CN1105603A - Methyl alcohol carbonylation homogeneous rhodium catalyst and its preparing method and use - Google Patents
Methyl alcohol carbonylation homogeneous rhodium catalyst and its preparing method and use Download PDFInfo
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- CN1105603A CN1105603A CN 94100505 CN94100505A CN1105603A CN 1105603 A CN1105603 A CN 1105603A CN 94100505 CN94100505 CN 94100505 CN 94100505 A CN94100505 A CN 94100505A CN 1105603 A CN1105603 A CN 1105603A
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- rhodium
- methyl alcohol
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- homogeneous
- carbonylation
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Abstract
The present invention firstly uses an organic compound containing nitrogen atom and oxygen atom or phosphorus atom and oxygen atom as ligand, and makes it react with carbonyl rhodium and after metal-organic compound is settled, said invention makes the above-mentioned materials form a quadratic plane cis-dicarbonyl rhodium cationic complex containing two coordinate bonds of N-Rh, O-Rh or P-Rh O-Rh. Said complex is used for catalyzing methyl alcohol carbonylation to prepare acetic acid, and under the relative temperate condition it only uses catalyst promoter iodomethane, and has no need of addition of hydroiodic acid, and can catalyze methyl alcoholc arbonylation into aceticacid and methyl acetate at a high speed with high selectivity.
Description
The invention belongs to homogeneous rhodium catalyst.
Methyl alcohol prepares acetate by means of the catalytic action of rhodium with reaction of carbon monoxide, is considered to the important breakthrough of Organometallic Chemistry, and wherein the rhodium catalyst of monsanto successfully is applied to suitability for industrialized production.
In the methanol carbonylation of the little molecule rhodium complex catalysis of solubility, its active specy is generally rhodium monodentate complex, [Brodrk.D.Ledere.c; Benise.B; Pannetier Gi Bull.Soc Chim, Fr.1976.61] or dicarbapentaborane diiodo-rhodium (I) anionic complex, for example [Rh(CO)
2I
2]
-NR
+ 4[Roth, J.F.et al.Chem Technol 1971,600], because monodentate rhodium compound instability, when this class catalyst surpassed 180 ℃ in reaction temperature, it began to decompose inactivation, for [Rh(CO)
2I
2]
-Complex, it is easy to be converted into dicarbapentaborane tetraiodo rhodium (III) anionic complex in course of reaction, and lose catalytic activity, helping reacting especially true under the high temperature that carries out, therefore in process of production except that the dividing potential drop that keeps carbon monoxide, also must add excessive hydrogen iodide and exist with rhodium (I) state, because the existence of excessive hydrogen iodide has greatly increased the corrosiveness to production equipment on ground to keep catalyst.
The present invention is for the ubiquitous monodentate rhodium compound of the homogeneous catalyst that solves present methanol carbonylation instability, lose catalytic activity easily, and in preparation acetate process, need to add hydrogen iodide, and cause the etching problem of equipment, the nitrogen (as the conjugation nitrogen on the pyridine ring) of the last one coordination ability and the oxygen of a weak coordination ability have been proposed to contain in the ligand molecular, link to each other to have certain flexible carbochain, the chelating type that forms new square plane with this part and rhodium carbonyl is along dicarbapentaborane rhodium (I) complex.Because the chelation of part, this complex has good relatively heat endurance.In catalytic reaction process, owing to there is the N → Rh of the last one to join the existence of key, make catalyst keep good stable, and weak O → Rh joins key, in reaction medium, be easy to disassociation, make the center rhodium atom of active specy be in the coordination undersaturated condition, the utmost point is beneficial to the oxidation addition of co-catalyst iodomethane, and weak coordination atom is because the existence of chelating chain, after its coordination disassociation, still be in the coordination scope of rhodium atom, after the oxidation addition process for the treatment of iodomethane is finished, its still can with the rhodium atom relocation bit, this strong, a little less than join the complex of key coexistence, in the reaction of catalysis methanol carbonylation system acetate, performance is to good catalytic activity, and under gentle relatively condition, directly the catalysis methanol carbonyl turns to acetate and methyl acetate.
The technology formation of catalyst of the present invention comprises that with the organic compound that contains two kinds of donor atoms be part, and forming the suitable dicarbapentaborane rhodium complex of chelating type and contain two kinds of strong, weak different coordinate bonds with rhodium carbonyl is the methanol carbonyl catalyst for reaction that works is levied.In the Preparation of catalysts process, the employing slaine is a precipitating reagent, making catalyst is the cation activated centre of chelating type, the part of this catalyst ad hoc structure is that be part with pyridine ring (as the conjugation nitrogen on the pyridine ring) with the organic compound that aliphatic carbon oxygen forms, or the organic compound that contains nitrogen and oxygen simultaneously is a part, or the organic compound that contains phosphorus and oxygen simultaneously is part, makes catalyst have the N → Rh of the last one or P → Rh joins key and a weak O → Rh joins key.
Because selected part difference, part will contain nitrogen and oxygen atom or phosphorus and oxygen atom respectively simultaneously.Rhodium carbonyl Rh and the aliphatic that contains the pyridine ring of nitrogen and carbon oxygen or nitrogenous and oxygen or phosphorous and organic compound part oxygen form the square planar complexes of the rhodium of chelating type, and this rhodium complex has 6-14 unit chelating loop configuration along the dicarbapentaborane rhodium.For example, select 2-methyl valerate pyridine for use, 2-methyl butyrate pyridine, the organic ligand compound of methyl-acetate-betanaphthyl phosphorus is a part.
The catalyst of the suitable dicarbapentaborane rhodium cationic structural of chelating type, its structure is:
Has Y → Rh in the formula, two coordinate bonds of O → Rh
Y is N or P
R
1, R
2For alkyl, cyclic hydrocarbon radical, contain the heterocycle alkyl
R
1And the key between the Y is three key or two key
R
2And the key between the O is two keys or singly-bound
R
3Be alkyl
X
-Be BPh
- 4, I
-, Cl
-, Br
-, BF
- 4, CH
2COO
-
This cation type rhodium complex, constant in the medium-term and long-term storage properties of air, stability is preferably arranged.Because selected part difference is measured through electron spectrum (XPS) research, proves N → Rh, O → Rh joins key, or has P → Rh, O → Rh to join the existence of key.Infrared spectrum shows, at 1950-2100cm
-1Between the terminal carbonyl characteristic absorption peak of complex rhodium is arranged, suitable-one dicarbapentaborane rhodium (I) functional group that illustrates that such complex contains.
The activated centre of rhodium complex of the present invention is a cation type structure, and it is different from the monodentate or the negative ion type composition catalyst of other type.The complex of this rhodium is to have 6-14 unit chelate ring along the version of dicarbapentaborane rhodium, for example:
N=1-5 in the formula
R is hydrocarbon, cyclic hydrocarbon, contain heterocyclic hydrocarbon
The selected rhodium carbonyl of the present invention is Rh
2(CO)
4Cl
2, Rh
2(CO)
4Br
2, Rh
2(CO)
4I
2When preparation catalyst of the present invention, selected precipitating reagent is to have BPh
- 4, I
-, Cl
-, Br
-, BF
- 4, CH
2COO
-The anion alkaline metal salt as precipitating reagent.As: tetraphenylboron sodium, sodium iodide, sodium chloride, KI etc.
The method for making of rhodium complex catalyst of the present invention is that the organic compound that will have the formation of pyridine ring and aliphatic oxygen is a part, or the organic compound that contains nitrogen and oxygen simultaneously is a part, or the organic compound that contains phosphorus and oxygen simultaneously is the solute of part, be dissolved in acetone, in methyl alcohol or other solvent, part, rhodium carbonyl, the ratio of precipitating reagent is 2: 1: the 2(mol ratio), 1 mole part is dissolved in the acetone or methyl alcohol of 10-100 mole, under agitation be dissolved with the methanol solution of rhodium carbonyl in 0 ℃ of-40 ℃ of dropping, methyl alcohol: rhodium carbonyl is 50-100: the 1(mol ratio), and after dropwising, isothermal reaction 15-120 minute, add the BPh that has that is dissolved with 2-10% again
- 4, I
-, Cl
-, Br
-, BF
- 4, CH
2COO
-Anion alkaline metal salt precipitant solution (available methyl alcohol or water etc. are as the solvent of slaine), Deng the product post precipitation, suction filtration, with 0 ℃ water and methyl alcohol cyclic washing, in reduced pressure at room temperature to constant weight, rhodium complex catalyst can be obtained, 100% rhodium complex catalyst can be obtained at most.
As, be example with 2-methyl valerate pyridine:
Adopt this catalyst methanol carbonylation, preparation acetate or methyl acetate, with methyl alcohol and iodomethane in 5: 1～8: the ratio 1(mol ratio) is mixed the back and is added above-mentioned catalyst and charge into carbon monoxide, methyl alcohol and reaction of carbon monoxide generate acetate and methyl acetate, its reaction temperature is 120-150 ℃, and reaction pressure is 20-40kg/cm
2, and reaction is only used the co-catalyst iodomethane and be need not to add hydroiodic acid.
Because catalyst of the present invention has high catalytic activity, so the condition that it is adopted at the catalysis methanol carbonylation is very gentle.A large amount of experiments show that this catalyst has good selectivity, and product is methyl acetate and acetate, stirring under the bad situation, having a small amount of dimethyl ether and generate, along with going deep into of reaction, dimethyl ether continues carbonyl and turns to acetate or methyl acetate, and this selection of catalysts is 100%.
Reaction system adopts this catalyst methanol carbonylation for low corrosion, need not to add hydrogen iodide in system, reaction just can be carried out at a high speed, experiment showed, that the concentration of its co-catalyst iodomethane just remains unchanged as long as the existence of methyl alcohol or methyl acetate is arranged in the system.React the hydrogen iodide that self produces, by the balance that keeps iodomethane of following reaction:
Because the carrying out of the flank speed of (1) (2) formula reduced the accumulation of hydrogen iodide in system, thereby alleviated the corrosiveness to equipment, and at present known industrial production, this reaction all need add hydrogen iodide.
Adopt this catalyst methanol carbonylation, except that need not to add the hydrogen iodide, also need not to add other solvent, in known industrial production,, need when initial, to add acetate to increase the polarity of medium owing to adopt the poorly soluble of catalyst, and catalyst of the present invention, because the existence of oxy radical is arranged, with medium better affinity interaction is arranged, directly raw material gets final product as reacting at the beginning by methyl alcohol and iodomethane.
In addition, in the reaction system of this catalyst, also need not to add entry, thereby reduced the corrosiveness of the hydrogen of water gas reaction generation equipment.
Example 1
The 2-methyl valerate that takes by weighing 0.1 gram is dissolved in 20 ml methanol, under stirring, bath temperature adds the 10 ml methanol solution that are dissolved with 0.2 gram, four carbonyl dichloros, two rhodiums, continue to stir, behind the temperature reaction 0.5hr, 10 ml waters that are dissolved with 0.1 gram tetraphenylboron sodium are added a little, product is a yellow mercury oxide, filter, with 0 ℃ of methyl alcohol cyclic washing product three times, reduced pressure at room temperature obtains along the dicarbapentaborane rhodium complex catalyst at last to constant weight.
Example 2
Take by weighing 2-methyl valerate pyridine rhodium (I) cationic complexes, add in the reactor, methyl alcohol and iodomethane add with 7: 1 molar ratios, and the addition of catalyst is calculated as 1 * 10 with rhodium
-5Mol methyl alcohol-iodomethane mixed liquor, behind air in the carbon monoxide exchange system, the power of boosting is 30kg/cm
2Be warming up to 130 ± 5 ℃ of stirring reactions after 3 hours (300 rev/mins of mixing speeds), methanol conversion 95% calculates with the methyl alcohol that has transformed, and wherein the acetate productive rate 45%, and the methyl acetate productive rate is 55%.
Example 3
Take by weighing 2-methyl butyrate pyridine rhodium (I) cationic complexes and add in the reactor, add methyl alcohol and the iodomethane mixed liquor with 6.05: 1 molar ratios then, rhodium content is 3.7 * 10 in the system
-4Mol methyl alcohol-iodomethane mixed liquor, behind the air in the carbon monoxide exchange system, given initial pressure 30kg/cm
2, being warming up to 140 ℃ ± 2 ℃, mixing speed is 350 rev/mins, react after 2.5 hours, and methanol conversion is 91%, calculates with the methyl alcohol that has transformed, and the acetate productive rate is 39%, and the methyl acetate productive rate is 61%.
Example 4
The complex that takes by weighing two phosphorus polyester radical derivatives and rhodium carbonyl adds in the reactor, adds the mixed liquor (6.35: 1 moles) of methyl alcohol and iodomethane then, calculates with rhodium, and rhodium content in system is 1 * 10
-4Mol, methyl alcohol-iodomethane mixed liquor behind carbon monoxide displacement system hollow gas, boosts to 30kg/cm
2, being warmed to 130 ± 5 ℃, mixing speed is 400 rev/mins, reacts after 90 minutes.Methanol conversion is 85%, calculates with the methyl alcohol that transforms, and the acetate productive rate is 28%, and the methyl acetate productive rate is 72%.
Claims (10)
1, a kind of methyl alcohol carbonylation homogeneous rhodium catalyst, it is characterized in that preparing the organic ligand with Y and O of acetate and methyl acetate chelating type--along dicarbapentaborane rhodium cationic structural catalyst, its structure is as follows:
Has Y → Rh in the formula, two coordinate bonds of O → Rh
Y is N or P
R
1, R
2For alkyl, cyclic hydrocarbon radical, contain the heterocycle alkyl
R
1And the key between the Y is three key or two key
R
2And the key between the O is two keys or singly-bound
R
3Be alkyl
Described rhodium carbonyl Rh and the aliphatic that contains the pyridine ring of nitrogen and carbon oxygen or nitrogenous and oxygen or phosphorous and organic compound part oxygen form the square planar complexes of chelating type rhodium, and this rhodium complex is suitable-and the dicarbapentaborane rhodium has 6-14 unit chelating loop configuration.
2, methyl alcohol carbonylation homogeneous rhodium catalyst as claimed in claim 1 is characterized in that described is the cation type along a dicarbapentaborane rhodium catalyst activated centre.
3, methyl alcohol carbonylation homogeneous rhodium catalyst as claimed in claim 1 is characterized in that described X
-Be BPh
- 4, I
-, Cl
-, Br
-, BF
- 4, CH
2COO
-
4, methyl alcohol carbonylation homogeneous rhodium catalyst as claimed in claim 1, it is characterized in that described chelating loop configuration along the dicarbapentaborane rhodium as:
N=1-5 in the formula
R is hydrocarbon, cyclic hydrocarbon, contain heterocyclic hydrocarbon
5, methyl alcohol carbonylation homogeneous rhodium catalyst as claimed in claim 1 is characterized in that described rhodium carbonyl is Rh
2(CO)
4Cl
2, Rh
2(CO)
4Br
2, Rh
2(CO)
4I
2
6, a kind of methyl alcohol carbonylation homogeneous rhodium catalyst method for making, it is characterized in that part, rhodium carbonyl, the ratio of precipitating reagent is 2: 1: the 2(mol ratio), 1 mole part is dissolved in the acetone, methyl alcohol of 10-100 mole, under agitation be dissolved with the methanol solution of rhodium carbonyl in 0 ℃ of-40 ℃ of dropping, methyl alcohol: rhodium carbonyl is 50-100: the 1(mol ratio), after dropwising, isothermal reaction 15-120 minute, the precipitating reagent aqueous solution that is dissolved with 2-10% is added, treat the product post precipitation, suction filtration, with 0 ℃ water and methyl alcohol cyclic washing, in reduced pressure at room temperature to constant weight.
7, the method for making of methyl alcohol carbonylation homogeneous rhodium catalyst as claimed in claim 6 is characterized in that described rhodium carbonyl is Rh
2(CO)
4Cl
2, Rh
2(CO)
4Br
2, Rh
2(CO)
4I
2
8, the method for making of methyl alcohol carbonylation homogeneous rhodium catalyst as claimed in claim 6 is characterized in that described precipitating reagent is that to have anion be BPh
- 4, I
-, Cl
-, Br
-, BF
- 4, CH
2COO
-The alkaline metal salt precipitating reagent.
9, the method for making of methyl alcohol carbonylation homogeneous rhodium catalyst as claimed in claim 6 is characterized in that described part is to contain the pyridine ring of nitrogen and carbon oxygen aliphatic and contain nitrogen and oxygen or contain phosphorus and the organic compound of oxygen.
10, a kind of purposes of methyl alcohol carbonylation homogeneous rhodium catalyst, it is characterized in that methyl alcohol and iodomethane in 5: 1～8: the ratio 1(mol ratio) is mixed the back and is added rhodium complex catalyst as claimed in claim 1 and charge into carbon monoxide, methyl alcohol and reaction of carbon monoxide generate acetate and methyl acetate, its reaction temperature is 120-150 ℃, and reaction pressure is 20-40kg/cm
2, and reaction is only used the co-catalyst iodomethane and be need not to add hydroiodic acid.
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|---|---|---|---|
| CN94100505A CN1053392C (en) | 1994-01-21 | 1994-01-21 | Methyl alcohol carbonylation homogeneous rhodium catalyst and its preparing method and use |
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|---|---|---|---|
| CN94100505A CN1053392C (en) | 1994-01-21 | 1994-01-21 | Methyl alcohol carbonylation homogeneous rhodium catalyst and its preparing method and use |
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| CN1053392C CN1053392C (en) | 2000-06-14 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376325C (en) * | 2004-03-25 | 2008-03-26 | 香港理工大学 | Oxo synthesis catalyst and its prepn process and application in preparing acetic acid and acetic anhydride |
| CN101182340B (en) * | 2007-12-20 | 2010-04-21 | 中国科学院化学研究所 | Method for producing acetic acid by carbonylation of methanol as well as special catalyst and preparation method thereof |
| WO2011005304A2 (en) | 2009-07-07 | 2011-01-13 | Celanese International Corporation | Acetic acid production by way of carbonylation with enhanced reaction and flashing |
| CN102319587A (en) * | 2011-06-15 | 2012-01-18 | 陕西煤业化工技术开发中心有限责任公司 | Catalyst used in carbonylation synthesis of acetic anhydride coproduced with acetic acid and preparation and application methods thereof |
| CN102476988A (en) * | 2010-11-22 | 2012-05-30 | 中国石油化学工业开发股份有限公司 | Method for preparing carboxyl anhydride |
| US8785684B2 (en) | 2010-06-14 | 2014-07-22 | Celanese International Corporation | Methanol carbonylation process with rhodium catalyst, an iodide salt and a metallic co-catalyst selected from transition metals, indium, strontium, barium, zinc, tin and heteropoly acids |
| US8835681B2 (en) | 2010-06-14 | 2014-09-16 | Celanese International Corporation | Methanol carbonylation process with rhodium catalyst and a lanthanide metal co-catalyst |
| US9024061B2 (en) | 2010-06-14 | 2015-05-05 | Celanese International Corporation | Methanol carbonylation process with rhodium catalyst and a metallic co-catalyst selected from transition metals, zinc, beryllium, indium, tin, strontium and barium |
| WO2016094351A1 (en) | 2014-12-09 | 2016-06-16 | Lyondellbasell Acetyls, Llc | Use of phosphate salts in the production of carboxylic acids |
| CN111195514A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Monoatomic dispersion rhodium-based catalyst, preparation method thereof and application thereof in methane low-temperature oxidation reaction |
| CN115445662A (en) * | 2022-08-31 | 2022-12-09 | 迈奇化学股份有限公司 | Catalyst for carbonylation of gamma-butyrolactone and process for synthesizing glutaric acid from gamma-butyrolactone |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1237728A (en) * | 1984-07-20 | 1988-06-07 | Anthony G. Abatjoglou | Production of carboxylic acids from alcohols using rhodium complex catalysts |
| CN1004750B (en) * | 1985-04-01 | 1989-07-12 | 中国科学院化学研究所 | Heterogeneous catalyst comprising shodium coordinated with polymer and its preparation |
| GB8904125D0 (en) * | 1989-02-23 | 1989-04-05 | British Petroleum Co Plc | Process for preparing carboxylic acids |
-
1994
- 1994-01-21 CN CN94100505A patent/CN1053392C/en not_active Expired - Fee Related
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|---|---|---|---|---|
| CN100376325C (en) * | 2004-03-25 | 2008-03-26 | 香港理工大学 | Oxo synthesis catalyst and its prepn process and application in preparing acetic acid and acetic anhydride |
| CN101182340B (en) * | 2007-12-20 | 2010-04-21 | 中国科学院化学研究所 | Method for producing acetic acid by carbonylation of methanol as well as special catalyst and preparation method thereof |
| WO2011005304A2 (en) | 2009-07-07 | 2011-01-13 | Celanese International Corporation | Acetic acid production by way of carbonylation with enhanced reaction and flashing |
| US8835681B2 (en) | 2010-06-14 | 2014-09-16 | Celanese International Corporation | Methanol carbonylation process with rhodium catalyst and a lanthanide metal co-catalyst |
| US9024061B2 (en) | 2010-06-14 | 2015-05-05 | Celanese International Corporation | Methanol carbonylation process with rhodium catalyst and a metallic co-catalyst selected from transition metals, zinc, beryllium, indium, tin, strontium and barium |
| US8785684B2 (en) | 2010-06-14 | 2014-07-22 | Celanese International Corporation | Methanol carbonylation process with rhodium catalyst, an iodide salt and a metallic co-catalyst selected from transition metals, indium, strontium, barium, zinc, tin and heteropoly acids |
| CN102476988A (en) * | 2010-11-22 | 2012-05-30 | 中国石油化学工业开发股份有限公司 | Method for preparing carboxyl anhydride |
| CN102319587A (en) * | 2011-06-15 | 2012-01-18 | 陕西煤业化工技术开发中心有限责任公司 | Catalyst used in carbonylation synthesis of acetic anhydride coproduced with acetic acid and preparation and application methods thereof |
| CN102319587B (en) * | 2011-06-15 | 2013-08-28 | 陕西煤业化工技术开发中心有限责任公司 | Catalyst used in carbonylation synthesis of acetic anhydride coproduced with acetic acid and preparation and application methods thereof |
| WO2016094351A1 (en) | 2014-12-09 | 2016-06-16 | Lyondellbasell Acetyls, Llc | Use of phosphate salts in the production of carboxylic acids |
| CN111195514A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Monoatomic dispersion rhodium-based catalyst, preparation method thereof and application thereof in methane low-temperature oxidation reaction |
| CN111195514B (en) * | 2018-11-20 | 2021-03-30 | 中国科学院大连化学物理研究所 | Monoatomic dispersion rhodium-based catalyst, preparation method thereof and application thereof in methane low-temperature oxidation reaction |
| CN115445662A (en) * | 2022-08-31 | 2022-12-09 | 迈奇化学股份有限公司 | Catalyst for carbonylation of gamma-butyrolactone and process for synthesizing glutaric acid from gamma-butyrolactone |
| CN115445662B (en) * | 2022-08-31 | 2023-08-15 | 迈奇化学股份有限公司 | Catalyst for gamma-butyrolactone carbonylation and method for synthesizing glutaric acid from gamma-butyrolactone |
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