CN102218344B - 3,5-dicarboxyl pyrazole iridium complex catalyst used for carbonylation synthesis of acetic acid as well as preparation method and application thereof - Google Patents
3,5-dicarboxyl pyrazole iridium complex catalyst used for carbonylation synthesis of acetic acid as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of acetic acid preparation by a methanol carbonylation reaction, and particularly relates to a 3,5-dicarboxyl pyrazole iridium complex catalyst which is formed by carrying out a complexing reaction on 3,5-dicarboxy pyrazole used as a ligand and iridium and is used for acetic acid synthesis by methanol carbonylation, as well as a preparation method and an application thereof. The complex catalyst has good catalysis performance in acetic acid preparation by methanol carbonylation. The catalyst is a 3,5-dicarboxyl pyrazole iridium complex catalyst which is formed by carrying out a complexing reaction on 3,5-dicarboxy pyrazole used as the ligand and an iridium compound used as an active central atom.
Description
Technical field
The invention belongs to methanol carbonylation and prepare the acetic acid field, particularly acetic acid synthesis from methanol carbonylation is 3 of part and iridium complexation reaction formation with 3,5-dicarboxyl pyrazoles, 5-dicarboxyl pyrazoles iridium complex catalyst; And the preparation method and application of this catalyst.
Technical background
Methyl alcohol and carbon monoxide carbonylation under the effect of rhodium catalyst prepares the invention that acetic acid is the people (US 3769329) such as the early 1970s U.S. Monsanto Paulik of company.This invention is that an important novel process route has been opened up in the preparation of acetic acid.Compare with traditional technique, because its economic benefit and to the advantage of the pollution less of environment is widely used in the world rapidly.
Since the synthetic preparation of low pressure carbonyl acetic acid technique was come out, the research of relevant catalyst was a focus always, and for the rhodium series catalysts, the most successful example is exactly that (US 5001259 for the low water reaction system of high iodine of Celanes company; EP 055618).This technique has not only improved reaction speed by the adding of inorganic salt compounded of iodine in the reaction medium; And solved the deposited phenomenon of catalyst.But, because the increase of iodine concentration in the reaction medium causes the raising of amount of iodine in the product, restricted the production difficulty of downstream product such as vinyl acetate, be the obvious deficiency of this technique.
Aspect the research of non-rhodium series catalysts, iridium series catalysts EP 0749948, EP 0752406 are present unique catalyst system and catalyzings that is successfully applied to suitability for industrialized production.This technology was succeeded in developing by BP chemical company in 1996, was called Cativa technique, compared with the rhodium series catalysts, and the iridium series catalysts has cheap, the advantage that byproduct of reaction is few.
As the main body catalytic metal, usually in use, add at least a promoter with the compound of iridium.Numerous slaine all is used as promoter and carried out research, and wherein the compound of ruthenium and osmium becomes preferred catalytic promoter.The suitable ruthenium compound that contains comprises: the oxide of ruthenic chloride, ruthenium bromide, ruthenium metal, ruthenium, formic acid ruthenium (III), ruthenium acetate (III), butyric acid ruthenium (III), pentacarbonyl ruthenium, [Ru (CO)
3I
3]
-H
+, tetrem chloride ruthenium (II, III) and ruthenium organic complex.
The promoter of osmium comprises; Osmium chloride (III), metal osmium, osmium tetrachloride, ten dicarbapentaborane, three osmiums and other organic osmium compound.In addition, the compound of tungsten, cadmium, mercury, zinc, gallium, indium also is taken as the selection material of promoter usually.
Summary of the invention
The objective of the invention is to solve the problem that above-mentioned prior art exists, provide a kind of for acetic acid synthesis from methanol carbonylation with 3,5-dicarboxyl pyrazoles be part and iridium complexation reaction form 3,5-dicarboxyl pyrazoles iridium complex catalyst.
Another object of the present invention provides a kind of for 3 of acetic acid synthesis from methanol carbonylation, the preparation method of 5-dicarboxyl pyrazoles iridium complex catalyst
An also purpose of the present invention provides for 3 of acetic acid synthesis from methanol carbonylation the application of 5-dicarboxyl pyrazoles iridium complex catalyst.
Of the present invention for 3 of carbonylation acetic acid, 5-dicarboxyl pyrazoles iridium complex catalyst is 3,3 of 5-dicarboxyl pyrazoles and iridic compound complexation reaction formation, 5-dicarboxyl pyrazoles iridium complex catalyst, part is 3,5-dicarboxyl pyrazoles, activated centre atom are iridium.
Described iridic compound is IrCl
3, IrI
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2Or Ir (OAc)
3(acetic acid iridium).
Of the present invention for 3 of carbonylation acetic acid, the preparation method of 5-dicarboxyl pyrazoles iridium complex catalyst: with 3 of 1 molar part, 5-dicarboxyl pyrazoles is dissolved in the acetic acid of 100-200 molar part, add hot reflux, under agitation add the iridic compound reaction of 1 molar part after 20-60 minute, be cooled to room temperature, add the ether solvent precipitation excessive with respect to the product volume; Filtration obtains described for 3 of carbonylation acetic acid, 5-dicarboxyl pyrazoles iridium complex catalyst, namely 3,3 of 5-dicarboxyl pyrazoles and iridic compound complexation reaction formation, 5-dicarboxyl pyrazoles iridium complex catalyst, part is 3,5-dicarboxyl pyrazoles, activated centre atom are iridium.
Iridic compound among this preparation method is IrCl
3, IrI
3Or Ir (OAc)
3
Of the present invention for 3 of carbonylation acetic acid, the preparation method of 5-dicarboxyl pyrazoles iridium complex catalyst is: with 3 of 1 molar part, 5-dicarboxyl pyrazoles is dissolved in the acetic acid of 100-200 molar part, under agitation add the reaction of 0.5 molar part iridic compound after 20-60 minute, add the ether solvent precipitation excessive with respect to the product volume; Filtration obtains 3 of 3,5-dicarboxyl pyrazoles and iridic compound complexation reaction formation, and 5-dicarboxyl pyrazoles iridium complex catalyst, part are 3,5-dicarboxyl pyrazoles, and the activated centre atom is iridium.
Iridic compound among this preparation method is [Ir (CO)
2I]
2Or [Ir (CO)
2Cl]
2
Of the present invention for 3 of carbonylation acetic acid, 5-dicarboxyl pyrazoles iridium complex catalyst is when being used for the catalysis methanol carbonylation acetic acid: will be for 3 of carbonylation acetic acid, 5-dicarboxyl pyrazoles iridium complex catalyst, methyl alcohol, co-catalyst iodomethane (can add part acetic acid as solvent) place reactor, pass into carbon monoxide, keeping the pressure of carbon monoxide is 4～5MPa, reaction temperature is 170～220 ℃, obtains acetic acid behind the stirring reaction; Wherein, be used for 3 of carbonylation acetic acid in reaction system, the consumption of 5-dicarboxyl pyrazoles iridium complex catalyst is in iridium, and iridium content is 500～5000ppm scope; The consumption of co-catalyst iodomethane in reaction system is 3～13wt%.
In above-mentioned reaction system, add a certain amount of promoter, can obviously improve the speed that reaction is carried out.The consumption of promoter in reaction system is with the mole of the metallic element in the promoter and described for 3 of carbonylation acetic acid, and the ratio of the mole of the iridium in the 5-dicarboxyl pyrazoles iridium complex catalyst is 0.01～9.5: 1.
Described promoter is selected from ruthenic chloride, [Ru (CO)
4I
2], [Ru (CO)
3I
2]
2, ruthenium acetate, propionic acid ruthenium, osmium chloride, osmium tetroxide, [Os (CO)
4I
2] and [Os (CO)
3I
2]
2In a kind of.
The present invention has following useful technique effect: the present invention is chosen in the reaction that carbonylation of methanol prepares acetic acid has 3 of good stabilization, and 5-dicarboxyl pyrazole compound forms complex as catalyst as part with iridic compound.This catalyst is owing to have conjugation N and the Ir atom generation coordination of stronger electron donation on the pyrazole ring, by reaction mechanism as can be known (Maitlis, P.M.; Haynes, A.jsunley, G.J.J Chem.Soc., Dalton Trans.1996,2187) this complexation reaction so that activated centre metal Ir Electronic Negative electrically change, so that affected the ability of the backdonation between Ir and the CO, the conjugation N on the pyrazole ring can make the backdonation that forms between Ir and the Co strengthen, so that catalyst has higher catalytic activity.In addition, because the existence of ligand molecular makes the active specy centered by Ir be in asymmetrical state, be conducive to the oxidation addition of co-catalyst iodomethane, important function has been played in the raising of catalyst activity.
The specific embodiment
Embodiment 1
Take by weighing 3 of 1 molar part, 5-dicarboxyl pyrazoles joins in the acetic acid of 100 molar part, adds hot reflux, under agitation adds the IrCl of 1 molar part
3, react after 30 minutes, be cooled to room temperature, add the ether solvent precipitation excessive with respect to the product volume, filter and obtain 3,5-dicarboxyl pyrazoles iridium complex catalyst; Part is 3,5-dicarboxyl pyrazoles, and the activated centre atom is iridium.
Use above-mentioned same procedure, with IrCl
3Replace with IrI
3Or Ir (OAc)
3, can obtain respectively 3,5-dicarboxyl pyrazoles and IrI
3Or Ir (OAc)
33 of complexation reaction formation, 5-dicarboxyl pyrazoles iridium complex catalyst; Part is 3,5-dicarboxyl pyrazoles, and the activated centre atom is iridium.
Embodiment 2
Take by weighing 3 of 1 molar part, 5-dicarboxyl pyrazoles under agitation joins in the acetum of 200 molar part, adds [the Ir (CO) of 0.5 molar part
2I]
2, stirring reaction added the ether solvent precipitation excessive with respect to the product volume after 50 minutes, filtered and obtained 3,5-dicarboxyl pyrazoles and [Ir (CO)
2I]
23 of complexation reaction formation, 5-dicarboxyl pyrazoles iridium complex catalyst; Part is 3,5-dicarboxyl pyrazoles, and the activated centre atom is iridium.
Use above-mentioned same procedure, with [Ir (CO)
2I]
2Replace with [Ir (CO)
2Cl]
2, can obtain 3,5-dicarboxyl pyrazoles and [Ir (CO)
2Cl]
23 of complexation reaction formation, 5-dicarboxyl pyrazoles iridium complex catalyst; Part is 3,5-dicarboxyl pyrazoles, and the activated centre atom is iridium.
Embodiment 3
Add in reactor that embodiment 1 prepares 3,5-dicarboxyl pyrazoles and IrCl
3The iridium complex catalyst 0.7g that reaction generates, methyl alcohol 20ml, iodomethane 15ml, acetic acid 60ml, ruthenium acetate 0.23g, after passing into CO, be warmed up to 190 ℃, mixing speed is 500 rev/mins, the control reaction pressure is 4.5MPa, reaction time is 15 minutes, and methanol conversion is 95%, and the acetic acid space-time yield is 11.5molAcOH/L.h.
Embodiment 4
Add in reactor that embodiment 2 prepares 3,5-dicarboxyl pyrazoles and [Ir (CO)
2I]
2The iridium complex catalyst 0.9g that reaction generates, methyl alcohol 30ml, iodomethane 20ml, acetic acid 60ml, osmium tetroxide 0.5g, after passing into CO, be warmed up to 200 ℃, mixing speed is 500 rev/mins, the control reaction pressure is 4.2MPa, reaction time is 20 minutes, and methanol conversion is 96%, and the acetic acid space-time yield is 15.7molAcOH/L.h.
Embodiment 5
Add in reactor that embodiment 1 prepares 3,5-dicarboxyl pyrazoles and Ir (OAC)
3The iridium complex catalyst 0.8g that reaction generates, methyl alcohol 35ml, iodomethane 16ml, acetic acid 55ml, osmium chloride 0.25g, after passing into CO, be warmed up to 170 ℃, mixing speed is 500 rev/mins, the control reaction pressure is 5.0MPa, reaction time is 17 minutes, and methanol conversion is 93%, and the acetic acid space-time yield is 14.4molAcOH/L.h.
Embodiment 6
Add in reactor that embodiment 2 prepares 3,5-dicarboxyl pyrazoles and [Ir (CO)
2Cl]
2The iridium complex catalyst 0.8g that reaction generates, methyl alcohol 25ml, iodomethane 18ml, acetic acid 60ml, ruthenic chloride 0.6g, after passing into CO, be warmed up to 220 ℃, mixing speed is 500 rev/mins, the control reaction pressure is 4.0MPa, reaction time is 14 minutes, and methanol conversion is 99%, and the acetic acid space-time yield is 18.8molAcOH/L.h.
Claims (4)
1. one kind is used for 3 of carbonylation acetic acid, the preparation method of 5-dicarboxyl pyrazoles iridium complex catalyst: it is characterized in that: with 3 of 1 molar part, 5-dicarboxyl pyrazoles is dissolved in the acetic acid of 100-200 molar part, add hot reflux, under agitation add the iridic compound reaction of 1 molar part after 20-60 minute, be cooled to room temperature, add the ether solvent precipitation excessive with respect to the product volume; Filtration obtains 3 of 3,5-dicarboxyl pyrazoles and iridic compound complexation reaction formation, and 5-dicarboxyl pyrazoles iridium complex catalyst, part are 3,5-dicarboxyl pyrazoles, and the activated centre atom is iridium.
2. preparation method according to claim 1, it is characterized in that: described iridic compound is IrCl
3, IrI
3Or Ir (OAc)
3
3. one kind is used for 3 of carbonylation acetic acid, the preparation method of 5-dicarboxyl pyrazoles iridium complex catalyst: it is characterized in that: with 3 of 1 molar part, 5-dicarboxyl pyrazoles is dissolved in the acetic acid of 100-200 molar part, under agitation add the iridic compound reaction of 0.5 molar part after 20-60 minute, add the ether solvent precipitation excessive with respect to the product volume; Filtration obtains 3 of 3,5-dicarboxyl pyrazoles and iridic compound complexation reaction formation, and 5-dicarboxyl pyrazoles iridium complex catalyst, part are 3,5-dicarboxyl pyrazoles, and the activated centre atom is iridium.
4. preparation method according to claim 3, it is characterized in that: described iridic compound is [Ir (CO)
2I]
2Or [Ir (CO)
2Cl]
2
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| CN103506160A (en) * | 2012-06-26 | 2014-01-15 | 中国科学院化学研究所 | 3-pyridazinone iridium complex catalyst for methanol carbonylation synthesis of acetic acid as well as preparation method and application thereof |
| CN103193829B (en) * | 2013-03-14 | 2015-09-09 | 西北大学 | 2-(2-carboxyl phenyl) benzoglyoxaline cobalt complex and the application in the synthesis of toluylic acid or derivatives thereof thereof |
| CN104312579A (en) * | 2014-10-09 | 2015-01-28 | 济南大学 | Synthesis and application of zinc-base complex blue-fluorescence luminescent material |
| CN113024826B (en) * | 2021-03-04 | 2022-08-02 | 江苏理工学院 | Pyrazole carboxylic acid CoNi complex with visible light catalytic performance and preparation method and application thereof |
| CN113893881B (en) * | 2021-10-12 | 2024-04-09 | 江苏索普化工股份有限公司 | Method for preparing iridium-based catalyst and application of iridium-based catalyst in catalyzing methanol carbonylation |
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| CN1345631A (en) * | 2000-09-28 | 2002-04-24 | 中国科学院化学研究所 | Homogeneous rhodium catalyst for carbonyl synthesis and preparation method thereof |
| CN101391232A (en) * | 2008-10-31 | 2009-03-25 | 中国科学院化学研究所 | Pyrazole acetic-acid rhodium complexes catalyst capable of catalyzing carbonylation reaction to preparing acetic acid and acetic anhydride and preparation method and use thereof |
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| CN1345631A (en) * | 2000-09-28 | 2002-04-24 | 中国科学院化学研究所 | Homogeneous rhodium catalyst for carbonyl synthesis and preparation method thereof |
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