CN112898149B - Method for preparing acetic acid by low-temperature catalytic oxidation of ethane with monatomic catalyst - Google Patents

Method for preparing acetic acid by low-temperature catalytic oxidation of ethane with monatomic catalyst Download PDF

Info

Publication number
CN112898149B
CN112898149B CN201911219976.7A CN201911219976A CN112898149B CN 112898149 B CN112898149 B CN 112898149B CN 201911219976 A CN201911219976 A CN 201911219976A CN 112898149 B CN112898149 B CN 112898149B
Authority
CN
China
Prior art keywords
catalyst
acetic acid
ethane
mpa
low
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911219976.7A
Other languages
Chinese (zh)
Other versions
CN112898149A (en
Inventor
丁云杰
李彬
宋宪根
姜淼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201911219976.7A priority Critical patent/CN112898149B/en
Publication of CN112898149A publication Critical patent/CN112898149A/en
Application granted granted Critical
Publication of CN112898149B publication Critical patent/CN112898149B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • 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

Abstract

Hair brushThe invention relates to a method for preparing acetic acid by low-temperature oxidation of ethane by using a bimetallic single-atom catalyst loaded on a triphenylphosphine polymer carrier, wherein the metals are two of Rh, Ir, Co, Pt, Pd and Cu, and mainly relates to a technology for oxidizing ethane low-carbon hydrocarbon under low-temperature conditions to convert the ethane low-carbon hydrocarbon into the acetic acid. The traditional low-carbon alkane oxidation technology has higher reaction temperature and large energy consumption, the reaction temperature is lower than 400 ℃, and the TOF for generating acetic acid is close to 100h‑1The gas phase product has basically no ethylene and the selectivity of acetic acid is higher.

Description

Method for preparing acetic acid by low-temperature catalytic oxidation of ethane with monatomic catalyst
Technical Field
The invention relates to a method for preparing acetic acid by low-temperature catalytic oxidation of ethane by using a bimetallic single-atom catalyst loaded on a triphenylphosphine polymer.
Background
Acetic acid is one of important organic acids, has wide application, and is mainly used for synthesizing vinyl acetate, cellulose acetate, acetic anhydride, acetate, metal acetate, PTA and the like; is also an important raw material for pharmacy, dye, pesticide and other organic synthesis.
Acetic acid is industrially produced by, for example, a methanol oxo process, an acetaldehyde oxidation process, or a butane (light oil) liquid phase oxidation process. Acetaldehyde is used as a raw material, and oxidation reaction is carried out on a manganese acetate, cobalt acetate or copper acetate homogeneous catalyst to realize effective conversion of the acetaldehyde. The selection of acetic acid is generally higher than 95%, currently, the acetic acid in China mainly adopts a methanol carbonylation synthesis method, the activation energy of the carbonylation synthesis of the acetic acid is very high, and the carbonylation synthesis of the acetic acid can be realized only under the catalytic condition. As early as 1913, BASF discovered that methanol could be carbonylated to produce acetic acid, and did not build a first pilot-scale carbonylated acetic acid plant until the end of the last 50 th century when equipment for corrosion-resistant Mo/Ni alloy materials became available. Thereafter, BASF corporation employed iodination (CoI) by 19602) A first set of device for synthesizing acetic acid by methanol carbonylation is built for the catalyst. The methanol carbonylation process of rhodium/iodide catalyst was developed by Monsanto in 1970 and improved the cobalt iodide catalyzed high pressure process pioneered by BASF in 1960. The rhodium/iodide catalyzed methanol oxo process is highly selective and can be operated at lower pressures. Since the noble metal is expensive, the recovery process is complicated and uneconomical. Non-dissimilar supports such as polymers, activated carbons, inorganic oxides, and molecular sieve supported catalytic systems have been studied in recent years.
Along with the rapid development of global economy in recent years, the demand of human beings on resources is increasing day by day, and meanwhile, the problem of resource shortage is becoming more serious, the apparent consumption of acetic acid in China is rapidly increased, 100 ten thousand tons is broken through for the first time in 2001, the annual consumption reaches 105 ten thousand tons, nearly 200 ten thousand tons in 2007 is 198.9 ten thousand tons, and the development of a novel technology for preparing acetic acid is an epoch requirement.
The direct oxidation of acetic acid by ethane is a new and potentially attractive synthetic route. The method for preparing acetic acid by directly oxidizing ethane can greatly simplify the process flow, has mild reaction conditions, cheap and easily-obtained ethane and low production cost, and has potential resource advantages. In recent years, the research on dehydrogenation and oxidation of light alkanes has been increasingly focused. The current research focuses on dehydrogenation, oxidative dehydrogenation and the like of ethane by taking alkali metal, alkaline earth metal oxide or transition metal oxide as a catalyst, but the research on direct oxidation of ethane to acetic acid or acetaldehyde is less, a mixture system of transition metal oxides is an effective catalyst for oxidation of ethane to generate oxygenated chemicals, the conversion of ethane follows Mars-Van-Krevelen redox mechanism, the products are ethylene, ethanol, acetaldehyde and acetic acid, and the byproduct is carbon oxide. At a lower ethane conversion (0.4%), using V-P-O or Pd-doped V-P-O as catalyst, the selectivity of acetic acid in the product is 55% at 250 ℃, and 37% of ethylene and 8% of CO and CO are added2. Compared with the prior literature reports, the invention has more advantages.
In conclusion, the method for preparing acetic acid by directly oxidizing ethane has the advantages of mild reaction conditions, cheap and easily-obtained raw materials and simple process flow, and can be used as an alternative way for producing acetic acid at present.
Disclosure of Invention
The key problem to be solved by the invention is to improve the selectivity of the target product acetic acid under mild reaction conditions, and simultaneously consider the economic problem of the catalyst, so that the method has the characteristics of low catalytic cost and high acetic acid yield.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
vinyl functionalized triphenylphosphine monomer is taken as polymerization raw material, azodiisobutyronitrile is taken as polymerization catalyst, the weight percentage concentration of the catalyst is 1-50%, and the polymerization is carried out for 12-48h at 50-300 ℃.
The catalyst system consists of a triphenylphosphine polymer self-supported transition metal single-atom heterogeneous catalyst, wherein the polymer with the hierarchical pore structure is obtained by triphenylphosphine monomer solvent thermal polymerization, and the metal is derived from one or more of nitrate, chloride, acetylacetone metal salt or acetate of Rh, Ir, Co, Pt, Pd and Cu.
The proportion of metal by weight relative to the triphenylphosphine polymer is in the range from 0.1 to 10%, calculated on the basis of the weight of the triphenylphosphine polymer.
The selected metal is introduced into the triphenylphosphine polymer catalyst by impregnating the support with a solution of the selected metal at atmospheric or reduced pressure, at an equal volume or over volume.
The impregnated catalyst is vacuum-dried by a Bush funnel at the temperature of 50-100 ℃ for 2-48 h.
The bimetallic monatomic catalyst prepared according to the scheme is subjected to a reaction activity evaluation experiment for preparing acetic acid by directly oxidizing ethane in a 50ml reactor, and the reaction conditions are as follows: the system pressure is 0.1-5MPa, the reaction temperature is 100-400 ℃, and the reaction time is 0.1-12 h. Can achieve the high-efficiency ethane conversion and the high-selectivity acetic acid conversion under the temperature condition which is obviously lower than that of the prior art.
The invention will be further elucidated below by means of some examples.
Detailed Description
[ example 1 ]
3g of triphenylphosphine polymer was weighed out, ground into powder, and 0.3g of copper acetylacetonate and 0.1g of gRhCl were added3Adding tetrahydrofuran solvent to soak in the same volume, placing the mixture into a flask, stirring for 24 hours, pumping the mixture for 24 hours at normal temperature until the mixture is completely dried, and then obtaining the catalyst, wherein the catalyst is 0.3 wt% of Cu-0.1 wt% of Rh (III)/PPh3And then identified by HAADF-STEM characterization, and the catalyst is an atomic-scale monodisperse catalyst.
The oxidation performance evaluation of the catalyst is carried out in a stainless steel pressure-resistant reaction kettle with the volume of 100ml, the loading amount of the catalyst is 220mg, 5g of water is added into the reaction kettle as a solvent, and 0.2 g of water is introducedMPa ethane, 2.0MPaCO, 2.0MPaO2The middle part of the reaction kettle is kept at 250 ℃ at constant temperature, the reaction pressure is 8.0MPa, after 24 hours of reaction, a liquid phase product is analyzed by an Agilent 7890B gas chromatograph, and an area normalization method is adopted for result calculation. The results of the reaction are summarized in Table 1 below.
[ example 2 ]
Weighing 3g of triphenylphosphine polymer, grinding into powder, adding 0.3g of copper acetylacetonate and 0.1g of rhodium acetylacetonate dicarbonyl, adding tetrahydrofuran solvent to be soaked in an equal volume, placing the mixture in a flask, stirring for 24 hours, pumping to dry for 24 hours at normal temperature till complete drying, and then obtaining the catalyst, wherein the weight percent of the catalyst is 0.3 wt% Cu, and the weight percent of the catalyst is 0.1 wt% Rh (I)/PPh3And then identified by HAADF-STEM characterization, and the catalyst is an atomic-scale monodisperse catalyst.
The oxidation performance evaluation experiment of the catalyst is equivalent to [ example 1 ], and details are not repeated herein.
[ example 3 ]
3g of triphenylphosphine polymer was weighed out, ground into powder, and 0.3g of PtCl was added4And 0.1gRhCl3Adding tetrahydrofuran solvent to soak in the same volume, placing the mixture into a flask, stirring for 24 hours, pumping the mixture for 24 hours at normal temperature until the mixture is completely dried to obtain the catalyst, wherein the catalyst is 0.3 wt% of Pt-0.1 wt% of Rh (III)/PPh3And then identified by HAADF-STEM characterization, and the catalyst is an atomic-scale monodisperse catalyst.
The oxidation performance evaluation experiment of the catalyst is equivalent to [ example 1 ], and details are not repeated herein.
[ example 4 ]
3g of triphenylphosphine polymer are weighed out, ground into a powder and 0.3g of PtCl are added4And 0.1g of acetylacetonatodicarbonylrhodium, then adding tetrahydrofuran solvent to be dipped in the same volume, putting the mixture into a flask and stirring the mixture for 24 hours, pumping the mixture for 24 hours at normal temperature till the mixture is completely dried, and obtaining the catalyst, wherein the weight percent of the catalyst is 0.3 percent of Pt, 0.1 percent of Rh (I) and the weight percent of the catalyst are PPh3And then identified by HAADF-STEM characterization, and the catalyst is an atomic-scale monodisperse catalyst.
The oxidation performance evaluation experiment of the catalyst is equivalent to [ example 1 ], and details are not repeated herein.
[ example 5 ]
3g of triphenylphosphine were weighed outPolymer, ground into powder, and added with 0.3g of CoCl2And 0.1gRhCl3Adding tetrahydrofuran solvent to soak in the same volume, placing the mixture into a flask, stirring for 24 hours, pumping and drying for 24 hours at normal temperature until the mixture is completely dried to obtain the catalyst, wherein the catalyst is 0.3 wt% of Co-0.1 wt% of Rh (III)/PPh3And then identified by HAADF-STEM characterization, and the catalyst is an atomic-scale monodisperse catalyst.
The oxidation performance evaluation experiment of the catalyst is equivalent to [ example 1 ], and details are not repeated herein.
[ example 6 ]
3g of triphenylphosphine polymer was weighed out, ground into a powder, and 0.3g of CoCl was added2And 0.1g of acetylacetonatodicarbonylrhodium, then adding tetrahydrofuran solvent to be dipped in the same volume, putting the mixture into a flask and stirring the mixture for 24 hours, pumping the mixture for 24 hours at normal temperature till the mixture is completely dried, and obtaining the catalyst, wherein the catalyst is 0.3 wt% of Co-0.1 wt% of Rh (I)/PPh3And then identified by HAADF-STEM characterization, and the catalyst is an atomic-scale monodisperse catalyst.
The oxidation performance evaluation experiment of the catalyst is equivalent to [ example 1 ], and details are not repeated herein.
[ example 7 ]
Weighing 3g of triphenylphosphine polymer, grinding into powder, adding 0.3g of PdCl2And 0.1gRhCl3Adding tetrahydrofuran solvent to soak in the same volume, placing the mixture into a flask, stirring for 24 hours, pumping the mixture for 24 hours at normal temperature until the mixture is completely dried to obtain the catalyst, wherein the catalyst is 0.3 wt% Pd-0.1 wt% Rh (III)/PPh3And then identified by HAADF-STEM characterization, and the catalyst is an atomic-scale monodisperse catalyst.
The oxidation performance evaluation experiment of the catalyst is equivalent to [ example 1 ], and details are not repeated herein.
[ example 8 ]
Weighing 3g of triphenylphosphine polymer, grinding into powder, adding 0.3g of PdCl2And 0.1g of acetylacetonatodicarbonylrhodium, then adding tetrahydrofuran solvent to be dipped in the same volume, putting the mixture into a flask and stirring the mixture for 24 hours, pumping the mixture for 24 hours at normal temperature till the mixture is completely dried, and then obtaining the catalyst, wherein the catalyst is 0.3 wt% Pd-0.1 wt% Rh (I)/PPh3And then identified by HAADF-STEM characterization, and the catalyst is an atomic-scale monodisperse catalyst.
The oxidation performance evaluation experiment of the catalyst is equivalent to [ example 1 ], and details are not repeated herein.
[ example 9 ]
Weighing 3g of triphenylphosphine polymer, grinding into powder, adding 0.3g of IrCl3And 0.1gRhCl3Adding tetrahydrofuran solvent to soak in the same volume, placing the mixture into a flask, stirring for 24 hours, pumping the mixture for 24 hours at normal temperature until the mixture is completely dried, and then obtaining the catalyst which is 0.3 wt% Ir-0.1 wt% Rh (III)/PPh3And then identified by HAADF-STEM characterization, and the catalyst is an atomic-scale monodisperse catalyst.
The oxidation performance evaluation experiment of the catalyst is equivalent to [ example 1 ], and details are not repeated herein.
[ example 10 ]
Weighing 3g of triphenylphosphine polymer, grinding into powder, adding 0.3g of IrCl3And 0.1g of acetylacetonatodicarbonylrhodium, then adding tetrahydrofuran solvent to be dipped in the same volume, putting the mixture into a flask and stirring the mixture for 24 hours, pumping the mixture for 24 hours at normal temperature till the mixture is completely dried, and then obtaining the catalyst, wherein the weight percent of the catalyst is 0.3% Ir-0.1% Rh (I)/PPh3And then identified by HAADF-STEM characterization, and the catalyst is an atomic-scale monodisperse catalyst.
The oxidation performance evaluation experiment of the catalyst is equivalent to [ example 1 ], and details are not repeated herein.
TABLE 1
Figure BDA0002300541240000041
Figure BDA0002300541240000051
Note: the products are mainly acetic acid, methanol, and trace amounts of methyl acetate, methyl formate and CO based on the converted ethane2。
The results show that: in the bimetallic supported catalyst, Rh is used as a main active metal and is kept unchanged, when Cu is used as a secondary active metal, the activity of the catalyst is highest, and the rest activities are Pt, Co, Ir and Pd in sequence; and when Rh is used as a main active metal, the valence state of Rh also has certain influence on the catalytic activity: the activity of the catalyst prepared by taking the precursor as the univalent Rh is better than that of the catalyst prepared by taking the precursor as the trivalent Rh.

Claims (9)

1. Method for preparing acetic acid by oxidizing ethane with ethane and O2Taking CO as protective gas as a raw material, and generating acetic acid and methanol by the catalytic action of a triphenylphosphine polymer carrier loaded bimetallic single-atom catalyst of a gas-phase raw material at the temperature of 100-250 ℃ and under the pressure of 0.5-25 MPa; the loaded bimetal is Rh and Co, Pt and Cu which are in a monoatomic dispersion state on a catalyst, wherein the Rh is Rh (I), the loading amounts of the Rh and the Co, the Pt and the Cu are respectively 0.1 percent and 0.3 percent, and water is used as a solvent in the reaction; the specific surface area of the triphenylphosphine polymer is 400-1200 m2The pore size distribution of the triphenylphosphine polymer is 1-200 nm.
2. The method of claim 1, wherein acetic acid and methanol are produced by the catalytic action of a triphenylphosphine polymer supported bimetallic single-atom catalyst on a gas phase feedstock at 0.8-5.0 MPa.
3. The method according to claim 1, wherein the specific surface area of the triphenylphosphine polymer is 680 to 1000 m2/g。
4. The method of claim 1, wherein said O is2The partial pressure is 0.1-8 MPa.
5. The method of claim 4, wherein said O is2The partial pressure is 0.4-3.0 MPa.
6. The method of claim 1, wherein the partial pressure of CO is 0.1 to 8 MPa.
7. The method of claim 6, wherein the partial pressure of CO is 0.4 to 2.5 MPa.
8. The process according to claim 1, characterized in that the ethane partial pressure is comprised between 0.1 and 8 MPa.
9. The process according to claim 8, characterized in that the ethane partial pressure is comprised between 0.4 and 3.0 MPa.
CN201911219976.7A 2019-12-03 2019-12-03 Method for preparing acetic acid by low-temperature catalytic oxidation of ethane with monatomic catalyst Active CN112898149B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911219976.7A CN112898149B (en) 2019-12-03 2019-12-03 Method for preparing acetic acid by low-temperature catalytic oxidation of ethane with monatomic catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911219976.7A CN112898149B (en) 2019-12-03 2019-12-03 Method for preparing acetic acid by low-temperature catalytic oxidation of ethane with monatomic catalyst

Publications (2)

Publication Number Publication Date
CN112898149A CN112898149A (en) 2021-06-04
CN112898149B true CN112898149B (en) 2022-05-06

Family

ID=76104261

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911219976.7A Active CN112898149B (en) 2019-12-03 2019-12-03 Method for preparing acetic acid by low-temperature catalytic oxidation of ethane with monatomic catalyst

Country Status (1)

Country Link
CN (1) CN112898149B (en)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5393922A (en) * 1993-07-22 1995-02-28 Gas Research Institute Catalytic direct oxidation of hydrocarbons to acids
GB0205016D0 (en) * 2002-03-04 2002-04-17 Bp Chem Int Ltd Process
KR101118938B1 (en) * 2003-08-21 2012-02-27 비피 케미칼즈 리미티드 Catalyst composition and use thereof in ethane oxidation
CN101411997A (en) * 2008-11-26 2009-04-22 中国科学院化学研究所 Single teeth syn-dicarbonyl rhodium-triphenylphosphine complex catalyst for carbonyl group combined to acetic acid as well as preparation method and use thereof
BR112013019663A2 (en) * 2011-02-02 2019-09-24 University College Cardiff Consultants Limited process for complete or partial oxidation of hydrocarbons
CN104707660B (en) * 2013-12-11 2017-03-08 中国科学院大连化学物理研究所 A kind of solid heterogeneous catalyst for hydroformylation of olefin and its preparation method and application
CN107537563B (en) * 2016-06-24 2020-06-02 中国科学院大连化学物理研究所 Quaternary phosphonium salt organic polymer catalyst and preparation method and application thereof
CN109453814B (en) * 2017-09-06 2021-07-27 中国科学院大连化学物理研究所 Multi-level pore polymer supported rhodium catalyst containing sulfonic group and phosphine ligand, preparation and application thereof
CN109453815B (en) * 2017-09-06 2021-09-07 中国科学院大连化学物理研究所 Organic phosphine-containing polymer carrier-loaded rhodium-based catalyst, and preparation and application thereof

Also Published As

Publication number Publication date
CN112898149A (en) 2021-06-04

Similar Documents

Publication Publication Date Title
Yang et al. Selective oxidation of glycerol in a base-free aqueous solution: A short review
CN109999880B (en) Nitrogen-doped porous carbon loaded bimetallic catalyst and preparation method and application thereof
CN108712931B (en) Catalyst for producing 2, 5-furandicarboxylic acid and method for producing 2, 5-furandicarboxylic acid using the same
Tichit et al. Layered double hydroxides: precursors for multifunctional catalysts
Wang et al. One-pot catalytic selective synthesis of 1, 4-butanediol from 1, 4-anhydroerythritol and hydrogen
Gholinejad et al. Applications of bimetallic PdCu catalysts
CN109603819B (en) Graphene-loaded PdRu bimetallic catalyst and preparation method and application thereof
CN108620127B (en) Catalyst for preparing 1, 5-pentanediol through hydrogenolysis of tetrahydrofurfuryl alcohol, preparation method and application thereof
CN107282045A (en) 1,4 cyclohexane dimethanol catalyst
CN111111775A (en) Organic phosphine-containing polymer carrier-loaded Rh-based catalyst, and preparation and application thereof
CN109438153B (en) Method for preparing 2, 6-dimethyl-2-heptene through citronellal selective decarbonylation reaction
CN109926056A (en) It is a kind of using carbon nanotube as the catalyst of carrier, preparation method and application
CN104549254B (en) Catalyst for preparing 1,6-hexanediol through direct reduction of adipic acid
CN109622050B (en) Catalyst and method for preparing nerol and geraniol by using same
Ji et al. A novel Ni/AC catalyst prepared by MOCVD method for hydrogenation of ethyl levulinate to γ-valerolactone
Hosaka et al. Vapor-phase dehydrogenation of 1-decanol to decanal over Cu/SiO2 catalyst prepared by organic additives-assisted impregnation
CN111167515B (en) Monomolecular heteropoly acid inlaid honeycomb-shaped carbon material loaded nano metal catalyst and preparation method and application thereof
CN112898149B (en) Method for preparing acetic acid by low-temperature catalytic oxidation of ethane with monatomic catalyst
CN107486191B (en) Iridium-based catalyst loaded on acid-treated carbon carrier and preparation method and application thereof
CN112892588B (en) Preparation method and application of atomic-scale monodisperse transition metal catalyst for preparing acetic acid by low-temperature catalytic oxidation of methane
CN109748777B (en) Method for preparing 1, 6-hexanediol by catalytic hydrogenolysis of 1,2, 6-hexanetriol
CN112979422A (en) Method for preparing nerol/geraniol
CN101992084B (en) Rhodium heterogeneous catalyst for carbonylation as well as preparation method and application thereof
CN108774135A (en) A kind of preparation method of 5- hydroxyl methyls
CN105435811B (en) 1,4 cyclohexanedimethanol catalyst and preparation method 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