CN1978055A - Hydroformylation catalytic system and use - Google Patents
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- CN1978055A CN1978055A CN 200510130441 CN200510130441A CN1978055A CN 1978055 A CN1978055 A CN 1978055A CN 200510130441 CN200510130441 CN 200510130441 CN 200510130441 A CN200510130441 A CN 200510130441A CN 1978055 A CN1978055 A CN 1978055A
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Abstract
The present invention relates to a catalysis system capable of utilizing methyl alcohol carbonylation to prepare acetic acid and utilizing methyl acetate carbonylation to prepare acetic anhydride. Said catalysis system contains rhodium compound as catalyst, tin compound as stabilizing agent and iodine alkyl as catalyst promoter. Under the condition of low temperature said catalysis system has high speed and high selectivity.
Description
Technical field
The present invention relates to a kind of hydroformylation catalytic system.
The invention still further relates to above-mentioned catalyst system and catalyzing prepares in acetic acid and the aceticanhydride at carbongl group synthesis reaction and uses.
Background technology
The seventies in 20th century, the people such as Paulik of Monsanto company invented homogeneous phase rhodium oxo catalyst (US 3769329), for carbon monoxide has been opened up new enforcement approach with the technology of the synthetic preparation of methanol carbonyl acetic acid under the effect of catalyst.Process is updated and is perfect, is the carbonyl synthetic technology of catalyst with the rhodium, has become the explained hereafter route of output maximum on the present acetic acid industry.
In existing suitability for industrialized production, the square plane anion structural coordination compound [Rh (CO) that adopt with rhodium more
2I
2]
-As catalytic active species.Though this class catalyst structure pattern has good catalytic activity, exist and easily be converted into trivalent rhodium [Rh (CO)
2I
4]
-Anionic complex and generation precipitation RhI
3And deactivated weakness, especially when temperature is higher, all the more so under the lower situation of catalyst separation circulation time carbon monoxide pressure of tension, but higher temperature is to reacting favourable, and carbon monoxide pressure of tension is low when separating is the feature of flash distillation operation.In addition, in order to increase the dissolubility of catalyst in the production of acetic acid process, need higher water of reaction system maintenance and hydroiodic acid content so that maintenance system high reaction activity and high [EP55618, EP161874], but therefore quickened water gas reaction, consumed the raw material carbon monoxide, the severe corrosive reaction medium has improved the requirement to equipment material simultaneously, and the big water gaging that exists in the system has also increased the complexity of product postprocessing operation.
For a long time, further improve [Rh (CO)
2I
2]
-As the stability of catalytic active species in reaction, and the water content in the reduction reaction system, be one of most important content of methanol carbonyl synthesized acetic acid catalyst research, and obtained tangible progress.Wherein comparatively effective method is with the little molecule that contains nitrogen, phosphorus, oxygen, sulphur functional group or macromolecule ligand and Rh formation complex, as catalyst precarsor, reaches and improves the purpose that rhodium active specy stability improves its catalytic activity.For example, adopt high polymer as the part of catalyst (CN10050, US 5281359, US 6458996), make catalyst in the higher carbonylation activity of maintenance, the heat endurance of proportioning, the especially catalyst of some performance such as optimizing reaction system medium also is improved.
In numerous all kinds of catalyst researches, the selection of reactive metal is except that rhodium, and many transition metal such as iridium, ruthenium, nickel, cobalt all have been carried out research, also get along with very much, and wherein (EP 849249 with the iridium catalyst system and catalyzing; US 5672743) best results, cause the reactivity worth of catalyst that great improvement has been arranged.
Adopt metal salt stabilizers to improve the research of rhodium catalyst system and catalyzing performance, also quite become effective.For example, (EP Appl 0161874,1985; JP 60-239434,1985) by adding the salt compounded of iodine of high level alkali metal (lithium or sodium), improved the stability of catalyst, and accelerated the oxidation addition speed (the speed control step of reaction) of MeI to a certain extent, greatly reduce the water content in the Processes for Producing Acetic Acid simultaneously, wherein particularly remarkable with the promoting catalysis of lithium iodide.Effect by salt compounded of iodine can than obtain under the low water content with high water content under identical reactivity, improved the utilization ratio of CO.But produce in the catalystic converter system of acetic acid at the high iodine concentration of this class, may cause the concentration of residual iodine in the product acid higher, and then can for example cause poison (Applied Catalysis A:221 (2001) 253-265) of catalyst in the preparation of VAM (VAM) in downstream product.Except the alkali metal salt compounded of iodine, to other different types of catalytic promoters (US 5922911) and transition metal salt Study of Stabilizers, good progress is all arranged, used the LiI stabilizing agent to be aided with VI B family slaine as (US 5218143), promptly adopting the acetate or the salt compounded of iodine of lower valency molybdenum, chromium, tungsten is co-stabilizer, or with Mo (CO)
6, W (CO)
6, Cr (CO)
6Carbonyls is a co-stabilizer, has also obtained result preferably in the reaction of acetic acid synthesis from methanol carbonylation.
In form, the synthetic aceticanhydride of acetic acid synthesis from methanol carbonylation and methyl acetate carbonylation is very similar, but these two reaction systems still have bigger difference [Catal.Today 18 (1993) 325～354], and the driving force Δ G of the synthetic aceticanhydride reaction of methyl acetate carbonylation
0More much smaller than acetic acid synthesis from methanol carbonylation, this is to cause difficultly to realize that the methyl acetate carbonyl synthesizes the thermodynamics reason of aceticanhydride, and CO pressure is when higher, to reaction favourable more [Catal.Today 1992,13:73-91].
In addition, the reaction of synthetic aceticanhydride needs carry out under the substantially anhydrous condition of system, needs to add a large amount of promoter of iodized salt except that iodomethane or other promoter, as quaternary amine, season phosphine or alkali-metal salt compounded of iodine and other transition metal additives.Alkali metal salt particularly lithium iodide, pyridine and hydrogen phosphide can stable catalytic activity species [Rh (CO)
2I
2]
-Anion; Also need feed CO/H in the system
2Mist makes the Rh of oxidized inactivation under the high temperature
IIIBe reduced to Rh
IActivated states etc. also need add at least a or two transition metal as united catalyst [Applied Homogeneous:Catalysis withOrganometallic Compounds, Vol.1, VCH, New York, 1996,116].Gerhard Luftand Manfred Schrod is in the presence of organic compound that contains nitrogen, phosphine and iodomethane, Dichlorodiphenyl Acetate methyl esters oxo-acetic anhydride is studied, the result shows, the Rh activity is the highest, Ru and Pd are the low activity transition metal, and Pt, Os, Ni's is active minimum, and its catalytic activity is in proper order: Rh＞Ir＞Ru＞Pd＞Pt＞Os＞Ni[J.Mol.Catal., 1983,20:175].Though people have done detailed research to the synthetic aceticanhydride of transition metal methyl acetate carbonylations such as Rh, Pd, Ru, Ni, Co, the catalytic efficiency that has the rhodium catalyst system and catalyzing at present only better is applied to suitability for industrialized production.On the basis of carbonylation of methanol system acetic acid and the continuous development of methyl acetate carbonylation system aceticanhydride technology, BP company uses the rhodium catalyst system and catalyzing in 1988 and has realized the carbonylation coproduction by acetic acid of methyl acetate/aqueous mixtures and the suitability for industrialized production of aceticanhydride technology [Applied Homogeneous:Catalysis with OrganometallicCompounds, Vol.1, VCH, New York, 1996,123].
Summary of the invention
The object of the present invention is to provide a kind of hydroformylation catalytic system.
For achieving the above object, hydroformylation catalytic system provided by the invention is made up of catalyst, co-catalyst and stabilizing agent, and wherein catalyst is a rhodium compound, and co-catalyst is an iodomethane, and stabilizing agent is inorganic or organo-tin compound; In reaction system, catalyst concn is counted 200-2000ppm with rhodium, and cocatalyst concentration is counted 200-3000ppm with lithium, and stabilizer concentration is counted 200-2000ppm with tin.
Described hydroformylation catalytic system, wherein rhodium compound is: RhCl
3, RhBr
3, RhI
3, Rh (OAc)
2, [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2Or [Rh (CO)
2I]
2
Described hydroformylation catalytic system, wherein inorganic tin compound is: SnX, SnX
2, SnX
4Wherein X=Cl, Br, I and other inorganic acid radical or oxygen group elements.
Described hydroformylation catalytic system, wherein inorganic tin compound is: SnCl
2, SnCl
4, SnBr
2, SnBr
4, SnI
2, SnI
4, the high tin of sulfuric acid, stannous sulfate or artificial gold.
Described hydroformylation catalytic system, wherein organo-tin compound is: tetra hydrocarbyl stannic compound, its expression formula are R
4Sn, trialkylated tin compound, its expression formula are R
3SnX, dialkyl tin compound, its expression formula are R
2SnX
2Or a diorganotin compound, its expression formula is RSnX
3R in the expression formula is an alkyl, and X is inorganic or organic acid, oxygen or halogen.
Described hydroformylation catalytic system, wherein alkyl is an alkyl or aryl.
Above-mentioned catalyst system and catalyzing provided by the invention can be applied in carbongl group synthesis reaction and prepare acetic acid and aceticanhydride.
During catalysis methanol carbonylation system acetic acid, make solvent with reactant methanol or product acetic acid in the reaction system; During catalytic methylester acetate carbonylation system aceticanhydride, make solvent with acetic acid, reactant methyl acetate and product aceticanhydride in the reaction system.
When catalyzed carbonylation prepared acetic acid, reaction temperature 150-180 ℃, carbon monoxide pressure was 3.0-5.0Mpa; When catalyzed carbonylation prepared aceticanhydride, reaction temperature was 150-220 ℃, and carbon monoxide pressure is 4.0～6.0Mpa, and wherein hydrogen is 2～10% with the carbon monoxide pressure of tension ratio.
The present invention improves the stability of catalyst by adding the stabilizing agent of function admirable, and improves its catalytic activity simultaneously to a certain extent.Especially when improving active specy stability, reach the simplification of catalyst system and catalyzing.This catalyst system and catalyzing not only gets final product under gentle relatively condition at a high speed, highly selective catalysis methanol carbonyl turns to acetic acid, and is satisfying substantially under the precondition of suitability for industrialized production to the activity requirement, and stably the catalytic methylester acetate carbonyl turns to aceticanhydride.
A class novel inorganic provided by the present invention and organo-tin compound additive, can make with the rhodium is the catalytic performance of the catalyst system and catalyzing of active specy, especially stability be improved significantly.Its reason is not subjected to the restriction of any existing theoretical explanation, but perhaps with catalytic active species and stabilizing agent atom (or its carbonyls) between certain interaction relevant.
The principal character of catalyst system and catalyzing provided by the invention is:
1. need not additionally to add entry catalysis methanol carbonylation generation efficiently acetic acid in the system.
Even 2. in above-mentioned course of reaction, generate water, the water gas reaction of denier only takes place with CO, the water gas reaction that can not monitor in the system (small part is tested to be had＜CO of 0.03mol%
2Generate).Reaction temperature is low, and temperature remains on below 160 ℃ can obtain acetic acid, and reactivity height, selectivity are good.
3. need not in the system to add as quaternary amine, season phosphine and transition metal salt additive promptly stably the catalytic methylester acetate carbonyl turn to aceticanhydride.
4. for the reaction system of the synthetic aceticanhydride of methyl acetate carbonylation, keep certain hydrogen content to help the generation of aceticanhydride in the reaction system, when in the closed reactor, reacting usually in the reactor hydrogen content remain between 0.1～0.5MPa, on continuous reacting device, adopt CO and H
2The mist charging, wherein hydrogen content is between 1～10%.
5. prepare in the reaction system of acetic acid, catalytic methylester acetate oxo-acetic anhydride in the catalyst carbonylation of methanol that the present invention relates to, acetic acid content is between 30～80% (Wt) of reaction medium.Acetic acid is a kind of excellent solvent, can not only make in the reaction system performance that mixes of the chemistry between each main component better, and can increase the solubility of catalyst in reaction medium, also carbonylation is had and significantly induce and facilitation, so help the raising of rate of catalysis reaction.
6. prepare in the reaction system of acetic acid, catalytic methylester acetate oxo-acetic anhydride in the catalyst carbonylation of methanol that the present invention relates to, do not need to carry out the catalyst precarsor preliminary treatment of any complexity, the formation of catalyst system and catalyzing is simple rapidly, catalytic process is convenient and easy.
The specific embodiment
Embodiment 1
In autoclave pressure, add [Rh (CO)
2Cl]
20.150g, methyl alcohol 0.79mol, acetic acid 1.12mol, iodomethane 0.20mol, stannous iodide 0.5g; Be warming up to 160 ℃ after feeding CO, mixing speed is 500 rev/mins, and reaction pressure keeps 5.0MPa, and the reaction time is 18min.Methanol conversion 89.1%, acetic acid space-time yield are 21.2mol AcOH/ (Lh).
Embodiment 2
In autoclave pressure, add Rh (OAc)
20.160g, methyl alcohol 0.79mol, acetic acid 1.12mol, iodomethane 0.20mol, the high tin 0.5g of iodate; Be warming up to 150 ℃ after feeding CO, mixing speed is 500 rev/mins, and reaction pressure keeps 4.0MPa, and the reaction time is 20min.Methanol conversion 92.0%, acetic acid space-time yield are 19.8mol AcOH/ (Lh).
Embodiment 3
In autoclave pressure, add RhBr
30.330g, methyl alcohol 0.72mol, acetic acid 1.12mol, iodomethane 0.20mol, tin tetrabromide 0.5g; Be warming up to 150 ℃ after feeding CO, mixing speed is 500 rev/mins, and reaction pressure keeps 3.5Mpa, and the reaction time is 21min.Methanol conversion 90.2%, acetic acid space-time yield are 18.5mol AcOH/ (Lh).
Embodiment 4
In autoclave pressure, add [Rh (CO)
2I]
20.210g, methyl alcohol 0.79mol, acetic acid 1.12mol, iodomethane 0.15mol, dibutyltin diacetate 0.5g; Be warming up to 180 ℃ after feeding CO, mixing speed is 500 rev/mins, and reaction pressure keeps 3.0Mpa, and the reaction time is 15min.Methanol conversion 63.3%, acetic acid space-time yield are 17.4mol AcOH/ (Lh).
Embodiment 5
In autoclave pressure, add [Rh (CO)
2Br]
20.225g, methyl acetate 0.53mol, acetic acid 0.52mol, iodomethane 0.23mol, lithium iodide 0.030mol.The high tin 0.5g of iodate; After feeding hydrogen 0.1MPa, feed CO, be warming up to 150 ℃, keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction 20min.Methyl acetate conversion ratio 24.6%, aceticanhydride space-time yield are 4.0mol/Lh.
Embodiment 6
In autoclave pressure, add RhI
30.30g, methyl acetate 0.53mol, acetic acid 0.52mol, iodomethane 0.23mol, lithium iodide 0.030mol, the high tin 1.0g of iodate.After feeding hydrogen 0.2MPa, feed CO, be warming up to 170 ℃ and keep reaction gross pressure 4.5MPa, 500 rev/mins of mixing speeds, reaction time 17min, methyl acetate conversion ratio are 33.5%, the aceticanhydride space-time yield is 6.5mol/Lh.
Embodiment 7
In autoclave pressure, add Rh (OAc)
20.20g, methyl acetate 0.53mol, acetic acid 0.52mol, iodomethane 0.23mol, lithium iodide 0.030mol, the high tin 1.5g of iodate.After feeding hydrogen 0.5MPa, feed CO, be warming up to 190 ℃ and keep reaction gross pressure 5.5MPa, 500 rev/mins of mixing speeds, reaction time 15min, methyl acetate conversion ratio are 40.3%, the aceticanhydride space-time yield is 8.5mol/Lh.
Embodiment 8
In autoclave pressure, add RhCl
30.15g, methyl acetate 0.53mol, acetic acid 0.52mol, iodomethane 0.23mol, lithium iodide 0.030mol, stannous iodide 1.5g.After feeding hydrogen 0.3MPa, feed CO, be warming up to 180 ℃, keep reaction gross pressure 6.0MPa, 500 rev/mins of mixing speeds, reaction time 20min.The methyl acetate conversion ratio is 48.7%, and the aceticanhydride space-time yield is 7.8mol/Lh.
Embodiment 9
In autoclave pressure, add RhI
30.25g, methyl acetate 0.53mol, acetic acid 0.52mol, iodomethane 0.23mol, lithium acetate 0.030mol, dibutyltin diacetate 0.5g.After feeding hydrogen 0.3MPa, feed CO, be warming up to 220 ℃, keep reaction gross pressure 5.0MPa, 500 rev/mins of mixing speeds, reaction time 18min.The methyl acetate conversion ratio is 46.7%, and the aceticanhydride space-time yield is 8.2mol/Lh.
Claims (9)
1. a hydroformylation catalytic system is made up of catalyst, co-catalyst and stabilizing agent, and wherein catalyst is a rhodium compound, and co-catalyst is an iodomethane, and stabilizing agent is inorganic or organo-tin compound;
In reaction system, catalyst concn is counted 200-2000ppm with rhodium, and cocatalyst concentration is counted 200-3000ppm with lithium, and stabilizer concentration is counted 200-2000ppm with tin.
2. hydroformylation catalytic system as claimed in claim 1 is characterized in that described rhodium compound is: RhCl
3, RhBr
3, RhI
3, Rh (OAc)
2, [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2Or [Rh (CO)
2I]
2
3. hydroformylation catalytic system as claimed in claim 1 is characterized in that, described inorganic tin compound is: SnX, SnX
2, SnX
4Wherein X=Cl, Br, I and other inorganic acid radical or oxygen group elements.
4. as claim 1 or 3 described hydroformylation catalytic systems, it is characterized in that described inorganic tin compound is: SnCl
2, SnCl
4, SnBr
2, SnBr
4, SnI
2, SnI
4, the high tin of sulfuric acid, stannous sulfate or artificial gold.
5. hydroformylation catalytic system as claimed in claim 1 is characterized in that, described organo-tin compound is: tetra hydrocarbyl stannic compound, its expression formula are R
4Sn, trialkylated tin compound, its expression formula are R
3SnX, dialkyl tin compound, its expression formula are R
2SnX
2Or a diorganotin compound, its expression formula is RSnX
3R in the expression formula is an alkyl, and X is inorganic or organic acid, oxygen or halogen.
6, hydroformylation catalytic system as claimed in claim 5 is characterized in that, described alkyl is an alkyl or aryl.
7. each described hydroformylation catalytic system of claim 1-6 prepares in acetic acid and the aceticanhydride at carbongl group synthesis reaction and uses.
8. the described application of claim 7 system is characterized in that, during catalysis methanol carbonylation system acetic acid, makes solvent with reactant methanol or product acetic acid in the reaction system; During catalytic methylester acetate carbonylation system aceticanhydride, make solvent with acetic acid, reactant methyl acetate and product aceticanhydride in the reaction system.
9. claim 7 or 8 described application is characterized in that, when catalyzed carbonylation prepared acetic acid, reaction temperature 150-180 ℃, carbon monoxide pressure was 3.0-5.0Mpa; When catalyzed carbonylation prepared aceticanhydride, reaction temperature was 150-220 ℃, and carbon monoxide pressure is 4.0～6.0Mpa, and wherein hydrogen is 2～10% with the carbon monoxide pressure of tension ratio.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102166531B (en) * | 2009-10-19 | 2013-04-03 | 山东华鲁恒升化工股份有限公司 | A catalyst system for acetic acid synthesis through methanol carbonylation and an application of the catalyst system |
| CN106694049A (en) * | 2016-11-29 | 2017-05-24 | 西南化工研究设计院有限公司 | Methyl acetate catalyst system and application |
| CN108067222A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院大连化学物理研究所 | The iridium based catalyst of the sulphur promotion of absorbent charcoal carrier load and its preparation and application |
| CN111111774A (en) * | 2018-11-01 | 2020-05-08 | 中国科学院大连化学物理研究所 | Organic phosphine-containing polymer carrier loaded rhodium and heteropoly acid catalyst, preparation and application thereof |
| 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 |
| CN114515605A (en) * | 2022-02-16 | 2022-05-20 | 江苏索普（集团）有限公司 | Preparation and application of ruthenium-palladium double-active-center catalyst for synthesizing acetic acid or acetic anhydride through carbonylation |
| 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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8904125D0 (en) * | 1989-02-23 | 1989-04-05 | British Petroleum Co Plc | Process for preparing carboxylic acids |
| US5672743A (en) * | 1993-09-10 | 1997-09-30 | Bp Chemicals Limited | Process for the production of acetic acid |
| GB9802027D0 (en) * | 1998-01-31 | 1998-03-25 | Bp Chem Int Ltd | Chemical process |
| US6211405B1 (en) * | 1998-10-23 | 2001-04-03 | Celanese International Corporation | Addition of iridium to the rhodium/inorganic iodide catalyst system |
| CN1212197C (en) * | 2003-01-17 | 2005-07-27 | 中国科学院化学研究所 | Catalytic system used for homogeneous hydroxylation reaction and its manufacturing method and application |
-
2005
- 2005-12-08 CN CN 200510130441 patent/CN1978055B/en active Active
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| CN108067222A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院大连化学物理研究所 | The iridium based catalyst of the sulphur promotion of absorbent charcoal carrier load and its preparation and application |
| CN106694049A (en) * | 2016-11-29 | 2017-05-24 | 西南化工研究设计院有限公司 | Methyl acetate catalyst system and application |
| CN106694049B (en) * | 2016-11-29 | 2019-07-30 | 西南化工研究设计院有限公司 | A kind of methyl acetate catalysis agent system and application |
| CN111111774A (en) * | 2018-11-01 | 2020-05-08 | 中国科学院大连化学物理研究所 | Organic phosphine-containing polymer carrier loaded rhodium and heteropoly acid catalyst, preparation and application thereof |
| 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 |
| CN114515605A (en) * | 2022-02-16 | 2022-05-20 | 江苏索普（集团）有限公司 | Preparation and application of ruthenium-palladium double-active-center catalyst for synthesizing acetic acid or acetic anhydride through carbonylation |
| 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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Address after: 100080 Haidian District, Zhongguancun, North Street, No. 1, No. 2, Beijing Patentee after: Institute of Chemistry, Chinese Academy of Sciences Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd Address before: 100080 Haidian District, Zhongguancun, North Street, No. 1, No. 2, Beijing Patentee before: Institute of Chemistry, Chinese Academy of Sciences Patentee before: Shanghai Coking Co., Ltd. |