CN111729686A - Cyclohexene selective oxidation catalyst with mesoporous silica HMS as carrier and preparation method and application thereof - Google Patents
Cyclohexene selective oxidation catalyst with mesoporous silica HMS as carrier and preparation method and application thereof Download PDFInfo
- Publication number
- CN111729686A CN111729686A CN202010616824.7A CN202010616824A CN111729686A CN 111729686 A CN111729686 A CN 111729686A CN 202010616824 A CN202010616824 A CN 202010616824A CN 111729686 A CN111729686 A CN 111729686A
- Authority
- CN
- China
- Prior art keywords
- hms
- cyclohexene
- selective oxidation
- oxidation catalyst
- carrier
- 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.)
- Pending
Links
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 47
- 230000003647 oxidation Effects 0.000 title claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 12
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 238000010992 reflux Methods 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 150000002940 palladium Chemical class 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 229920004482 WACKER® Polymers 0.000 abstract description 5
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 4
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000005576 amination reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 17
- 239000000243 solution Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a cyclohexene selective oxidation catalyst taking mesoporous silica HMS as a carrier, and a preparation method and application thereof, wherein the preparation method comprises the following steps: firstly, preparing mesoporous molecular sieve HMS; performing amination modification on the mesoporous molecular sieve HMS by adopting an aminosilane coupling agent; then, adopting O, S-containing ligand to perform grafting synthesis on the aminated HMS to obtain an organic-inorganic composite carrier; and finally, loading palladium on the organic-inorganic composite carrier through coordination reaction to obtain the cyclohexene selective oxidation catalyst. Compared with the prior art, the invention successfully designs a novel functional heterogeneous catalyst by designing the ligand and carrying out operations such as improved immobilization and the like on the traditional Wacker reaction catalyst, so that the catalytic material has excellent catalytic performance, is convenient to separate, realizes the repeated recycling of the catalyst, and accords with the principle of green chemistry.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysts, and relates to a cyclohexene selective oxidation catalyst taking mesoporous silica HMS as a carrier, and a preparation method and application thereof.
Background
Cyclohexanone is a saturated cyclic ketone in which the carbonyl carbon atoms are contained within a six-membered ring, of the formula: c6H10O, colorless or light yellow transparent liquid, strong irritation, slight solubility in water, and miscibility in organic solvents such as alcohol, ether, benzene, acetone, etc. Cyclohexanone is an important chemical raw material, is a main intermediate for preparing nylon, adipic acid and caprolactam, is also an important industrial solvent, is particularly used for preparing nitrocellulose and vinyl chloride polymer paint products, is widely used as a solvent for a plurality of high molecular polymers, has the characteristics of high solubility, low toxicity, low price and the like, and has a huge potential market.
The processes for obtaining cyclohexanone in industrial production today mainly employ the air oxidation of cyclohexane and the hydrogenation of phenol. The production raw material resources of the cyclohexanol oxidation method are in short supply, the price cost is high, the byproduct cyclohexane is generated, more byproducts are generated in the reaction process of the production process scheme of the cyclohexanol oxidation method, more three wastes are discharged, the product yield is not high, and the safety requirement in the industrial production process is also high. Because of the high energy consumption and serious pollution of these processes, there is an urgent need to develop a process that is more compatible with green chemistry. According to research reports, the cyclohexanone can be prepared by selective oxidation of cyclohexene at present, but most of the reported catalytic reaction systems are homogeneous catalysis, which causes inconvenience for separation of subsequent product mixtures and recycling of catalysts, and a new catalytic reaction system needs to be developed.
Disclosure of Invention
The invention aims to provide a cyclohexene selective oxidation catalyst taking mesoporous silica HMS as a carrier, and a preparation method and application thereof. The method specifically comprises the steps of loading divalent palladium serving as an active component capable of effectively catalyzing the reaction of preparing cyclohexanone by oxidizing cyclohexene on a mesoporous molecular sieve HMS with mild synthesis conditions and large specific surface area, and facilitating the inlet and outlet of reactants and products through a large pore structure of the HMS, so that the catalytic reaction is facilitated, and the efficient composite catalyst for selective catalytic oxidation of cyclohexene prepared based on the HMS is obtained.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a cyclohexene selective oxidation catalyst with mesoporous silica HMS as a carrier comprises the following steps:
1) preparing a mesoporous molecular sieve HMS;
2) modifying mesoporous molecular sieve HMS by adopting an aminosilane coupling agent to obtain aminated HMS;
3) adopting O, S-containing ligand to perform grafting synthesis on the aminated HMS to obtain an organic-inorganic composite carrier;
4) and (2) loading palladium on the organic-inorganic composite carrier through coordination reaction to obtain the cyclohexene selective oxidation catalyst.
Further, in step 1), the preparation method of the mesoporous molecular sieve HMS comprises: sequentially adding hydrochloric acid and ethanol into deionized water, and uniformly mixing to obtain a mixed solution; adding hexadecylamine into the mixed solution, and stirring for 20-40min at 40-50 ℃; then adding a mixed solution of isopropanol and ethyl orthosilicate, stirring for 12-24h at 40-50 ℃, and sequentially centrifuging, washing, drying and roasting the obtained product to obtain the mesoporous molecular sieve HMS;
wherein in the drying process, the drying temperature is 90-120 ℃, and the drying time is 8-12 h;
the feed ratio of the deionized water, the hydrochloric acid, the ethanol, the hexadecylamine, the isopropanol and the ethyl orthosilicate is (30-35) mL, (0.5-1.5) mL, (10-20) g, (3-4) g, (2-4) g and (10-11) g;
in the roasting process, the roasting temperature is 500-600 ℃, and the roasting time is 8-12 h.
Further, in step 2), the aminosilane coupling agent comprises a 3- (2-aminoethyl) -aminopropyltrimethoxysilane coupling agent.
Further, the step 2) is specifically as follows: uniformly mixing an aminosilane coupling agent and mesoporous molecular sieve HMS in an organic solvent, and sequentially carrying out heating reflux, filtering, washing and drying processes to obtain the aminated HMS;
wherein the organic solvent comprises toluene, xylene or chloroform;
the mass ratio of the mesoporous molecular sieve HMS to the aminosilane coupling agent is 1 (1.5-2);
the heating reflux process is carried out under the protection of inert gas, the reflux temperature is 90-110 ℃, and the reflux time is 20-28 h;
in the drying process, the drying temperature is 100-140 ℃, and the drying time is 3-8 h.
Further, in step 3), the O, S-containing ligand comprises a 2-acetylthiophene ligand.
Further, the step 3) is specifically as follows: uniformly mixing aminated HMS and O, S-containing ligand in an organic solvent, heating and refluxing to graft O, S-containing ligand on the aminated HMS, and sequentially carrying out solid-liquid separation, washing and drying to obtain the organic-inorganic composite carrier;
wherein the organic solvent comprises toluene or xylene;
the feeding ratio of the aminated HMS to the O, S-containing ligand is 1g/(1.5-2.5) mmol;
the heating reflux process is carried out under the protection of inert gas, the reflux temperature is 90-110 ℃, and the reflux time is 20-28 h;
in the drying process, the drying temperature is 90-120 ℃, and the drying time is 3-8 h.
In the washing process, the detergent sequentially selects toluene and ethanol or xylene and ethanol.
Further, the step 4) is specifically as follows: under the protection of inert gas, uniformly mixing an organic-inorganic composite carrier and palladium salt in an organic solvent, and sequentially carrying out stirring, filtering, washing and drying processes to obtain the cyclohexene selective oxidation catalyst;
wherein the mass ratio of the organic-inorganic composite carrier to the palladium salt is (10-50) to 1;
the palladium salt is PdCl2;
The organic solvent is acetone;
in the stirring process, the stirring temperature is 40-60 ℃, and the stirring time is 24-48 h;
in the washing process, the washing agent is distilled water and acetone in turn;
in the drying process, the drying temperature is 90-120 ℃, and the drying time is 8-12 h.
The cyclohexene selective oxidation catalyst with mesoporous silica HMS as a carrier is prepared by the method.
The cyclohexene selective oxidation catalyst with mesoporous silica HMS as a carrier can be used for catalyzing the reaction of preparing cyclohexanone by selective oxidation of cyclohexene.
Further, the reaction for preparing cyclohexanone by selective oxidation of cyclohexene comprises the following steps: respectively adding cyclohexene, a cyclohexene selective oxidation catalyst, a hydrogen peroxide solution and concentrated sulfuric acid into a reaction solvent, uniformly mixing, and reacting at 45-85 ℃ for 3-10h to obtain cyclohexanone;
wherein the reaction solvent is selected from one of acetonitrile, ethanol, acetone, N-dimethylformamide, N-dimethylacetamide or ethyl acetate.
Preferably, the reaction solvent is ethanol.
In the invention. In the preparation process of the catalyst, the proportion or the addition of the raw materials and the range of preparation process parameters are the optimum conditions obtained through experimental research, and if the raw materials or the process parameters exceed the appropriate range, the optimum result is difficult to ensure, namely, the novel Wacker reaction catalyst cannot be prepared or the prepared catalyst cannot efficiently catalyze the Wacker reaction.
Compared with the prior art, the invention has the following characteristics:
1) according to the invention, by designing a ligand and carrying out operations such as improved immobilization and the like on the traditional Wacker reaction catalyst, a novel functional heterogeneous catalyst is successfully designed, so that the catalytic material has excellent catalytic performance, and is convenient to separate, the catalyst can be recycled for many times, and the green chemical principle is met;
2) the carrier used in the invention is a porous carrier HMS, compared with conventional carriers such as SBA-15 and the like, the carrier has the advantages of simple preparation method, cheap and easily available raw materials and the like, and has wide industrial application prospect;
3) according to the invention, O, S-containing ligand (2-acetylthiophene) is grafted onto the porous carrier HMS through an aminosilane coupling agent, compared with a conventional pyridine ligand, the ligand has the advantages of low price, easiness in obtaining and the like, and can form a polydentate ligand with a coupling agent containing an N element, so that a chelate can be formed with an active component palladium for catalyzing Wacker reaction, and a high-efficiency heterogeneous catalyst convenient for separation and recycling is generated.
Detailed Description
The present invention will be described in detail with reference to specific examples.
A preparation method of a cyclohexene selective oxidation catalyst with mesoporous silica HMS as a carrier comprises the following steps:
1) sequentially adding deionized water, hydrochloric acid and ethanol into a reaction container, and uniformly mixing to obtain a mixed solution; adding hexadecylamine into the mixed solution, and stirring at 40-50 deg.C (preferably 45 deg.C) for 20-40min (preferably 30 min); then adding a mixed solution of isopropanol and ethyl orthosilicate, stirring for 12-24h (preferably 18h) at 40-50 ℃ (preferably 45 ℃), sequentially centrifuging, washing and drying the obtained product for 8-12h (preferably 10h) at 90-120 ℃ (preferably 100 ℃), and roasting the obtained powdery product for 8-12h (preferably 10h) at 500-600 ℃ (preferably 550 ℃), so as to obtain the mesoporous molecular sieve HMS; wherein the feeding ratio of the deionized water, the hydrochloric acid, the ethanol, the hexadecylamine, the isopropanol and the ethyl orthosilicate is (30-35) mL, (0.5-1.5) mL, (10-20) g, (3-4) g, (2-4) g and (10-11) g;
2) adding a 3- (2-aminoethyl) -aminopropyltrimethoxysilane coupling agent and mesoporous molecular sieve HMS into an organic solvent (such as toluene or xylene) according to a mass ratio of 1 (1.5-2) (preferably 1:1.67), uniformly mixing, heating and refluxing for 20-28h at 90-110 ℃ under the protection of inert gas (such as nitrogen), and then sequentially filtering, washing and drying (the drying temperature is 100-;
3) adding aminated HMS and O, S-containing ligand (such as 2-acetylthiophene ligand) into an organic solvent (such as toluene or xylene) according to a feeding ratio of 1g/(1.5-2.5) mmol, uniformly mixing, heating and refluxing for 20-28h (preferably 24h) under the protection of inert gas (such as nitrogen) at 90-110 ℃ (preferably 100 ℃), grafting O, S-containing ligand onto the aminated HMS, sequentially carrying out solid-liquid separation (such as filtration), washing (the detergent sequentially selects toluene and ethanol or xylene and ethanol), and drying (the drying temperature is 90-120 ℃, and the drying time is 3-8h) to obtain the organic-inorganic composite carrier;
4) under the protection of inert gas (such as nitrogen), mixing organic-inorganic composite carrier with palladium salt (such as PdCl)2) Adding the raw materials into an organic solvent (such as acetone) according to a mass ratio of (10-50):1 (preferably 10:1), uniformly mixing, stirring AT 40-60 ℃ for 24-48h, sequentially filtering and washing (the detergent sequentially selects distilled water and acetone) to obtain light yellow powder, and drying the light yellow powder AT 90-120 ℃ (preferably 120 ℃) for 8-12h (preferably 10h) to obtain the cyclohexene selective oxidation catalyst (Pd-AT-APTS-HMS).
The prepared catalyst can be used for catalyzing the reaction of preparing cyclohexanone by selective oxidation of cyclohexene, and specifically comprises the following steps: respectively adding cyclohexene, a cyclohexene selective oxidation catalyst, a hydrogen peroxide solution and concentrated sulfuric acid into a reaction solvent, uniformly mixing, reacting for 3-10h (preferably 4-8h) at 40-85 ℃ (preferably 40-70 ℃), performing conventional separation operations such as extraction, rotary evaporation and the like on the obtained product, and performing test analysis on the target product cyclohexanone in an organic phase solution obtained by separation by using a gas chromatograph (such as GC-9790);
wherein the reaction solvent is selected from one of acetonitrile, ethanol, acetone, N-dimethylformamide, N-dimethylacetamide or ethyl acetate;
the volume ratio of the cyclohexene to the reaction solvent is 1 (1-2) (preferably 1:1.5), the volume ratio of the cyclohexene to concentrated sulfuric acid is (30-50):1 (preferably 40:1), the feeding ratio of the cyclohexene to the selective cyclohexene oxidation catalyst is (3-5) mL:0.05g, the feeding ratio of the cyclohexene to concentrated sulfuric acid is (3-5) mL:2g, the mass fraction of the hydrogen peroxide solution is 20-40%, and the mass fraction of the concentrated sulfuric acid is 60-80%.
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
a cyclohexene selective oxidation catalyst with mesoporous silica HMS as a carrier is prepared by the following steps:
1) preparation of mesoporous molecular sieve HMS: 32.4mL of deionized water and 1.0mL (1 mol. L)-1) Adding hydrochloric acid and 15.0g of absolute ethyl alcohol into a 100mL beaker in sequence, and uniformly mixing to obtain a mixed solution; adding the mixed solution into a three-neck flask filled with 3.62g of hexadecylamine; then plugging two side openings of the three-opening flask, putting the three-opening flask into a water bath at 45 ℃, inserting a stirring paddle into the upper opening, and stirring for 30min at constant temperature; then preparing a mixed solution containing 3.0g of isopropanol and 10.4g of ethyl orthosilicate in a 100mL beaker, slowly dripping the mixed solution into the three-neck flask from a side port through a dropping funnel, and continuously stirring for 18 hours under the condition of a water bath at 45 ℃; then, carrying out high-speed centrifugation on the obtained product, washing for a plurality of times to obtain solid powder, and carrying out forced air drying on the solid powder at 100 ℃ for 10 hours; taking out, placing into a crucible, transferring into a muffle furnace, and heating from room temperature under air atmosphere (heating rate of 2 deg.C. min)-1) Roasting at the constant temperature of 550 ℃ for 10 hours to obtain mesoporous silica HMS;
2) amination of mesoporous silica HMS: adding 1.2g of mesoporous silica HMS and 80mL of anhydrous xylene into a three-neck flask provided with a condensing device, discharging air in the device by using nitrogen, refluxing and stirring for 30min at normal temperature, then adding 2g of 3- (2-aminoethyl) -aminopropyltrimethoxysilane coupling agent and 25mL of trichloromethane solution into a reaction system, heating and refluxing for 24h at 100 ℃, and after the reaction system is cooled, sequentially carrying out suction filtration, repeated washing of trichloromethane and forced air drying at 120 ℃ for 5h to obtain solid powder aminated HMS;
3) preparing an organic-inorganic composite carrier: under the protection of nitrogen, mixing 1g of aminated HMS and 25mL of anhydrous xylene, stirring until the mixture is transparent, then adding 2mmol of 2-acetylthiophene ligand, stirring and refluxing at 100 ℃ for 24 hours to graft the 2-acetylthiophene ligand on the aminated HMS, after the reaction is finished, standing and cooling a reaction system to room temperature, carrying out suction filtration, washing the obtained solid for multiple times by using xylene and ethanol in sequence, and drying at 100 ℃ for 6 hours to obtain a light yellow powdery organic-inorganic composite carrier;
4) preparation of a supported palladium catalyst: under the protection of nitrogen, 1g of organic-inorganic composite carrier and 0.1g of PdCl2Adding the mixed solution into 60mL of acetone, stirring the mixed solution AT 50 ℃ for 36 hours, carrying out suction filtration AT room temperature, washing the obtained solid product with water and acetone for multiple times to obtain a light yellow powdery supported catalyst, and drying the obtained catalyst AT 100 ℃ for 10 hours to obtain the cyclohexene selective oxidation catalyst (Pd-AT-APTS-HMS).
Example 2:
in this example, the catalyst Pd-AT-APTS-HMS prepared in example 1 is used for selective catalytic oxidation of cyclohexene, and the specific process is as follows:
in a 50mL round-bottom flask, 4mL of reactant cyclohexene and 6mL of solvent acetonitrile are mixed, 0.05g of catalyst Pd-AT-APTS-HMS, 2g of 30 wt% hydrogen peroxide solution and 0.1mL of 70 wt% concentrated sulfuric acid are sequentially added, then reflux stirring is carried out for 5 hours AT 60 ℃, after the reaction is finished, the reaction solution is sequentially extracted and rotary evaporated, and the organic phase solution obtained by separation is tested and analyzed by a GC-9790 gas chromatograph, so that the cyclohexene conversion rate is 75.44%, the cyclohexanone selectivity is 80.2%, and the cyclohexanone yield is 60.5%.
Example 3:
in this example, the catalyst Pd-AT-APTS-HMS prepared in example 1 is used for selective catalytic oxidation of cyclohexene, and the specific process is as follows:
in a 50mL round-bottom flask, 4mL of reactant cyclohexene is mixed with 6mL of solvent ethanol, 0.05g of catalyst Pd-AT-APTS-HMS, 2g of 30 wt% hydrogen peroxide solution and 0.1mL of 70 wt% concentrated sulfuric acid are sequentially added, then reflux stirring is carried out for 8 hours AT 60 ℃, after the reaction is finished, the reaction solution is sequentially extracted and rotary evaporated, and the organic phase solution obtained by separation is tested and analyzed by a GC-9790 gas chromatograph, so that the cyclohexene conversion rate is 81.31%, the cyclohexanone selectivity is 76.5%, and the cyclohexanone yield is 62.2%.
Example 4:
in this example, the catalyst Pd-AT-APTS-HMS prepared in example 1 is used for selective catalytic oxidation of cyclohexene, and the specific process is as follows:
in a 50mL round-bottom flask, 4mL reactant cyclohexene and 6mL solvent ethanol are mixed, 0.05g of catalyst Pd-AT-APTS-HMS, 2g of 30 wt% hydrogen peroxide solution and 0.1mL of 70 wt% concentrated sulfuric acid are sequentially added, then reflux stirring is carried out for 5 hours AT 60 ℃, after the reaction is finished, the reaction solution is sequentially extracted and rotary evaporated, and the organic phase solution obtained by separation is tested and analyzed by a GC-9790 gas chromatograph, so that the cyclohexene conversion rate is 76.5%, the cyclohexanone selectivity is 82.6%, and the cyclohexanone yield is 63.18%.
Example 5:
in this example, the catalyst Pd-AT-APTS-HMS prepared in example 1 is used for selective catalytic oxidation of cyclohexene, and the specific process is as follows:
in a 50mL round-bottom flask, 4mL of reactant cyclohexene is mixed with 6mL of solvent ethanol, 0.05g of catalyst Pd-AT-APTS-HMS, 2g of 30 wt% hydrogen peroxide solution and 0.1mL of 70 wt% concentrated sulfuric acid are sequentially added, then reflux stirring is carried out for 5 hours AT 50 ℃, after the reaction is finished, the reaction solution is sequentially extracted and rotary evaporated, and the organic phase solution obtained by separation is tested and analyzed by a GC-9790 gas chromatograph, so that the cyclohexene conversion rate is 70.82%, the cyclohexanone selectivity is 80.59%, and the cyclohexanone yield is 56.6%.
Example 6:
in this embodiment, after the solid product obtained in the separation process in example 5 is sequentially washed and dried, the solid product is added to the selective catalytic oxidation reaction system of cyclohexene as a regenerated catalyst, and the specific process is as follows:
in a 50mL round-bottom flask, 2mL of reactant cyclohexene and 3mL of solvent ethanol are mixed, 0.025g of regenerated catalyst, 1g of 30 wt% hydrogen peroxide solution and 0.05mL of 70 wt% concentrated sulfuric acid are sequentially added, then reflux stirring is carried out at 60 ℃ for 5 hours, after the reaction is finished, the reaction solution is sequentially extracted and rotary evaporated, and the organic phase solution obtained by separation is tested and analyzed by a GC-9790 gas chromatograph, so that the cyclohexene conversion rate is 74.35%, the cyclohexanone selectivity is 81.47%, and the cyclohexanone yield is 60.58%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a cyclohexene selective oxidation catalyst with mesoporous silica HMS as a carrier is characterized by comprising the following steps:
1) preparing a mesoporous molecular sieve HMS;
2) modifying mesoporous molecular sieve HMS by adopting an aminosilane coupling agent to obtain aminated HMS;
3) adopting O, S-containing ligand to perform grafting synthesis on the aminated HMS to obtain an organic-inorganic composite carrier;
4) and (2) loading palladium on the organic-inorganic composite carrier through coordination reaction to obtain the cyclohexene selective oxidation catalyst.
2. The method for preparing the cyclohexene selective oxidation catalyst using mesoporous silica HMS as the carrier according to claim 1, wherein the method for preparing the mesoporous molecular sieve HMS in the step 1) comprises: adding hydrochloric acid and ethanol into water in sequence, and uniformly mixing to obtain a mixed solution; adding hexadecylamine into the mixed solution, and stirring for 20-40min at 40-50 ℃; then adding a mixed solution of isopropanol and ethyl orthosilicate, stirring for 12-24h at 40-50 ℃, and sequentially centrifuging, washing, drying and roasting the obtained product to obtain the mesoporous molecular sieve HMS;
wherein in the drying process, the drying temperature is 90-120 ℃, and the drying time is 8-12 h;
the feed ratio of the water, the hydrochloric acid, the ethanol, the hexadecylamine, the isopropanol and the ethyl orthosilicate is (30-35) mL, (0.5-1.5) mL, (10-20) g, (3-4) g, (2-4) g and (10-11) g;
in the roasting process, the roasting temperature is 500-600 ℃, and the roasting time is 8-12 h.
3. The method for preparing a cyclohexene selective oxidation catalyst using mesoporous silica HMS as a carrier according to claim 1, wherein in step 2), the aminosilane coupling agent comprises 3- (2-aminoethyl) -aminopropyltrimethoxysilane coupling agent.
4. The method for preparing the cyclohexene selective oxidation catalyst by using the mesoporous silica HMS as the carrier according to claim 1, wherein the step 2) specifically comprises: uniformly mixing an aminosilane coupling agent and mesoporous molecular sieve HMS in an organic solvent, and sequentially carrying out heating reflux, filtering, washing and drying processes to obtain the aminated HMS;
wherein the mass ratio of the mesoporous molecular sieve HMS to the aminosilane coupling agent is 1 (1.5-2);
the heating reflux process is carried out under the protection of inert gas, the reflux temperature is 90-110 ℃, and the reflux time is 20-28 h;
in the drying process, the drying temperature is 100-140 ℃, and the drying time is 3-8 h.
5. The method for preparing the catalyst for selective oxidation of cyclohexene on the basis of mesoporous silica HMS as claimed in claim 1, wherein in step 3), the O, S-containing ligand comprises a 2-acetylthiophene ligand.
6. The method for preparing the cyclohexene selective oxidation catalyst by using the mesoporous silica HMS as the carrier according to claim 1, wherein the step 3) specifically comprises: uniformly mixing aminated HMS and O, S-containing ligand in an organic solvent, heating and refluxing to graft O, S-containing ligand on the aminated HMS, and sequentially carrying out solid-liquid separation, washing and drying to obtain the organic-inorganic composite carrier;
wherein the feeding ratio of the aminated HMS to the O, S-containing ligand is 1g/(1.5-2.5) mmol;
the heating reflux process is carried out under the protection of inert gas, the reflux temperature is 90-110 ℃, and the reflux time is 20-28 h.
7. The method for preparing the cyclohexene selective oxidation catalyst by using the mesoporous silica HMS as the carrier according to claim 1, wherein the step 4) specifically comprises: uniformly mixing an organic-inorganic composite carrier and palladium salt in an organic solvent, and sequentially carrying out stirring, filtering, washing and drying processes to obtain the cyclohexene selective oxidation catalyst;
wherein the mass ratio of the organic-inorganic composite carrier to the palladium salt is (10-50) to 1;
the palladium salt is PdCl2;
In the stirring process, the stirring temperature is 40-60 ℃, and the stirring time is 24-48 h.
8. A cyclohexene selective oxidation catalyst using mesoporous silica HMS as a carrier, prepared by the method of any of claims 1 to 7.
9. The application of the cyclohexene selective oxidation catalyst using mesoporous silica HMS as the carrier according to claim 8, wherein the cyclohexene selective oxidation catalyst is used for catalyzing the reaction of preparing cyclohexanone by selective oxidation of cyclohexene.
10. The application of the cyclohexene selective oxidation catalyst as claimed in claim 9, wherein the reaction for preparing cyclohexanone by selective oxidation of cyclohexene comprises: respectively adding cyclohexene, a cyclohexene selective oxidation catalyst, a hydrogen peroxide solution and concentrated sulfuric acid into a reaction solvent, uniformly mixing, and reacting at 45-85 ℃ for 3-10h to obtain cyclohexanone;
wherein the reaction solvent is selected from one of acetonitrile, ethanol, acetone, N-dimethylformamide, N-dimethylacetamide or ethyl acetate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010616824.7A CN111729686A (en) | 2020-06-30 | 2020-06-30 | Cyclohexene selective oxidation catalyst with mesoporous silica HMS as carrier and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010616824.7A CN111729686A (en) | 2020-06-30 | 2020-06-30 | Cyclohexene selective oxidation catalyst with mesoporous silica HMS as carrier and preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111729686A true CN111729686A (en) | 2020-10-02 |
Family
ID=72653885
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010616824.7A Pending CN111729686A (en) | 2020-06-30 | 2020-06-30 | Cyclohexene selective oxidation catalyst with mesoporous silica HMS as carrier and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111729686A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114457064A (en) * | 2022-03-17 | 2022-05-10 | 江南大学 | Immobilized lipase catalyst and preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110975926A (en) * | 2019-11-28 | 2020-04-10 | 上海应用技术大学 | Preparation method and application of catalyst for synthesizing benzophenone by dehydrogenating benzhydrol |
CN110975924A (en) * | 2019-11-19 | 2020-04-10 | 上海应用技术大学 | Catalyst for preparing cyclohexanone by catalytic oxidation of cyclohexene, preparation method and application thereof |
-
2020
- 2020-06-30 CN CN202010616824.7A patent/CN111729686A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110975924A (en) * | 2019-11-19 | 2020-04-10 | 上海应用技术大学 | Catalyst for preparing cyclohexanone by catalytic oxidation of cyclohexene, preparation method and application thereof |
CN110975926A (en) * | 2019-11-28 | 2020-04-10 | 上海应用技术大学 | Preparation method and application of catalyst for synthesizing benzophenone by dehydrogenating benzhydrol |
Non-Patent Citations (1)
Title |
---|
曹佩: "MCM-41介孔分子筛负载Pd催化剂的制备及在合成2’-氟-4"-乙基-4-正戊基三联苯中的应用", 《中国海洋大学硕士学位论文》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114457064A (en) * | 2022-03-17 | 2022-05-10 | 江南大学 | Immobilized lipase catalyst and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11033884B2 (en) | Catalyst for benzene hydroxylation for preparation of phenol and preparation method thereof | |
CN110560170A (en) | Novel Pd @ MOF material, preparation method thereof and application thereof in biphenyl preparation | |
CN110746602A (en) | Metal cobalt porphyrin-based porous organic polymer and preparation method and application thereof | |
CN110433862B (en) | Preparation method and application of porous catalyst based on waste plastic | |
CN112934267B (en) | Alkylated hydrophobic MOFs material and application thereof in cyclohexene hydration | |
CN111995635A (en) | Method for preparing organic silicon compound by catalysis of chitosan loaded copper film material | |
CN111729686A (en) | Cyclohexene selective oxidation catalyst with mesoporous silica HMS as carrier and preparation method and application thereof | |
CN102309983B (en) | Method for regenerating inactivated titanium silicon molecular sieve | |
CN110975924B (en) | Catalyst for preparing cyclohexanone by catalytic oxidation of cyclohexene, preparation method and application thereof | |
CN103433071A (en) | IPN (interpenetrating polymer network)-loaded palladium nano catalyst as well as preparation method and applications thereof | |
WO2016184038A1 (en) | Method for preparing cyclohexene oxide using micro-flow field reaction technology | |
CN102276422B (en) | Method for catalyzing benzene and hydrogen peroxide to synthesize phenol by using Cu-loading Schiff base | |
CN103212444A (en) | Synthesis method of organic-inorganic hybrid porous solid material with quadruple catalysis and adsorption functions | |
CN112961110B (en) | Olefin functionalized IPr HCl monomer and preparation method and application thereof | |
CN110918122A (en) | Heterogeneous copper porphyrin and preparation method and application thereof | |
CN103447088A (en) | Cross-linked polyvinyl alcohol supported palladium nano catalyst as well as preparation and application thereof | |
CN107537576B (en) | Immobilized catalyst of silane coupling molecular sieve and double-salt ionic liquid | |
CN110628022B (en) | Phenazine group-containing organic polymer, preparation method thereof and catalytic application thereof to benzylamine oxidative coupling reaction | |
CN111848932A (en) | Preparation of porphyrin-based porous polymer and application of porphyrin-based porous polymer in styrene oxidation catalysis | |
CN107746452A (en) | Palladium load different-phase catalyst based on micro- mesoporous phenolic resin and preparation method thereof | |
CN105712849A (en) | Method for preparing aromatic ketone by oxidation of aromatic hydrocarbon under catalytic action of metalloporphyrin framework catalyst | |
CN110252406A (en) | A kind of catalyst and preparation method thereof of oxidation of ethanol carbonylation synthesizing diethyl carbonate | |
CN111215149B (en) | MOF @ POP-n composite catalyst and preparation method and application thereof | |
CN105642363A (en) | Double-supported catalyst for synthesizing styrene cyclic carbonate through carbon dioxide, and preparation method and application thereof | |
CN111389462B (en) | Method for preparing biphenyl by using carboxylic acid functionalized super-crosslinked porous organic polymer loaded with nanogold |
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 | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201002 |