CN113996328B - Catalyst and application thereof in preparation of geraniol by hydrogenating citral - Google Patents
Catalyst and application thereof in preparation of geraniol by hydrogenating citral Download PDFInfo
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- CN113996328B CN113996328B CN202111427356.XA CN202111427356A CN113996328B CN 113996328 B CN113996328 B CN 113996328B CN 202111427356 A CN202111427356 A CN 202111427356A CN 113996328 B CN113996328 B CN 113996328B
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- boron nitride
- active center
- metal active
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- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 title claims abstract description 54
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 title claims abstract description 24
- 239000005792 Geraniol Substances 0.000 title claims abstract description 24
- 229940043350 citral Drugs 0.000 title claims abstract description 24
- 229940113087 geraniol Drugs 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052582 BN Inorganic materials 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- DQZWMOWSTWWMPP-UHFFFAOYSA-N 3-diphenylphosphanylpropan-1-amine Chemical compound C=1C=CC=CC=1P(CCCN)C1=CC=CC=C1 DQZWMOWSTWWMPP-UHFFFAOYSA-N 0.000 claims description 8
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- DZDGRVHIUYIMDS-UHFFFAOYSA-N 2-ditert-butylphosphanylethanamine Chemical compound CC(C)(C)P(C(C)(C)C)CCN DZDGRVHIUYIMDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 claims description 3
- RVKSUPMPCDJZRG-UHFFFAOYSA-N 3-di(propan-2-yl)phosphanylpropan-1-amine Chemical compound CC(C)P(C(C)C)CCCN RVKSUPMPCDJZRG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 8
- -1 phosphine amine Chemical class 0.000 abstract description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910052573 porcelain Inorganic materials 0.000 description 24
- 239000010453 quartz Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 241000134874 Geraniales Species 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- WTEVQBCEXWBHNA-YFHOEESVSA-N citral B Natural products CC(C)=CCC\C(C)=C/C=O WTEVQBCEXWBHNA-YFHOEESVSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000003755 preservative agent Substances 0.000 description 6
- 230000002335 preservative effect Effects 0.000 description 6
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000009740 moulding (composite fabrication) Methods 0.000 description 5
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GLZPCOQZEFWAFX-JXMROGBWSA-N (E)-Geraniol Chemical group CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000005922 Phosphane Substances 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000686 essence Substances 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 229910000064 phosphane Inorganic materials 0.000 description 3
- 241000220317 Rosa Species 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229930003651 acyclic monoterpene Natural products 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- 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
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
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- 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
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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- 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
- B01J2531/824—Palladium
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- 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
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a novel catalyst comprising four parts: heteroatom doped boron nitride material, porous dispersing aid, metal active center and phosphine amine ligand. The novel catalyst is suitable for catalyzing citral to carry out hydrogenation reaction, is particularly suitable for catalyzing citral to generate geraniol products with different brands, and has the advantages of high catalytic activity, high selectivity and adjustable product brands.
Description
Technical Field
The invention relates to a novel catalyst and application thereof in the field of citral hydrogenation.
Technical Field
Geraniol, also called geraniol or geraniol, is an acyclic monoterpene compound, has mild rose smell, is widely applied to flower fragrance type daily essences, is a main agent of the rose fragrance type essences, is an indispensable flavoring raw material of various flower fragrance type essences, can be used in the fields of antibiosis and insect repellent, and has wide application in daily life.
There are a number of brands of geraniol products, but currently there are two main types of products currently in the market, one is geraniol 60 (i.e., the geraniol content in the product is 60 wt%), one is geraniol 98 (i.e., the geraniol content in the product is 98 wt%), and geraniol 60 is the main product.
For many years, the chemical world has been devoted to research on the synthesis of geraniol, one of the main methods being to prepare geraniol from citral by hydrogenation, and further, the methods for obtaining geraniol products of different brands all rely on rectification separation processes. The first method is that raw material citral is rectified to obtain raw materials with different geranial contents, and then hydrogenation reaction is carried out to obtain geraniol with different brands; the second method is to rectify the product of citral hydrogenation (the ratio of nerol to geraniol is close to 50:50), and obtain geraniol with different brands through segmentation.
Patent CN201811516330.0 discloses a method for preparing nerol and geraniol with different proportions by preparing a homogeneous catalyst and adding two auxiliary agents of organic amine and phosphine ligand, but the method is easy to produce organic amine with unpleasant smell, has serious influence on the smell of the product, and in addition, a homogeneous reaction system is unfavorable for the application of the catalyst.
Therefore, aiming at the defects in the prior art, the invention provides a novel solution, and the catalyst can flexibly and efficiently regulate and control the proportion of geraniol in the product through the catalytic action of the catalyst, and has the advantages of high catalytic activity, high selectivity and adjustable product brands.
Disclosure of Invention
The invention provides a preparation method of a novel catalyst, which can be used for obtaining geraniol products with different brands by directly carrying out hydrogenation reaction on citral with high selectivity.
The invention provides the following technical scheme for achieving the purpose:
the invention provides a novel catalyst, which comprises the following four parts: boron nitride material doped with hetero atoms, porous dispersing auxiliary, metal active center and phosphine amine ligand.
The hetero atoms are one or more of Al, cu and Fe, preferably Al, and the Al element can be derived from all compounds containing Al;
the doping amount of the hetero atoms on the boron nitride is 1wt% to 15wt%, preferably 5wt% to 10wt%, and the doping amount means that the hetero atoms account for the mass fraction of the boron nitride;
the doping method is a high-temperature gas-phase chemical deposition method, and the gas-phase deposition temperature is 400-1200 ℃, preferably 700-1000 ℃.
The porous dispersing auxiliary agent is one or more of active carbon, molecular sieve, porous ceramic and montmorillonite, preferably molecular sieve, and the molecular sieve can be one or more of beta molecular sieve, ZSM series molecular sieve and MCM series molecular sieve, more preferably beta molecular sieve. The mass ratio of the porous dispersion auxiliary agent to the boron nitride is 1:1-5:1, preferably 2:1-4:1.
The metal active center is one or more of Pd, co, ru, ni, preferably Ni, which can be derived from all Ni-containing compounds. The amount of the metal active center is 2wt% to 15wt%, preferably 5wt% to 10wt%, by which is meant the mass percentage of the metal element in the porous dispersion aid.
The phosphinamine ligand is preferably one or more of 3- (diphenylphosphino) propylamine, 3- (diisopropylphosphino) propylamine and 2- (di-tert-butylphosphino) ethylamine, and more preferably 3- (diphenylphosphino) propylamine. The amount of the phosphane ligand is 40% -120%, preferably 60% -100% of the amount of the metal active center, wherein the amount means that the mol amount of the phosphane ligand is a percentage of the mol amount of the metal active center.
The invention provides a preparation method of the novel catalyst, which comprises the following steps:
putting a certain amount of boron nitride into a porcelain boat, weighing a certain amount of compound containing elements to be doped, covering the surface of the boron nitride, putting the porcelain boat into a quartz tube, putting the quartz tube into a muffle furnace, placing the porcelain boat in a constant-temperature position in the center of the muffle furnace, introducing argon into the quartz tube, slowly heating to 400-1200 ℃, preferably 700-1000 ℃, maintaining for 3-5 h, naturally cooling to below 100 ℃, taking out the porcelain boat, and obtaining a boron nitride material doped with hetero atoms, and marking as A;
placing a certain amount of porous dispersion auxiliary agent and a compound containing a metal active center into a beaker, uniformly mixing, dropwise adding ethanol until the liquid level just exceeds the solid surface, coating the mouth of the beaker with a preservative film, standing for more than 24 hours, and obtaining the porous dispersion auxiliary agent loaded by the metal active center, wherein the porous dispersion auxiliary agent is denoted as B;
placing the obtained heteroatom doped boron nitride material and a porous dispersion auxiliary agent loaded by a metal active center in a mortar, uniformly mixing, adding pseudo-boehmite, wherein the amount of the pseudo-boehmite is 3-5wt% of the total mass of the boron nitride material before heteroatom doping and the porous dispersion auxiliary agent before metal active center loading, kneading and forming by dilute nitric acid with 1-3wt%, drying at 80-100 ℃, roasting at 300-400 ℃, and grinding the obtained solid particles into 50-100 meshes, and marking the solid particles as C;
adding a phosphamide ligand into the C, then adding a solvent with 3-5 times of solid volume, wherein the solvent is one or more selected from normal hexane, ethanol and ethyl acetate, the solid volume refers to the volume of 50-100 mesh solid particles obtained in the last step, stirring for 1-3 hours at room temperature, and then filtering, washing and drying to obtain a finished catalyst, which is marked as D.
The invention also relates to the application of the catalyst in preparing geraniol by hydrogenating citral.
Placing a certain amount of catalyst into a high-pressure reaction kettle, adding a certain amount of citral, replacing the reaction kettle with nitrogen and hydrogen in sequence, filling hydrogen to 1MPa (G) -2MPa (G), and heating to 40-50 ℃ for reaction; the catalyst is added in an amount ranging from 1wt% to 3wt% of the substrate citral.
The catalyst is used for carrying out citral hydrogenation reaction, and the catalyst has isomerization capacities of different degrees by regulating and controlling the dosage of doped metal and phosphane ligand in the catalyst, so that the purpose of producing geraniol products of different brands is met.
The ratio of the neral to the geranial in the raw material citral disclosed by the invention can be 40:60-70:30, and the content ratio range covers the composition ratio of most of commercially available citral in the market.
The technical scheme of the invention has the following beneficial effects:
boron nitride is selected as a matrix material, and as the boron nitride skeleton contains two electronegativity different elements, chemical bonds in the boron nitride have covalent bonds and ionic bonds, and the characteristic endows the boron nitride with special electronic cloud structure characteristics; the method has the advantages that the impurity energy level is formed by doping the hetero atoms into the boron nitride, on one hand, the forbidden bandwidth of the boron nitride is reduced, the response wavelength is increased, the photocatalytic activity of the catalyst is enhanced, and on the other hand, a new active site different from the surface load is formed, so that the selective isomerization catalysis effect can be generated on the carbon-carbon double bond conjugated with the carbon-oxygen double bond in the citral molecule, and the conversion of neral to geranial is promoted.
Introducing metal active center and porous dispersing assistant. The metal active center, the metal element doped on the boron nitride and the boron nitride material generate synergistic effect, so that the hydrogenation activity of the catalyst can be obviously enhanced; the porous dispersion auxiliary agent is introduced, so that the occurrence of the phenomenon of metal active center clusters can be effectively prevented, and the effect of improving the stability of the catalyst is achieved.
The phosphine amine ligand is introduced into the catalyst, and phosphine element in the ligand can coordinate with the supported metal active center, so that on one hand, the effect of inhibiting metal active center clusters is achieved, on the other hand, amine groups in the ligand are introduced to the vicinity of the metal active center, and the metal active center plays a role in isomerization while playing a role in promoting the conversion of neral into geranial or the conversion of nerol into geraniol.
Detailed Description
Boron nitride with purity of 99.5% and particle size of 45 μm or less, ara Ding Shiji Co., ltd
Aluminum iodide, purity 95%, ala Ding Shiji Co., ltd
Copper iodide with a purity of 98% and an ala Ding Shiji Co., ltd
Nickel iodide, purity 98%, ala Ding Shiji Co., ltd
Palladium acetate, purity 98%, ala Ding Shiji Co., ltd
N-hexane, purity > 99%, ara Ding Shiji Co., ltd
Ethanol with purity > 99%, ala Ding Shiji Co., ltd
Ethyl acetate with purity > 99%, arla Ding Shiji limited
3- (diphenylphosphino) propylamine, 97% pure, ara Ding Shiji Co., ltd
2- (Di-t-butylphosphino) ethylamine 97% pure, ama Ding Shiji Co., ltd
Activated carbon, 100 mesh, ara Ding Shiji Co., ltd
Beta molecular sieves, aba Ding Shiji Co
Ru/C, ruthenium content 5%, ala Ding Shiji Co., ltd
Citral with a total purity of not less than 98%, neral: geranial=40:60, hubei julong pharmaceutical chemical company limited
Citral with a total purity of not less than 98%, neral: geranial=50:50, hubei julong pharmaceutical chemical company limited
Citral with a total purity of not less than 98%, neral: geranial=70:30, hubei julong pharmaceutical chemical company limited
Analysis method
Gas chromatograph: agilent 7890, column DB-5, sample inlet temperature: 300 ℃; the split ratio is 50:1; carrier gas flow rate: 50ml/min; heating program: maintaining at 120deg.C for 15min, increasing to 250deg.C at 10deg.C/min, maintaining for 10min, and detecting temperature: 280 ℃.
Example 1
5g of boron nitride is placed in a porcelain boat, 3.8g of aluminum iodide is weighed and covered on the surface of boron nitride, the porcelain boat is placed in a quartz tube, then the quartz tube is placed in a muffle furnace, the porcelain boat is placed in a constant-temperature position in the center of the muffle furnace, argon is introduced into the quartz tube, the temperature is slowly raised to 700 ℃, after the temperature is maintained for 3 hours, the temperature is naturally lowered to below 100 ℃, the porcelain boat is taken out, and an Al-atom-doped boron nitride material is obtained and is marked as A1.
After uniformly mixing 10g of beta molecular sieve and 5.3g of nickel iodide, putting the mixture into a beaker, dropwise adding ethanol until the liquid level just drops over the solid surface, coating the mouth of the beaker with a preservative film, standing for 24h, and obtaining a porous dispersing auxiliary agent loaded by Ni in a metal active center, which is denoted as B1.
Putting A1 and B1 into a mortar, uniformly mixing, adding 0.45g of pseudo-boehmite, kneading with 1wt% of dilute nitric acid to form, drying at 100 ℃, roasting at 300 ℃, and grinding the obtained product into solid particles with 50-100 meshes, and marking as C1.
3.3g of 3- (diphenylphosphino) propylamine was added to C1, followed by addition of 3 times the solid volume of n-hexane, stirring at room temperature for 1h, followed by filtration, washing and drying to obtain the final catalyst, designated as D1.
Example 2
Putting 5g of boron nitride into a porcelain boat, weighing 1.2g of cuprous iodide, covering the surface of the boron nitride, putting the porcelain boat into a quartz tube, putting the quartz tube into a muffle furnace, placing the porcelain boat into the center constant temperature position of the muffle furnace, introducing argon into the quartz tube, slowly heating to 900 ℃, maintaining for 3 hours, naturally cooling to below 100 ℃, taking out the porcelain boat, and obtaining the boron nitride material doped with Cu atoms, and marking as A2.
After 20g of beta molecular sieve and 5.3g of nickel iodide are uniformly mixed, putting the mixture into a beaker, dropwise adding ethanol until the liquid level just drops over the solid surface, coating the mouth of the beaker with a preservative film, standing for 24h, and obtaining a porous dispersing auxiliary agent loaded by Ni in a metal active center, which is denoted as B2.
Putting A2 and B2 into a mortar, adding 1.00g of pseudo-boehmite after uniform mixing, kneading and forming with 2wt% of dilute nitric acid, drying at 100 ℃, roasting at 300 ℃, and grinding the obtained product into solid particles with 50-100 meshes, and recording as C2.
3.6g of 2- (di-tert-butylphosphino) ethylamine was added to C2, followed by 5 times the solid volume of ethyl acetate, stirred at room temperature for 1h, and then filtered, washed and dried to give a finished catalyst designated as D2.
Example 3
5g of boron nitride is placed in a porcelain boat, 7.6g of aluminum iodide is weighed and covered on the surface of boron nitride, the porcelain boat is placed in a quartz tube, then the quartz tube is placed in a muffle furnace, the porcelain boat is placed in a constant-temperature position in the center of the muffle furnace, argon is introduced into the quartz tube, the temperature is slowly raised to 1000 ℃, after the temperature is maintained for 3 hours, the temperature is naturally lowered to below 100 ℃, the porcelain boat is taken out, and an Al-atom-doped boron nitride material is obtained and is marked as A3.
After 15g of active carbon and 6.4g of nickel iodide are uniformly mixed, the mixture is placed in a beaker, ethanol is dropwise added until the liquid level just drops over the solid surface, the mouth of the beaker is coated with a preservative film, and the mixture is left stand for 24 hours, so that a porous dispersing auxiliary agent loaded by Ni in a metal active center is obtained and is marked as B3.
Putting A3 and B3 into a mortar, adding 1.00g of pseudo-boehmite after uniform mixing, kneading and forming with 2wt% of dilute nitric acid, drying at 100 ℃, roasting at 300 ℃, and grinding the obtained product into solid particles with 50-100 meshes, and recording as C3.
3.0g of 3- (diphenylphosphino) propylamine was added to C3, followed by addition of 3 times the solid volume of n-hexane, stirring at room temperature for 1 hour, followed by filtration, washing and drying, to give a finished catalyst, designated as D3.
Example 4
5g of boron nitride is placed in a porcelain boat, 6.0g of aluminum iodide is weighed and covered on the surface of boron nitride, the porcelain boat is placed in a quartz tube, then the quartz tube is placed in a muffle furnace, the porcelain boat is placed in a constant-temperature position in the center of the muffle furnace, argon is introduced into the quartz tube, the temperature is slowly raised to 800 ℃, after the temperature is maintained for 3 hours, the temperature is naturally lowered to below 100 ℃, the porcelain boat is taken out, and an Al-atom-doped boron nitride material is obtained and is marked as A4.
After evenly mixing 15g of beta molecular sieve and 2.5g of palladium acetate, putting the mixture into a beaker, dropwise adding ethanol until the liquid level just drops over the solid surface, coating the mouth of the beaker with a preservative film, standing for 24h, and obtaining the porous dispersing auxiliary agent loaded by Pd in the metal active center, which is marked as B4.
Putting A4 and B4 into a mortar, adding 0.80g of pseudo-boehmite after uniformly mixing, kneading and forming by 3wt% of dilute nitric acid, drying at 100 ℃, roasting at 300 ℃, and grinding the obtained product into solid particles of 50-100 meshes, and recording as C4.
To C4, 1.6g of 3- (diphenylphosphino) propylamine was added, followed by addition of 4 times the solid volume of ethanol, stirring at room temperature for 1 hour, followed by filtration, washing and drying, to obtain the final catalyst, designated as D4.
Example 5
5g of boron nitride is placed in a porcelain boat, 7.6g of aluminum iodide is weighed and covered on the surface of boron nitride, the porcelain boat is placed in a quartz tube, then the quartz tube is placed in a muffle furnace, the porcelain boat is placed in a constant-temperature position in the center of the muffle furnace, argon is introduced into the quartz tube, the temperature is slowly raised to 800 ℃, after the temperature is maintained for 3 hours, the temperature is naturally lowered to below 100 ℃, the porcelain boat is taken out, and an Al-atom-doped boron nitride material is obtained and is marked as A5.
After 20g of beta molecular sieve and 8.5g of nickel iodide are uniformly mixed, putting the mixture into a beaker, dropwise adding ethanol until the liquid level just drops over the solid surface, coating the mouth of the beaker with a preservative film, standing for 24h, and obtaining a porous dispersing auxiliary agent loaded by Ni in a metal active center, which is denoted as B5.
Putting A5 and B5 into a mortar, adding 1.00g of pseudo-boehmite after uniform mixing, kneading and forming by dilute nitric acid with the weight percent of 1, drying at 100 ℃, roasting at 300 ℃, and grinding the obtained product into solid particles with the size of 50-100 meshes, and recording as C5.
6.6g of 3- (diphenylphosphino) propylamine was added to C5, followed by addition of 3 times the solid volume of n-hexane, stirring at room temperature for 1h, followed by filtration, washing and drying, to give the finished catalyst, designated as D5.
Catalyst activity evaluation results:
2G of the catalyst prepared in the above example was placed in a high-pressure reaction vessel, then 100G of citral was added, then the reaction vessel was replaced with nitrogen and hydrogen successively, then hydrogen was charged to 1MPa (G), the temperature was raised to 50℃and after 4 hours of reaction, sampling analysis was performed.
The catalyst activity was evaluated as follows:
comparative example
2G of Ru/C catalyst (Ru content is 5 wt%) is placed in a high-pressure reaction kettle, then 100G of citral is added, the reaction kettle is replaced by nitrogen and hydrogen successively, then hydrogen is filled to 1MPa (G), the temperature is raised to 50 ℃, and sampling analysis is carried out after the reaction is carried out for 4 hours. The catalyst activity was evaluated as follows:
Claims (8)
1. a catalyst comprising the following four parts: boron nitride material doped with hetero atoms, a porous dispersing auxiliary, a metal active center and a phosphinamine ligand;
the heteroatom is one or more of Al, cu and Fe; the doping amount of the hetero atoms on the boron nitride is 1wt% to 15wt%;
the porous dispersing auxiliary is one or more of active carbon, molecular sieve, porous ceramic and montmorillonite; the mass ratio of the porous dispersion auxiliary agent to the boron nitride is 1:1-5:1;
the metal active center is one or more of Pd, co, ru, ni; the dosage of the metal active center is 2-15 wt% of the porous dispersion auxiliary agent;
the phosphinamine ligand is one or more of 3- (diphenylphosphino) propylamine, 3- (diisopropylphosphino) propylamine and 2- (di-tert-butylphosphino) ethylamine; the dosage of the phosphamide ligand is 40% -120% of the molar quantity of the metal active center.
2. The catalyst of claim 1 wherein the heteroatom is doped on boron nitride in an amount of 5wt% to 10wt%.
3. A method of preparing the catalyst of any one of claims 1-2, comprising:
covering the surface of boron nitride with a compound containing hetero atoms, slowly heating to 400-1200 ℃ in a muffle furnace, maintaining for 3-5 h, and naturally cooling to below 100 ℃ to obtain a boron nitride material doped with hetero atoms, which is marked as A;
uniformly mixing a porous dispersion auxiliary agent and a compound containing a metal active center, adding ethanol until the liquid level is beyond the solid surface, and standing to obtain a porous dispersion auxiliary agent loaded by the metal active center, which is denoted as B;
placing the A and the B in a mortar, uniformly mixing, adding pseudo-boehmite, kneading with dilute nitric acid for molding, drying and roasting, grinding the obtained product into solid particles with the size of 50-100 meshes, and marking as C;
and adding a phosphamide ligand into the C, adding a solvent, filtering, washing and drying to obtain a finished catalyst, which is marked as D.
4. A process according to claim 3, wherein, in the preparation of a, the temperature is slowly raised in the muffle to 700-1000 ℃.
5. A method according to claim 3, wherein in preparing C, the amount of pseudo-boehmite is 3-5% by weight of the total mass of the boron nitride material before doping with the heteroatom and the porous dispersion aid before loading the metal active center; the drying temperature is 80-100 ℃, and the roasting temperature is 300-400 ℃.
6. The method according to claim 3, wherein the solvent is selected from one or more of n-hexane, ethanol and ethyl acetate in the amount of 3-5 times the volume of solid C.
7. Use of a catalyst according to any one of claims 1-2 for the preparation of geraniol by hydrogenating citral.
8. The use according to claim 7, comprising: placing a certain amount of catalyst into a high-pressure reaction kettle, adding a certain amount of citral, replacing the reaction kettle with nitrogen and hydrogen in sequence, then charging hydrogen to 1MPa (G) -2MPa (G), and heating to 40-50 ℃ for reaction; the addition amount of the catalyst is 1-3 wt% of the substrate citral.
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| JPH09294932A (en) * | 1996-03-08 | 1997-11-18 | Takasago Internatl Corp | Ruthenium-phosphine complex |
| CN110743556A (en) * | 2019-09-29 | 2020-02-04 | 浙江工业大学 | Copper-based alloy catalyst and preparation method and application thereof |
| CN110922298A (en) * | 2019-12-20 | 2020-03-27 | 万华化学集团股份有限公司 | Method for preparing geraniol from citral |
| CN110981707A (en) * | 2019-12-19 | 2020-04-10 | 万华化学集团股份有限公司 | Method for isomerically synthesizing chiral citronellal from nerol or geraniol |
| CN112844317A (en) * | 2020-12-24 | 2021-05-28 | 南京工业大学 | High-dispersion metal or metal oxide doped adsorbent, preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1317959B1 (en) * | 2001-12-07 | 2007-11-14 | Basf Aktiengesellschaft | Process for producing carbon-supported ruthenium/iron-catalysts |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09294932A (en) * | 1996-03-08 | 1997-11-18 | Takasago Internatl Corp | Ruthenium-phosphine complex |
| CN110743556A (en) * | 2019-09-29 | 2020-02-04 | 浙江工业大学 | Copper-based alloy catalyst and preparation method and application thereof |
| CN110981707A (en) * | 2019-12-19 | 2020-04-10 | 万华化学集团股份有限公司 | Method for isomerically synthesizing chiral citronellal from nerol or geraniol |
| CN110922298A (en) * | 2019-12-20 | 2020-03-27 | 万华化学集团股份有限公司 | Method for preparing geraniol from citral |
| CN112844317A (en) * | 2020-12-24 | 2021-05-28 | 南京工业大学 | High-dispersion metal or metal oxide doped adsorbent, preparation method and application thereof |
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