CN101391232A - Pyrazole acetic-acid rhodium complexes catalyst capable of catalyzing carbonylation reaction to preparing acetic acid and acetic anhydride and preparation method and use thereof - Google Patents
Pyrazole acetic-acid rhodium complexes catalyst capable of catalyzing carbonylation reaction to preparing acetic acid and acetic anhydride and preparation method and use thereof Download PDFInfo
- Publication number
- CN101391232A CN101391232A CNA2008102253930A CN200810225393A CN101391232A CN 101391232 A CN101391232 A CN 101391232A CN A2008102253930 A CNA2008102253930 A CN A2008102253930A CN 200810225393 A CN200810225393 A CN 200810225393A CN 101391232 A CN101391232 A CN 101391232A
- Authority
- CN
- China
- Prior art keywords
- acetic acid
- pyrazoles
- rhodium
- catalyst
- acetic
- 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.)
- Granted
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of acetic acid and acetic anhydride prepared by carbonylation synthesis, which relates to a pyrazole acetic rhodium complex catalyst used to synthesize the acetic acid by methanol carbonylation and synthesize the acetic anhydride by methyl acetate carbonylation, as well as a preparation method and applications of the catalyst. The catalyst has excellent catalytic activity and reaction stability when being used to prepare the acetic acid through catalyzing the methanol carbonylation reaction and prepare the acetic anhydride through the methyl acetate carbonylation reaction. The pyrazole acetic rhodium complex catalyst, methanol, cocatalyst methyl iodide are added into a pressurized vessel which is then input with carbon monoxide with the pressure being kept at 3 to 4MPa, the reaction temperature is between 150DEG C and 200DEG C, and the acetic acid is obtained after the agitation reaction; and the catalyst takes rhodium as an active species, and the rhodium active species and pyrazole form a unidentate coordination structure having the above structure.
Description
Technical field
The invention belongs to synthetic acetic acid of carbonylation and acetic anhydride field, relate to pyrazoles acetic acid rhodium complex catalyst with acetic acid synthesis from methanol carbonylation and the synthetic acetic anhydride of methyl acetate carbonylation, and these Preparation of catalysts methods and applications.
Background technology
Methyl alcohol and carbon monoxide carbonylation under the effect of homogeneous rhodium catalyst prepares the invention that acetic acid is people (US 3 769 329) such as the early 1970s U.S. Monsanto Paulik of company, and to be that the carbonyl of methyl alcohol is synthetic opened up a new important process route in this invention.On this basis, later Halcon (BE 819 455) Ealtman, Ajinamoto (Japan Kokai 50/30,820), Showa Denko (Japan Kokai 50/47,922), BP (B.Von Schlotheim, Chem.Industrie 1994,9/89.80) and Hoechst (DE 24 50 965) with same [Rh (CO)
2I
2]
-The catalyst activity species of anion version are used for the research that the methyl acetate carbonylation prepares acetic anhydride and have obtained breakthrough progress.
By continuous improvement and perfect, use the homogeneous phase rhodium to become the process route of present most important in the world acetic acid and acetic anhydride production as the carbonylation of catalyst methyl alcohol and methyl acetate.Active higher, selectivity is well this class catalyst remarkable advantages; But the unstability of this class catalyst is easy to generate trivalent rhodium precipitation, especially is being beneficial under the higher temperature of reaction, or all the more so when flash separation part carbon monoxide pressure of tension reduces, and above-mentioned these shortcomings are generally acknowledged by people.The design of catalyst structure and the improvement of reaction system are the hot research problem for a long time always, and annual all have a large amount of research papers and patent of invention to emerge.Research work is mostly round the selection of catalyst ligand; Or employing non-rhodium metal active specy; Or in reaction system, add different additives, and have activity of such catalysts and stability by selection now to improve to new additive agent, its objective is the novel catalyst system that obtains being better than existing industrial catalyst, reach the raising of catalytic efficiency.Aspect the part selection of catalyst, carried out many trials to contain phosphine compound as part, adopt [RhCl (CO) (PEt3) 2] complex at 150 ℃ as people such as J.Rankin, with reaction rate STY (mol AcOH/L.h) by [Rh (CO)
2Cl
2]
25.0 (STY-space-time yields) bring up to 9.2 (Chem.Commun.1997,1835); C.ACarral etc. select bidentate type phosphine composition, and its STY reaches 13.7 (Chem.Commun。2000,1277) .C.M.Thomas etc. is 732 (Chem.Eur.J., 2002.8,3343) with the catalytic rate TON (turn over number) of the synthetic acetic acid of phosphine rhodium complex catalysis methanol carbonylation; The catalytic rate TON of the cis phosphine rhodium dicarbapentaborane complex of Z.Freixa etc. reaches 902 (Angew.Chem.Int.Ed, 2005,44,4305).Same is the emphasis that the research of coordination is still such catalyst research with the nitrogen-containing compound, and its TON 150 ℃ the time reaches 1382 as the monodentate nitrogen rhodium complex of preparations such as D.Panriaj.
In Study of Novel Catalyst, increasing auxiliary agent in the reaction system is effective ways that improve carbonylation rate.This class research is by add the performance that the inorganic salts co-catalyst improves catalyst in reaction system, wherein successful example is a Hoechst Celanese company, the said firm is by the improvement to Monsanto technology, developed the carbonylic synthesis technology of low water content in early 1980s, its characteristics are exactly the inorganic salt compounded of iodine that adds high level in reaction system, the technical advantage of this technology is very obvious, and the patent No. of its application is US 5 001 259, and EP055 618.Same methyl acetate carbonylation prepares that lithium iodide also is most important co-catalyst in the reaction system of acetic anhydride.Joseph R.Zoeller etal Catal.Today, 1992,13.73～91 people such as grade have reported the acetic anhydride catalyst system and catalyzing of Eastman company, and the effect of lithium iodide in reaction has been discussed, and propose to be total to by Li-Rh the reaction mechanism of the methyl acetate carbonylation of catalyst system and catalyzing catalysis.
Summary of the invention
The objective of the invention is to select and to be formed on the pyrazoles acetic acid rhodium complex that has good thermal stability in the air with rhodium, thereby be provided for the pyrazoles acetic acid rhodium complex catalyst of carbonyl synthesis acetic acid and acetic anhydride, this catalyst has high-effect in carbonyl is synthetic.
Another object of the present invention provides a kind of preparation method who is used for the pyrazoles acetic acid rhodium complex catalyst of carbonyl synthesis acetic acid and acetic anhydride.
An also purpose of the present invention provides the application of the pyrazoles acetic acid rhodium complex catalyst that is used for carbonyl synthesis acetic acid and acetic anhydride.
The pyrazoles acetic acid rhodium complex catalyst that is used for carbonyl synthesis acetic acid and acetic anhydride of the present invention is to be active specy with the rhodium, and this rhodium active specy and pyrazoles form the monodentate type coordination structure with following structure:
The preparation method who is used for the pyrazoles acetic acid rhodium complex catalyst of carbonyl synthesis acetic acid and acetic anhydride of the present invention is: the methyl alcohol that 1 mole pyrazoles is dissolved in 50～200 moles, the acetic acid rhodium that under ice bath stirs, adds 1 mole, continue to stir after 10 minutes, the ether solvent precipitation that adding is excessive with respect to product is filtered and is obtained pyrazoles acetic acid rhodium complex catalyst solid.
Catalyst of the present invention is when being used for acetic acid synthesis from methanol carbonylation: pyrazoles acetic acid rhodium complex catalyst, methyl alcohol, co-catalyst iodomethane (also can add part acetic acid as solvent) are joined autoclave pressure, feed carbon monoxide, keeping the pressure of carbon monoxide is 3～4MPa, reaction temperature is 150 ℃～200 ℃, obtains acetic acid behind the stirring reaction; Wherein, the consumption of pyrazoles acetic acid rhodium complex catalyst is in rhodium in reaction system, and rhodium content is 200～3000PPm scope; The consumption of co-catalyst iodomethane in reaction system is 0.1～5mol/L scope.
Can further add lithium iodide in above-mentioned reaction system, add lithium iodide and can obviously improve catalytic activity, the consumption of lithium iodide is 1～1000:1 scope with the lithium in the lithium iodide than the mol ratio of rhodium.
When catalyst of the present invention synthesizes acetic anhydride at the catalytic methylester acetate carbonylation: pyrazoles acetic acid rhodium complex catalyst, methyl acetate, co-catalyst iodomethane and acetate solvate are joined in the autoclave pressure, feeding carbon monoxide continues to feed carbon monoxide and add hydrogen after with air displacement in the autoclave pressure, reaction temperature is 170 ℃～200 ℃, obtains acetic anhydride behind the stirring reaction; The consumption of pyrazoles acetic acid rhodium complex catalyst is in rhodium in reaction system, and rhodium content is 400～2000PPm scope; The consumption of co-catalyst iodomethane in reaction system is 0.1～5mol/L scope; The mixture pressure of carbon monoxide and hydrogen is 3.5～4.5MPa, and wherein the volume content of hydrogen in mist is 1～10%.
When the synthetic acetic anhydride of above-mentioned methyl acetate carbonylation, in reaction system, further add the stability that a certain amount of pyrazoles part can increase reaction system, the addition of pyrazoles part is a pyrazoles than the mol ratio of rhodium is 1～500:1 scope.
Add lithium iodide and can obviously improve catalytic activity in above-mentioned reaction system, the consumption of lithium iodide is 1～1000:1 scope with the lithium in the lithium iodide than the mol ratio of rhodium.
From catalyst structure of the present invention, can find out, its essential characteristic is that the pyrazoles that catalyst has been selected to have good stabilization in carbonyl is synthetic makes part, form metastable version with the acetic acid rhodium, pyrazoles is joined trial in the reactor as promoter or stabilizing agent and be different from the common carbonylation.
Catalyst of the present invention prepares and has excellent catalytic activity and reaction stability when acetic acid and methyl acetate carbonylation prepare acetic anhydride being used for the catalysis methanol carbonylation.
The specific embodiment
Embodiment 1
The pyrazoles of 1 molar part is dissolved in the methyl alcohol of 50 molar part, under ice bath stirs, adds the acetic acid rhodium of 1 molar part, continue stir about after 10 minutes, add the ether sedimentation excessive, filter and obtain pyrazoles acetic acid rhodium complex catalyst solid with respect to product.
Embodiment 2
The pyrazoles of 1 molar part is dissolved in the methyl alcohol of 200 molar part, under ice bath stirs, adds the acetic acid rhodium of 1 molar part, continue stir about after 10 minutes, add the ether sedimentation excessive, filter and obtain pyrazoles acetic acid rhodium complex catalyst solid with respect to product.
Embodiment 3
The pyrazoles of 1 molar part is dissolved in the methyl alcohol of 100 molar part, under ice bath stirs, adds the acetic acid rhodium of 1 molar part, continue stir about after 10 minutes, add the ether sedimentation excessive, filter and obtain pyrazoles acetic acid rhodium complex catalyst solid with respect to product.
Embodiment 4
In the 250ml autoclave pressure, add the pyrazoles acetic acid rhodium complex catalyst 0.30g that embodiment 1 prepares, methyl alcohol 0.80mol, iodomethane 0.19mol, acetic acid 1.10mol, lithium iodide 2g; Feed carbon monoxide, be warming up to 170 ℃, 500 rev/mins of mixing speeds, the control reaction pressure is 4.0MPa, in 30 minutes reaction time, obtains acetic acid.Methanol conversion 86%, acetic acid space-time yield 17.7molAcOH/L.h.
Embodiment 5
In the 250ml reactor, add the pyrazoles acetic acid rhodium complex catalyst 0.31g that embodiment 1 prepares, methyl alcohol 1.0mol, iodomethane 0.192mol, acetic acid 0.80mol; After feeding carbon monoxide, be warming up to 150 ℃, mixing speed is 500 rev/mins, control reaction pressure 3.5MPa, and the reaction time is 30 minutes, obtains acetic acid.Methanol conversion is 84%, and the acetic acid space-time yield is 15.1mol/L.h.
Embodiment 6
In the 250mol reactor, add the pyrazoles acetic acid rhodium complex catalyst 0.34g that embodiment 1 prepares, methyl acetate 0.70mol, iodomethane 0.21mol, acetic acid 0.24mol, lithium iodide 6.0g; Continue to feed carbon monoxide and add hydrogen after with carbon monoxide air displacement in the autoclave pressure, hydrogen 0.2MPa, carbon monoxide 4.0MPa, be warming up to 180 ℃, mixing speed is 500 rev/mins, constant reaction pressure 4.2MPa, and the reaction time is 20 minutes, the methyl acetate conversion ratio is 45.4% in the product, and the acetic anhydride space-time yield is 10.7mol/L.h.
Embodiment 7
In the reactor of 250mol, add the pyrazoles acetic acid rhodium complex catalyst 0.35g that embodiment 1 prepares, methyl alcohol 0.80mol, iodomethane 0.20mol, acetic acid 1.12mol; Feed carbon monoxide, 178 ℃ of reaction temperatures, carbon monoxide pressure 4.0MPa, in 25 minutes reaction time, 500 rev/mins of mixing speeds obtain acetic acid.Methanol conversion 100%, acetic acid space-time yield are 23.1mol/L.h.
Embodiment 8
In the 250mol reactor, add the pyrazoles acetic acid rhodium complex catalyst 0.28g that embodiment 1 prepares, methyl acetate 0.52mol, iodomethane 0.22mol, acetic acid 0.50mol, lithium iodide 6.5g; Air in the reactor with after the carbon monoxide displacement, is fed hydrogen 0.2MPa, feed 185 ℃ of carbon monoxide control reaction temperatures, reaction gross pressure 4.5MPa, 500 rev/mins of mixing speeds, 16 minutes reaction time.Methyl acetate conversion ratio 47%, acetic anhydride space-time yield are 7.80mol/L.h.
Embodiment 9
In the 250mol reactor, add the pyrazoles acetic acid rhodium complex catalyst 0.31g that embodiment 2 prepares, methyl acetate 0.5mol, iodomethane 0.23mol, acetic acid 0.52mol, lithium iodide 7.5g, with the air in the reactor with after the carbon monoxide displacement, feed hydrogen 0.2MPa, add carbon monoxide and keep reaction gross pressure 3.5MPa, 195 ℃ of reaction temperatures, 500 rev/mins of mixing speeds, 18 minutes reaction time.Methyl acetate conversion ratio 65%, acetic anhydride space-time yield are 11.21mol/L.h.
Embodiment 10
In the 250mol reactor, add the pyrazoles acetic acid rhodium complex catalyst 0.28g that embodiment 1 prepares, methyl acetate 0.52mol, iodomethane 0.22mol, acetic acid 0.50mol, lithium iodide 6.5g, the pyrazoles part, wherein the addition of pyrazoles part be pyrazoles than the mol ratio of rhodium is 100:1; Air in the reactor with after the carbon monoxide displacement, is fed hydrogen 0.2MPa, feed 185 ℃ of carbon monoxide control reaction temperatures, reaction gross pressure 4.5MPa, 500 rev/mins of mixing speeds, 16 minutes reaction time.Methyl acetate conversion ratio 47%, acetic anhydride space-time yield are 7.80mol/L.h.
Claims (7)
1. the pyrazoles acetic acid rhodium complex catalyst of carbonyl synthesis acetic acid and acetic anhydride, it is characterized in that: this catalyst is to be active specy with the rhodium, this rhodium active specy and pyrazoles form the monodentate type coordination structure with following structure:
2. the preparation method of the pyrazoles acetic acid rhodium complex catalyst of carbonyl synthesis acetic acid according to claim 1 and acetic anhydride, it is characterized in that: 1 mole pyrazoles is dissolved in 50～200 moles the methyl alcohol, the acetic acid rhodium that under ice bath stirs, adds 1 mole, continue to stir after 10 minutes, the ether solvent precipitation that adding is excessive with respect to product is filtered and is obtained pyrazoles acetic acid rhodium complex catalyst solid.
An application rights require 1 described carbonyl synthesis acetic acid and acetic anhydride pyrazoles acetic acid rhodium complex catalyst when being used for acetic acid synthesis from methanol carbonylation: pyrazoles acetic acid rhodium complex catalyst, methyl alcohol, co-catalyst iodomethane are joined autoclave pressure, feed carbon monoxide, keeping the pressure of carbon monoxide is 3～4MPa, reaction temperature is 150 ℃～200 ℃, obtains acetic acid behind the stirring reaction; Wherein, the consumption of pyrazoles acetic acid rhodium complex catalyst is in rhodium in reaction system, and rhodium content is 200～3000PPm scope; The consumption of co-catalyst iodomethane in reaction system is 0.1～5mol/L scope.
4. application according to claim 3 is characterized in that: add lithium iodide in reaction system, the consumption of lithium iodide is 1～1000:1 scope with the lithium in the lithium iodide than the mol ratio of rhodium.
5. the application rights pyrazoles acetic acid rhodium complex catalyst that requires 1 described carbonyl synthesis acetic acid and acetic anhydride is when being used for the synthetic acetic anhydride of catalytic methylester acetate carbonylation: pyrazoles acetic acid rhodium complex catalyst, methyl acetate, co-catalyst iodomethane and acetate solvate are joined autoclave pressure, feeding carbon monoxide continues to feed carbon monoxide and add hydrogen after with air displacement in the autoclave pressure, reaction temperature is 170 ℃～200 ℃, obtains acetic anhydride behind the stirring reaction; The consumption of pyrazoles acetic acid rhodium complex catalyst is in rhodium in reaction system, and rhodium content is 400～2000PPm scope; The consumption of co-catalyst iodomethane in reaction system is 0.1～5mol/L scope; The mixture pressure of carbon monoxide and hydrogen is 3.5～4.5MPa, and wherein the volume content of hydrogen in mist is 1～10%.
6. application according to claim 5 is characterized in that: add the pyrazoles part in reaction system, the addition of pyrazoles part is a pyrazoles than the mol ratio of rhodium is 1～500:1 scope.
7. according to claim 5 or 6 described application, it is characterized in that: add lithium iodide in reaction system, the consumption of lithium iodide is 1～1000:1 scope with the lithium in the lithium iodide than the mol ratio of rhodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102253930A CN101391232B (en) | 2008-10-31 | 2008-10-31 | Pyrazole acetic-acid rhodium complexes catalyst capable of catalyzing carbonylation reaction to preparing acetic acid and acetic anhydride and preparation method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102253930A CN101391232B (en) | 2008-10-31 | 2008-10-31 | Pyrazole acetic-acid rhodium complexes catalyst capable of catalyzing carbonylation reaction to preparing acetic acid and acetic anhydride and preparation method and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101391232A true CN101391232A (en) | 2009-03-25 |
| CN101391232B CN101391232B (en) | 2011-03-30 |
Family
ID=40491860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102253930A Expired - Fee Related CN101391232B (en) | 2008-10-31 | 2008-10-31 | Pyrazole acetic-acid rhodium complexes catalyst capable of catalyzing carbonylation reaction to preparing acetic acid and acetic anhydride and preparation method and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101391232B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218344A (en) * | 2011-06-09 | 2011-10-19 | 中国科学院化学研究所 | 3,5-dicarboxyl pyrazole iridium complex catalyst used for carbonylation synthesis of acetic acid as well as preparation method and application thereof |
| CN104193606A (en) * | 2014-09-28 | 2014-12-10 | 中国科学院山西煤炭化学研究所 | Technique for preparing acetone from synthetic gas |
| CN110605145A (en) * | 2018-06-15 | 2019-12-24 | 万华化学集团股份有限公司 | Catalyst for methyl hydrogen esterification reaction and method for preparing isononanoic acid |
-
2008
- 2008-10-31 CN CN2008102253930A patent/CN101391232B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218344A (en) * | 2011-06-09 | 2011-10-19 | 中国科学院化学研究所 | 3,5-dicarboxyl pyrazole iridium complex catalyst used for carbonylation synthesis of acetic acid as well as preparation method and application thereof |
| CN102218344B (en) * | 2011-06-09 | 2013-04-10 | 中国科学院化学研究所 | 3,5-dicarboxyl pyrazole iridium complex catalyst used for carbonylation synthesis of acetic acid as well as preparation method and application thereof |
| CN104193606A (en) * | 2014-09-28 | 2014-12-10 | 中国科学院山西煤炭化学研究所 | Technique for preparing acetone from synthetic gas |
| CN110605145A (en) * | 2018-06-15 | 2019-12-24 | 万华化学集团股份有限公司 | Catalyst for methyl hydrogen esterification reaction and method for preparing isononanoic acid |
| CN110605145B (en) * | 2018-06-15 | 2022-04-22 | 万华化学集团股份有限公司 | Catalyst for methyl hydrogen esterification reaction and method for preparing isononanoic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101391232B (en) | 2011-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ren et al. | Review of heterogeneous methanol carbonylation to acetyl species | |
| CN102218343A (en) | Lithium pyridine carboxylate-rhodium acetate complex catalyst for synthesizing acetic acid and acetic anhydride through carbonylation, and preparation method and application thereof | |
| CN101391232B (en) | Pyrazole acetic-acid rhodium complexes catalyst capable of catalyzing carbonylation reaction to preparing acetic acid and acetic anhydride and preparation method and use thereof | |
| CN101053841A (en) | Rhodium catalyst with organometallic lithium salts as ligand | |
| CN101391231B (en) | Imidazole acetic-acid rhodium complexes catalyst capable of catalyzing carbonylation reaction to preparing acetic acid and acetic anhydride and preparation method and use thereof | |
| WO1994004479A1 (en) | Improved process for the preparation of 3-pentenoic acid from butadiene | |
| US4935547A (en) | Homologation process making higher alcohols | |
| US3944604A (en) | Production of propionic acid | |
| CN100381204C (en) | Catalyst system for synthesizing acetic acid and acetic anhydride from carbonyl compound and its uses | |
| CN111686818A (en) | Catalyst composition and application thereof in propylene hydroformylation reaction | |
| CN111558395B (en) | Bimetallic catalyst for methanol carbonylation reaction, and preparation method and application thereof | |
| CN101367051A (en) | Rhodium carbonyl complex catalyst for carbonyl synthesis of acetate, acetic anhydride | |
| CN1978055B (en) | Hydroformylation catalytic system and use | |
| CN100443173C (en) | Catalyst system for synthetizing acetic acid from methanol or synthetizing ethylanhydride from methyl acetate and use thereof | |
| CN101992084B (en) | Rhodium heterogeneous catalyst for carbonylation as well as preparation method and application thereof | |
| CN102050711B (en) | Method for preparing acraldehyde | |
| CN101703946B (en) | Copolymer-iridium catalyst used for preparing acetic acid through carbonylation reaction | |
| CN111036306B (en) | Cobalt-phosphine catalyst and preparation method and application thereof | |
| CN100372608C (en) | Catalyst system of catalytic methylester acetate or methylether synthetic acetoanhy dride and use thereof | |
| CN102259028A (en) | Iridium catalyst for homogeneously catalyzing carbonylation of methanol to synthesize acetic acid as well as preparation method and application thereof | |
| CN102294265B (en) | Catalyst for synthesis of acetic acid through carbonylation at low water concentration, preparation method and application thereof | |
| CN100569788C (en) | Rhodium acetic anhydride complex and preparation method thereof and application | |
| CN101411997A (en) | Single teeth syn-dicarbonyl rhodium-triphenylphosphine complex catalyst for carbonyl group combined to acetic acid as well as preparation method and use thereof | |
| CN101722047B (en) | Homogeneous phase iridium complex catalyst of methanol oxo-synthesis acetic acid, preparation method and application thereof | |
| CN101716522A (en) | Complex catalyst for synthesizing acetic acid from methanol carbonyl and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110330 Termination date: 20201031 |