CN101693209A - Iridium picolinate complex catalyst for synthesizing acetic acid by methanol carbonylation - Google Patents
Iridium picolinate complex catalyst for synthesizing acetic acid by methanol carbonylation Download PDFInfo
- Publication number
- CN101693209A CN101693209A CN200910184273A CN200910184273A CN101693209A CN 101693209 A CN101693209 A CN 101693209A CN 200910184273 A CN200910184273 A CN 200910184273A CN 200910184273 A CN200910184273 A CN 200910184273A CN 101693209 A CN101693209 A CN 101693209A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- copolymer
- acetic acid
- iridium
- weight
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an iridium picolinate complex catalyst for synthesizing acetic acid by methanol carbonylation and a preparation method and an application thereof, a ligand of the catalyst is a copolymer of 2-vinyl pyridine and methyl acrylate, and a copolymer iridium complex catalyst is formed by the complexation reaction with an iridium compound. The preparation method comprises the steps of preparing the ligand of the catalyst, then dissolving 1 part by weight of the copolymer in 10-100 parts by weight of the acetic acid, stirring, heating under reflux, adding the iridium compound which accounts for 3-10% of the weight of the copolymer, carrying out reaction for 10-60min, cooling to the room temperature, using ether for precipitation, filtering and then obtaining a copolymer iridium catalyst. The 1 part by weight of the copolymer is added into the acetic acid solution containing (Ir(CO)2I)2 or (Ir(CO)2Cl)2 under stirring, the feeding is 3-10% of the weight of the copolymer calculated by the weight of iridium, the reaction is carried out for 10-30min under stirring, the ether is used for precipitation, and the copolymer iridium catalyst is obtained by filtering. The copolymer iridium catalyst is used for preparing the acetic acid by methanol carbonylation reaction and has good catalytic performance.
Description
Technical field
The invention belongs to the field that methanol carbonylation prepares acetic acid, particularly above-mentioned Catalysts and its preparation method.
Background technology
It is the most extensive and state-of-the-art technology path of present industrial use that methanol carbonylation prepares acetic acid.(US5 001 259, and EP055618) being with the rhodium is the catalyst activity component to invent the low water reaction system of high iodine of Celanes company from (US3 769 329) of original M onsanto company.Because rhodium costs an arm and a leg, make that non-rhodium series catalysts research is the problem of a focus always, wherein the most successful is iridium series catalysts (EP0749948, EP0752406) application in industrial production.This technology was developed by BP chemical company in 1996, was called Catva technology, compared with the rhodium series catalysts, and the iridium series catalysts has cheap, the advantage that byproduct of reaction is few.
Research work finds that (US5 942 460 for known employing iridium series catalyzer to catalyse methanol carbonylation, US5 883 295, US5 877 347), if in reaction system, add a certain amount of insoluble pyridine polymers, reactivity worth can be significantly improved (the open CN1431931A of Chinese invention patent), and iridium is about 100-6000PPM in the reaction system of its selection; Ethyl acetate 1-70%; Iodomethane 1-50%; Water 0.1-15% contains the insoluble polymer of pyridine ring and the weight ratio of iridium and is less than 10.
The report that the rhodium catalyst of relevant polymeric resin load is used for used for preparing acetic acid through carbonylation reaction is existing a lot, usually raising has certain effect this class heterogeneous catalytic system to catalytic performance in some aspects, but because the limitation of gas, solid, liquid phase reaction system; Separation, circulation to product are made troubles, and especially directly use all the more so for existing commercial plant.
Summary of the invention
It is that key component and methyl acrylate form non-crosslinked soluble copolymers part that the present invention selects carbonyl synthesis acetic acid is reacted the polyvinylpyridine with good facilitation, forms composition catalyst with iridic compound.Because this part and formed composition catalyst have fine solubility in reaction medium, so existing production technology is had good adaptability.
The copolymer-iridium composition catalyst that is used for acetic acid synthesis from methanol carbonylation that the present invention proposes, have in reactive metal iridium and the copolymer than the conjugation N on the pyridine ring of strong electron donation complexation reaction takes place, form N → Ir and join key, and the existence of methyl acrylate has strengthened the dissolubility of complex in reaction medium, helps the carrying out of catalytic reaction.
Technical scheme of the present invention is: a kind of pyridine carboxylic acid iridium complex catalyst of methanol carbonyl synthesized acetic acid, the part of catalyst is the copolymer of 2-vinylpyridine and methyl acrylate, forms the copolymer-iridium composition catalyst with iridic compound by complexation reaction.The part of catalyst is the copolymer of 2-vinylpyridine and methyl acrylate, and the molar ratio of 2-vinylpyridine (V) and methyl acrylate (M) is V: M=9-5: 1-5 in the copolymer.Catalyst ligand adopts the free radical solution polymerization method to obtain, make solvent with benzene, azodiisobutyronitrile is an initator, two kinds of monomers of V and M join in the solvent benzol by specified amount, wherein the solvent benzol volume be two kinds of monomer volumes 5-10 doubly, initiator amount is the 0.5-5% of two kinds of monomer weights, 60 ℃ polymerization 5-24 hour, use petroleum ether precipitation, obtain catalyst ligand.Iridic compound is IrCl
3, IrI
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2Or Ir (OAc)
3
The preparation method who is used for the copolymer-iridium composition catalyst of carbonyl synthesis acetic acid of the present invention is:
The preparation catalyst ligand: the molar ratio according to 2-vinylpyridine (V) and methyl acrylate (M) is the ratio of V: M=9-5: 1-5, with the azodiisobutyronitrile is initator, V and two kinds of monomers of M are joined in the solvent benzol, wherein the solvent benzol volume be two kinds of monomer volumes 5-10 doubly, initiator amount is the 0.5-5% of two kinds of monomer weights, 60 ℃ polymerization 5-24 hour, use petroleum ether precipitation, obtain catalyst ligand;
The copolymer of 1 part of weight is dissolved in the acetic acid of 10-100 weight portion, and agitating heating refluxes, and adds iridic compound, and the weight that adds iridium is the 3-10% of copolymer, reacts 10-60 minute, is cooled to room temperature, uses ether sedimentation, filters and obtains copolymer-iridium catalyst.Described iridic compound is IrCl
3, IrI
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2Or among the Ir (OAc) any one.
With the copolymer of 1 weight portion under agitation, join and contain [Ir (CO)
2I]
2Or [Ir (CO)
2Cl]
2Acetum in, feeding intake in Ir weight is the 3-10% of copolymer, stirring reaction 10-30 minute, use ether sedimentation, filter and to obtain copolymer-iridium catalyst.
When copolymer-iridium catalyst of the present invention was used for methanol carbonylation and prepares acetic acid, reaction system was formed and is comprised copolymer-iridium catalyst, methyl alcohol, co-catalyst iodomethane, solvent acetic acid and promoter.Reaction condition is: carbon monoxide pressure 3-5MPa, reaction temperature 170-220 ℃, wherein catalyst amount is to count 500-5000PPM with iridium.Co-catalyst iodomethane, content are the 3.0-13.0wt% of reaction medium weight,
Promoter in the above-mentioned reaction system comprises; Ruthenic chloride, [Ru (CO)
4I
2], [Ru (CO)
3I
2]
2, ruthenium acetate, propionic acid ruthenium and osmium chloride, osmium tetrachloride, [Os (CO)
4I
2], [Os (CO)
3I
2]
2, the promoter addition is 0.01-9.5 in the proportion of compound institute's containing metal and Ir: 1.
The specific embodiment
A kind of pyridine carboxylic acid iridium complex catalyst of methanol carbonyl synthesized acetic acid, the part of catalyst are the copolymer of 2-vinylpyridine and methyl acrylate, form the copolymer-iridium composition catalyst with iridic compound by complexation reaction.The part of catalyst is the copolymer of 2-vinylpyridine and methyl acrylate, and the molar ratio of 2-vinylpyridine (V) and methyl acrylate (M) is V: M=9-5: 1-5 in the copolymer.Catalyst ligand adopts the free radical solution polymerization method to obtain, make solvent with benzene, azodiisobutyronitrile is an initator, two kinds of monomers of V and M join in the solvent benzol by specified amount, wherein the solvent benzol volume be two kinds of monomer volumes 5-10 doubly, initiator amount is the 0.5-5% of two kinds of monomer weights, 60 ℃ polymerization 5-24 hour, use petroleum ether precipitation, obtain catalyst ligand.Iridic compound is IrCl
3, IrI
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2Or Ir (OAc)
3
The preparation method who is used for the copolymer-iridium composition catalyst of carbonyl synthesis acetic acid of the present invention is:
The preparation catalyst ligand: the molar ratio according to 2-vinylpyridine (V) and methyl acrylate (M) is the ratio of V: M=9-5: 1-5, with the azodiisobutyronitrile is initator, V and two kinds of monomers of M are joined in the solvent benzol, wherein the solvent benzol volume be two kinds of monomer volumes 5-10 doubly, initiator amount is the 0.5-5% of two kinds of monomer weights, 60 ℃ polymerization 5-24 hour, use petroleum ether precipitation, obtain catalyst ligand;
The copolymer of 1 part of weight is dissolved in the acetic acid of 10-100 weight portion, and agitating heating refluxes, and adds iridic compound, and the weight that adds iridium is the 3-10% of copolymer, reacts 10-60 minute, is cooled to room temperature, uses ether sedimentation, filters and obtains copolymer-iridium catalyst.Described iridic compound is IrCl
3, IrI
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2Or among the Ir (OAc) any one.
With the copolymer of 1 weight portion under agitation, join and contain [Ir (CO)
2I]
2Or [Ir (CO)
2Cl]
2Acetum in, feeding intake in Ir weight is the 3-10% of copolymer, stirring reaction 10-30 minute, use ether sedimentation, filter and to obtain copolymer-iridium catalyst.
When copolymer-iridium catalyst of the present invention was used for methanol carbonylation and prepares acetic acid, reaction system was formed and is comprised copolymer-iridium catalyst, methyl alcohol, co-catalyst iodomethane, solvent acetic acid and promoter.Reaction condition is: carbon monoxide pressure 3-5MPa, reaction temperature 170-220 ℃, wherein catalyst amount is to count 500-5000PPM with iridium.Co-catalyst iodomethane, content are the 3.0-13.0wt% of reaction medium weight,
Promoter in the above-mentioned reaction system comprises; Ruthenic chloride, [Ru (CO)
4I
2], [Ru (CO)
3I
2]
2, ruthenium acetate, propionic acid ruthenium and osmium chloride, osmium tetrachloride, [Os (CO)
4I
2], [Os (CO)
3I
2]
2, the promoter addition is 0.01-9.5 in the proportion of compound institute's containing metal and Ir: 1.
Embodiment 1
The 2-vinylpyridine monomer of weighing 0.20mol and the methacrylate monomer of 0.1mol mix with the 1.2g azodiisobutyronitrile, join in the benzene solvent of 70ml, under agitation, be cooled to room temperature in 60 ℃ of reactions 10 hours, use petroleum ether precipitation, obtain copolymer ligand.
Obtain the copolymer ligand of 2-vinylpyridine and the different proportionings of methyl acrylate with said method.
Embodiment 2
2-vinylpyridine-the methyl acrylate copolymer that takes by weighing 1 weight portion among the embodiment 1 is dissolved in the acetic acid of 50 weight portions.Agitating heating refluxes, and adds IrCl3 or IrI3 or Ir (OAc) 3, and addition is the 3-10% of copolymer in iridium weight, reacts after 30 minutes, is cooled to room temperature, uses ether sedimentation, filters and obtains copolymer-iridium catalyst.
The copolymer that obtains different 2-vinylpyridines-methyl acrylate proportioning with said method respectively with IrCl
3, IrI
3, Ir (OAc)
3Copolymer-iridium catalyst.
Embodiment 3
Take by weighing 1 weight portion copolymer among the embodiment 1, under agitation join and contain in [Ir (CO) 2I] 2 acetums, addition is Ir: copolymer=0.03-0.1: 1, reacted 20 minutes, and filter with ether sedimentation and obtain copolymer-iridium catalyst.
The copolymer that obtains different 2-vinylpyridines-methyl acrylate proportioning with said method respectively with [Ir (CO)
2I]
2[Ir (CO)
2Cl]
2Catalyst.
Embodiment 4
With copolymer and Ir (OAc) among the embodiment 2
3The catalyst that forms, wherein 2-vinylpyridine: methyl acrylate is 7: 3, and iridium content is 6.5%, takes by weighing this catalyst 3.8g, methyl alcohol 25ml, and iodomethane 17ml, acetic acid 60ml, ruthenium acetate 0.28g places reactor.Be warming up to 187 ℃ after feeding CO, 500 rev/mins of mixing speeds, control reaction pressure 4.0MPa, 17 minutes reaction time.Methanol conversion 94%, acetic acid space-time yield 11.9mol AcOH/L.h.
Embodiment 5
Take by weighing copolymer and [Ir (CO) among the embodiment 3
2I]
2The catalyst that forms, wherein 2-vinylpyridine-methyl acrylate is 8: 2, iridium content is 5.5%, takes by weighing this catalyst 4.2g, methyl alcohol 30ml, iodomethane 18ml, osmium chloride 0.30g places reactor.After feeding CO, be warming up to 195 ℃, 500 rev/mins of mixing speeds, control reaction pressure 4.2MPa, 15 minutes reaction time.Methanol conversion 97%, acetic acid space-time yield 18.2mol AcOH/L.h.
Embodiment 6
Take by weighing copolymer and IrCl among the embodiment 2
3The catalyst that forms, wherein 2-vinylpyridine-methyl acrylate is 9: 1, iridium content is 7.1%, takes by weighing this catalyst 4.0g, methyl alcohol 35ml, iodomethane 20ml, osmium tetrachloride 0.40g places reactor.After feeding CO, heat up and put 200 ℃, 500 rev/mins of mixing speeds, control reaction pressure 3.5MPa, 20 minutes reaction time.Methanol conversion 96%, acetic acid space-time yield 16.4mol AcOH/L.h.
Claims (8)
1. the pyridine carboxylic acid iridium complex catalyst of a methanol carbonyl synthesized acetic acid is characterized in that, the part of catalyst is the copolymer of 2-vinylpyridine and methyl acrylate, forms the copolymer-iridium composition catalyst with iridic compound by complexation reaction.
2. the pyridine carboxylic acid iridium complex catalyst of methanol carbonyl synthesized acetic acid according to claim 1, it is characterized in that, the part of catalyst is the copolymer of 2-vinylpyridine and methyl acrylate, and the molar ratio of 2-vinylpyridine (V) and methyl acrylate (M) is V: M=9-5: 1-5 in the copolymer.
3. the pyridine carboxylic acid iridium complex catalyst of methanol carbonyl synthesized acetic acid according to claim 1 and 2, it is characterized in that, catalyst ligand adopts the free radical solution polymerization method to obtain, and makes solvent with benzene, and azodiisobutyronitrile is an initator, two kinds of monomers of V and M join in the solvent benzol by specified amount, wherein the solvent benzol volume be two kinds of monomer volumes 5-10 doubly, initiator amount is the 0.5-5% of two kinds of monomer weights, 60 ℃ polymerization 5-24 hour, use petroleum ether precipitation, obtain catalyst ligand.
4. the pyridine carboxylic acid iridium complex catalyst of methanol carbonyl synthesized acetic acid according to claim 1 is characterized in that, iridic compound is IrCl
3, IrI
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2Or Ir (OAc)
3
5. the preparation method of the pyridine carboxylic acid iridium complex catalyst of methanol carbonyl synthesized acetic acid according to claim 1 is characterized in that, step is:
1) preparation catalyst ligand: the molar ratio according to 2-vinylpyridine (V) and methyl acrylate (M) is the ratio of V: M=9-5: 1-5, with the azodiisobutyronitrile is initator, V and two kinds of monomers of M are joined in the solvent benzol, wherein the solvent benzol volume be two kinds of monomer volumes 5-10 doubly, initiator amount is the 0.5-5% of two kinds of monomer weights, 60 ℃ polymerization 5-24 hour, use petroleum ether precipitation, obtain catalyst ligand;
The part of 1 weight portion is dissolved in the acetic acid of 10-100 weight portion, and agitating heating refluxes, and adds iridic compound, addition is the 3-10% of copolymer in iridium weight, reacts after 10-60 minute, is cooled to room temperature, use ether sedimentation, filter and obtain copolymer-iridium catalyst;
2) with the copolymer of 1 weight portion under agitation, join and contain [Ir (CO)
2I]
2Or [Ir (CO)
2Cl]
2Acetum in, both feed intake is to be the 3-10% of copolymer in Ir weight, stirring reaction 10-30 minute, use ether sedimentation, filter and to obtain the copolymer catalyst.
6. the preparation method of the pyridine carboxylic acid iridium complex catalyst of methanol carbonyl synthesized acetic acid according to claim 5 is characterized in that, described iridic compound is IrCl
3, IrI
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2Or among the Ir (OAc) any one.
7. the application of pyridine carboxylic acid iridium complex catalyst in catalysis of carbonyl is acetic acid synthesized of methanol carbonyl synthesized acetic acid according to claim 1 is characterized in that, when using, adds promoter in the reaction system, and described promoter is ruthenic chloride, [Ru (CO)
4I
2], [Ru (CO)
3I
2]
2, ruthenium acetate, propionic acid ruthenium or osmium chloride, osmium tetroxide, [Os (CO)
4I
2], [Os (CO)
3I
2]
2, wherein the promoter addition is 0.01-9.5 in the ratio of weight metal and Ir: 1.
8. the application of pyridine carboxylic acid iridium complex catalyst in catalysis of carbonyl is acetic acid synthesized of methanol carbonyl synthesized acetic acid according to claim 1, it is characterized in that, add the co-catalyst iodomethane during application, content is the 3.0-13.0wt% of reaction medium weight, the concentration of Ir is 500-5000ppm in the reaction system, reaction temperature is 170-220 ℃, and reaction pressure is 3.0-5.0MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910184273A CN101693209A (en) | 2009-08-24 | 2009-08-24 | Iridium picolinate complex catalyst for synthesizing acetic acid by methanol carbonylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910184273A CN101693209A (en) | 2009-08-24 | 2009-08-24 | Iridium picolinate complex catalyst for synthesizing acetic acid by methanol carbonylation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101693209A true CN101693209A (en) | 2010-04-14 |
Family
ID=42092234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910184273A Pending CN101693209A (en) | 2009-08-24 | 2009-08-24 | Iridium picolinate complex catalyst for synthesizing acetic acid by methanol carbonylation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101693209A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645810A (en) * | 2020-12-17 | 2021-04-13 | 南京延长反应技术研究院有限公司 | Enhanced reaction system and method for preparing acetic acid by methanol carbonylation |
| CN113019460A (en) * | 2020-12-17 | 2021-06-25 | 南京延长反应技术研究院有限公司 | Iridium complex catalyst and preparation method thereof |
-
2009
- 2009-08-24 CN CN200910184273A patent/CN101693209A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645810A (en) * | 2020-12-17 | 2021-04-13 | 南京延长反应技术研究院有限公司 | Enhanced reaction system and method for preparing acetic acid by methanol carbonylation |
| CN113019460A (en) * | 2020-12-17 | 2021-06-25 | 南京延长反应技术研究院有限公司 | Iridium complex catalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101531725B (en) | Alpha-nickel diimine compound olefin polymerization catalyst and preparation method thereof, and method for preparing branched polyethylene | |
| CN102190583A (en) | Method for synthesizing low carbon alcohol ester of acrylic acid by catalyzing acetylene carbonyl through palladium-phosphine complex | |
| CN100411738C (en) | Rhodium catalyst with organometallic lithium salts as ligand | |
| CN101001827A (en) | Alkoxycarbonylation of vinyl esters | |
| CN111889141A (en) | Ionic liquid functionalized bipyridine porous polymer catalyst for catalyzing cycloaddition reaction of carbon dioxide and epoxide | |
| CN113929813B (en) | Multifunctional metalloporphyrin complex, preparation method thereof and preparation method of polycarbonate | |
| CN100381204C (en) | Catalyst system for synthesizing acetic acid and acetic anhydride from carbonyl compound and its uses | |
| CN102218344B (en) | 3,5-dicarboxyl pyrazole iridium complex catalyst used for carbonylation synthesis of acetic acid as well as preparation method and application thereof | |
| CN101693209A (en) | Iridium picolinate complex catalyst for synthesizing acetic acid by methanol carbonylation | |
| CN101722047B (en) | Homogeneous phase iridium complex catalyst of methanol oxo-synthesis acetic acid, preparation method and application thereof | |
| CN102794198A (en) | Preparation method of catalyst for synthesizing propionic acid by ethanol carbonylation, and application thereof | |
| CN102050840A (en) | Naphthalene nucleus containing alpha-diketiminato nickel (II) composition as well as preparation method and application thereof | |
| CN100522362C (en) | Double active species catalyst and its application | |
| CN114870901B (en) | Bisphosphite polymer catalyst for olefin hydroformylation, preparation method and application thereof | |
| CN108864327A (en) | 5,6- dimethyl acenaphthene（Alpha-diimine）Nickel alkene catalyst and its preparation and application | |
| CN101613425A (en) | Has catalyst of polyethylene bimodal and/or broad peak distribution molecular weight distribution | |
| CN101703946B (en) | Copolymer-iridium catalyst used for preparing acetic acid through carbonylation reaction | |
| CN100522364C (en) | Catalyst and preparation process of the catalyst and its ligand, acetic acid and acetic anhydride | |
| CN102259028A (en) | Iridium catalyst for homogeneously catalyzing carbonylation of methanol to synthesize acetic acid as well as preparation method and application thereof | |
| CN115466177A (en) | Method for preparing 1, 4-diacetyloxy-2-butene | |
| CN1228141C (en) | Copolymer ligand rhodium-lithium bimetal catalyst and its manufacturing method and application | |
| 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 | |
| CN101391232A (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 | |
| CN1117626C (en) | Bimetallic catalyst with Rh and Li as copolymer ligand and its preparation | |
| CN101240059A (en) | Method for preparing norbornene open-loop translocation polymer or addition polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100414 |