CN100417445C - Catalytic composition for preparing acetic anhydride - Google Patents
Catalytic composition for preparing acetic anhydride Download PDFInfo
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- CN100417445C CN100417445C CNB2005101111445A CN200510111144A CN100417445C CN 100417445 C CN100417445 C CN 100417445C CN B2005101111445 A CNB2005101111445 A CN B2005101111445A CN 200510111144 A CN200510111144 A CN 200510111144A CN 100417445 C CN100417445 C CN 100417445C
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- aceticanhydride
- catalyst composition
- acetate
- iodomethane
- rhodium
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Abstract
The present invention discloses a catalysis composition for preparing acetic anhydride. Said composition is composed of rhodium compound, quaternary ammonium salt, iodomethane and alkali metal salt. Said invention also discloses a method for preparing acetic anhydride by busing said catalysis composition. Said method includes the following steps: adding raw material methyl acetate, the described catalysis composition and acetic acid solvent into a reactor, then introducing hydrogen gas and carbon monoxide mixed gas into the reactor, controlling reaction condition so as to obtain the invented acetic anhydride.
Description
Technical field
The present invention relates to a kind of catalyst for preparing aceticanhydride, relating to a kind of in particular is raw material prepares aceticanhydride by carbonylation catalyst composition and application thereof with the methyl acetate.
Background technology
Aceticanhydride is not only used 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 wood pulp way of distillation has been experienced in the production of aceticanhydride, the ketenes method, acetaldehyde oxidation is the most popular with the methyl acetate carbonylation method at present.
So-called methyl acetate carbonylation method is under the effect of catalyst, is raw material prepares aceticanhydride by carbonylation method with the methyl acetate.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, as Application No. 3,927,078,4,046,807,4,115,444,4,374,070,5,003,104 and European Patent Application No. 87,869 and 87,870.In the homogeneous phase methyl acetate carbonylation of the little molecule rhodium complex catalysis of solubility, catalytic active substance is generally rhodium monodentate complex or dicarbapentaborane diiodo-rhodium.Yet monodentate rhodium complex instability, when surpassing 180 ℃, reaction temperature just begins to decompose inactivation, dicarbapentaborane diiodo-rhodium (I) also is easy to be converted into dicarbapentaborane tetraiodo rhodium (III) anionic complex in course of reaction and loses catalytic activity, is helping reacting especially true under the high temperature that carries out.Therefore, as catalytic active species, people consider to help catalytic additive to improve and to promote the methyl acetate carbonylation method of above-mentioned rhodium catalysis to prepare the aceticanhydride reaction by add one or more in catalyst system and catalyzing always with the square plane anion respective outer side edges of rhodium in many employings in existing suitability for industrialized production.
People such as M.Gauss are at [Applied Homogeneous:Catalysis with OrganometallicCompounds, New York, VHC, 1996, P104] and people such as M.A.Murphy people such as [JOrganomet Chem, 1986,303:P257～272.] and B.L.Smith at [J Mol Catal, 1987,39:P115～136.] in point out that salt compounded of iodine and acetate have promoting catalysis for rhodium catalyst.Since salt compounded of iodine and acetate can with [Rh (CO)
2I
2]
-Form 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 salt compounded of iodine and acetate 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, also improved the utilization ratio of CO.At the rhodium complex catalyst of different ligands, researchers have carried out fruitful exploration, and many in the last few years rhodium complex salt are synthesized out, and have shown and can compare favourably with the Monsanto catalyst or than its better catalytic activity.
Summary of the invention
It is the catalyst composition of active component with the rhodium complex that first technical problem to be solved by this invention provides a kind of more stable methyl acetate carbonylation method; Second technical problem to be solved by this invention provides a kind of method that above-mentioned catalyst composition prepares aceticanhydride of using.The technical solution adopted in the present invention: a kind of catalyst composition for preparing aceticanhydride, be made up of following component: rhodium complex, chemical formula are (I), (II) or (III) any one quaternary ammonium salt, iodomethane and alkali metal salt,
Described rhodium complex is selected from [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, [Rh (CO)
2I]
2, RhI
3, RhBr
3, RhCl
3Or Rh (OAc)
2
Described alkali metal salt is selected from lithium iodide or lithium acetate.
A kind ofly use the method that described catalyst composition prepares aceticanhydride, comprise the following steps: in reactor, to add the raw material methyl acetate, described catalyst composition and acetate solvate, in container, feed hydrogen and Co mixed gas then, the content of rhodium is 200～2000ppm in the control reaction system, quaternary ammonium salt is 1～1000 with the mole ratio of rhodium catalyst, the content of iodomethane is 1～5mol/L in reaction system, lithium iodide or the lithium acetate content in reaction system is counted 300～3000ppm with lithium, reaction temperature is 170～230 ℃, carbon monoxide pressure is 4.0～6.0MPa, and the ratio of hydrogen in mist is 2～10% to make the product aceticanhydride.
The consumption of acetate solvate is 10～120% (percentage by weights) of methyl acetate and aceticanhydride total amount.
The invention has the beneficial effects as follows: lithium iodide has stabilization to catalyst rhodium in the described catalyst composition, the dissolubility of lithium iodide in reaction medium better can keep higher content in reaction system, too high give product follow-up removed iodinate and brought trouble but too much lithium iodide makes content of iodine in the system.Quaternary ammonium salt in the catalyst composition (I), (II), (III) itself is very stable, heating also is difficult for decomposing in air, described quaternary ammonium salt is bigger to improving the activity of such catalysts contribution, the stability that has improved catalyst composition on the one hand on the other hand also the iodine consumption in the suitably minimizing system solved the too high trouble of bringing for the product subsequent treatment of content of iodine.The method of the invention has been imitated industrial production environment, and the aceticanhydride space-time yield for preparing under popular response temperature and reaction pressure is 5.5～11.6mol (CH
3CO)
2O/ (Lh).
The specific embodiment
Below in conjunction with embodiment the present invention is described in further detail: a kind of catalyst composition for preparing aceticanhydride, be made up of following component: rhodium complex, chemical formula are (I), (II) or (III) any one quaternary ammonium salt, iodomethane and alkali metal salt,
Described rhodium complex is selected from [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, [Rh (CO)
2I]
2, RhI
3, RhBr
3, RhCl
3Or Rh (OAc)
2
Described chemical formula prepares with following method for the quaternary ammonium salt of (I): add toluene in container, diethylamine is joined stirring and dissolving in the container, container is put into ice-water bath, under agitation dropwise drip iodomethane, treat to stop to drip iodomethane when crystallized product no longer increases in the container, after the reactant mixture cooling, filter, obtain the quaternary ammonium salt of described chemical formula for (I) with acetone washing, drying.Described chemical formula prepares with following method for the quaternary ammonium salt of (II): add toluene in container, triethylamine is joined stirring and dissolving in the container, container is put into ice-water bath, under agitation dropwise drip iodomethane, treat to stop to drip iodomethane when crystallized product no longer increases in the container, after the reactant mixture cooling, filter, obtain the quaternary ammonium salt of described chemical formula for (II) with acetone washing, drying.Described chemical formula prepares with following method for the quaternary ammonium salt of (III): add toluene in container, ethylenediamine is joined stirring and dissolving in the container, container is put into ice-water bath, under agitation dropwise drip iodomethane, treat to stop to drip iodomethane when crystallized product no longer increases in the container, after the reactant mixture cooling, filter, obtain the quaternary ammonium salt of described chemical formula for (III) with acetone washing, drying.Described alkali metal salt is selected from lithium iodide or lithium acetate.
A kind ofly use the method that described catalyst composition prepares aceticanhydride, comprise the following steps: in reactor, to add raw material methyl acetate, described catalyst composition and acetate solvate, in container, feed hydrogen and Co mixed gas then, the content of rhodium is 200～2000ppm in the control reaction system, catalyst activity height when rhodium concentration is higher, but cause precipitation easily, also can produce the recovery difficult problem of catalyst simultaneously.Quaternary ammonium salt is 1～1000 with the mole ratio of rhodium catalyst.The content of iodomethane content in overall reaction liquid is 1～5mol/L, and the amount of iodomethane causes catalyst precipitation easily when big, so need careful control.Lithium iodide or the lithium acetate content in reaction system is counted 300～3000ppm with lithium, lithium iodide or lithium acetate normally play crucial effects to reaction in catalyst system and catalyzing, its content suitably can be improved according to working condition, control lithium iodide or the lithium acetate content in reaction system usually and count more than the 1000ppm with lithium.Reaction temperature is 170～230 ℃, and carbon monoxide pressure is 4.0～6.0MPa, and the ratio of hydrogen in mist is 2～10% to make the product aceticanhydride.The consumption of acetate solvate is 10～120% (percentage by weights) of methyl acetate and aceticanhydride total amount.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, adds acetic acid and makes solvent, can improve reaction speed.
Embodiment 1
In the 250ml flask, add the toluene of 150ml, diethylamine 15g is added this flask and stirring and dissolving.Flask is put into ice-water bath, under agitation dropwise drip iodomethane, note the speed that control drips, in case the bumping phenomenon occurs.When treating that crystallized product in the flask no longer increases, stop to drip iodomethane.After the reactant mixture cooling, filter, with acetone washing, dry gained quaternary ammonium salt (I) product.
Embodiment 2
The benzene that adds 150ml in the 250ml flask adds this flask and stirring and dissolving as solvent with triethylamine 20g.Flask is put into ice-water bath, under agitation dropwise drip iodomethane, note the speed that control drips, in case the bumping phenomenon occurs.When treating that crystallized product in the flask no longer increases, stop to drip iodomethane.After the reactant mixture cooling, filter, with acetone washing, dry gained quaternary ammonium salt (II) product.
Embodiment 3
The benzene that adds 100ml in the 200ml flask adds this flask and stirring and dissolving as solvent with ethylenediamine 10g.Flask is put into ice-water bath, under agitation dropwise drip iodomethane, note the speed that control drips, in case the bumping phenomenon occurs.When treating that crystallized product in the flask no longer increases, stop to drip iodomethane.After the reactant mixture cooling, filter, with acetone washing, dry gained quaternary ammonium salt (III) product.
Embodiment 4
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.144g, methyl acetate 0.70mol, acetic acid 0.24mol, iodomethane 0.22mol, LiI3H
2O 6.0g, (CH
3CO)
2O 0.15mol, quaternary ammonium salt (I) 2.0g; Behind twice of the air in the hydrogen exchange reactor, charging into Hydrogen Vapor Pressure to system is 0.08MPa, heat temperature raising to 180 ± 5 ℃ then, and setting mixing speed is 400 rev/mins, control reaction gross pressure 4.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 32.8%, aceticanhydride space-time yield are 5.5mol (CH
3CO)
2O/ (Lh).
Embodiment 5
In 250ml zirconium matter autoclave pressure, add RhBr
30.254g, methyl acetate 0.70mol, acetic acid 0.24mol, iodomethane 0.22mol, LiI3H
2O 6.0g, (CH
3CO)
2O 0.15mol, quaternary ammonium salt (II) 1.5g; Behind twice of the air in the hydrogen exchange reactor, charging into Hydrogen Vapor Pressure to system is 0.5MPa, heat temperature raising to 220 ± 5 ℃ then, and setting mixing speed is 400 rev/mins, control reaction gross pressure 5.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 37.3%, aceticanhydride space-time yield are 9.6mol (CH
3CO)
2O/ (Lh).
Embodiment 6
In 250ml zirconium matter autoclave pressure, add RhCl
30.144g, methyl acetate 0.70mol, acetic acid 0.24mol, iodomethane 0.22mol, LiI3H
2O 6.0g, (CH
3CO)
2O 0.15mol, quaternary ammonium salt (III) 1.0g; Behind twice of the air in the hydrogen exchange reactor, charging into Hydrogen Vapor Pressure to system is 0.3MPa, heat temperature raising to 180 ± 5 ℃ then, and setting mixing speed is 400 rev/mins, control reaction gross pressure 6.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 26.7%, aceticanhydride space-time yield are 6.8mol (CH
3CO)
2O/ (Lh).
Embodiment 7
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2I]
20.315g, methyl acetate 0.70mol, acetic acid 0.24mol, iodomethane 0.22mol, Li (OAc) 1.0g, (CH
3CO)
2O 0.15mol, quaternary ammonium salt (I) 1.0g; Behind twice of the air in the hydrogen exchange reactor, charging into Hydrogen Vapor Pressure to system is 0.2MPa, heat temperature raising to 190 ± 5 ℃ then, and setting mixing speed is 400 rev/mins, control reaction gross pressure 5.0MPa, the reaction time is 20min.Methyl acetate conversion ratio 47.2%, aceticanhydride space-time yield are 9.5mol (CH
3CO)
2O/ (Lh).
Embodiment 8
In 250ml zirconium matter autoclave pressure, add Rh (OAc)
20.186g, methyl acetate 0.70mol, acetic acid 0.24mol, iodomethane 0.22mol, Li (OAc) 5.0g, (CH
3CO)
2O 0.15mol, quaternary ammonium salt (III) 1.0g; Behind twice of the air in the hydrogen exchange reactor, charging into Hydrogen Vapor Pressure to system is 0.2MPa, heat temperature raising to 190 ± 5 ℃ then, and setting mixing speed is 400 rev/mins, control reaction gross pressure 6.0MPa, the reaction time is 20min.Methyl acetate conversion ratio 52.9%, aceticanhydride space-time yield are 10.3mol (CH
3CO)
2O/ (Lh).
Embodiment 9
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2Br]
20.225g, methyl acetate 0.70mol, acetic acid 0.24mol, iodomethane 0.22mol, LiI3H
2O 6.0g, (CH
3CO)
2O 0.15mol, quaternary ammonium salt (II) 1.5g; Behind twice of the air in the hydrogen exchange reactor, charging into Hydrogen Vapor Pressure to system is 0.5MPa, heat temperature raising to 190 ± 5 ℃ then, and setting mixing speed is 400 rev/mins, control reaction gross pressure 5.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 37.8%, aceticanhydride space-time yield are 9.7mol (CH
3CO)
2O/ (Lh).
Embodiment 10
In 250ml zirconium matter autoclave pressure, add RhI
30.400g, methyl acetate 0.70mol, acetic acid 0.24mol, iodomethane 0.22mol, LiI3H
2O 6.0g, (CH
3CO)
2O 0.15mol, quaternary ammonium salt (II) 1.5g; Behind twice of the air in the hydrogen exchange reactor, charging into Hydrogen Vapor Pressure to system is 0.2MPa, heat temperature raising to 200 ± 5 ℃ then, and setting mixing speed is 400 rev/mins, control reaction gross pressure 6.0MPa, the reaction time is 15min.Methyl acetate conversion ratio 44.7%, aceticanhydride space-time yield are 11.6mol (CH
3CO)
2O/ (Lh).
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. catalyst composition for preparing aceticanhydride, be made up of following component: rhodium complex, chemical formula are (I), (II) or (III) any one quaternary ammonium salt, iodomethane and alkali metal salt,
2. a kind of catalyst composition for preparing aceticanhydride according to claim 1 is characterized in that: described rhodium complex is selected from [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, [Rh (CO)
2I]
2, RhI
3, RhBr
3, RhCl
3Or Rh (OAc)
2
3. a kind of catalyst composition for preparing aceticanhydride according to claim 1, it is characterized in that: described alkali metal salt is selected from lithium iodide or lithium acetate.
4. an application rights requires any described catalyst composition in 1～3 to prepare the method for aceticanhydride, comprise the following steps: in reactor, to add the raw material methyl acetate, described catalyst composition and acetate solvate, in container, feed the mist of hydrogen and carbon monoxide then, the content of rhodium is 200～2000ppm in the control reaction system, quaternary ammonium salt is 1～1000 with the mole ratio of rhodium catalyst, the content of iodomethane in reaction system is 1～5mol/L, lithium iodide or the lithium acetate content in reaction system is counted 300～3000ppm with lithium, reaction temperature is 170～230 ℃, carbon monoxide pressure is 4.0～6.0MPa, and the ratio of hydrogen in mist is 2～10% to make the product aceticanhydride.
5. according to the described a kind of method for preparing aceticanhydride of claim 4, it is characterized in that: the consumption of acetate solvate is 10～120% (percentage by weights) of methyl acetate and aceticanhydride total amount.
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|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062524A (en) * | 1990-12-20 | 1992-07-08 | 伊斯曼柯达公司 | The continuation method of preparation diacetyl oxide or diacetyl oxide and acetate mixture |
| CN1113655A (en) * | 1993-08-18 | 1995-12-20 | 大世吕化学工业株式会社 | Process for producing acetic anhydride alone or both of acetic anhydride and acetic acid |
| US6130355A (en) * | 1998-01-31 | 2000-10-10 | Bp Chemicals Limited | Anhydrous carbonylation process for the production of acetic acid |
| US20010007912A1 (en) * | 1999-12-23 | 2001-07-12 | Allan Robert Edward | Process for the co-production of acetic anhydride and acetic acid |
-
2005
- 2005-12-05 CN CNB2005101111445A patent/CN100417445C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062524A (en) * | 1990-12-20 | 1992-07-08 | 伊斯曼柯达公司 | The continuation method of preparation diacetyl oxide or diacetyl oxide and acetate mixture |
| CN1113655A (en) * | 1993-08-18 | 1995-12-20 | 大世吕化学工业株式会社 | Process for producing acetic anhydride alone or both of acetic anhydride and acetic acid |
| US6130355A (en) * | 1998-01-31 | 2000-10-10 | Bp Chemicals Limited | Anhydrous carbonylation process for the production of acetic acid |
| US20010007912A1 (en) * | 1999-12-23 | 2001-07-12 | Allan Robert Edward | Process for the co-production of acetic anhydride and acetic acid |
| US6541666B2 (en) * | 1999-12-23 | 2003-04-01 | Bp Chemicals Limited | Process for the co-production of acetic anhydride and acetic acid |
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|---|---|
| CN1978059A (en) | 2007-06-13 |
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Owner name: SHANGHAI HUAYI ENERGY + CHEMICAL INDUSTRY CO., LTD Free format text: FORMER NAME: SHANGHAI COKING CO., LTD. |
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Address after: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd Patentee after: Institute of Chemistry, Chinese Academy of Sciences Address before: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee before: Shanghai Coking Co., Ltd. Patentee before: Institute of Chemistry, Chinese Academy of Sciences |