CN100457269C - Methanol carbonylated primary aromatic amine N-pyridine ethyl derivative chelating rhodium catalyst - Google Patents
Methanol carbonylated primary aromatic amine N-pyridine ethyl derivative chelating rhodium catalyst Download PDFInfo
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- CN100457269C CN100457269C CNB200610007593XA CN200610007593A CN100457269C CN 100457269 C CN100457269 C CN 100457269C CN B200610007593X A CNB200610007593X A CN B200610007593XA CN 200610007593 A CN200610007593 A CN 200610007593A CN 100457269 C CN100457269 C CN 100457269C
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Abstract
The invention relates to a methanol carbonylation amine N- pyridine ethyl derivatives chelation rhodium catalyst, the positive ion part is N- pyridine derivatives ligand and rhodium formed chelation carbonyl structure, the negative ion part is iodine ion. The preparation method: after the same mole amine and 2- vinyl pyridine mixed add into its 1-3% quality trifluoroacetic acid react in the100-140degree centigradefor 10-24 hours, vacuum distillation distilled recrystalled to get N-pyridine ethyl ramification; extract the one mole N-pyridine ethyl ramification dissolved into 50-200 mole parts methanol, string with adding 1/2 mole part of [Rh(CO)2Cl]2, and adding the 50-200 mole parts water solution of one mole NaI or KI, string react 2-5 minutes and filtrate to get catalyst. The catalysts have good activity in the acetic acid reaction.
Description
Technical field
The present invention relates to a kind of methanol carbonylated primary aromatic amine N-pyridine ethyl derivative chelate type rhodium catalyst.
The invention still further relates to above-mentioned Preparation of catalysts method.
The invention still further relates to the application of above-mentioned catalyst in the acetic acid synthesis from methanol carbonylation reaction.
Background technology
In the reaction system of methanol carbonyl synthesized acetic acid, be one of important contents to the research of catalyst.Since the homogeneous rhodium catalyst technology path that the end of the seventies in last century, people (US 3 769 329) such as Paulik proposed, because its reaction condition is gentle relatively, reaction rate and selectivity all have remarkable advantages.Become of paramount importance production technology in the acetic acid industry at present.
Though the technology path of methanol carbonyl synthesized acetic acid has formed large-scale industrial production already in the whole world.But the improvement of catalyst and reaction system is international hot research problem for a long time always, all has every year many research papers and patent of invention to emerge.Research work is mostly round the selection of catalyst ligand, the adding of different additive in the reaction, and the exploitation of non-rhodium type metal active species.One of purpose of these research work is the new catalyst that the development performance is better than existing industrial catalyst.Be exactly adding in addition, improve existing activity of such catalysts, or increase the rhodium concentration in the reaction system, reach the purpose that improves reaction rate by additive in reaction system.
Aspect catalyst research, make the interest that the research of part has caused many researchers to contain phosphine compound.Adopt [RhCl (CO) (PEt as people such as J.Rankin
3)
2] when complex is 150 ℃ in reaction temperature, with reaction rate STY (mol AcOH/Lh) by [Rh (CO)
2Cl]
25.0 bring up to 9.2 (Chem.Commun.1997,1835).C.A.Carraz etc. select bidentate type phosphine composition, and its STY reaches 13.7 (Chem.Commun, 2000,1277).C.M.Thomas etc. are 732 (Chem.Eur.J., 2002,8 with the catalysis speed TON of the synthetic acetic acid of phosphine rhodium complex catalysis methanol carbonylation, 3343), the active TON of the cis phosphine rhodium dicarbapentaborane complex of Z.Freixa etc. reaches 902 (Angew.Chem.Int.Ed., 2005,44,4305).The research that with the nitrogen-containing compound is part also has a lot of reports, 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, adding auxiliary agent in the reaction system is effective ways that improve carbonylation rate.Wherein the adding of metal lithium salts obtains obvious effects (US6,130,355)
Summary of the invention
The object of the present invention is to provide a kind of methanol carbonylated primary aromatic amine N-pyridine ethyl derivative chelate type rhodium catalyst
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned catalyst.
For achieving the above object, the present invention selects to contain that can to form strong and weak different aromatic amine N-pyridine ethyl derivatives of joining key with rhodium be part, and selection iodine is the anion part of catalyst, the cation that forms catalyst partly is the suitable dicarbonyl structure of chelating type that primary aromatic amine N-pyridine derivative ligand and rhodium form, anion partly is an iodide ion, and its structure is shown below:
In the formula: R is positioned at the contraposition of amido, and R=-CH
3, F, Cl or Br.
Described methanol carbonylated primary aromatic amine N-pyridine ethyl derivative chelate type rhodium catalyst, wherein the precursor of rhodium is [Rh (CO)
2Cl]
2
Described methanol carbonylated primary aromatic amine N-pyridine ethyl derivative chelate type rhodium catalyst, wherein the iodide ion precursor of anion part is NaI or KI.
Described methanol carbonylated primary aromatic amine N-pyridine ethyl derivative chelate type rhodium catalyst, wherein uncle's arylamine is the N-pyridine ethyl derivative to methylaniline, para-fluoroaniline, parachloroanilinum or para-bromoaniline.
The method of the above-mentioned catalyst of preparation provided by the invention, its key step is:
A) take by weighing equimolar uncle's arylamine and 2-vinylpyridine and mix the trifluoroacetic acid that the back adds its 1-3% weight, 100-140 ℃ of reaction 10-24 hour, decompression distillation was extracted the back recrystallization and is obtained primary aromatic amine N-pyridine ethyl derivative;
B) primary aromatic amine N-pyridine ethyl derivative of getting 1 molar part steps A preparation is dissolved in the methyl alcohol of 50-200 molar part, adds [the Rh (CO) of 1/2 molar part under ice bath stirs
2Cl]
2, continue to stir, add the aqueous solution of the 50-200 molar part that is dissolved with 1 molar part NaI or KI, stirring reaction 2-5 minute, filter and obtain catalyst.
Described preparation method, decompression distillation is used NaHCO earlier before extracting in the steps A
3In and behind the trifluoroacetic acid, use benzinum extraction product repeatedly under room temperature to 60 ℃ condition, then benzinum is evaporated, again the product decompression distillation is extracted, in benzinum, be recrystallized then, obtain primary aromatic amine N-pyridine ethyl derivative.
In the catalyst of the present invention, active specy is a cation type structure.In its active specy, contain two kinds of N → Rh keys that mating capability is different, i.e. rhodium and the strong N → Rh of the conjugation N formation of pyridine ring and the relative more weak N → Rh of rhodium and arylamine N formation.Joining key for two kinds makes the cation active specy become the chelating type coordination structure.This structure is different from common anion active specy and monodentate composition catalyst.
In addition, the anion of catalyst adopts iodide ion.Because iodine is the most effective auxiliary agent of carbonylation, direct introducing iodide ion in catalyst molecule, this feature is different from usually with transition metal salt or contains salt compounded of iodine does Study on Additive work.
The application of methanol carbonylated primary aromatic amine N-pyridine ethyl derivative chelate type rhodium catalyst provided by the invention in the acetic acid synthesized reaction of catalysis methanol carbonylation, co-catalyst is an iodomethane, its content is 1-5mol/L, catalyst amount is in rhodium 100-2000ppm in the reaction system, reactant is a methyl alcohol, reaction temperature 140-200 ℃, carbon monoxide pressure 3.0-5.0MPa.
Described application wherein also can add acetic acid as solvent in the reaction system, the acetic acid addition is the 3-97wt% of methyl alcohol and acetic acid total amount.
Provided by the invention is the primary aromatic amine N-pyridine ethyl derivative chelating rhodium negative ions type catalyst of anion with iodine, prepare in the reaction response of acetic acid at the catalysis methanol carbonylation, compare the monodentate catalyst or non-iodine tetraethylammonium difluoride has tangible activity advantage.
The specific embodiment
Embodiment 1
Take by weighing 0.1mol 4-methylaniline and 0.1mol 2-vinylpyridine evenly mixes with the 2ml trifluoroacetic acid, place 140 ℃ of reactions 24 hours.With excessive N aHCO
3In and behind the trifluoroacetic acid, reactant extracts three times with boiling petroleum ether (bp 60-90 ℃), after the extract steaming petroleum ether, carries out decompression distillation.Cut is collected at 150 ℃ of-170 ℃/0.3-0.4mmHg.With the benzinum recrystallization, obtain 4-methylaniline N-pyridine ethyl.
Obtain 4-fluoroaniline N-pyridine ethyl, 4-chloroaniline N-pyridine ethyl, 4-bromaniline N-pyridine ethyl with quadrat method.
Take by weighing 0.01mol 4-methylaniline N-pyridine ethyl, be dissolved in the methyl alcohol of 1mol, under ice bath stirs, add [the Rh (CO) of 0.005mol
2Cl]
2, continue to stir after 10 minutes, drip the aqueous solution that 1mol is dissolved with 0.01mol KI or NaI, react after 5 minutes, filter, product washs three times with 0 ℃ of ether, and reduced pressure at room temperature obtains 4-methylaniline N-pyridine ethyl rhodium catalyst to constant weight.
Obtain 4-fluoroaniline N-pyridine ethyl rhodium with said method, 4-chloroaniline N-pyridine ethyl rhodium, 4-bromaniline N-pyridine ethyl rhodium.
Embodiment 2
Take by weighing and made among the embodiment 1 methylaniline N-pyridine ethyl rhodium catalyst 0.25g is placed reactor, add methyl alcohol 2.50mol, iodomethane 0.35mol, be warming up to 170 ℃ after feeding CO, keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 40min, methanol conversion 100%, methyl acetate yield 0.85mol, acetic acid yield 1.47mol.
Embodiment 3
Take by weighing that made para-fluoroaniline N-pyridine ethyl rhodium catalyst 0.30g places reactor among the embodiment 1, add methyl alcohol 1.24mol, acetic acid 0.87mol, iodomethane 0.25mol is warming up to 180 ℃ behind the feeding CO, reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 20min, methanol conversion 100%, methyl acetate yield 0.029mol, acetic acid increment are 1.18mol.
Embodiment 4
Take by weighing that made parachloroanilinum N-pyridine ethyl rhodium catalyst 0.28g places reactor among the embodiment 1, add methyl alcohol 1.24mol, acetic acid 0.87mol, iodomethane 0.24mol is warming up to 160 ℃ behind the feeding CO, reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 25min, methanol conversion 100%, methyl acetate yield 0.03mol, acetic acid increment are 1.19mol.
Embodiment 5
Take by weighing that made 4-bromaniline N-pyridine ethyl rhodium catalyst 0.30g places reactor among the embodiment 1, add methyl alcohol 1.24mol, acetic acid 0.87mol, iodomethane 0.24mol is warming up to 150 ℃ behind the feeding CO, keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 20min, methanol conversion 100%, methyl acetate yield 0.01mol, acetic acid increment 1.18mol.
Claims (6)
1. methanol carbonylated primary aromatic amine N-pyridine ethyl derivative chelate type rhodium catalyst, its architectural feature is that the cation of catalyst partly is the suitable dicarbonyl structure of chelating type that primary aromatic amine N-pyridine ethyl derivative part and rhodium form, anion partly is an iodide ion, and its structure is shown below:
In the formula: R is positioned at the contraposition of amido, and R=-CH
3, F, Cl or Br.
2. methanol carbonylated primary aromatic amine N-pyridine ethyl derivative chelate type rhodium catalyst according to claim 1, wherein, primary aromatic amine N-pyridine ethyl derivative is the N-pyridine ethyl derivative to methylaniline, para-fluoroaniline, parachloroanilinum or para-bromoaniline.
3. prepare the method for the described methanol carbonylated primary aromatic amine N-pyridine ethyl derivative chelate of claim 1 type rhodium catalyst, its key step is:
A) equimolar uncle's arylamine and 2-vinylpyridine mix the trifluoroacetic acid that the back adds its 1-3% weight, and 100-140 ℃ of reaction 10-24 hour, decompression distillation was extracted the back recrystallization and obtained primary aromatic amine N-pyridine ethyl derivative;
B) primary aromatic amine N-pyridine ethyl derivative of getting 1 molar part steps A preparation is dissolved in the methyl alcohol of 50-200 molar part, adds [the Rh (CO) of 1/2 molar part under ice bath stirs
2Cl]
2, continue to stir, add the aqueous solution of the 50-200 molar part that is dissolved with 1 molar part NaI or KI, stirring reaction 2-5 minute, filter and obtain catalyst.
4. according to the described method of claim 3, it is characterized in that decompression distillation is used NaHCO earlier before extracting in the steps A
3In and trifluoroacetic acid, use benzinum extraction product under room temperature to 60 ℃ condition, then benzinum is evaporated, again the product decompression distillation is extracted.
5. the application of methanol carbonylated primary aromatic amine N-pyridine ethyl derivative chelate type rhodium catalyst according to claim 1 in the acetic acid synthesized reaction of catalysis methanol carbonylation, co-catalyst is an iodomethane, its content is 1-5mol/L, catalyst amount is in rhodium 100-2000ppm in the reaction system, reactant is a methyl alcohol, reaction temperature 140-200 ℃, carbon monoxide pressure 3.0-5.0MPa.
6. application according to claim 5 is characterized in that, adds acetic acid in the reaction system as solvent, and the acetic acid addition is the 3-97wt% of methyl alcohol and acetic acid total amount.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1349967A (en) * | 2000-10-24 | 2002-05-22 | 中国科学院化学研究所 | Copolymer ligand Rh catalyst for methanol carbonylation to synthesize acetic acid and ethyl anhydride and its prepn |
| US20040059153A1 (en) * | 2002-05-23 | 2004-03-25 | Institut Francais Du Petrole | Process for carbonylating alcohols, employing a catalyst based on rhodium or iridium in a non-aqueous ionic liquid, with efficient catalyst recycling |
| CN1517385A (en) * | 2003-01-17 | 2004-08-04 | 中国科学院化学研究所 | Binitrogen ligand chelated palladium catalyst system and preparation method and application |
-
2006
- 2006-02-20 CN CNB200610007593XA patent/CN100457269C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1349967A (en) * | 2000-10-24 | 2002-05-22 | 中国科学院化学研究所 | Copolymer ligand Rh catalyst for methanol carbonylation to synthesize acetic acid and ethyl anhydride and its prepn |
| US20040059153A1 (en) * | 2002-05-23 | 2004-03-25 | Institut Francais Du Petrole | Process for carbonylating alcohols, employing a catalyst based on rhodium or iridium in a non-aqueous ionic liquid, with efficient catalyst recycling |
| CN1517385A (en) * | 2003-01-17 | 2004-08-04 | 中国科学院化学研究所 | Binitrogen ligand chelated palladium catalyst system and preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| [顺-二羰基(N-2-(2-吡啶)乙基芳胺)铑]的四苯硼酸盐的合成及其催化性能. 袁国卿等.分子催化，第9卷第4期. 1995 * |
| 新型甲醇羰基化反应的催化剂结构设计及应用. 柳忠阳等.科学通报，第44卷第12期. 1999 * |
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Effective date of registration: 20200121 Address after: 212006 No. 88 Qiusuo Road, Jingkou District, Zhenjiang City, Jiangsu Province Co-patentee after: Institute of Chemistry, Chinese Academy of Sciences Patentee after: Jiangsu Sopo Chemical Co.,Ltd. Address before: 212006 Long Gang, Dantu, Jiangsu, Zhenjiang Co-patentee before: Institute of Chemistry, Chinese Academy of Sciences Patentee before: Jiangsu Soap (Group) Co., Ltd. |