CN107001218B - 氢甲酰化方法 - Google Patents

氢甲酰化方法 Download PDF

Info

Publication number
CN107001218B
CN107001218B CN201580064234.5A CN201580064234A CN107001218B CN 107001218 B CN107001218 B CN 107001218B CN 201580064234 A CN201580064234 A CN 201580064234A CN 107001218 B CN107001218 B CN 107001218B
Authority
CN
China
Prior art keywords
evaporator
stream
catalyst
partial pressure
kpa
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
Application number
CN201580064234.5A
Other languages
English (en)
Chinese (zh)
Other versions
CN107001218A (zh
Inventor
M·A·布莱默
G·R·菲利普斯
T·C·埃森施密特
I·B·考克斯
R·亨特尔利
M·J·班布里奇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Technology Investments LLC
Original Assignee
Dow Technology Investments LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Technology Investments LLC filed Critical Dow Technology Investments LLC
Publication of CN107001218A publication Critical patent/CN107001218A/zh
Application granted granted Critical
Publication of CN107001218B publication Critical patent/CN107001218B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00033—Continuous processes
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
CN201580064234.5A 2014-12-04 2015-11-18 氢甲酰化方法 Active CN107001218B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201462087572P 2014-12-04 2014-12-04
US62/087572 2014-12-04
PCT/US2015/061332 WO2016089602A1 (en) 2014-12-04 2015-11-18 Hydroformylation process

Publications (2)

Publication Number Publication Date
CN107001218A CN107001218A (zh) 2017-08-01
CN107001218B true CN107001218B (zh) 2021-02-26

Family

ID=54705909

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201580064234.5A Active CN107001218B (zh) 2014-12-04 2015-11-18 氢甲酰化方法

Country Status (13)

Country Link
US (1) US10023516B2 (cg-RX-API-DMAC10.html)
EP (1) EP3230248B1 (cg-RX-API-DMAC10.html)
JP (2) JP7128622B2 (cg-RX-API-DMAC10.html)
KR (1) KR102507703B1 (cg-RX-API-DMAC10.html)
CN (1) CN107001218B (cg-RX-API-DMAC10.html)
BR (1) BR112017011447B1 (cg-RX-API-DMAC10.html)
CA (1) CA2969527C (cg-RX-API-DMAC10.html)
MX (1) MX381950B (cg-RX-API-DMAC10.html)
MY (1) MY184826A (cg-RX-API-DMAC10.html)
PL (1) PL3230248T3 (cg-RX-API-DMAC10.html)
RU (1) RU2699368C2 (cg-RX-API-DMAC10.html)
TW (1) TWI586644B (cg-RX-API-DMAC10.html)
WO (1) WO2016089602A1 (cg-RX-API-DMAC10.html)

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3374340B1 (en) * 2015-11-10 2021-12-29 Dow Technology Investments LLC Process for producing aldehydes
CA3014177C (en) 2016-02-11 2023-12-12 Dow Technology Investments Llc Processes for converting olefins to alcohols, ethers, or combinations thereof
CN107469860B (zh) * 2017-08-22 2020-05-19 中国海洋石油集团有限公司 一种提高铑/双亚膦酸酯催化剂稳定性的方法
TWI793216B (zh) 2017-12-07 2023-02-21 美商陶氏科技投資公司 氫甲醯化方法
CN113179638B (zh) * 2018-11-29 2023-11-28 陶氏技术投资有限责任公司 加氢甲酰化工艺
GB201907659D0 (en) * 2019-05-30 2019-07-17 Johnson Matthey Davy Technologies Ltd Process
US20210380510A1 (en) * 2020-06-05 2021-12-09 SCION Holdings LLC Branched Compounds
US20230159422A1 (en) 2020-06-05 2023-05-25 SCION Holdings LLC Alcohols Production
US12221404B2 (en) 2020-06-05 2025-02-11 SCION Holdings LLC Composition comprising branched aldehydes
US11396488B2 (en) * 2020-07-30 2022-07-26 Evonik Operations Gmbh Process for preparing aldehydes and separation of the catalyst system by membrane separation
GB202012930D0 (en) 2020-08-19 2020-09-30 Johnson Matthey Davy Technologies Ltd Process for hydroformylation with removal of dissolved hydrogen
KR20230087523A (ko) 2020-10-13 2023-06-16 다우 실리콘즈 코포레이션 알데히드 작용기를 갖는 유기규소 화합물의 제조
CN112403401B (zh) * 2020-11-06 2022-06-21 中国海洋石油集团有限公司 一种烯烃氢甲酰化制醛中醛和催化剂分离的装置和方法
US12698251B2 (en) 2020-12-14 2026-08-04 Dow Technology Investments Llc Processes to improve catalytic metal accountability in hydroformylation processes
US12145904B2 (en) 2020-12-17 2024-11-19 SCION Holdings LLC Branched products
WO2023060155A1 (en) 2021-10-06 2023-04-13 Dow Global Technologies Llc Preparation of propylimine-functional organosilicon compounds and primary aminopropyl-functional organosilicon compounds
WO2023060153A1 (en) 2021-10-06 2023-04-13 Dow Global Technologies Llc Preparation of amino-functional organosilicon compounds
CN118019747A (zh) 2021-10-06 2024-05-10 陶氏环球技术有限责任公司 丙基亚胺官能化有机硅化合物和伯氨基丙基官能化有机硅化合物的制备
CN118103532A (zh) 2021-11-11 2024-05-28 陶氏技术投资有限责任公司 用于从加氢甲酰化过程中回收铑的方法
JP2024543086A (ja) 2021-11-22 2024-11-19 ダウ グローバル テクノロジーズ エルエルシー カルビノール官能基を有する有機ケイ素化合物の調製
CN118338965A (zh) 2021-12-16 2024-07-12 陶氏技术投资有限责任公司 包含此类化合物的过渡金属络合物加氢甲酰化催化剂前体组合物和加氢甲酰化方法
US20250128245A1 (en) 2021-12-16 2025-04-24 Dow Technology Investments Llc Compounds, transition metal complex hydroformylation catalyst precuror compositions comprising such compounds, and hydroformylation processes
JP2025509182A (ja) 2022-03-21 2025-04-11 ダウ グローバル テクノロジーズ エルエルシー カルボキシ官能性を有する有機ケイ素化合物の調製
JP2025512331A (ja) 2022-04-13 2025-04-17 ダウ グローバル テクノロジーズ エルエルシー ポリエーテル官能性有機ケイ素化合物の製造
KR20250003711A (ko) 2022-04-13 2025-01-07 다우 글로벌 테크놀로지스 엘엘씨 실리콘 ― 비닐에스테르 관능성 화합물 및 이의 제조 방법 및 퍼스널 케어 조성물에서의 용도
EP4508054A1 (en) 2022-04-13 2025-02-19 Dow Global Technologies LLC Preparation of organosilicon compounds with vinylester functionality
JP2025512318A (ja) 2022-04-13 2025-04-17 ダウ シリコーンズ コーポレーション 組成物、ウレタンプレポリマー、並びに関連の方法及び使用
CN114773172B (zh) * 2022-06-20 2022-10-18 中海油天津化工研究设计院有限公司 一种烯烃氢甲酰化制醛工艺优化方法
GB202213997D0 (en) 2022-09-26 2022-11-09 Johnson Matthey Davy Technologies Ltd Parallel zone hydroformylation reaction
CN120225491A (zh) 2022-12-06 2025-06-27 陶氏技术投资有限责任公司 控制再循环催化剂料流中的重质物的方法
GB202303617D0 (en) 2023-03-13 2023-04-26 Johnson Matthey Davy Technologies Ltd Method and apparatus for producing aldehyde
CN121532373A (zh) 2023-08-03 2026-02-13 陶氏技术投资有限责任公司 用于改善基于铑/亚磷酸酯的均相加氢甲酰化催化剂活性的方法
KR20260045840A (ko) 2023-08-03 2026-04-03 다우 테크놀로지 인베스트먼츠 엘엘씨. 하이드로포르밀화 공정
EP4762112A1 (en) 2023-08-14 2026-06-24 Dow Global Technologies Llc Cobalt catalyzed hydroformylation of vinyl-functional polyorganosiloxanes
WO2025170891A1 (en) * 2024-02-06 2025-08-14 Eastman Chemical Company Composition of matter for gas-stripping oxo aldehydes hydroformylation process
WO2025170897A1 (en) * 2024-02-06 2025-08-14 Eastman Chemical Company Optimized gas-stripping hydroformylation process for oxo aldehydes
WO2025170887A1 (en) * 2024-02-06 2025-08-14 Eastman Chemical Company Gas distribution in gas-stripping hydroformylation reactor for oxo aldehydes
WO2025170886A1 (en) * 2024-02-06 2025-08-14 Eastman Chemical Company Purge for a gas-stripping hydroformylation reactor for oxo aldehydes

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4774361A (en) * 1986-05-20 1988-09-27 Union Carbide Corporation Transition metal complex catalyzed reactions

Family Cites Families (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415906A (en) 1964-05-29 1968-12-10 Hooker Chemical Corp Phosphite phospholane and phosphorinane compounds
US3527809A (en) 1967-08-03 1970-09-08 Union Carbide Corp Hydroformylation process
US4148830A (en) 1975-03-07 1979-04-10 Union Carbide Corporation Hydroformylation of olefins
DE2646792C2 (de) 1975-10-23 1985-05-09 Mitsubishi Petrochemical Co., Ltd., Tokio/Tokyo Verfahren zur Herstellung einer α-(arylsubstituierten)-Propionsäure und/oder eines Esters derselben
US4247486A (en) 1977-03-11 1981-01-27 Union Carbide Corporation Cyclic hydroformylation process
US4518809A (en) 1981-06-11 1985-05-21 Monsanto Company Preparation of pentyl nonanols
US4528403A (en) 1982-10-21 1985-07-09 Mitsubishi Chemical Industries Ltd. Hydroformylation process for preparation of aldehydes and alcohols
GB8334359D0 (en) 1983-12-23 1984-02-01 Davy Mckee Ltd Process
ZA851189B (en) * 1984-02-17 1985-09-25 Union Carbide Corp Transition metal complex catalyzed reactions
US4599206A (en) 1984-02-17 1986-07-08 Union Carbide Corporation Transition metal complex catalyzed reactions
US5110990A (en) 1984-03-30 1992-05-05 Union Carbide Chemicals & Plastics Technology Corporation Process for recovery of phosphorus ligand from vaporized aldehyde
US4567302A (en) 1984-07-20 1986-01-28 Angus Chemical Polymeric quaternary ammonium salts possessing antimicrobial activity and methods for preparation and use thereof
US4737588A (en) 1984-12-28 1988-04-12 Union Carbide Corporation Transition metal complex catalyzed reactions
US4748261A (en) 1985-09-05 1988-05-31 Union Carbide Corporation Bis-phosphite compounds
US4668651A (en) 1985-09-05 1987-05-26 Union Carbide Corporation Transition metal complex catalyzed processes
US4885401A (en) 1985-09-05 1989-12-05 Union Carbide Corporation Bis-phosphite compounds
US4835299A (en) 1987-03-31 1989-05-30 Union Carbide Corporation Process for purifying tertiary organophosphites
US5113022A (en) 1988-08-05 1992-05-12 Union Carbide Chemicals & Plastics Technology Corporation Ionic phosphites used in homogeneous transition metal catalyzed processes
US5001274A (en) 1989-06-23 1991-03-19 Union Carbide Chemicals And Plastics Company Inc. Hydroformylation process
US5277532A (en) 1989-07-31 1994-01-11 Cefin S.P.A. Mechanical acceleration device in can welding machines
DE4026406A1 (de) 1990-08-21 1992-02-27 Basf Ag Rhodiumhydroformylierungskatalysatoren mit bis-phosphit-liganden
US5179055A (en) 1990-09-24 1993-01-12 New York University Cationic rhodium bis(dioxaphosphorus heterocycle) complexes and their use in the branched product regioselective hydroformylation of olefins
US5102505A (en) 1990-11-09 1992-04-07 Union Carbide Chemicals & Plastics Technology Corporation Mixed aldehyde product separation by distillation
TW213465B (cg-RX-API-DMAC10.html) 1991-06-11 1993-09-21 Mitsubishi Chemicals Co Ltd
US5360938A (en) 1991-08-21 1994-11-01 Union Carbide Chemicals & Plastics Technology Corporation Asymmetric syntheses
DE4204808A1 (de) 1992-02-18 1993-08-19 Basf Ag Verfahren zur herstellung von (omega)-formylalkancarbonsaeureestern
US5312996A (en) 1992-06-29 1994-05-17 Union Carbide Chemicals & Plastics Technology Corporation Hydroformylation process for producing 1,6-hexanedials
US5364950A (en) 1992-09-29 1994-11-15 Union Carbide Chimicals & Plastics Technology Corporation Process for stabilizing phosphite ligands in hydroformylation reaction mixtures
FR2700535B1 (fr) 1993-01-19 1995-04-14 Hoechst France Procédé continu de fabrication industrielle du diméthoxyéthanal.
US5426238A (en) 1993-06-10 1995-06-20 Mitsubishi Kasei Corporation Method for producing an aldehyde
BE1008017A3 (nl) 1994-01-06 1995-12-12 Dsm Nv Werkwijze voor de bereiding van 5-formylvaleriaanzure ester.
US5756855A (en) 1994-08-19 1998-05-26 Union Carbide Chemicals & Plastics Technology Corporation Stabilization of phosphite ligands in hydroformylation process
US5648553A (en) 1994-12-09 1997-07-15 Mitsubishi Chemical Corporation Method for producing aldehydes
DE19530698A1 (de) 1995-08-21 1997-02-27 Basf Ag Verfahren zur Aufarbeitung eines flüssigen Hydroformylierungsaustrags
US5744650A (en) 1995-12-06 1998-04-28 Union Carbide Chemicals & Plastics Technology Corporation Metal-Ligand complex catalyzed processes
US5731472A (en) 1995-12-06 1998-03-24 Union Carbide Chemicals & Plastics Technology Corporation Metal-ligand complex catalyzed processes
JP3812095B2 (ja) 1997-10-28 2006-08-23 三菱化学株式会社 アルデヒド類の製造方法及びこれに用いるビスホスファイト
DE19913352A1 (de) 1999-03-24 2000-09-28 Basf Ag Katalysator, umfassend einen Komplex eines Metalls der VIII. Nebengruppe auf Basis eines Phospinamiditliganden
DE10048301A1 (de) * 2000-09-29 2002-04-11 Oxeno Olefinchemie Gmbh Stabilisierung von Rhodiumkatalysatoren für die Hydroformylierung von Olefinen
US6841502B2 (en) 2002-04-24 2005-01-11 Symyx Technologies, Inc. Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
IN2007CN00473A (cg-RX-API-DMAC10.html) 2004-08-02 2007-08-24 Union Carbide Chem Plastic
BRPI0808297B1 (pt) 2007-03-20 2017-02-07 Dow Technology Investments Llc processo de hidroformilação
KR101060375B1 (ko) 2007-05-29 2011-08-29 주식회사 엘지화학 하이드로포르밀화 방법 및 장치
WO2010003073A1 (en) 2008-07-03 2010-01-07 Dow Technology Investments Llc Process of controlling heavies in a recycle catalyst stream
KR101310552B1 (ko) 2010-04-20 2013-09-23 주식회사 엘지화학 올레핀의 하이드로포르밀화에 의한 알데히드 제조 방법
WO2011146291A1 (en) 2010-05-17 2011-11-24 Dow Global Technologies Llc Process for selectively polymerizing ethylene and catalyst therefor
CN102826972B (zh) 2011-06-17 2015-05-13 中国石油化工股份有限公司 一种烯烃氢甲酰化反应制备醛的方法
IN2014CN04444A (cg-RX-API-DMAC10.html) 2011-12-20 2015-09-04 Dow Global Technologies Llc
DE102012223572A1 (de) 2012-12-18 2014-06-18 Evonik Industries Ag Steuerung der Viskosität von Reaktionslösungen in Hydroformylierungverfahren

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4774361A (en) * 1986-05-20 1988-09-27 Union Carbide Corporation Transition metal complex catalyzed reactions

Also Published As

Publication number Publication date
BR112017011447A2 (pt) 2018-02-27
RU2699368C2 (ru) 2019-09-05
WO2016089602A1 (en) 2016-06-09
CN107001218A (zh) 2017-08-01
RU2017121307A3 (cg-RX-API-DMAC10.html) 2019-02-01
MX2017006792A (es) 2017-09-08
MX381950B (es) 2025-03-13
TWI586644B (zh) 2017-06-11
CA2969527A1 (en) 2016-06-09
KR20170093152A (ko) 2017-08-14
CA2969527C (en) 2023-08-22
PL3230248T3 (pl) 2020-05-18
EP3230248B1 (en) 2019-12-25
US20170355656A1 (en) 2017-12-14
RU2017121307A (ru) 2018-12-19
BR112017011447B1 (pt) 2020-12-15
JP2017537918A (ja) 2017-12-21
JP7128622B2 (ja) 2022-08-31
KR102507703B1 (ko) 2023-03-09
TW201620863A (zh) 2016-06-16
JP2021008477A (ja) 2021-01-28
EP3230248A1 (en) 2017-10-18
MY184826A (en) 2021-04-24
US10023516B2 (en) 2018-07-17

Similar Documents

Publication Publication Date Title
US10023516B2 (en) Hydroformylation process
KR102362007B1 (ko) 하이드로포르밀화 공정
JP7187556B2 (ja) ヒドロホルミル化プロセス
US10478812B2 (en) Methods to store transition metal organophosphorous ligand based catalysts
JP6885963B2 (ja) オレフィンを、アルコール、エーテル、またはそれらの組み合わせに転化するためのプロセス
CN111278560A (zh) 从氢甲酰化方法回收铑的方法
US9382180B2 (en) Hydroformylation process
US9539566B2 (en) Catalyst preparation process
US20220143590A1 (en) Process to prepare solution from hydroformylation process for precious metal recovery
WO2025029349A1 (en) Hydroformylation process

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