A patent/JP7336539B2/ja active Active
- 2020-06-09 EP EP20827643.6A patent/EP3988210A4/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001170485A (ja) * | 1999-12-16 | 2001-06-26 | Asahi Kasei Corp | アントラキノン類の水素化触媒 |
| JP2001300327A (ja) * | 2000-04-21 | 2001-10-30 | Mitsubishi Gas Chem Co Inc | 担持触媒及びその製造方法 |
| JP2006511334A (ja) * | 2002-12-20 | 2006-04-06 | ハイドロカーボン テクノロジーズ インコーポレイテッド | 使用済の担持された金属触媒の再生 |
| JP2009034663A (ja) * | 2007-07-11 | 2009-02-19 | Mitsubishi Gas Chem Co Inc | 過酸化水素製造に用いる作動溶液の再生触媒の製造方法 |
| CN101497040A (zh) * | 2008-02-03 | 2009-08-05 | 中国科学院大连化学物理研究所 | 一种用于双氧水生产的整体催化剂及其制备和应用 |
| CN102451685A (zh) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | 一种选择性加氢催化剂及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7336539B2 (ja) | 2023-08-31 |
| EP3988210A4 (en) | 2023-07-05 |
| EP3988210A1 (en) | 2022-04-27 |
| KR20200145337A (ko) | 2020-12-30 |
| CN113950371B (zh) | 2023-12-29 |
| US20220331789A1 (en) | 2022-10-20 |
| WO2020256328A1 (ko) | 2020-12-24 |
| JP2022535021A (ja) | 2022-08-04 |
| KR102220225B1 (ko) | 2021-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5853693A (en) | Hydrogenation catalyst for production of hydrogen peroxide, and method for preparation of same | |
| CN111215060A (zh) | 一种负载型铂族金属单原子催化剂的制备及其在脱氧反应中的应用 | |
| JP2841411B2 (ja) | アンモニアから水素の取得方法 | |
| CN111054424B (zh) | 一种含钯单原子整体催化剂及其制备方法和用途 | |
| CN107626329B (zh) | 一种铂/氧化铝催化剂及其制备方法和应用 | |
| EP0611126A1 (en) | A hydrogenation catalyst for use in a hydrogen peroxide process, and a method for the preparation thereof | |
| CN117380183B (zh) | 一种负载型钯纳米颗粒催化剂的制备方法及其应用 | |
| US3879311A (en) | Catalyst regeneration | |
| CN113634275B (zh) | 一种催化加氢脱氯用催化剂及其制备方法和应用 | |
| CN114345408A (zh) | 黑磷负载钯纳米颗粒复合材料及其制备方法 | |
| CN112452340B (zh) | 一种用于丙炔选择性加氢制备丙烯的催化剂、其制备方法及应用 | |
| CN113950371B (zh) | 过氧化氢合成以及再生催化剂及其制造方法 | |
| CN110721707B (zh) | 一种合成气低温脱氧催化剂及其制备和应用 | |
| CN112191243A (zh) | 高分散的氮硫共掺杂催化剂及其制备与合成n,n-二苄基乙二胺的应用 | |
| CN112191244B (zh) | 一种活性炭负载的金基催化剂及其制备方法和在乙炔加氢中的应用 | |
| JP2841410B2 (ja) | アンモニア分解用触媒 | |
| US20210370274A1 (en) | ACTIVATED CARBON/Pd-Ga LIQUID ALLOY COMPOSITE CATALYST, PREPARATION METHOD AND USE THEREOF | |
| CN109433200B (zh) | 一种稀硝酸还原低负载量贵金属催化剂、制备及应用 | |
| JP2001300327A (ja) | 担持触媒及びその製造方法 | |
| CN113134372B (zh) | 一种耐co蒽醌加氢催化剂及其制备方法 | |
| CN116583347A (zh) | 过氧化氢合成以及再生催化剂 | |
| CN111054383A (zh) | 用于有机液体储氢材料脱氢反应的催化剂及其制备方法 | |
| KR102464147B1 (ko) | 과산화수소 합성용 작동용액의 재생 촉매 | |
| CN112439432B (zh) | 一种蒽醌加氢催化剂及其制备方法 | |
| CN116265085A (zh) | 一种多功能浆态床蒽醌加氢催化剂及其应用 |
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 |