CN1053392C - 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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- CN1053392C CN1053392C CN94100505A CN94100505A CN1053392C CN 1053392 C CN1053392 C CN 1053392C CN 94100505 A CN94100505 A CN 94100505A CN 94100505 A CN94100505 A CN 94100505A CN 1053392 C CN1053392 C CN 1053392C
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- rhodium
- methyl alcohol
- methyl
- rhodium catalyst
- acetate
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Abstract
本发明首创以含有氮和氧原子或磷和氧原子的有机化合物为配体，与羰基铑反应，经金属有机化合物沉淀后，形成含有N→Rh，，O→Rh或P→Rh，O→Rh两种配键的正方平面顺二羰基铑阳离子配合物，该配合物用于催化甲醇羰基化制备乙酸，在相对温和的条件下，且仅使用助催化剂碘甲烷而无需外加氢碘酸，即可高速度，高选择性地催化甲醇羰基化为乙酸和乙酸甲酯。The present invention is the first to use an organic compound containing nitrogen and oxygen atoms or phosphorus and oxygen atoms as a ligand to react with rhodium carbonyl, and after precipitation of a metal organic compound, a compound containing N→Rh, O→Rh or P→Rh, O→ The square planar cis-dicarbonyl rhodium cation complex of Rh two kinds of bonds, the complex is used to catalyze the carbonylation of methanol to prepare acetic acid, under relatively mild conditions, and only uses methyl iodide as a cocatalyst without adding hydroiodic acid, It can catalyze the carbonylation of methanol into acetic acid and methyl acetate with high speed and high selectivity.
Description
The invention belongs to homogeneous rhodium catalyst.
Methyl alcohol prepares acetate by means of the katalysis 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 catalytic methanol carbonylation of small molecules rhodium complex of solubility, its active specy is generally rhodium monodentate title 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 Technol1971,600], because monodentate rhodium compound instability, when this class catalyzer surpassed 180 ℃ in temperature of reaction, it began to decompose inactivation, for [Rh (CO)
2I
2]
-Title complex, it is easy to be converted into dicarbapentaborane tetraiodo rhodium (III) anionic complex in reaction process, 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 corrosive nature to production unit on ground to keep catalyzer.
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) title complex.Because the sequestering action of part, this title complex has good relatively thermostability.In catalytic reaction process, owing to there is the N → Rh of the last one to join the existence of key, make catalyzer keep satisfactory stability, 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 promotor methyl iodide, and weak ligating atom since 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 methyl iodide is finished, its still can with the rhodium atom relocation bit, this strong, a little less than join the title complex of key coexistence, in the reaction of catalysis methanol carbonylation system acetate, performance is to good catalytic activity.Under gentle relatively condition, directly the catalysis methanol carbonyl turns to acetate and methyl acetate.
The technology formation of catalyzer 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 of constitutional features.In the Preparation of catalysts process, the employing metal-salt is a precipitation agent, making catalyzer is the positive ion active centre of chelating type, the part of this catalyzer 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 catalyzer 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 Sauerstoffatom or phosphorus and Sauerstoffatom respectively simultaneously.Rhodium carbonyl Rh and the aliphatics 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 5-12 unit chelating ring structure along the dicarbapentaborane rhodium.For example, select 2-methyl valerate pyridine for use, 2-methyl-butyrate pyridine, the organic ligand compound of [methyl-acetoxyl-betanaphthyl] phosphorus is a part.
The catalyzer of the suitable dicarbapentaborane rhodium cationic structural of chelating type, its structure is:
Have Y → Rh in the formula, two coordinate bond Y of O → Rh are N or PR
1, R
2For alkyl, cyclic hydrocarbon radical, contain 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 -Or CH
2COO
-
This positive ion 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 electronic spectrum (XPS) research, proves N → Rh, O → Rh joins key, or has P → Rh, O → Rh to join the existence of key.Infrared spectra shows, at 1950-2100cm
-1Between the terminal carbonyl charateristic avsorption band of title complex rhodium is arranged, suitable-one dicarbapentaborane rhodium (I) functional group that illustrates that such title complex contains.
The active centre of rhodium complex of the present invention is a positive ion type structure, and it is different from the monodentate or the negative ion type composition catalyst of other type.The title complex of this rhodium is to have 5-12 unit chelate ring along the structure formation 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, or Rh
2(CO)
4I
2When preparation catalyzer of the present invention, selected precipitation agent is to have BPh
4 -, I
-, Cl
-, Br
-, BF
4 -, CH
2COO
-The negative ion alkaline metal salt as precipitation agent.As: sodium tetraphenylborate, sodium iodide, sodium-chlor, potassiumiodide 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 aliphatics 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 precipitation agent is 5.37: 5.2: 2.8 (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: 1 (mol ratio), 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
-Negative ion alkaline metal salt precipitant solution (available methyl alcohol or water etc. are as the solvent of metal-salt), Deng the product post precipitation, suction filtration, with 0 ℃ water and methyl alcohol repetitive scrubbing, 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, methyl alcohol and methyl iodide are added above-mentioned catalyzer after by the mixed of 5: 1～8: 1 (mol ratio) charge into carbon monoxide, methyl alcohol and reaction of carbon monoxide generate acetate and methyl acetate, its temperature of reaction is 120-150 ℃, and reaction pressure is 20-40kg/cm
2, and reaction is only used the promotor methyl iodide and be need not to add hydroiodic acid HI.
Because catalyzer of the present invention has high catalytic activity, so the condition that it is adopted at the catalysis methanol carbonylation reaction is very gentle.A large amount of experiments show that this catalyzer has good selectivity, and reaction product is methyl acetate and acetate, stirring under the bad situation, having a small amount of dme and generate, along with going deep into of reaction, dme continues carbonyl and turns to acetate or methyl acetate, and this selectivity of catalyst 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 promotor methyl iodide 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 methyl iodide 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 corrosive nature to equipment, and in 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 catalyzer, and catalyzer 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 methyl iodide.
In addition, in the reaction system of this catalyst, also need not to add entry, thereby reduced the corrosive nature of the hydrogen of water-gas reaction generation equipment.
Example 1
Take by weighing 0.1 gram (5.37 * 10
-4Mol) 2-methyl valerate pyridine is dissolved in 20 ml methanol, adds to be dissolved with 0.2 gram (5.2 * 10 under bath temperature stirs
-4Mol) 10 ml methanol solution of four carbonyl dichloros, two rhodiums continue to stir, and behind the temperature reaction 0.5hr, will be dissolved with 0.1 gram (2.8 * 10 a little
-4Mol) 10 ml waters of sodium tetraphenylborate add, and product is a yellow mercury oxide, filter, and with 0 ℃ of methyl alcohol repetitive scrubbing product three times, reduced pressure at room temperature obtains suitable 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 methyl iodide add with 7: 1 molar ratios, and the add-on of catalyzer is calculated as 1 * 10 with rhodium
-5Mol methyl alcohol-methyl iodide mixed solution, 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 stirring velocitys), 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 methyl iodide mixed solution then with 6.05: 1 molar ratios.Rhodium content is 3.7 * 10 in the system
-4Mol methyl alcohol-methyl iodide mixed solution, behind the air in the carbon monoxide exchange system, given original pressure 30kg/cm
-1, being warming up to 140 ℃=2 ℃, stirring velocity 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 title complex that takes by weighing methyl-betanaphthyl-second carboxyl phosphine and rhodium carbonyl adds in the reactor, adds the mixed solution (6.35: 1 moles) of methyl alcohol and methyl iodide then, calculates with rhodium, and rhodium content in system is 1 * 10
-4Mol, methyl alcohol-methyl iodide mixed solution.Behind carbon monoxide displacement system hollow gas, boost to 30kg/cm
-1, being warmed to 130 ± 5 ℃, stirring velocity is 400 rev/mins, reacts after 90 minutes, and methanol conversion is 85%, and calculating the acetate productive rate with the methyl alcohol that transforms is 28%, and the methyl acetate productive rate is 72%.
Claims (5)
1, a kind of methyl alcohol carbonylation homogeneous rhodium catalyst, the chelating type that it is characterized in that preparing acetate and methyl acetate is along dicarbapentaborane rhodium cationic structural catalyzer, and its structure is as follows:
Described rhodium carbonyl Rh and nitrogenous and organic compound part oxygen, the square planar complexes of formation chelating type rhodium.
2, methyl alcohol carbonylation homogeneous rhodium catalyst as claimed in claim 1, it is characterized in that described suitable-dicarbapentaborane rhodium catalyst active centre is the positive ion type.
3, methyl alcohol carbonylation homogeneous rhodium catalyst as claimed in claim 1 is characterized in that described rhodium carbonyl is Rh
2(CO)
4Cl
2
4, a kind of methyl alcohol carbonylation homogeneous rhodium catalyst method for making as claimed in claim 1, it is characterized in that part 2-methyl valerate pyridine is dissolved in the methyl alcohol, at 0-40 ℃, reacted 15-120 minute, the methanol solution that adds four carbonyl dichloros, two rhodiums, the aqueous solution of adding sodium tetraphenylborate is through precipitation, suction filtration, washing makes.Above-mentioned part: four carbonyl dichloros, two rhodiums: sodium tetraphenylborate is 5.37: 5.2: 2.8 in molar ratio.
5, the purposes of a kind of methyl alcohol carbonylation homogeneous rhodium catalyst as claimed in claim 1 is characterized in that being used to prepare acetate or ethyl acetate.
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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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|---|---|
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| CN1053392C true CN1053392C (en) | 2000-06-14 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376325C (en) * | 2004-03-25 | 2008-03-26 | 香港理工大学 | Oxo catalyst, process for its preparation and process for the preparation of acetic acid and acetic anhydride |
| CN100522362C (en) * | 2004-03-25 | 2009-08-05 | 香港理工大学 | Double-active-species catalyst and application |
| CN101182340B (en) * | 2007-12-20 | 2010-04-21 | 中国科学院化学研究所 | A method for producing acetic acid by carbonylation of methanol and its special catalyst and preparation method |
| US8168822B2 (en) | 2009-07-07 | 2012-05-01 | Celanese International Corporation | Acetic acid production by way of carbonylation with enhanced reaction and flashing |
| 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 |
| SG186330A1 (en) | 2010-06-14 | 2013-01-30 | Celanese Int Corp | Carbonylation process |
| CN102476988A (en) * | 2010-11-22 | 2012-05-30 | 中国石油化学工业开发股份有限公司 | Process for producing carboxylic anhydride |
| 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 |
| KR102452292B1 (en) | 2014-12-09 | 2022-10-06 | 라이온델바젤 아세틸, 엘엘씨 | Use of phosphate salts in the production of carboxylic acids |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100883A (en) * | 1985-04-01 | 1985-12-20 | 中国科学院化学研究所 | Polymer ligand heterogeneous rhodium catalyst and its preparation method |
| CN85106097A (en) * | 1984-07-20 | 1987-01-14 | 联合碳化公司 | Produce carboxylic acid by using rhodium complex catalysts by alcohol |
| CN1045096A (en) * | 1989-02-23 | 1990-09-05 | 英国石油有限公司 | The method of preparing carboxylie acids |
-
1994
- 1994-01-21 CN CN94100505A patent/CN1053392C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106097A (en) * | 1984-07-20 | 1987-01-14 | 联合碳化公司 | Produce carboxylic acid by using rhodium complex catalysts by alcohol |
| CN85100883A (en) * | 1985-04-01 | 1985-12-20 | 中国科学院化学研究所 | Polymer ligand heterogeneous rhodium catalyst and its preparation method |
| CN1045096A (en) * | 1989-02-23 | 1990-09-05 | 英国石油有限公司 | The method of preparing carboxylie acids |
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