CN115057841A - Method for preparing 1, 2-methylenedioxybenzene - Google Patents
Method for preparing 1, 2-methylenedioxybenzene Download PDFInfo
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- CN115057841A CN115057841A CN202210296761.0A CN202210296761A CN115057841A CN 115057841 A CN115057841 A CN 115057841A CN 202210296761 A CN202210296761 A CN 202210296761A CN 115057841 A CN115057841 A CN 115057841A
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- mass fraction
- photocatalyst
- catechol
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- 238000000034 method Methods 0.000 title claims abstract description 37
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical compound C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000011941 photocatalyst Substances 0.000 claims abstract description 17
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003254 radicals Chemical class 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 5
- 238000007342 radical addition reaction Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 6
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004471 Glycine Substances 0.000 claims description 6
- 235000013922 glutamic acid Nutrition 0.000 claims description 6
- 239000004220 glutamic acid Substances 0.000 claims description 6
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 6
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 claims description 5
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 5
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 5
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 5
- 235000004279 alanine Nutrition 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- 239000004475 Arginine Substances 0.000 claims description 2
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 2
- 235000009697 arginine Nutrition 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 claims description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 3
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- 238000012856 packing Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical class O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 2
- 229940081310 piperonal Drugs 0.000 description 2
- ZMQAAUBTXCXRIC-UHFFFAOYSA-N safrole Chemical compound C=CCC1=CC=C2OCOC2=C1 ZMQAAUBTXCXRIC-UHFFFAOYSA-N 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 238000006257 total synthesis reaction Methods 0.000 description 2
- MJRFDVWKTFJAPF-UHFFFAOYSA-K trichloroiridium;hydrate Chemical compound O.Cl[Ir](Cl)Cl MJRFDVWKTFJAPF-UHFFFAOYSA-K 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 241000252804 Cinnamomum insularimontanum Species 0.000 description 1
- 235000002428 Cinnamomum japonicum Nutrition 0.000 description 1
- 241000732800 Cymbidium Species 0.000 description 1
- 244000227633 Ocotea pretiosa Species 0.000 description 1
- 235000004263 Ocotea pretiosa Nutrition 0.000 description 1
- 241001493421 Robinia <trematode> Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OQMUXQPCUBYTEB-UHFFFAOYSA-N benzene-1,2-diol;sodium Chemical compound [Na].OC1=CC=CC=C1O OQMUXQPCUBYTEB-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000911 decarboxylating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 125000004591 piperonyl group Chemical group C(C1=CC=2OCOC2C=C1)* 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940083037 simethicone Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
-
- 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J35/39—Photocatalytic 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
- 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
- B01J2531/827—Iridium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for preparing 1, 2-methylenedioxybenzene. Comprises the steps of carrying out free radical addition reaction on catechol and ketene under the action of a supported Ir photocatalyst to generate 1, 2-methylenedioxybenzene, and separating to obtain a product. The invention has the main advantages that the use of dichloromethane and potassium hydroxide is avoided, and the environment is not polluted; the metal photocatalyst has high activity, the catalyst is not easy to run off, the operation is simple, and the economic benefit is good.
Description
Technical Field
The invention relates to a method for preparing a heliotropin intermediate 1, 2-methylenedioxybenzene, and belongs to the technical field of chemical industry.
Background
Heliotropin, also known as piperonal, has the chemical name 3, 4-methylenedioxybenzaldehyde. It is a fragrant white crystal which is soluble in organic solvent and insoluble in water and glycerin. Heliotropin exists in nature in plants such as robinia pseudoacacia, sassafras, cinnamomum japonicum leaves, and cymbidium violaceum. However, the content of the plant is small and the plant is dispersed, and the artificial synthesis is a main source at present. Heliotropin is widely used in the blending of various essences, can be used as a blending agent and a fixative, can be used as a brightening agent for nickel plating in the electroplating industry, and can be used for synthesizing some alkaloids and some special chemicals in the chemical pharmaceutical industry.
The synthesis of heliotropin at present mainly adopts a semi-synthesis method taking safrole as a raw material and a total synthesis method taking catechol as a raw material. Total synthesis using catechol as raw material, and non-natural extraction of catechol from industrial synthesisThe method is cheap and easy to obtain, so that the method is mostly applied to the industrial production of the heliotropin. Firstly, catechol is utilized in the alkaline condition 2 Cl 2 Synthesizing piperonyl, condensing with N-alkyl formanilide, or oxidizing and decarboxylating with glyoxylic acid under acidic condition, or reacting with formaldehyde in the presence of zinc chloride, and finally reacting to obtain piperonal.
Patent CN110590732B proposes mixing catechol, sodium hydroxide, water and simethicone to obtain catechol sodium solution; and then mixing the sodium catechol solution, tetrabutyl ammonium chloride and dichloromethane, and carrying out condensation reaction to obtain a target product. In the method, sodium hydroxide and dichloromethane are respectively used, equipment is greatly corroded due to the existence of strong alkali, the production cost is increased, and the generated chloride ions can pollute the environment.
Patent CN111004205A proposes that catechol reacts with dichloromethane under the protection of nitrogen, and the final product is obtained after a series of reactions. The method has complicated reaction procedures, uses methylene chloride and also pollutes the environment.
Therefore, the heliotropin intermediate 1, 2-methylenedioxybenzene is synthesized by the reaction of catechol and dichloromethane under the action of potassium hydroxide, and the dichloromethane can generate chloride ions when used, so that the requirements on equipment materials are high, and meanwhile, the dichloromethane is not environment-friendly and has a large taste; the use of strong alkali has the disadvantages of high corrosion to equipment, no reuse of catalyst, high cost and more three wastes. The 1, 2-methylenedioxybenzene is an important intermediate for synthesizing the heliotropin, and the improvement of the synthesis process of the 1, 2-methylenedioxybenzene has important significance for the synthesis process of the heliotropin. Therefore, the research on a new, efficient and environment-friendly preparation method of the heliotropin intermediate 1, 2-methylenedioxybenzene is of great significance.
Aiming at the defects in the process, a novel method for synthesizing the heliotropin intermediate 1, 2-methylenedioxybenzene is urgently needed to be developed.
Disclosure of Invention
The invention aims to provide a preparation method of 1, 2-methylenedioxybenzene, which avoids the use of dichloromethane and potassium hydroxide, reduces the requirement on equipment, reduces the generation of three wastes, can reuse a catalyst and reduces the cost. In addition, the method uses the supported metal photocatalyst, is easy to separate, can effectively reduce the operation steps of post-reaction treatment, reduces energy consumption, is environment-friendly, and avoids the problem of environmental pollution.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a process for preparing 1, 2-methylenedioxybenzene comprising the steps of: under the action of a supported Ir photocatalyst, catechol and ketene undergo a free radical addition reaction to generate 1, 2-methylenedioxybenzene.
The reaction route of the invention is as follows:
without being bound to any theory, the reaction mechanism may be: the catechol is influenced by a photocatalyst to generate a form of a phenoxy radical, and the form of the phenoxy radical and ketene are subjected to addition reaction to generate a target product 1, 2-methylenedioxybenzene.
In the preparation method, the dosage of the metal photocatalyst is 5-10 wt% relative to pyrocatechol.
In the preparation method, the molar ratio of catechol to ketene is 1:1.1-1.5, preferably 1:1.1-1: 1.3.
In the preparation method, the condition of free radical addition reaction is that the reaction is carried out for 5 to 6 hours at the reaction temperature of 25 to 30 ℃.
In the preparation method, the reaction solvent is acetonitrile, and the mass ratio of the solvent to catechol is 2:1-4: 1.
The supported Ir photocatalyst is represented as Ir-X/Y/Z, wherein Ir is an active component, X is a ligand and is selected from one or more of arginine, alanine, glutamic acid, glycine and tryptophan, and preferably from one or more of alanine, glutamic acid, glycine and tryptophan; y is a photoinitiator selected from one or more of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, methyl benzoylformate, diphenylethanone and 2, 4-dihydroxy benzophenone, preferably one or more of 2-hydroxy-2-methyl-1-phenyl acetone, methyl benzoylformate, diphenylethanone and 2, 4-dihydroxy benzophenone; z is a carrier and is selected from one or more of activated carbon, silica, kaolin, glass fiber mesh, neutral alumina and diatomite, and preferably from one or more of activated carbon, kaolin, glass fiber mesh and diatomite.
In the supported Ir photocatalyst, based on the total weight of the catalyst (calculated by the total weight of Ir + X + Y + Z), the mass fraction of Ir is 5-20%, the mass fraction of X is 10-30%, the mass fraction of Y is 20-40%, and the mass fraction of Z is 20-56%; preferably, the mass fraction of Ir is 5-15%, the mass fraction of X is 15-30%, the mass fraction of Y is 25-40%, and the mass fraction of Z is 20-55%.
The photoinitiator quickly collects light to generate electrons, and the electrons are transferred through the action of the photoinitiator and metal, so that the electrons are quickly and efficiently transferred; the d-p feedback pi coordination bond formed by the lone-pair electrons on the ligand and the central metal shows lower over potential and charge transfer resistance, good conductivity and unique electronic structure, so that the catalyst can inhibit charge recombination, generate free radicals and promote the generation of free radical addition reaction. The carrier is used for immobilizing the catalyst, so that the high-efficiency separation and cyclic utilization of the catalyst can be realized.
The invention also provides a preparation method of the supported Ir photocatalyst, which comprises the following steps:
(1) mixing an Ir-containing compound and a ligand X in water, mixing at 40-70 ℃, and then mixing a photoinitiator Y and a carrier Z in the aqueous solution to obtain a suspension;
(2) dripping an alkaline precipitator into the suspension until the pH value is 8-12, and aging to obtain slurry;
(3) and carrying out post-treatment on the slurry to obtain the supported Ir photocatalyst.
In the preparation method of the catalyst, in the step (1), the amount of water is not particularly limited, and the Ir-containing compound and the ligand X added may be completely dissolved.
In the preparation method of the catalyst, in the step (1), the Ir-containing compound is selected from one or more of iridium acetate, iridium trichloride, sodium chloroiridate and potassium chloroiridate, and preferably, the sodium chloroiridate and/or iridium trichloride are/is selected.
In the preparation method of the catalyst, in the step (2), the alkaline precipitator is selected from one or more of lithium hydroxide, sodium carbonate, potassium carbonate and potassium hydroxide, and the alkaline precipitator can be an aqueous solution with the concentration of 20-40 wt%.
In the preparation method of the catalyst, in the step (2), the aging time is 2-7h, and the aging temperature is 45-75 ℃.
In the preparation method of the catalyst, in the step (2), the temperature is controlled to be 30-50 ℃ in the dropping process.
In the preparation method of the catalyst, in the step (3), the post-treatment specifically comprises the following steps: and filtering and washing the slurry to obtain a filter cake, drying the filter cake, and then roasting, crushing, tabletting and forming the filter cake. Wherein the drying temperature is 107-123 ℃, and the drying time is 7-17 h; the roasting temperature is 237-327 ℃, and the roasting time is 7-16 h.
The invention has the beneficial effects that:
1. the method has the advantages of simple process route, simple operation and low raw material cost; the influence caused by using dichloromethane and potassium hydroxide is avoided.
2. The supported Ir photocatalyst is environment-friendly, easy to separate and recyclable, and reduces the cost.
4. The method can produce the 1, 2-methylenedioxybenzene at a lower operation temperature, the conversion rate of the raw materials reaches more than 97%, and the selectivity of the product is more than 94%.
Detailed Description
The present invention is further illustrated in detail by the following examples, but the scope of the present invention is not limited to these examples.
Gas chromatography analysis conditions of the product: shimadzu gas chromatograph, RTX-DB-5 column, 5 ℃/min up to 100 ℃; raising the temperature to 200 ℃ at a speed of 10 ℃/min; raising the temperature to 240 ℃ at the temperature of 20 ℃/min, and keeping the temperature for 5 min.
The instrument sources in the following examples are as in table 1 below:
TABLE 1 Instrument sources
| Instrument and reagent | Source | Specification of |
| ICP spectrometer | Agilent | ICP-OES 720 model |
| Gas chromatograph | Shimadzu | GC-2014C |
| Nuclear magnetic resonance spectrometer | Bruker | Advance Bruker 400M |
Example 1
55.84g of sodium chloroiridate hexahydrate and 57.6g of alanine are mixed in 500g of distilled water, the mixture is heated to 40 ℃ and stirred to be fully mixed, 96g of 2-hydroxy-2-methyl-1-phenyl acetone and 211.2g of activated carbon are added under the stirring state, and suspension A is obtained; dissolving lithium hydroxide in water to prepare a 35 wt% lithium hydroxide solution, namely an alkaline precipitant B, heating the suspension A and the alkaline precipitant B to 30 ℃, respectively, slowly dropwise adding the alkaline precipitant B into the suspension A until the pH of the system is 8, and controlling the reaction temperature in the precipitation process to be 30 ℃; then aging the mixture at 45 ℃ for 7 hours to obtain slurry; and filtering the slurry, washing with deionized water, drying the filter cake at 107 ℃ for 17h, roasting at 327 ℃ for 7h, crushing, tabletting and forming to obtain the catalyst 1.
ICP analysis determined that, in catalyst 1, the following components in percentage by mass (i.e., Ir + ligand + photoinitiator + support total mass, the same applies below) are in the total mass of catalyst 1 (if no particular label is given, the above metal salt starting material crystal water is not counted): ir 5%, alanine 15%, 2-hydroxy-2-methyl-1-phenyl acetone 25%, carrier 55%.
Example 2
Mixing 63.31g of iridium chloride monohydrate and 109.83g of glutamic acid in 1000g of distilled water, heating to 50 ℃, stirring and fully mixing, adding 164.74g of methyl benzoylformate and 236.13g of kaolin under stirring, and mixing to obtain a suspension A; dissolving sodium carbonate in water to prepare 35 wt% of sodium carbonate solution, namely alkaline precipitant B, respectively heating the suspension A and the alkaline precipitant B to 40 ℃, slowly dropwise adding the alkaline precipitant B into the suspension A until the pH of the system is 9, and controlling the reaction temperature in the precipitation process to be 40 ℃; then aging for 5h at 55 ℃ to obtain slurry; and filtering the slurry, washing with deionized water, drying the filter cake at 117 ℃ for 16h, roasting at 307 ℃ for 11h, crushing, tabletting and forming to obtain the catalyst 2.
ICP analysis determines that the catalyst 2 comprises the following components in percentage by mass of the total mass of the catalyst 2: ir 7%, glutamic acid 20%, methyl benzoylformate 30% and carrier 43%.
Example 3
68.92g of sodium chloroiridate hexahydrate and 47.4g of glycine are mixed in 500g of distilled water, the mixture is heated to 60 ℃ and stirred to be fully mixed, 55.3g of diphenylethanone and 31.6g of glass fiber net are added under the stirring state to be mixed to obtain suspension A; dissolving potassium carbonate in water to prepare a 35 wt% potassium carbonate solution, namely an alkaline precipitant B, heating the suspension A and the alkaline precipitant B to 30 ℃, respectively, slowly dropwise adding the alkaline precipitant B into the suspension A until the pH of the system is 10, and controlling the reaction temperature of the precipitation process to be 30 ℃; then aging for 4 hours at 65 ℃ to obtain slurry; and filtering the slurry, washing with deionized water, drying the filter cake at 127 ℃ for 9h, roasting at 290 ℃ for 11h, crushing, tabletting and forming to obtain the catalyst 3.
ICP analysis determines that the following components in the catalyst 3 account for the total mass of the catalyst 3 in percentage by mass: 15% of Ir, 30% of glycine, 35% of diphenylethanone and 20% of carrier.
Example 4
Mixing 31.62g of iridium chloride monohydrate and 57.6g of tryptophan in 500g of distilled water, heating to 70 ℃, stirring and fully mixing, adding 76.8g of 2, 4-dihydroxy benzophenone and 38.4g of diatomite while stirring, and mixing to obtain a suspension A; dissolving potassium hydroxide in water to prepare 35 wt% of hydroxide solution, namely alkaline precipitant B, heating the suspension A and the alkaline precipitant B to 50 ℃, respectively, slowly dropwise adding the alkaline precipitant B into the suspension A until the pH of the system is 12, and controlling the reaction temperature in the precipitation process to be 50 ℃; then aging the mixture at 75 ℃ for 2 hours to obtain slurry; and filtering the slurry, washing with deionized water, drying the filter cake at 123 ℃ for 7h, roasting at 237 ℃ for 16h, crushing, tabletting and forming to obtain the catalyst 4.
ICP analysis determines that the catalyst 4 comprises the following components in percentage by mass of the total mass of the catalyst 4: ir 10%, tryptophan 30%, 2, 4-dihydroxy benzophenone 40% and a carrier 20%.
Example 5
Catalyst 1(5.51g, 5 wt%) was charged into a 1000mL three-necked flask equipped with a mechanical stirrer, a thermocouple, catechol (110.11g, 1mol), ketene (46.24g, 1.1mol) and acetonitrile (330.33g) were added to the three-necked flask, and the three-necked flask was placed in an oil bath, and then the mechanical stirring was turned on, the temperature of the oil bath was raised to 25 ℃, and the reaction was carried out for 5 hours under the irradiation of incandescent light. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, rectifying the obtained crude mixture, using triangular spiral packing, having the number of plates of 20, the reflux ratio of 1.5 and the pressure of 10hPa, obtaining 1, 2-methylenedioxybenzene as a product at 173 ℃/760mmHg of 172-class benzene, and confirming that the product is 1, 2-methylenedioxybenzene through nuclear magnetism.
Nuclear magnetic analysis results of the product: 1 H NMR(CDCl 3 ,400MHz):δ6.94(m,2H),6.86(m,2H),6.06(s,2H).
example 6
Catalyst 2(15.42g, 7 wt%) was charged into a 1000mL three-necked flask equipped with a mechanical stirrer, a thermocouple, catechol (220.22g, 2mol), ketene (100.90g, 2.4mol) and acetonitrile (660.66g) were added to the three-necked flask, and the three-necked flask was placed in an oil bath, and then the mechanical stirring was turned on, the temperature of the oil bath was raised to 27 ℃, and the reaction was carried out for 5.5 hours under the irradiation of incandescent light. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, rectifying the obtained crude mixture, and obtaining 1, 2-methylenedioxybenzene as a product with the temperature of 172-173 ℃/760mmHg by using a triangular spiral packing with the number of plates of 20, the reflux ratio of 1.5 and the pressure of 10 hPa.
Example 7
Catalyst 3(9.91g, 9 wt%) was charged into a 1000mL three-necked flask equipped with a mechanical stirrer, a thermocouple, catechol (110.11g, 1mol), ketene (54.65g, 1.3mol) and acetonitrile (330.33g) were added to the three-necked flask, and the three-necked flask was placed in an oil bath, and then the mechanical stirring was turned on, the temperature of the oil bath was raised to 29 ℃ and the reaction was carried out for 6 hours under illumination of incandescent light. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, rectifying the obtained crude mixture, and obtaining 1, 2-methylenedioxybenzene as a product with the temperature of 172-173 ℃/760mmHg by using a triangular spiral packing with the number of plates of 20, the reflux ratio of 1.5 and the pressure of 10 hPa.
Example 8
Catalyst 4(16.52g, 10 wt%) was charged into a 1000mL three-necked flask equipped with a mechanical stirrer, a thermocouple, catechol (165.17g, 1.5mol), ketene (75.67g, 1.8mol), and acetonitrile (495.50g) were added to the three-necked flask, and the three-necked flask was placed in an oil bath, and then the mechanical stirring was turned on, the temperature of the oil bath was raised to 30 ℃, and the reaction was carried out for 5 hours under illumination of incandescent light. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, rectifying the obtained crude mixture, and obtaining 1, 2-methylenedioxybenzene as a product with the temperature of 172-173 ℃/760mmHg by using a triangular spiral packing with the number of plates of 20, the reflux ratio of 1.5 and the pressure of 10 hPa.
Comparative example 9 (without addition of photoinitiator)
44.495g of sodium chloroiridate hexahydrate and 57.38g of glycine are mixed in 500g of distilled water, the temperature is increased to 60 ℃, the mixture is stirred and fully mixed, 95.625g of glass fiber net is added under the stirring state, and suspension A is obtained; dissolving potassium carbonate in water to prepare 35 wt% potassium carbonate solution, namely alkaline precipitant B, heating the suspension A and the alkaline precipitant B to 30 ℃, respectively, slowly dropwise adding the alkaline precipitant B into the suspension A until the pH of the system is 10, and controlling the reaction temperature in the precipitation process to be 30 ℃; then aging for 4 hours at 65 ℃ to obtain slurry; and filtering the slurry, washing with deionized water, drying the filter cake at 127 ℃ for 9h, roasting at 290 ℃ for 11h, crushing, tabletting and forming to obtain the catalyst 5.
Comparative example 10
Catalyst 5(9.91g, 9 wt%) was charged into a 1000mL three-necked flask equipped with a mechanical stirrer, a thermocouple, catechol (110.11g, 1.0mol), ketene (54.65g, 1.3mol) and acetonitrile (330.33g) were added to the three-necked flask, and the three-necked flask was placed in an oil bath, and then the mechanical stirring was turned on, the temperature of the oil bath was raised to 29 ℃ and the reaction was carried out for 6 hours under illumination of incandescent light. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, rectifying the obtained crude mixture, and obtaining a final product, wherein the triangular spiral packing has the column number of 20, the reflux ratio of 1.5 and the pressure of 10 hPa.
COMPARATIVE EXAMPLE 11 (without Metal)
Mixing 61.25g glutamic acid in 500g distilled water, heating to 60 ℃, stirring and fully mixing, adding 91.875g methyl benzoylformate and 153.13g activated carbon under stirring to obtain suspension A; dissolving potassium carbonate in water to prepare 35 wt% potassium carbonate solution, namely alkaline precipitant B, heating the suspension A and the alkaline precipitant B to 30 ℃, respectively, slowly dropwise adding the alkaline precipitant B into the suspension A until the pH of the system is 10, and controlling the reaction temperature in the precipitation process to be 30 ℃; then aging for 4 hours at 65 ℃ to obtain slurry; and filtering the slurry, washing with deionized water, drying the filter cake at 127 ℃ for 9h, roasting at 290 ℃ for 11h, crushing, tabletting and forming to obtain the catalyst 6.
Comparative example 12
Catalyst 6(8.81g, 10 wt%) was charged into a 1000mL three-necked flask equipped with a mechanical stirrer, a thermocouple, catechol (88.09g, 0.8mol), ketene (42.04g, 1.0mol) and acetonitrile (264.264g) were added to the three-necked flask, and the three-necked flask was placed in an oil bath, and then the mechanical stirring was turned on, the temperature of the oil bath was raised to 30 ℃ and the reaction was carried out for 6 hours under the irradiation of incandescent light. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, rectifying the obtained crude mixture, and obtaining a final product, wherein the triangular spiral packing has the column number of 20, the reflux ratio of 1.5 and the pressure of 10 hPa.
Comparative example 13 (no ligand added)
Mixing 22.56g of sodium chloroiridate monohydrate in 500g of distilled water, heating to 70 ℃, stirring and fully mixing, adding 54.80g of 2, 4-dihydroxy benzophenone and 68.5g of diatomite while stirring, and mixing to obtain a suspension A; dissolving potassium hydroxide in water to prepare 35 wt% of hydroxide solution, namely alkaline precipitant B, heating the suspension A and the alkaline precipitant B to 50 ℃, respectively, slowly dropwise adding the alkaline precipitant B into the suspension A until the pH value of the system is 12, and controlling the reaction temperature in the precipitation process to be 50 ℃; then aging for 2h at 75 ℃ to obtain slurry; and filtering the slurry, washing with deionized water, drying the filter cake at 123 ℃ for 7h, roasting at 237 ℃ for 16h, crushing, tabletting and forming to obtain the catalyst 7.
Comparative example 14
Catalyst 7(16.52g, 10 wt%) was charged into a 1000mL three-necked flask equipped with a mechanical stirrer, a thermocouple, catechol (165.17g, 1.5mol), ketene (75.67g, 1.8mol) and acetonitrile (495.495g) were added to the three-necked flask, and the three-necked flask was placed in an oil bath, and then the mechanical stirring was turned on, the temperature of the oil bath was raised to 30 ℃ and the reaction was carried out for 6 hours under the irradiation of incandescent light. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, rectifying the obtained crude mixture, and obtaining 1, 2-methylenedioxybenzene as a product with the temperature of 172-173 ℃/760mmHg by using a triangular spiral packing with the number of plates of 20, the reflux ratio of 1.5 and the pressure of 10 hPa.
The results for the examples and comparative examples are shown in Table 2:
TABLE 2 results of examples and comparative examples
| Catalyst and process for preparing same | Conversion ratio of catechol% | 1, 2-methylenedioxybenzene Selectivity% |
| 1 | 99 | 94 |
| 2 | 97 | 97 |
| 3 | 98 | 96 |
| 4 | 99 | 97 |
| 7 | 76 | 53 |
Claims (10)
1. A process for preparing 1, 2-methylenedioxybenzene comprising the steps of: under the action of a supported Ir photocatalyst, catechol and ketene undergo a free radical addition reaction to generate 1, 2-methylenedioxybenzene.
2. The method according to claim 1, wherein the supported Ir photocatalyst is used in an amount of 5 to 10 wt% with respect to catechol; the molar ratio of the catechol to the ketene is 1:1.1-1.5, preferably 1:1.1-1: 1.3; the reaction is carried out for 5 to 6 hours at the reaction temperature of between 25 and 30 ℃.
3. The method according to claim 1, wherein the reaction solvent is acetonitrile and the mass ratio of the solvent to catechol is 2:1 to 4: 1.
4. The method according to any one of claims 1-3, wherein the supported Ir photocatalyst is represented by Ir-X/Y/Z, wherein Ir is an active component, X is a ligand selected from one or more of arginine, alanine, glutamic acid, glycine, tryptophan; y is a photoinitiator selected from one or more of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, methyl benzoylformate, diphenylethanone and 2, 4-dihydroxy benzophenone; z is carrier selected from one or more of activated carbon, silicon dioxide, kaolin, glass fiber net, neutral alumina and diatomite.
5. The method according to claim 4, wherein the supported Ir photocatalyst has a mass fraction of Ir ranging from 5 to 20%, a mass fraction of X ranging from 10 to 30%, a mass fraction of Y ranging from 20 to 40%, and a mass fraction of Z ranging from 20 to 56%, based on the total weight of the catalyst; preferably, the mass fraction of Ir is 5-15%, the mass fraction of X is 15-30%, the mass fraction of Y is 25-40%, and the mass fraction of Z is 20-55%.
6. The method according to claim 4 or 5, wherein the method for preparing the supported Ir photocatalyst comprises the steps of:
(1) mixing an Ir-containing compound and a ligand X in water, mixing at 40-70 ℃, and then mixing a photoinitiator Y and a carrier Z in the aqueous solution to obtain a suspension;
(2) dripping an alkaline precipitator into the suspension until the pH value is 8-12, and aging to obtain slurry;
(3) and carrying out post-treatment on the slurry to obtain the supported Ir photocatalyst.
7. The process according to claim 6, wherein in step (1), the Ir-containing compound is selected from the group consisting of iridium acetate, iridium trichloride, sodium chloroiridate and potassium chloroiridate.
8. The method according to claim 6, wherein in the step (2), the alkaline precipitant is one or more selected from lithium hydroxide, sodium carbonate, potassium carbonate and potassium hydroxide.
9. The method according to claim 6, wherein in the step (2), the aging time is 2-7h, and the aging temperature is 45-75 ℃; the temperature is controlled to be 30-50 ℃ in the dropping process.
10. The method according to claim 6, wherein in the step (3), the post-processing specifically comprises: and filtering and washing the slurry to obtain a filter cake, drying the filter cake, and then roasting, crushing, tabletting and forming the filter cake. Wherein the drying temperature is 107-123 ℃, and the drying time is 7-17 h; the roasting temperature is 237-327 ℃, and the roasting time is 7-16 h.
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