CN1939586A - Homogeneous rhodium catalytic system of oxo-acetic anhydride and its use - Google Patents
Homogeneous rhodium catalytic system of oxo-acetic anhydride and its use Download PDFInfo
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Abstract
A Ru catalyst system with high activity and stability for preparing oxo acetoanhydride from methyl acetate by catalytic homogenizing reaction features that the phosphate additive is used in it besides the alkyl iodine and the iodate of alkali metal are used as its cocatalyst.
Description
Technical field
The present invention relates to the homogeneous reaction catalyst system of oxo-acetic anhydride.
The invention still further relates to the application of above-mentioned catalyst system.
Background technology
Acetic anhydride is not only a kind of compound that uses in a large number as the raw material of producing cellulose acetate, but also is the important source material of chemical products such as synthetic drug, spices and dyestuff.
The production of aceticanhydride is by the wood pulp way of distillation at first, is the ketenes method based on acetic acid, acetone then, is acetaldehyde oxidation at last.The methyl acetate carbonylation method has now partly replaced the expensive method of these traditional prices.
Under the driving that the seventies in 20th century, the oil and the prices of raw and semifnished materials went up, the aceticanhydride production technology of new type of metal catalysis has obtained deep research, and to have produced with the synthesis gas be the production technology of raw material.Synthesis gas is mainly derived from coal and heavy oil residue, also can obtain by natural gas and naphtha cut.The broad development of homogeneous catalysis production aceticanhydride technology is directly related with the process exploitation of several companies.Wherein, the rhodium Catalytic processes based on synthesis gas of Tennesee Eastman exploitation has special meaning.
(US 2 729 651 at BASF, US 2 730 546) with Co, Ni or Fe are the methyl acetate carbonylation of catalyst, and on the basis of the carbonylation of methanol research of the early stage rhodium catalysis of Monsanto, Halcon (BE 819 455), Eastman, Ajinamoto (Japan Kokai 50/30.820), Showa Denko (Japan Kokai 50/47.922), BP (B.von Schlotheim, Chem.Industrie 1994,9/89,80) and Hoechst (DE 24 50 965) etc. in research work, obtained substantial progress to the aceticanhydride production of Group VIII metal catalytic.More promising catalyst metals is Rh, Pd, Ni and Co, and wherein, Rh has the core that outstanding relatively activity is in research because of it.
Apparently, the methyl acetate carbonylation is a directly expansion of carbonylation of methanol, and the guidance of this simple understanding is also being followed in the work at researchers' initial stage.Yet, when the methyl acetate carbonylation transition of under intrinsic anhydrous condition, carrying out by the carbonylation of methanol that has water to exist, found marked difference between the two immediately, and run into a relevant difficult problem.Before the beginning experimental study, people have found that at first the thermodynamic driving force of methyl acetate carbonylation is far smaller than methanol carbonylation.This is indicating that will there be a poised state in the methyl acetate carbonylation, rather than as methanol carbonylation, just can successfully react completely theoretically.This poised state is the function of temperature and carbon monoxide pressure, and this conclusion has obtained confirmation in practice.
The existence of this chemical reaction equilibrium has limited the conversion ratio that methyl acetate may reach in the carbonylation, and theoretically, the participation of back reaction can make and be reflected at the production efficiency that reduces reactor when proceeding to poised state.In commercially producing, when reaction temperature surpassed 175 ℃, the conversion ratio of reaction was generally 50～75%.Reaction pressure is controlled on the 5.25Mpa usually, to avoid entering the equilibrium region that reaction is had a negative impact.These force value are higher than the force value in most of Monsanto acetic acid technologies of reporting, but they are necessary for the optimum performance of keeping reactor in the carbonylation production aceticanhydride technology.
When using carbonylation of methanol to produce the rhodium base catalyst catalytic methylester acetate carbonylation of acetic acid, reaction is carried out very slowly, even when temperature reaches 220 ℃, this reaction rate commercial also be not develop value.In the commodity production practice, the catalyst of acetic acid synthesis from methanol carbonylation and process application thereof also need two critical improvement in the synthetic aceticanhydride of methyl acetate carbonylation.
At first be the introducing of hydrogen at reaction system.Before the effect of finding hydrogen, the methyl acetate carbonylation has a very long induction period, and should induction period and the speed of reaction all be unrepeatable.Test on pilot plant, if do not introduce hydrogen, reaction rate can reduce as time passes and constantly.But when hydrogen and carbon monoxide were introduced reaction system simultaneously, disappeared induction period, and reaction rate has also had repeatability, and reaction is successfully carried out towards the poised state of thermodynamics decision.In pilot plant test, because the introducing of hydrogen, reaction rate also reduces no longer in time.The final effect of hydrogen has obtained explanation by under this catalytic reaction condition system being carried out the high pressure infrared spectroscopy monitor.Its trivalent rhodium in can reduction system is to the state of activation of monovalence rhodium, makes that the activity of such catalysts component can be able to long term maintenance in the reaction system.In case it should be noted that it no longer further influences reaction rate when having enough hydrogen to come reducing catalyst in the system.The methanol carbonylation system is carried out having under the water condition, the trivalent rhodium can be finished by the on-the-spot hydrogen that produces in the water gas reaction to the reduction of monovalence rhodium, and this process is non-existent in the methyl acetate carbonylation reaction system, because after aceticanhydride began to generate, this system had just become no water system.
Another improvement be to use help catalytic additive and co-catalyst promote in the catalysis system labile coordination compound stability and active, such as: alkali metal, phosphine, ammonium salt etc., and alkaline metal catalysts Ti, Zr, V, Nb, Ta, Cr, Mo, W, Sn, Mn, Re, Fe, Co and Ni.The patent of Halcon (US 4 335 059, and US 4 284 585) has been introduced the concerted catalysis co-catalyst that contains Zr, Mo/Ni or Sn/Ni.
In the patent documentation wide coverage in liquid phase in the presence of the rhodium catalyst by making the mixture that contains methyl acetate and/or dimethyl ether and iodomethane and reaction of carbon monoxide produce the method for aceticanhydride, referring to United States Patent (USP) 3,927,078,4,046,807,4,115,444,4,374,070,5,003,104 and European patent 87,869 and 87,870.If these patent disclosures added the promoter of some amine and quaternary ammonium compound, phosphine compound and inorganic compound in the catalyst system, then can improve reaction rate.Usually reactant mixture and crude product are and contain reactant and catalyst component at interior anhydrous uniform liquid.Because use acetate as reaction dissolvent, therefore the liquid crude product that obtains from this method generally contains the mixture of aceticanhydride and acetic acid.
Under the effect of catalyst, the methyl acetate carbonylation prepares the important technology route that aceticanhydride is present aceticanhydride industry.In the homogeneous phase methyl acetate carbonylation of the little molecule rhodium complex catalysis of solubility, its active specy is generally rhodium monodentate complex or dicarbapentaborane diiodo-rhodium version.Because monodentate rhodium complex instability, when reaction temperature surpasses 180 ℃, just begin to decompose inactivation, dicarbapentaborane diiodo-rhodium (I) 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.
At existing catalyst these deficiencies in course of reaction, people are groping the better catalyst of performance always, and hope can have advantages of high catalytic activity and better stable simultaneously.Institute of Chemistry, Academia Sinica, once having proposed a kind of metallo-organic compound that contains nitrogen, oxygen is part, forms the chelating type of new square plane along dicarbapentaborane bimetal complexes [Chinese patent 1105603A] with rhodium carbonyl.This system can be used for the catalysis methanol carbonyl and turns to acetate and methyl acetate, also can obtain acetic anhydride by the catalysis methyl acetate.
In existing suitability for industrialized production, adopt square plane anion structural coordination compound with rhodium as catalytic active species, so the improvement Journal of Sex Research based on this catalyst is devoted in a large amount of work more.Adding one or more in catalyst system and catalyzing helps catalytic additive to improve and to promote that reaction is an important research contents.In numerous research, the research of salt compounded of iodine and acetate is more deep.M.Gauss[M.Gauss et al.Applied Homogeneous:Catalysis with OrganometallicCompounds, New York, VHC, 1996,104.] and the M.A.Murphy[M.A.Murphy et al.J Organomet Chem of Hoechst Celanese company, 1986,303:257～272.] and B.L.Smith[B.L.Smith et al.J Mol Catal, 1987,39:115～136.] etc. the people think that by the methyl alcohol homogeneous carbonylation of rhodium catalysis is studied the promoting catalysis of salt compounded of iodine and acetate is because this salt and [Rh (CO)
2I
2]
-Formed Rh (I) the complex anion of pentacoordinate, this anion can react with speed faster with MeI as reaction intermediate, and this step reaction is the committed step that influences overall reaction rates.And these salt have suppressed RhI by forming easily molten rhodium complex with catalyst
3The generation of precipitation, thus the stability of catalyst system and catalyzing improved.By selecting salt compounded of iodine and suitable methyl acetate concentration, can than obtain under the low water content with high water content under identical reactivity and stability, improved the utilization ratio of CO simultaneously.In addition, people such as M.A.Murphy is also to LiBF
4Wait other additive to study.
Common liquid-phase catalysis carbonylation processes comprises: in the liquid phase medium of rhodium-containing salt catalyst, acetate, iodomethane, methyl acetate and ionic iodide catalyst stabilizer/co-promoter, catalysis carbon monoxide and corresponding methyl alcohol, dimethyl ether or methyl acetate synthetic reaction generate carbonylation product.At the rhodium complex catalyst of different ligands, researchers have carried out fruitful exploration, and in the last few years, many rhodium complex salt were synthesized out, and have shown and can compare favourably with the Monsanto catalyst or than its better catalytic activity.Wherein contain such as PEt
3Rhodium complex etc. simple organophosphor ligand is considered to most important gang [Christophe M.Thomas, etal Coordin.Chem.Rev., 2003,243:125-142].People such as Cole-Hamijlton have studied the use trialkyl phosphine as rhodium base carbonylating catalyst, because they are the strong electronics parts of giving.
The biphosphine ligand rhodium complex also is proved to be carbonylating catalyst efficiently.People such as Pringle [C.-A.Carraz etal.Chem.Commun., 2000,14,1277] have reported that the two phosphine rhodium complexs of asymmetric ethene are than the catalyzed carbonylation reaction more efficiently of its symmetrical homologue.And under the industrial production condition, the two phosphine rhodium complexs of asymmetric ethene have better stability than all other catalyst that improve part of reporting.Studies have shown that asymmetry is vital for the biphosphine ligand rhodium complex.
Summary of the invention
The object of the present invention is to provide the homogeneous rhodium catalytic system of oxo-acetic anhydride.
For achieving the above object, the catalyst system and catalyzing of oxo-acetic anhydride provided by the invention as the activity of such catalysts species, adds iodomethane, lithium iodide and phosphate as co-catalyst with rhodium salt, and is aided with polar solvent and forms; Wherein:
The consumption of rhodium salt is counted 400～1200ppm with rhodium;
The content of iodomethane in reaction system is 1～5mol/L;
The content of lithium iodide in reaction system is counted 500～3000ppm with lithium;
Phosphate is 1～100 with the mole ratio of rhodium catalyst.
In the catalyst system of described oxo-acetic anhydride, used rhodium complex is [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, [Rh (CO)
2I]
2, RhI
3Or Rh (OAc)
2
In the catalyst system of described oxo-acetic anhydride, the phosphate co-catalyst is Zn, ammonium and alkali metal phosphate.
In the catalyst system of described oxo-acetic anhydride, used alkali metal phosphate is Li
3PO
4, Na
3PO
4, K
3PO
4Or their salt that contains the crystallization water.
In the catalyst system of described oxo-acetic anhydride, the phosphate of Zn or ammonium is respectively Zn
3(PO
4)
2(NH
4)
3PO
4Or it contains the salt of the crystallization water.
In the catalyst system of described oxo-acetic anhydride, when catalyzed carbonylation prepared aceticanhydride, reactant was a methyl acetate in the reaction system.
In the catalyst system of described oxo-acetic anhydride, polar solvent is acetic acid and aceticanhydride, and wherein the acetic acid consumption is 20～120% of methyl acetate and an aceticanhydride total amount.
Catalyst system provided by the invention is used in the method that the catalysis methyl acetate is the reaction of aceticanhydride, undertaken by add following ingredients in reactor: (I) methyl acetate is as the raw material of reaction, (II) rhodium compound, (III) iodomethane, (IV) lithium iodide, (V) phosphate co-catalyst, (VI) acetate solvate, (VII) treat that aforementioned each component joins reactor after, feed hydrogen and reactant carbon monoxide to wherein material and catalyst.Its reaction temperature is 170～230 ℃, and reaction pressure is 4.0～6.0Mpa, and wherein hydrogen partial pressure is 2～10% of a stagnation pressure.
An advantage of the invention is that alkali metal salt compounded of iodine and phosphate in this catalyst system and catalyzing all have stabilization to catalyst, make that the stability of catalyst is better, operating mode scope applicatory is wideer, helps the adjustment and the optimization of production technology.
Another advantage of the present invention is that alkali metal salt compounded of iodine and the phosphate in this catalyst system and catalyzing is all benefited to improving activity of such catalysts.The dissolubility of lithium iodide in reaction medium is better, can keep its higher content in reaction system, but too much lithium iodide makes the content of iodine in the system too high, and this follow-up iodinate process of removing for product has been brought trouble.The addition of phosphate in system is less relatively, but it is bigger to improving the activity of such catalysts contribution, and this has alleviated the too high problem of content of iodine in the system to a certain extent.
Phosphate is cheap and easy to get, and stable in properties, and the condition of providing convenience is promoted in this industry for this catalyst system and catalyzing.
The specific embodiment
When catalyst of the present invention prepares aceticanhydride at the catalytic methylester acetate carbonylation, catalyst consumption in the reaction system is counted 400～1200ppm scope with rhodium, catalyst activity height when rhodium concentration is higher, but cause precipitation easily, also can produce the recovery difficult problem of catalyst simultaneously.The co-catalyst iodomethane content that adds be in overall reaction liquid between 1～5mol/L scope, and the amount of iodomethane causes catalyst precipitation easily when big, so need carefully control.The content of lithium iodide in reaction system is: in lithium 500～3000ppm scope.Lithium iodide in catalyst system and catalyzing to reaction normally play crucial effects, its content suitably can be improved according to working condition, be controlled at usually in more than the lithium 1000ppm.Reactant is a methyl acetate, because this reaction pair methyl acetate is the non-zero order reaction, in the finite concentration scope, improve its concentration in reaction solution and can improve carbonylation rate, the excessive concentration reaction rate reduces on the contrary, and can cause precipitation, this problem is more obvious in industrial production.Add acetate and make solvent, can improve reaction speed, the acetate consumption is between 20～120% (Wt) of methyl acetate and aceticanhydride total amount.Reaction condition control is as follows: reaction temperature is 170～230 ℃, and reaction pressure is 4.0～6.0Mpa, and wherein hydrogen partial pressure is 2～10% of a stagnation pressure.
Embodiment 1
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.144g, methyl acetate 0.70mol, acetate 0.24mol, iodomethane 0.22mol, LiI
33H
2O 6.0g, (CH
3CO)
2O 0.15mol, (NH
4)
3PO
44H
2O 1.0g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charging into Hydrogen Vapor Pressure to system is 0.10MPa, and carbon monoxide pressure is 3.0MPa; Heat temperature raising to 180 ± 5 ℃ then, setting mixing speed is 400 rev/mins, control reaction gross pressure 5.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 48.2%, aceticanhydride space-time yield are 9.8mol (CH
3CO)
2O/ (Lh).
Embodiment 2
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2Br]
20.200g, methyl acetate 0.70mol, acetate 0.24mol, iodomethane 0.22mol, LiI
33H
2O 10.0g, (CH
3CO)
2O 0.15mol, Zn
3(PO
4)
24H
2O 1.0g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charging into Hydrogen Vapor Pressure to system is 0.5MPa, and carbon monoxide pressure is 3.0MPa; Heat temperature raising to 200 ± 5 ℃ then, setting mixing speed is 400 rev/mins, control reaction gross pressure 5.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 57.5%, aceticanhydride space-time yield are 13.8mol (CH
3CO)
2O/ (Lh).
Embodiment 3
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2I]
20.250g, methyl acetate 0.60mol, acetate 1.15mol, iodomethane 0.22mol, LiI
33H
2O 6.0g, (CH
3CO)
2O 0.15mol, Li
3PO
41.5g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charging into Hydrogen Vapor Pressure to system is 0.2MPa, and carbon monoxide pressure is 3.0MPa; Heat temperature raising to 180 ± 5 ℃ then, setting mixing speed is 400 rev/mins, control reaction gross pressure 6.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 83.2%, aceticanhydride space-time yield are 12.7mol (CH
3CO)
2O/ (Lh).
Embodiment 4
In 250ml zirconium matter autoclave pressure, add RhI
30.300g, methyl acetate 0.75mol, acetate 0.45mol, iodomethane 0.22mol, LiI
33H
2O 6.0g, (CH
3CO)
2O 0.35mol, Na
3PO
412H
2O 1.50g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charging into Hydrogen Vapor Pressure to system is 0.3MPa, and carbon monoxide pressure is 3.0MPa; Heat temperature raising to 220 ± 5 ℃ then, setting mixing speed is 400 rev/mins, control reaction gross pressure 5.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 61.5%, aceticanhydride space-time yield are 11.3mol (CH
3CO)
2O/ (Lh).
Embodiment 5
In 250ml zirconium matter autoclave pressure, add RhI
30.450g, methyl acetate 0.70mol, acetate 0.24mol, iodomethane 0.22mol, LiI
33H
2O 6.0g, (CH
3CO)
2O 0.15mol, K
3PO
41.5g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charging into Hydrogen Vapor Pressure to system is 0.3MPa, and carbon monoxide pressure is 3.0MPa; Heat temperature raising to 190 ± 5 ℃ then, setting mixing speed is 500 rev/mins, control reaction gross pressure 5.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 54.6%, aceticanhydride space-time yield are 13.3mol (CH
3CO)
2O/ (Lh).
Embodiment 6
In 250ml zirconium matter autoclave pressure, add Rh (OAc)
20.160g, methyl acetate 0.70mol, acetate 0.24mol, iodomethane 0.25mol, LiI
33H
2O 10.0g, (CH
3CO)
2O 0.18mol, Zn
3(PO
4)
24H
2O 0.5g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charging into Hydrogen Vapor Pressure to system is 0.4MPa, and carbon monoxide pressure is 3.0MPa; Heat temperature raising to 180 ± 5 ℃ then, setting mixing speed is 500 rev/mins, control reaction gross pressure 5.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 75.3%, aceticanhydride space-time yield are 12.4mol (CH
3CO)
2O/ (Lh).
Embodiment 7
In 250ml zirconium matter autoclave pressure, add Rh (OAc)
20.160g, methyl acetate 0.70mol, acetate 0.60mol, iodomethane 0.25mol, LiI
33H
2O 3.0g, (CH
3CO)
2O 0.18mol, K
3PO
48.0g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charging into Hydrogen Vapor Pressure to system is 0.2MPa, and carbon monoxide pressure is 3.0MPa; Heat temperature raising to 200 ± 5 ℃ then, setting mixing speed is 500 rev/mins, control reaction gross pressure 5.5MPa, the reaction time is 10min.Methyl acetate conversion ratio 51.3%, aceticanhydride space-time yield are 14.9mol (CH
3CO)
2O/ (Lh).
Embodiment 8
In 250ml zirconium matter autoclave pressure, add RhI
30.90g, methyl acetate 0.75mol, acetate 0.45mol, iodomethane 0.22mol, LiI
33H
2O 6.0g, (CH
3CO)
2O 0.35mol, (NH
4)
3PO
412H
2O 1.0g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charging into Hydrogen Vapor Pressure to system is 0.2MPa, and carbon monoxide pressure is 3.0MPa; Heat temperature raising to 190 ± 5 ℃ then, setting mixing speed is 400 rev/mins, control reaction gross pressure 5.5MPa, the reaction time is 15min.Methyl acetate conversion ratio 79.8% aceticanhydride space-time yield is 15.3mol (CH
3CO)
2O/ (Lh).
Claims (8)
1. the catalyst system and catalyzing of an oxo-acetic anhydride as the activity of such catalysts species, adds iodomethane, lithium iodide and phosphate as co-catalyst with rhodium salt, and is aided with polar solvent and forms; Wherein:
The consumption of rhodium salt is counted 400～1200ppm with rhodium;
The content of iodomethane in reaction system is 1～5mol/L;
The content of lithium iodide in reaction system is counted 500～3000ppm with lithium;
Phosphate is 1～100 with the mole ratio of rhodium catalyst.
2. the catalyst system of oxo-acetic anhydride according to claim 1 is characterized in that, used rhodium complex is [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, [Rh (CO)
2I]
2, RhI
3Or Rh (OAc)
2
3. the catalyst system of oxo-acetic anhydride according to claim 1 is characterized in that, used phosphate co-catalyst is Zn, ammonium and alkali metal phosphate.
4. according to the catalyst system of claim 1 or 3 described oxo-acetic anhydrides, it is characterized in that used alkali metal phosphate is Li
3PO
4, Na
3PO
4, K
3PO
4Or their salt that contains the crystallization water.
5. according to the catalyst system of claim 1 or 3 described oxo-acetic anhydrides, it is characterized in that the used Zn or the phosphate of ammonium are respectively Zn
3(PO
4)
2(NH
4)
3PO
4Or it contains the salt of the crystallization water.
6. the catalyst system of oxo-acetic anhydride according to claim 1 is characterized in that, when catalyzed carbonylation prepared aceticanhydride, reactant was a methyl acetate in the reaction system.
7. the catalyst system of oxo-acetic anhydride according to claim 1 is characterized in that, the polar solvent in the system is acetic acid and aceticanhydride, and wherein the acetic acid consumption is 20～120% of methyl acetate and an aceticanhydride total amount.
8. the caltalyst of the described oxo-acetic anhydride of claim 1 ties up to catalyzed carbonylation when preparing aceticanhydride, and reaction temperature is 170～230 ℃, and reaction pressure is 4.0～6.0Mpa, and wherein hydrogen partial pressure is 2～10% of a stagnation pressure.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109453815A (en) * | 2017-09-06 | 2019-03-12 | 中国科学院大连化学物理研究所 | The rhodium base catalyst of organic load of polymer support containing phosphine and its preparation and application |
| CN112794801A (en) * | 2021-01-11 | 2021-05-14 | 山东华鲁恒升化工股份有限公司 | Method for inhibiting byproduct tar in low-pressure carbonyl synthesis acetic anhydride process |
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2005
- 2005-09-28 CN CN 200510105257 patent/CN1939586A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109453815A (en) * | 2017-09-06 | 2019-03-12 | 中国科学院大连化学物理研究所 | The rhodium base catalyst of organic load of polymer support containing phosphine and its preparation and application |
| CN109453815B (en) * | 2017-09-06 | 2021-09-07 | 中国科学院大连化学物理研究所 | Organic phosphine-containing polymer carrier-loaded rhodium-based catalyst, and preparation and application thereof |
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