CN111138253B - Cyclohexene oxide process - Google Patents
Cyclohexene oxide process Download PDFInfo
- Publication number
- CN111138253B CN111138253B CN201911296008.6A CN201911296008A CN111138253B CN 111138253 B CN111138253 B CN 111138253B CN 201911296008 A CN201911296008 A CN 201911296008A CN 111138253 B CN111138253 B CN 111138253B
- Authority
- CN
- China
- Prior art keywords
- cyclohexene
- metal complex
- transition metal
- ozone
- microchannel reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- 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
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/56—Vanadium
-
- 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
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a process for oxidizing cyclohexene, which comprises the following steps: and (2) reacting the mixed solution containing the cyclohexene and the transition metal complex catalyst with the mixed gas containing ozone in a microchannel reactor to prepare the hexanedial. The method adopts the combination of a transition metal complex catalyst and an ozone oxidant, realizes the selective oxidation of cyclohexene into hexanedial, overcomes the defect that a noble metal complex and sodium periodate are required to be used in the cyclohexene oxidation reaction, effectively strengthens the mass transfer between two-phase materials by adopting a microchannel reactor and utilizing the high-efficiency mass transfer and heat transfer efficiency in a microreactor, and has the product selectivity of 91.2 percent.
Description
Technical Field
The application relates to a process for preparing hexanedial based on a microchannel reactor, belonging to the field of chemical engineering.
Background
The 1, 6-hexanedial is an important fine chemical product, is a quick-acting broad-spectrum chemical sterilizing agent, can quickly and efficiently kill most bacteria, bacteria propagules, fungi, spores, viruses and the like, does not corrode metal instruments, glass and plastic products, and can be widely used for disinfection and sterilization of medical instruments, food appliances and the like because of no harm to human bodies. The trans-1, 2-cyclohexanediol is prepared by oxidizing cyclohexene with a sodium periodate/silica gel system, and the 1, 6-hexanedial (perfume and essence cosmetics, 2006(6):17-20) can be prepared with high selectivity. Periodate, though effective, has the drawback of being expensive, not easy to handle and store, for which many companies are constantly seeking processes which are simple to prepare, stable in nature, inexpensive and readily available, combining carbonation chemicals and plastics technology companies (US5312996 and CN1087078A) reacting butadiene with hydrogen and carbon monoxide in the presence of a catalyst rhodium which complexes with certain polyphosphites to produce 1, 6-hexanedial in high conversion. At 110 ℃ and 900psig, the conversion was 99% and the selectivity to adipaldehyde was 30%.
CN109369356A discloses a method for preparing 1, 6-hexanedial by selective oxidation of cyclohexene with a cobalt complex of an isosteryl alcohol derivative. The literature reports that the yield of glutaraldehyde obtained by oxidizing cyclopentene with 50% hydrogen peroxide by using peroxyniobic acid as a catalyst and ethanol as a solvent is as high as 72%, which indicates that the peroxyniobic acid is an excellent catalyst with good activity and selectivity for preparing glutaraldehyde by oxidizing cyclopentene through ring opening. While the cyclohexene oxide is used for preparing 1, 6-hexanedial, the cyclohexene conversion rate is 100%, but the selectivity of the 1, 6-hexanedial is only 40% (the Redding university (Nature science edition), 2002, 41(3): 317-.
CN102746127A discloses that cyclohexene is used as a raw material, ozone is used as an oxidant, an organic solvent and glacial acetic acid are used as a mixed solvent, ozonization reaction is carried out at a reaction temperature of-20 ℃ to 10 ℃ to obtain ozonized reaction liquid, and ozonides are directly subjected to reduction reaction without separation; the method for preparing the 1, 6-hexanedial comprises the steps of carrying out reduction decomposition on the 1, 6-hexanedial by using zinc powder, and reacting at room temperature for 0.5-1.5 h under the protection of nitrogen, wherein the yield of the 1, 6-hexanedial in the method is up to 60%.
In conclusion, in the reaction for preparing the hexanedial by oxidizing the cyclohexene, a metal complex-NaIO is mostly adopted4The catalyst system and the preparation method of the catalyst are complex and expensive. The problem of over-oxidation exists when cyclohexene is oxidized by adopting high-concentration hydrogen peroxide as an oxidant, high selectivity of the hexanedial is difficult to obtain, and further industrial application of the process is hindered.
Disclosure of Invention
According to one aspect of the application, a process for oxidizing cyclohexene is provided, the process effectively strengthens the mass transfer between two-phase materials by utilizing the high-efficiency mass transfer and heat transfer efficiency in a microreactor, selectively oxidizes cyclohexene into hexanedial in the presence of an ozone oxidant and a transition metal complex catalyst, and solves the problems that high selectivity can be obtained only by using noble metal and sodium periodate in the process of preparing hexanedial by oxidizing cyclohexene, and high hexanedial selectivity is difficult to obtain when ozone is used as an oxidant.
The cyclohexene oxide process comprises the following steps:
introducing mixed liquid containing cyclohexene and a transition metal complex catalyst and mixed gas containing ozone into a microchannel reactor for reaction to obtain the hexanedial.
Optionally, the hydraulic diameter of a reaction channel of the microchannel reactor is 20-2000 um, the effective contact time of the mixed liquid and the mixed gas in the microchannel reactor is 0.1-60 s, and the specific hydraulic diameter of the microchannel reactor and the effective contact time of the mixed liquid and the mixed gas in the microchannel reactor can be adjusted according to specific requirements; has excellent heat and mass transfer capacity, and can realize instant mixing and high-efficiency heat transfer of materials.
Optionally, the transition metal complex is selected from at least one of vanadyl acetylacetonate, molybdyl acetylacetonate, and titanyl acetylacetonate; vanadyl acetylacetonate or molybdyl acetylacetonate is preferred.
Optionally, the reaction conditions include:
the reaction temperature is-70-50 ℃; preferably-20 to 20 ℃;
the reaction pressure is 0.10-1.0 MPa;
alternatively, the upper limit of the reaction temperature may be selected from 50 ℃, 40 ℃, 30 ℃, 10 ℃, 5 ℃, 0 ℃, -5 ℃, -15 ℃, -10 ℃ or-20 ℃, and the lower limit may be selected from 40 ℃, 30 ℃, 10 ℃, 5 ℃, 0 ℃, -5 ℃, -15 ℃, -10 ℃, -20 ℃ or-70 ℃.
Optionally, the molar ratio of the ozone to the cyclohexene is 0.30-3.0
Optionally, the gas mixture consists of ozone and at least one of the following gases:
oxygen, air or inert gas;
the concentration of ozone in the mixed gas is 10-140 mg/L.
Optionally, the upper limit of the concentration of ozone in the mixed gas is selected from 140mg/L, 130mg/L, 120mg/L, 110mg/L, 100mg/L, 90mg/L, 80mg/L, 70mg/L, 60mg/L, 50mg/L, 40mg/L, 30mg/L or 20mg/L, and the lower limit is selected from 130mg/L, 120mg/L, 110mg/L, 100mg/L, 90mg/L, 80mg/L, 70mg/L, 60mg/L, 50mg/L, 40mg/L, 30mg/L, 20mg/L or 10 mg/L;
optionally, the mass ratio of the transition metal complex catalyst to the cyclohexene is (0.05-0.3): 1; preferably (0.10 to 0.2): 1.
optionally, the mixed solution further comprises an organic solvent;
the organic solvent is at least one of ethanol, acetonitrile and acetone.
Optionally, the step of introducing the mixed solution containing cyclohexene and the transition metal complex catalyst and the mixed gas containing ozone into the microchannel reactor specifically includes the following steps:
dissolving an auxiliary agent, cyclohexene and a transition metal complex catalyst in an organic solvent, and mixing by ultrasonic oscillation to obtain a mixed solution containing the cyclohexene and the transition metal complex catalyst;
and injecting the mixed liquid containing the cyclohexene and the transition metal complex catalyst into a microchannel reactor through a pump, and injecting the mixed gas containing ozone into the microchannel reactor through a mass flow meter.
In one embodiment, a method for preparing adipaldehyde by selective oxidation of cyclohexene comprises:
adopts a micro-channel reactor and takes ozone as an oxidant, and cyclohexene is oxidized into hexanedial in the presence of a catalyst and an auxiliary agent.
Specifically, cyclohexene and a catalyst are dissolved in an organic solvent, the mixture is subjected to ultrasonic oscillation and uniform mixing, a pump is adopted to inject the material into a microchannel reactor, and ozone is introduced into the microchannel reactor through a mass flow meter to react.
The reaction temperature in the microchannel reactor is-70-50 ℃, and the reaction pressure is 0.10-1.0 MPa.
The ozone is an oxidant, and the concentration of the ozone in the ozone-containing mixed gas is 10-140 mg/L.
The catalyst is selected from one of vanadyl acetylacetonate, molybdyl acetylacetonate and titanyl acetylacetonate.
The solvent is acetone, acetonitrile or ethanol.
In the embodiment, the microchannel reactor is adopted, and the mass transfer between two-phase materials is effectively enhanced by utilizing the high-efficiency mass transfer and heat transfer efficiency in the microreactor. The method has the advantages that cyclohexene is selectively oxidized into the hexanedial in the presence of an ozone oxidant, a catalyst and an auxiliary agent, so that the problem that high selectivity can be obtained only by using noble metal and sodium periodate in the process of preparing the hexanedial by oxidizing the cyclohexene, and high hexanedial selectivity is difficult to obtain when ozone is used as the oxidant is solved. The method adopts ozone as an oxidant to selectively oxidize cyclohexene into the hexanedial, has high product selectivity, and is an environment-friendly process without three wastes. Therefore, the invention not only has innovativeness, but also has economic advantages and industrial application prospects.
The beneficial effects that this application can produce include:
1) the application realizes the selective oxidation of cyclohexene into hexanedial by combining a transition metal complex catalyst with ozone, overcomes the defect that a precious metal complex and sodium periodate are required to be used in the cyclohexene oxidation reaction, and has the product selectivity as high as 60 percent; by adopting a microchannel reactor and utilizing high-efficiency mass transfer and heat transfer efficiency in the microreactor, the mass transfer between two-phase materials is effectively enhanced, the maximum cyclohexene conversion rate can reach 100 percent, and the product selectivity is further improved to 91.2 percent;
2) the preparation process provided by the invention can prepare the product through one-step oxidation, is simple to operate, and is an environment-friendly process without generating three wastes.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
The hydraulic diameter of the reaction channel of the microchannel reactor used in the embodiment of the invention is 500um, and the effective contact time of the mixed liquid and the mixed gas in the microchannel reactor is 10 s.
Ozone is prepared by an ozone generator.
The raw materials in the examples of the present invention were all purchased from commercial sources unless otherwise specified.
The analytical methods and conversion, selectivity in the examples were calculated as follows:
automated analysis was performed using an Agilent7890 gas chromatograph with an autosampler. Adding n-dodecane into the reaction solution after the reaction as an internal standard, and quantifying by adopting an internal standard method.
In some embodiments of the invention, both conversion and selectivity are calculated based on carbon moles:
cyclohexene conversion (mol) ═ [ (cyclohexene amount in feed) - (cyclohexene amount in discharge) ]/(cyclohexene amount in feed) × 100%
Selectivity (mol) of adipaldehyde (amount of adipaldehyde in the discharge)/amount of cyclohexene converted x 100%.
Example 1 Oxidation of cyclohexene to adipaldehyde in a Microchannel reactor
Mixing 50g of cyclohexene and 116g of acetone to prepare a cyclohexene solution with the mass concentration of 30%, adding 7.89g of vanadyl acetylacetonate into the cyclohexene solution, and uniformly mixing by ultrasonic oscillation to obtain a mixed solution;
injecting the mixed solution into a microchannel reactor by using a pump, wherein the flow rate of the mixed solution is 10g/min, injecting the mixed gas into the microchannel reactor through a mass flow meter, and controlling the flow rate of the mixed gas to be 15.1L/min, wherein the mixed gas consists of oxygen and ozone, and the concentration of the ozone is 100 mg/L;
the reaction temperature in the microchannel reactor is 10 ℃, the reaction pressure is 0.10MPa, the materials are collected after 10min of reaction, and gas chromatography is adopted for analysis.
Examples 2-11 Oxidation of cyclohexene to adipaldehyde in a Microchannel reactor
The reaction was carried out by changing the pressure, solvent, catalyst and reaction temperature of the reaction by the procedure described in example 1, and the specific reaction conditions and results are shown in Table 1.
TABLE 1 reaction conditions and results tabulated for cyclohexene oxidation to hexanedial in microchannel reactor
As can be seen from table 1, the preparation process provided by the present application generally has a high selectivity of adipaldehyde, which can reach 53.8% or more, and can reach 91.2% at the highest, and the conversion rate of cyclohexene can reach 35.2% or more, and can reach 100% at the highest.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (6)
1. A process for oxidizing cyclohexene, the process comprising:
introducing mixed liquid containing cyclohexene and a transition metal complex catalyst and mixed gas containing ozone into a microchannel reactor for reaction to obtain hexanedial;
the process specifically comprises the following steps:
dissolving cyclohexene and a transition metal complex catalyst in an organic solvent, and mixing by ultrasonic oscillation to obtain a mixed solution containing the cyclohexene and the transition metal complex catalyst;
injecting the mixed liquid containing cyclohexene and the transition metal complex catalyst into a microchannel reactor through a pump, and injecting the mixed gas containing ozone into the microchannel reactor through a mass flow meter;
the transition metal complex is selected from at least one of vanadyl acetylacetonate, molybdyl acetylacetonate and titanyl acetylacetonate;
the mass ratio of the transition metal complex catalyst to the cyclohexene is (0.05-0.3): 1;
the reaction conditions include: the molar ratio of the ozone to the cyclohexene is 0.30-3.0;
the reaction temperature is-20 to 20 ℃.
2. The process of claim 1, wherein the hydraulic diameter of the reaction channel of the microchannel reactor is 20 to 2000um, and the effective contact time of the mixed liquid and the mixed gas in the microchannel reactor is 0.1 to 60 s.
3. The process according to claim 1, wherein the mass ratio of the transition metal complex catalyst to the cyclohexene is (0.10-0.2): 1.
4. the process of claim 1, wherein the gas mixture is comprised of ozone and at least one of the following gases:
oxygen, air or inert gas;
the concentration of ozone in the mixed gas is 10-140 mg/L.
5. The process of claim 1, wherein the reaction conditions comprise:
the reaction pressure is 0.10-1.0 MPa.
6. The process according to claim 1, wherein the mixed solution further contains an organic solvent;
the organic solvent is at least one of ethanol, acetonitrile and acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911296008.6A CN111138253B (en) | 2019-12-16 | 2019-12-16 | Cyclohexene oxide process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911296008.6A CN111138253B (en) | 2019-12-16 | 2019-12-16 | Cyclohexene oxide process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111138253A CN111138253A (en) | 2020-05-12 |
| CN111138253B true CN111138253B (en) | 2021-06-22 |
Family
ID=70518463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911296008.6A Active CN111138253B (en) | 2019-12-16 | 2019-12-16 | Cyclohexene oxide process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111138253B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3972944A (en) * | 1972-10-27 | 1976-08-03 | Bayer Aktiengesellschaft | Process for preparing aldehydes from olefins |
| CN1629120A (en) * | 2004-09-02 | 2005-06-22 | 湖南大学 | Process for preparing aldehyde ketone and acid by oxidation of olefin |
| CN102603500A (en) * | 2011-11-07 | 2012-07-25 | 常州大学 | Method for preparing glutaraldehyde by utilizing microchannel reactor |
| CN102746127A (en) * | 2012-07-23 | 2012-10-24 | 中国平煤神马能源化工集团有限责任公司 | Method for preparing 1,6-adipaldehyde |
| CN109369356A (en) * | 2018-12-29 | 2019-02-22 | 郑州大学 | A kind of cyclohexene selective oxidation preparation 1,6- hexandial method |
-
2019
- 2019-12-16 CN CN201911296008.6A patent/CN111138253B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3972944A (en) * | 1972-10-27 | 1976-08-03 | Bayer Aktiengesellschaft | Process for preparing aldehydes from olefins |
| CN1629120A (en) * | 2004-09-02 | 2005-06-22 | 湖南大学 | Process for preparing aldehyde ketone and acid by oxidation of olefin |
| CN102603500A (en) * | 2011-11-07 | 2012-07-25 | 常州大学 | Method for preparing glutaraldehyde by utilizing microchannel reactor |
| CN102746127A (en) * | 2012-07-23 | 2012-10-24 | 中国平煤神马能源化工集团有限责任公司 | Method for preparing 1,6-adipaldehyde |
| CN109369356A (en) * | 2018-12-29 | 2019-02-22 | 郑州大学 | A kind of cyclohexene selective oxidation preparation 1,6- hexandial method |
Non-Patent Citations (1)
| Title |
|---|
| 戊二醛合成方法;周晓霜等;《辽宁师范大学学报（自然科学版）》;20020331;第25卷(第1期);第68-71页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111138253A (en) | 2020-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2001096324A3 (en) | Process for operating the epoxidation of ethylene | |
| CN109331839A (en) | A kind of preparation method and applications for the catalyst producing methyl methacrylate | |
| CN102140073A (en) | Cocoyl dimethyl ammonium iodine oxide complex | |
| CN101440028B (en) | Process for synthesizing p-tertiary butyl benzaldehyde | |
| CN101537371B (en) | Modification method for titanium-silicon molecular sieve | |
| MY122574A (en) | Catalysts for production of unsaturated aldehyde and unsaturated carboxylic acid and a process for producing unsaturated aldehyde and unsaturated carboxylic acid using the catalysts | |
| CN109731571A (en) | A kind of catalyst and its preparation method and application being converted into ethyl alcohol for high selection catalytic methane | |
| CN111138253B (en) | Cyclohexene oxide process | |
| CN101658798B (en) | Method for modifying titanium silicate molecular sieve material | |
| CN111138257B (en) | Method for preparing hexanedial | |
| CN101670298A (en) | Method for modifying titanium silicalite zeolite | |
| CN111138255B (en) | Process for preparing hexanedial from cyclohexene | |
| CN101664696B (en) | Modification treatment method for titanium silicate molecular sieve | |
| CN106391123B (en) | A kind of catalyst and its application method for catalytic oxidation of cyclohexane | |
| CN110075894A (en) | A kind of metal/metal composite oxide/g-C3N4The preparation method of catalyst and 4- ketoisophorone | |
| Murahashi | Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts | |
| KR101515677B1 (en) | Process for Direct Synthesis of H2O2 from H2 and O2 Using Hihgly Uniform Palladium Nanoparticles | |
| CN109053379A (en) | A kind of reduced form oxide material for toluene oxidation preparation high added value product | |
| CN107602393A (en) | A kind of method that benzyl position C H keys are direct oxidation into ketone or acid | |
| CA2434894A1 (en) | Method for manufacturing alkanedicarboxylic acid | |
| CN113105380A (en) | Novel process for preparing peroxyacetic acid by using acetic acid as raw material through microreactor | |
| CN111138256B (en) | Preparation method of hexanediol | |
| CN108484504A (en) | A kind of method that bionic catalysis is broken C-N keys in aryl nitrogenous compound | |
| JPS5931728A (en) | Preparation of nootkatone | |
| CN113717394B (en) | End-capped 3D cobalt (II) porphyrin POF material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |