CN100372608C - Catalyst system of catalytic methylester acetate or methylether synthetic acetoanhy dride and use thereof - Google Patents
Catalyst system of catalytic methylester acetate or methylether synthetic acetoanhy dride and use thereof Download PDFInfo
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Abstract
The present invention relates to a catalytic system for catalyzing methyl acetate or dimethyl ether to be synthesized into acetic oxide. Rhodium coordination compounds are used as active constituents, and alkyl iodide, phosphate and alkali metal iodized salt are used as catalyst promoters. The catalytic system catalyzes methyl acetate into acetic oxide through carbonyl synthesis, methyl acetate or dimethyl ether is used as reacting substances, and carbon monoxide and hydrogen gas are supplied. Solvent of acetic acid is added, and the dosage of the solvent is 10 to 120 wt% of the total weight of the reacting substances. The dosage of the active constituents is 200 to 2000 ppm measured by rhodium, and the molar weight ratio of phosphate to the active constituents is 1 to 100. The content of alkyl iodide is 1 to 5 mol/L, and the content of alkali metal iodized salt is 500 to 4000 ppm measured by alkali metal. The reaction temperature is from 150 to 250 DEG C, the pressure of carbon monoxide is from 3.0 to 6.0MPa, and the pressure of hydrogen is from 0.2 to 0.5MPa. Due to the addition of phosphate, the catalytic system has favorable catalytic activity and stability.
Description
Technical field
The present invention relates to a kind of homogeneous reaction catalyst system that is used for oxo-acetic anhydride, particularly, relate to a kind of catalyst system that is used for catalytic methylester acetate or the synthetic aceticanhydride of dimethyl ether.
The invention still further relates to the application of above-mentioned catalyst system and catalyzing in oxo-acetic anhydride reaction, particularly, is to be application in the aceticanhydride reaction at catalytic methylester acetate or dimethyl ether.
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.
At BASF (US2729651, US2730546) 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 (BE819455), Eastman, Ajinamoto (Japan Kokai50/30.820), ShowaDenko (Japan Kokai50/47.922), BP (B.von Schlotheim, Chem.Industrie 1994,9/89,80) and Hoechst (DE2450965) 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.(US4335059 US4284585) has introduced the concerted catalysis co-catalyst that contains Zr, Mo/Ni or Sn/Ni to the patent of Halcon.
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 acetic acid 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 acetic acid and methyl acetate, also can obtain acetic anhydride by catalytic methylester 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 withOrganometallic Compounds, New York, VHC, 1996,104.] and the M.A.Murphy[M.A.Murphy et al.J Organomet Chem of HoechstCelanese 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, acetic acid, 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 catalyst system of the synthetic aceticanhydride of a kind of catalytic methylester acetate or dimethyl ether.
Another purpose of the present invention is to provide the application of above-mentioned catalyst system and catalyzing in catalytic methylester acetate or dimethyl ether synthetic vinegar anhydride reactant.
For achieving the above object, the catalyst system of the synthetic aceticanhydride of catalytic methylester acetate provided by the invention or dimethyl ether is active component with the rhodium complex, and alkyl iodide, phosphate and alkali metal salt compounded of iodine are co-catalyst.
Above-mentioned catalyst system and catalyzing provided by the invention is a application process in the reaction of aceticanhydride at catalytic methylester acetate or dimethyl ether, specifically, this method is by in the carbon monoxide atmosphere, and methyl acetate or dimethyl ether are the raw material of reaction, add active component and co-catalyst, feed hydrogen.Catalyst consumption in the reaction system of the present invention is counted the 200-2000ppm 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 mol ratio of phosphatic addition and active component is between the 1-100.The co-catalyst iodomethane content that adds be in overall reaction liquid between the 1-5mol/L scope, and the amount of iodomethane causes catalyst precipitation easily when big, so need carefully control.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 lithium 500-4000ppm.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, and this problem is more obvious in industrial production.In order to imitate industrial production environment, added a certain amount of aceticanhydride among the embodiment.Add acetic acid in the reaction and make solvent, can improve reaction speed, the acetic acid consumption is between the 10-120% of methyl acetate and aceticanhydride total amount (Wt).Reaction temperature is controlled at 150-250 ℃, and carbon monoxide pressure is 3.0-6.0Mpa, and Hydrogen Vapor Pressure is 0.2-0.5MPa.
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
Embodiment 1
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.044g, methyl acetate 0.70mol, acetic acid 0.09mol, iodomethane 0.22mol, LiI
33H
2O 1.6g, (CH
3CO)
2O 0.15mol, (NH
4)
3PO
44H
2O 2.5g; 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 160 ± 5 ℃ then, setting mixing speed is 400 rev/mins, control reaction gross pressure 5.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 25.2%, aceticanhydride space-time yield are 5.8mol (CH
3CO)
2O/ (Lh).
Embodiment 2
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.144g, methyl acetate 0.63mol, acetic acid 0.93mol, iodomethane 0.10mol, LiI33H
2O 6.0g, (CH
3CO)
2O 0.15mol, Zn
3(PO
4)
24H
2O 0.17g; 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 6.0MPa; 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 57.5%, aceticanhydride space-time yield are 12.8mol (CH
3CO)
2O/ (Lh).
Embodiment 3
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.91g, methyl acetate 0.63mol, acetic acid 0.40mol, 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 0.5MPa, and carbon monoxide pressure is 3.0MPa; Heat temperature raising to 240 ± 5 ℃ then, setting mixing speed is 400 rev/mins, control reaction gross pressure 4.5MPa, the reaction time is 15min.Methyl acetate conversion ratio 48.2%, aceticanhydride space-time yield are 10.7mol (CH
3CO)
2O/ (Lh).
Embodiment 4
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.144g, methyl acetate 0.63mol, acetic acid 0.40mol, iodomethane 0.50mol, LiI
33H
2O 13.0g, (CH
3CO)
2O 0.15mol, 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 190 ± 5 ℃ then, setting mixing speed is 400 rev/mins, control reaction gross pressure 5.0MPa, the reaction time is 10min.Methyl acetate conversion ratio 49.8%, aceticanhydride space-time yield are 15.3mol (CH
3CO)
2O/ (Lh).
Embodiment 5
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.144g, methyl acetate 0.63mol, acetic acid 0.40mol, 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 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 52.6%, aceticanhydride space-time yield are 13.3mol (CH
3CO)
2O/ (Lh).
Embodiment 6
In 250ml zirconium matter autoclave pressure, add Rh (OAc)
20.16g, methyl acetate 0.70mol, acetic acid 0.24mol, iodomethane 0.25mol, LiI
33H
2O 8.0g, (CH
3CO)
2O 0.18mol, Zn
3(PO
4)
24H
2O 3.0g; 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 180 ± 5 ℃ then, setting mixing speed is 500 rev/mins, control reaction gross pressure 5.0MPa, the reaction time is 10min.Methyl acetate conversion ratio 49.3%, aceticanhydride space-time yield are 13.9mol (CH
3CO)
2O/ (Lh).
Embodiment 7
In 250ml zirconium matter autoclave pressure, add RhI
30.30g, methyl acetate 0.60mol, acetic acid 0.30mol, iodomethane 0.25mol, LiI
33H
2O 8.0g, (CH
3CO)
2O 0.15mol, (NH
4)
3PO
44H
2O 1.5g; 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 3.5MPa; Heat temperature raising to 240 ± 5 ℃ then, setting mixing speed is 450 rev/mins, control reaction gross pressure 5.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 51.2%, aceticanhydride space-time yield are 12.1mol (CH
3CO)
2O/ (Lh).
Claims (5)
1. catalyst that is used for the synthetic aceticanhydride of catalytic methylester acetate or dimethyl ether, active component is a rhodium complex, co-catalyst is alkyl iodide, phosphate and alkali metal salt compounded of iodine;
Described rhodium complex is [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, [Rh (CO)
2I]
2, RhI
3Or Rh (CH
3COO)
2
Described alkyl iodide is an iodomethane;
Described phosphate is Zn, ammonium or alkali-metal phosphate.
2. catalyst as claimed in claim 1 is characterized in that, the alkali metal salt compounded of iodine is a lithium iodide.
3. catalyst as claimed in claim 1 is characterized in that, alkali-metal phosphate is Li
3PO
4, Na
3PO
4, K
3PO
4Or their salt that contains the crystallization water.
4. catalyst as claimed in claim 1 is characterized in that, Zn or ammonium phosphate are Zn
3(PO
4)
2, (NH
4)
3PO
4Or it contains the salt of the crystallization water.
5. the application of catalyst in catalytic methylester acetate or dimethyl ether synthetic vinegar anhydride reactant according to claim 1, reactant is methyl acetate or dimethyl ether, and carbon monoxide; Add acetate solvate, solvent load is the 10-120% of reaction-ure mixture by weight, the consumption of active component is counted 200-2000ppm with rhodium, phosphate is 1-100 with the ratio of active component mole, the content of alkyl iodide is 1-5mol/L, and the content of alkali metal salt compounded of iodine is counted 500-4000ppm with alkali metal; Feed hydrogen, reaction temperature is 150-250 ℃, and carbon monoxide pressure is 3.0-6.0MPa, and Hydrogen Vapor Pressure is 0.2-0.5MPa;
Described alkyl iodide is an iodomethane;
Described phosphate is Zn, ammonium or alkali-metal phosphate.
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| TW200930698A (en) | 2008-01-07 | 2009-07-16 | China Petrochemical Dev Corp | Method for manufacturing carboxylic acid anhydride |
| TW201022202A (en) | 2008-12-04 | 2010-06-16 | China Petrochemical Dev Corp | Method for producing carboxylic acid anhydride |
| TW201209034A (en) | 2010-08-31 | 2012-03-01 | China Petrochemical Dev Corp | Production method for carboxylic acid 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 |
Citations (5)
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|---|---|---|---|---|
| CN85100883A (en) * | 1985-04-01 | 1985-12-20 | 中国科学院化学研究所 | Polymkeric substance part heterogenize rhodium catalyst and method for making thereof |
| WO2002016297A1 (en) * | 2000-08-24 | 2002-02-28 | Celanese International Corporation | Method and apparatus for sequestering entrained and volatile catalyst species in a carbonylation process |
| CN1380141A (en) * | 2001-04-12 | 2002-11-20 | 中国科学院化学研究所 | Homogeneous carbonylation reaction catalyst and its preparation and application |
| US20040059153A1 (en) * | 2002-05-23 | 2004-03-25 | Institut Francais Du Petrole | Process for carbonylating alcohols, employing a catalyst based on rhodium or iridium in a non-aqueous ionic liquid, with efficient catalyst recycling |
| CN1517150A (en) * | 2003-01-17 | 2004-08-04 | 中国科学院化学研究所 | Catalytic system used for homogeneous hydroxylation reaction and its manufacturing method and application |
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2004
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| CN85100883A (en) * | 1985-04-01 | 1985-12-20 | 中国科学院化学研究所 | Polymkeric substance part heterogenize rhodium catalyst and method for making thereof |
| WO2002016297A1 (en) * | 2000-08-24 | 2002-02-28 | Celanese International Corporation | Method and apparatus for sequestering entrained and volatile catalyst species in a carbonylation process |
| CN1380141A (en) * | 2001-04-12 | 2002-11-20 | 中国科学院化学研究所 | Homogeneous carbonylation reaction catalyst and its preparation and application |
| US20040059153A1 (en) * | 2002-05-23 | 2004-03-25 | Institut Francais Du Petrole | Process for carbonylating alcohols, employing a catalyst based on rhodium or iridium in a non-aqueous ionic liquid, with efficient catalyst recycling |
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