CN101658800B - Catalyst system for use in preparation of acetic acid and acetic anhydride or synchronous preparation of acetic acid and acetic anhydride and preparation method thereof - Google Patents
Catalyst system for use in preparation of acetic acid and acetic anhydride or synchronous preparation of acetic acid and acetic anhydride and preparation method thereof Download PDFInfo
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- CN101658800B CN101658800B CN 200810042293 CN200810042293A CN101658800B CN 101658800 B CN101658800 B CN 101658800B CN 200810042293 CN200810042293 CN 200810042293 CN 200810042293 A CN200810042293 A CN 200810042293A CN 101658800 B CN101658800 B CN 101658800B
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Abstract
The invention discloses a catalyst system for use in the preparation of an acetic acid and an acetic anhydride or the synchronous preparation of the acetic acid and the acetic anhydride, which is characterized by comprising: a mixture of rhodium or one or more selected from rhodium compounds and iridium or one or more selected from iridium compounds; a methyl iodide; at least one selected from a mixture of an amino acid and an amino acid derivative and the amino acid or the amino acid derivative; and an accelerant. The catalyst system disclosed by the invention overcomes the disadvantages of high tar content of reaction liquid, low product purity and poor stability of the catalyst in the production of the acetic acid and the acetic anhydride in the presence of a rhodium-based catalyst.
Description
Technical field
The present invention relates to a kind ofly be used to prepare acetate, acetic anhydride or prepare catalyst system of acetate and acetic anhydride and preparation method thereof simultaneously.
Background technology
As the important basic Organic Chemicals of a class, acetate and acetic anhydride and downstream derived product thereof are widely used in the synthetic of medicine, synthetic fibers, light industry, weaving, leather, agricultural chemicals, explosive, rubber and metal processing, food and Fine Organic Chemical product.At present, the market prospects of world's acetate and acetic anhydride are quite had an optimistic view of.
Producing the method for acetate and acetic anhydride in the prior art, is to take continuous process units, is made by methyl alcohol and methyl acetate or dimethyl ether and methyl alcohol and reaction of carbon monoxide.
Catalyst system and catalyzing by carbonyl synthesis of acetic acid or acetic anhydride has experienced 3 stages, phase I is the cobaltous iodide catalyst, the earliest be nineteen sixty BASF AG on the research basis of Reppe etc., what develop first is that catalyst, iodomethane are the cobalt series catalyst of co-catalyst with the carbonyl cobalt, this catalyst system and catalyzing shortcomings such as condition harshness (65MPa, 250 ℃), acetic acid selectivity low (counting 87% with methyl alcohol), accessory substance are many that respond fail to realize industrialization.Second stage is that U.S. Monsanto company in 1970 has succeeded in developing rhodium base catalyst, and its technology relies on advantages such as reaction condition gentle relatively (3～4MPa, 175 ℃), acetic acid selectivity higher (counting 99% with methyl alcohol), accessory substance are few to realize industrialization rapidly.But rhodium base catalyst exists water-gas reforming reaction, accessory substance propionic acid content high relatively, acetyl group iodide and hydrogen iodide effect generation acetaldehyde takes place, and is settled out RhI
3Make defectives such as catalysqt deactivation.Rhodium base catalyst is used for then synthesis of acetic acid acid anhydride of methyl acetate carbonylation, improves oxonation speed, equally also exist the defective that reaction system tar formation speed is fast, rhodium catalyst is separated out precipitation by adding auxiliary agent LiI or lithium acetate.Phase III is Britain BP company succeeded in developing, realized in 1996 commercial Application in nineteen ninety a kind of novel carbinol carbonylation system acetic acid process, this process using iridium catalyst based (Cativa catalyst), compare with rhodium base catalyst, have higher reaction rate, higher catalyst stability, carbonylation and significantly advantage such as can under low water content, finish, become at present the most rising technology in this field.At present applying to the unique patent of carbonyl synthesis of acetic acid acid anhydride with regard to iridium base catalyst system and catalyzing is the GB2333773 of BP company.As seen it is less relatively that the iridium catalyst system and catalyzing is used for the research of methyl acetate synthesizing acetic acid by carbonylation acid anhydride, reason is that the acetic anhydride itself that (1) generates is a good part, acetic anhydride and rhodium have certain weak coordination ability, the coordination ability of iridium is higher than rhodium, so acetic anhydride and iridium are stablized coordination and then formed the inertia species; (2) acetic anhydride can carry out the oxidation addition reaction with the species of iridium, forms the inertia species; (3) in the rhodium system, produce acetic anhydride and need add a certain amount of alkali metal salt, as LiI or Li (OAc), help methyl acetate and LiI effect on the one hand, form iodomethane, the Li of Sheng Chenging (OAc) helps the generation of acetic anhydride with the acetyl iodide effect on the other hand, but in the iridium system, adds too much lithium salts, can cause more I-ion free, cause the inertia species to generate.Because severe reaction conditions, catalyst amount are big, replace rhodium production acetic anhydride difficulty bigger with the iridium catalyst system and catalyzing.
With rhodium as the patent of the catalyst of preparation acetate and acetic anhydride mixture also wide coverage, referring to for example United States Patent (USP) 3,927,078,4,046807,4,115,444,4,252,741,4374070,4,430,273,4,559,183,5,003,104,5,292,948 and European patent 8,396,8,7869,87,870.If these patent disclosures rhodium catalytic system comprised as some amine and quarternary ammonium salt compound, phosphine and phosphorus compound, inorganic compound (as alkali metal salt: promoter lithium iodide), the content of iodomethane account for the reactant liquor gross weight 12～30% between, carbonylation rate can improve.If add methyl alcohol and/or water in the reaction raw materials, acetate also is one of product of carbonylation.Therefore, the acetic anhydride product liquid that obtains of this carbonylation method is the mixture that contains acetic anhydride and acetate.
There are following three problems in the mixture that adopts this rhodium base catalyst carbonylation method to prepare acetic anhydride or acetate, acetic anhydride: can produce tar (mixture of big molecule organic polymer) in the time of (1) reaction; (2) acetate and the acetic anhydride product permanganate indices height that obtain of this carbonylation method, the purity difference of product; (3) the rhodium catalyst poor stability of this carbonylation method use, precipitation easily.
The price of rhodium metal climbs up and up year after year at present, and the cost of producing acetate and acetic anhydride is risen significantly, and many manufacturers are about to face the problem of selecting a kind of low price, catalytic performance can replace rhodium base catalyst.And BP has at first found iridium catalyst based in acetic acid production.But the research for the acetic anhydride new catalyst does not have very big breakthrough.
Be still rhodium base catalyst and the carbonylation device of world production acetate associating acetic anhydride adopts, production cost is still in continuous rising.Novel thus catalyst replaces the research of rhodium base catalyst to become very urgent.
Summary of the invention
The present invention provides a kind of catalyst system that is used to prepare acetate and acetic anhydride cheaply according to deficiency of the prior art.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of catalyst system that is used to prepare acetate, acetic anhydride or prepares acetate and acetic anhydride simultaneously is characterized in that, comprises
In selected from rhodium or the rhodium compound one or more and one or more the mixture that is selected from iridium or the iridic compound;
Iodomethane;
Amino acid and amino acid derivativges mixture, amino acid or amino acid derivativges; And promoter.
Wherein, each composition weight umber of described catalyst system is respectively:
In selected from rhodium or the rhodium compound one or more and one or more the mixture 7～30 that is selected from iridium or the iridic compound;
Iodomethane 500～1600;
Amino acid and amino acid derivativges mixture, amino acid or amino acid derivativges are benchmark with the molfraction of iridium or iridic compound, 0.1～3;
With promoter 0.50～5.
Wherein, described rhodium compound selected from rhodium metal, iodate rhodium, hydration iodate rhodium, bromination rhodium, hydration bromination rhodium, radium chloride, hydration radium chloride, [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, RhCl
33H
2O, Rh (OAc)
3, Rh
2O
3, Rh (acac) (CO)
2, Rh
4(CO)
12Or Rh
6(CO)
16
Wherein, described iridic compound is selected from iridium metals, iodate iridium, hydration iodate iridium, bromination iridium, hydration bromination iridium, iridium chloride, hydration iridium chloride, oxalic acid iridium, acetoacetate iridium, yttrium oxide, iridous oxide, Ir (acac) (CO)
2, Ir (acac)
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2, [Ir (CO)
2Br]
2, Ir
4(CO)
12, [Ir (CO)
2I
2]
-H
+, [Ir (CO)
2Br
2]
-H
+, [Ir (CO)
2I
4]
-H
+Or [Ir (CH
3) (CO)
2I
3]
-H
+
Wherein, in one or more in selected from rhodium or the rhodium compound and one or more the mixture that is selected from iridium or the iridic compound, the weight ratio of rhodium and iridium is (2～10): (5～20).
Wherein, described amino acid is selected from glycine, alanine, proline, threonine, tryptophan, leucine or tyrosine.
Wherein, described amino acid derivativges is selected from N, N-dimethylglycine, N-methylalanine, leucine benzyl ester, tyrosine tert-butyl ester, glycine methyl ester or cyclopropyl alanine.
Wherein, described promoter is selected from lithium salts.
Wherein, described lithium salts is selected from lithium iodide, lithium bromide, lithium chloride or lithium acetate.
Wherein, described catalyst system also comprises one or both in nickel compound and the platinum compounds.Described platinum compounds is selected from halide, oxide, carbonyl iodide of platinum etc., as platinum diiodide, platinic bromide, platinum chloride, hydration platinum diiodide, hydration platinic bromide, hydration platinum chloride, platinum oxide, [PtI (CO)]
2, acetate platinum; Described nickel compound is selected from nickel chloride, nickel iodide, nickel acetate, nickel acetylacetonate, nickel carbonyl.
Another object of the present invention provides a kind of method for preparing aforementioned catalyst, it is characterized in that, other raw material except that promoter is added in the reactor with water, under 150～250 ℃ and 2.0～6.0MPa, fully stir, react after 2～8 hours, add promoter again and can make described catalyst system.
When being used to prepare acetate and acetic anhydride, the catalyst among the present invention is in course of reaction, and rhodium and iridium are understood a kind of complex of each self-forming, and described complex is [Rh (CO)
2I
2]
-[Ir (CO)
2I
2]
-Described catalyst raw material also can prepare this complex in advance before being used to prepare acetate and acetic anhydride.
Catalyst system among the present invention both can be used for preparing acetate, also can be used to prepare acetic anhydride, also can be used for preparing simultaneously acetate and acetic anhydride.
Catalyst system among the present invention, manufacturing cost has descended 40% on the one hand, can avoid rhodium base catalyst to produce the defective of acetate and acetic anhydride on the other hand.
Catalyst system disclosed by the invention has solved rhodium base catalyst and has produced in the reactant liquor that acetate and acetic anhydride exist tar and generate many, product purity difference and catalyst stability not good shortcoming, be in particular in that (1) tar growing amount has reduced, every generation 1kg acetate, acetic anhydride mix product, the tar of generation is lower than 0.0002kg; (2) reducing substances content is low in the acetic anhydride product, by the method among the present invention, not needing increases the device of handling reducing substances, and the permanganate indices of the acetic anhydride product that can obtain just can reach the requirement of high-class product among the GB10668-89, is lower than 60mg/100ml; (3) stability of the catalyst system among the present invention improves, and deposited phenomenon does not take place.And the anhydrous corrosion to device of reaction system has also reduced.
The present invention also will solve the problem that iridium catalyst is produced acetic anhydride.In the iridium catalyst system and catalyzing, add lithium salts and make I
-Stable existence, I
-With CO competition and the coordination of iridium central atom, thereby restrain reaction speed, thereby be called as catalyst influential " poisonous " reagent.Thereby make acetyl iodide and the easier generation acetic anhydride of lithium acetate promote oxonation but in the rhodium catalyst system and catalyzing, add lithium salts, improve reaction speed.By adding a certain amount of amino acid or amino acid derivativges, make the amino cationic moiety of amino acid and amino acid derivativges and the hydrogen bond action of amino acid whose-COOH group come complexing I jointly in the iridium catalyst system and catalyzing
-Ion, thus part I reduced
-Free, weaken influence to reaction speed.
Patent CN02102066.3 proposes to stablize rhodium catalyst by nitrogenous oxygen organic compound, stablizes rhodium catalyst by the organic ligand complexing of nitrogenous oxygen, thereby in order to increase stablizing effect, needs to add the organic ligand that adds a large amount of nitrogenous oxygen.And in the present invention as long as add a spot of amino acid and amino acid derivativges thereof contain oxynitrides, the amino of amino acid and amino acid derivativges and the H in the system
+Or Me
+Form cation, play the effect of partially stabilized activity of such catalysts iridium anionic species, the cationic formation of amino acid has simultaneously also suitably increased I
-Dissociating of ion, thus iridium catalyst further stablized.
Description of drawings
Fig. 1 is the process chart of preparation acetate and acetic anhydride.
The specific embodiment
The present invention further specifies below in conjunction with accompanying drawing.
As shown in Figure 1, use this method to prepare acetate and the acetic anhydride mixture normally carries out in the device in three districts.First district comprises a high-pressure reactor 1 for reaction zone, also has to use second reactor, and for example Yi Si Man is at Chinese patents CN1,298,380.Second district is the Disengagement zone of reactant mixture, generally include one or two flash vessel 2, at this, catalyst separates with reactant liquor, light component methyl acetate, iodomethane and a part of acetate, acetic anhydride enter the 3rd district as gas phase, return reaction zone and carry catalyst, promoter, stabilizing agent, just first district as acetate, the acetic anhydride of heavy ends.The 3rd district is a rectification zone, and the realization product separates with light component methyl acetate, iodomethane, and light component returns first district.
According to the concentration of producing needs, squeeze into a kind of and iridium in rhodium or the rhodium compound or a kind of mixture in the iridic compound by pump toward reactor 1, squeeze into iodomethane, acetate, acetic anhydride, the lithium salts in addition of reactor 1 simultaneously.The purpose that adds acetic anhydride is to consume the water of bringing into when Preparation of Catalyst.After the catalyst of reaction system needs comprises that promoter, stabilizing agent and iodomethane, acetate meet production requirement, reactor 1 charge into CO and an amount of hydrogen to reactor pressure at 1.0MPa, reactor and flash vessel are set up catalyst circulation then, and reactor 1 heats up, charges into CO and a certain proportion of hydrogen.After reaction temperature, reaction pressure satisfy the production technology index, formally drop into material benzenemethanol and methyl acetate.
Catalyst system among the present invention, in the time of can or preparing acetate and acetic anhydride simultaneously at preparation acetate, acetic anhydride each raw material is joined in the reactant liquor, it is suitable that temperature and pressure is adjusted to, and gets final product catalytic preparation acetate, acetic anhydride or prepare acetate and acetic anhydride simultaneously.In order to save time, also can before preparing acetate, acetic anhydride or preparing acetate and acetic anhydride simultaneously, make each raw material reaction a period of time of catalyst system in advance.
All embodiment carry out in continuous apparatus as shown in Figure 1, by such continuous apparatus, can make the composition of reactant liquor relatively stable, and carry out macrocyclic test, the generating rate of tar in the test reaction system, the permanganate indices of acetic anhydride product.Need to prove that there are three rectifying columns in the 3rd district shown in the accompanying drawing 1, first rectifying column is a lights column, separating acetic acid methyl esters, iodomethane and acetate, acetic anhydride, the methyl acetate of cat head, iodomethane Returning reactor; Second rectifying column separating acetic acid and acetic anhydride, the acetate that cat head or side line obtain making with extra care; The 3rd rectifying column is the acetic anhydride rectifying column, and acetate described in this specification and acetic anhydride product mix are light component rectifying column bottom product.
From the detailed description that hereinafter provides, will further specify scope of the present invention and practicality.Yet, should know when narration optimum implementation of the present invention, detailed description and specific embodiments only are to provide in order to say something, the professional in present technique field from this is described in detail with distinct various changes and modifications in the scope of the invention and spirit.
Embodiment A
Add rhodium precursor iodate rhodium and iodate iridium in the reactor of Preparation of Catalyst, make the mass ratio of rhodium and iridium be (2～10): (5～20) add N-methylalanine and water with iridium molfraction 1:1; Add iodomethane, solvent acetic acid; Feed CO then, 150 ℃ of reaction temperatures, pressure 3.0MPa stirred 2 hours down.The cooling back detects with infrared spectrometer, and rhodium is with [Rh (CO) in the catalyst solution
2I
2]
-Form exist, iridium is with [Ir (CO)
2I
2]
-Form exist.
Embodiment B
Add rhodium precursor iodate rhodium in the reactor of Preparation of Catalyst, add iodomethane, solvent acetic acid again, feed CO then, 150 ℃ of reaction temperatures, pressure 3.0MPa reacted 2 hours down, prepared the complex of rhodium, and this complex is the solution shape.
This embodiment is not embodiments of the invention, because do not have amino acid or amino acid derivativges stabilizing agent in this catalyst system and catalyzing.
Embodiment 1
Each raw material consumption of catalyst system is: iodate rhodium 8 weight portions; Iodate iridium 10 weight portions; Iodomethane 1200 weight portions; The mol ratio of N-methylalanine and iridium is 1.0; Lithium acetate 2.5 weight portions.
Adopt the described method preparation of embodiment A.
In the continuous apparatus of flow process such as accompanying drawing 1, above-mentioned product adds in the reactor together with iodomethane, acetate, acetic anhydride, lithium acetate, the addition visual response of iodomethane, acetate, acetic anhydride need be determined, the water that adds in the purpose spent catalyst preparation of acetic anhydride.In reaction temperature is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm, iridium mass concentration 1000ppm in the control reactant liquor, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the iodomethane consumption is 12% of a mixed reaction solution weight, methyl acetate is 15% of a mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is an acetate, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Device moves 500 hours continuously, the about 8.9mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00015kg, permanganate indices is 35mg/100ml, product acetate and acetic anhydride are water white transparency, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.After device moves 500 hours continuously, extract reaction solution and make rhodium, iridium content analysis, find that content does not descend.
Need to prove that in the device of flow process such as accompanying drawing 1, the control method of methyl acetate and iodomethane content is: before (1) reaction beginning, drop into the methyl acetate and the iodomethane of desired constituent content to reactor; (2) after the reaction beginning, (such as one hour) extracts reaction solution analysis at regular intervals, calculates reaction rate, requires to adjust corresponding raw material according to reaction process and drops into ratio, to guarantee the requirement of reactant liquor component.
It should be noted that also the mass concentration of reacting back acetate and acetic anhydride only refers to acetate and the acetic anhydride that generates, and does not comprise the concentration of the solvent acetic acid that contains in the reaction system.
Comparative Examples 1
In the continuous apparatus of flow process such as accompanying drawing 1, with the product of Embodiment B preparation together with iodomethane, acetate, lithium acetate adds in the reactor together, iodomethane, acetate, the addition visual response of acetic anhydride need be determined, in reaction temperature is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reactant liquor, the lithium mass concentration is 250ppm, the iodomethane consumption is 12% of a mixed reaction solution weight, methyl acetate is 15% of a mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is an acetate, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Operation is 500 hours continuously, the about 6.7mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00032kg, permanganate indices is 75mg/100ml, product acetate and acetic anhydride are brown liquid after placing a period of time, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 650ppm.
Need explanation because under rhodium catalyst in carbonyl reaction synthesis of acetic acid and the acetic anhydride process, a part of catalyst has been wrapped up in the generation of tar, causes catalyst precipitation to be separated out, and the reaction system catalyst concn descends.
Embodiment C
Repeat the method for Preparation of Catalyst embodiment A, change the process conditions of preparation, adopt 200 ℃ of reaction temperatures, the technology that pressure 4.5MPa stirred 5 hours down prepares rhodium and iridium mixed ligand complex.The catalyst solution cooling back of preparation detects with infrared spectrometer, and rhodium is with [Rh (CO)
2I
2]
-Form exist, iridium is with [Ir (CO)
2I
2]
-Form exist.
Each raw material consumption of catalyst system is: iodate rhodium 8 weight portions; Iodate iridium 10 weight portions; Iodomethane 1200 weight portions; The mol ratio of N-methylalanine and iridium is 1.0; Lithium acetate 0.5 weight portion.
Adopt the described method preparation of Embodiment C.
The product of preparation is added in the reactor together with iodomethane, acetate, small amount of acetic acid acid anhydride, lithium acetate, and the addition visual response of iodomethane, acetate, acetic anhydride need determine that making the rhodium mass concentration is that 200ppmppm, iridium mass concentration are 1000ppmppm.Reaction temperature is 150 ℃, pressure is 2.0MPa, the rhodium mass concentration is 200ppm, iridium mass concentration 1000ppmppm in the control reactant liquor, the lithium mass concentration is 50ppm, the mol ratio of N-methylalanine and iridium is 1.0, the iodomethane consumption is 12% of a mixed reaction solution weight, methyl acetate is 15% of a mixed reaction solution weight, reaction raw materials is 43% methyl alcohol and 57% methyl acetate of calculating by weight, solvent is an acetate, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Operation is 500 hours continuously, the about 5.3mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00003kg, permanganate indices is 40mg/100ml, product acetate and acetic anhydride are water white transparency, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.Device operation continuously extracted reaction solution and makes rhodium, iridium content analysis after 500 hours, found that content does not descend.
Comparative Examples 2
Repeat Embodiment B, change the consumption of the iodate rhodium that adds, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with iodomethane, acetate, lithium acetate adds in the reactor together, iodomethane, acetate, the addition visual response of acetic anhydride need be determined, making the rhodium mass concentration is 200ppmppm, reaction temperature is 150 ℃, pressure is 2.0MPa, the rhodium mass concentration is 200ppm in the control reactant liquor, the lithium mass concentration is 50ppm, and the iodomethane consumption is 12% of a mixed reaction solution weight, and methyl acetate is 15% of a mixed reaction solution weight, reaction raw materials is 43% methyl alcohol and 57% methyl acetate of calculating by weight, solvent is an acetate, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Continuously operation is 500 hours, the about 0.55mol/lh of reaction rate, and average every kilogram of acetic anhydride product correspondence generates to such an extent that tar content is 0.00001kg, and permanganate indices is 65mg/100ml, and product after placement a period of time is faint yellow.Because the reaction rate of carbonyl synthesis of acetic acid or acetic anhydride is directly relevant with the concentration of rhodium catalyst, rhodium content is low, and reaction speed is slow.So after the successive reaction 500 hours, reactant liquor tar formation speed is slower, the reactant liquor rhodium content does not obviously descend.
Embodiment 3
Each raw material consumption of catalyst system is: iodate rhodium 2 weight portions; Iodate iridium 5 weight portions; Iodomethane 1200 weight portions; The mol ratio of N-methylalanine and iridium is 1.0; Lithium acetate 5.0 weight portions.
Repeat Embodiment C, with the preparation product together with iodomethane, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, iodomethane, acetate, the addition visual response of acetic anhydride need be determined, making the rhodium mass concentration is 200ppmppm, the iridium mass concentration is 500ppmppm, reaction temperature is 250 ℃, pressure is 6.0MPa, the rhodium mass concentration is 200ppm in the control reactant liquor, iridium mass concentration 500ppmppm, the lithium mass concentration is 500ppm, the mol ratio of N-methylalanine and iridium is 1.0, the iodomethane consumption is 12% of a mixed reaction solution weight, the methyl acetate consumption is 15% of a mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is an acetate, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Operation is 500 hours continuously, the about 3.9mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00019kg, permanganate indices is 48mg/100ml, product acetate and acetic anhydride are water white transparency, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.Device operation continuously extracted reaction solution and makes rhodium, iridium content analysis after 500 hours, found that content does not obviously descend.
Comparative Examples 3
Repeat Embodiment B, change the consumption of the iodate rhodium that adds, making the rhodium mass concentration is 200ppmppm.In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with iodomethane, acetate, lithium acetate adds in the reactor together, iodomethane, acetate, the addition visual response of acetic anhydride need be determined, reaction temperature is 250 ℃, pressure is 6.0MPa, the rhodium mass concentration is 1000ppm in the control reactant liquor, the lithium mass concentration is 500ppm, the iodomethane consumption is 12% of a mixed reaction solution weight, the methyl acetate consumption is 15% of a mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is an acetate, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Operation is 500 hours continuously, the about 0.59mol/1h of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00003kg, permanganate indices is 70mg/100ml, product acetate and acetic anhydride are weak yellow liquid after placing a period of time, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 850ppmppm.。
Embodiment 4
Each raw material consumption of catalyst system is: Rh (acac)
3, 8 weight portions; Ir (acac)
310 weight portions; Iodomethane 1200 weight portions; The mol ratio of N-methylalanine and iridium is 1.0; Lithium chloride 2.5 weight portions.
Repeat Embodiment C, changing the precursor that adds rhodium is Rh (acac)
3, the iridium precursor is Ir (acac)
3.In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with iodomethane, acetate, the small amount of acetic acid acid anhydride, lithium chloride adds in the reactor together, iodomethane, acetate, the addition visual response of acetic anhydride need be determined, reaction temperature is 190 ℃, pressure is 3.0MPa, the rhodium mass concentration is 800ppm in the control reactant liquor, iridium mass concentration 1000ppmppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the iodomethane consumption is 12% of a mixed reaction solution weight, the methyl acetate consumption is 15% of a mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is an acetate, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Operation is 500 hours continuously, the about 8.8mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00014kg, permanganate indices is 32mg/100ml, product acetate and acetic anhydride are water white transparency, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.The device operation extracted reaction solution and makes rhodium, iridium content analysis after 500 hours, found that content does not obviously descend.
Comparative Examples 4
Repeat Embodiment B, changing the adding precursor is Rh (acac)
3, in the continuous apparatus of flow process such as accompanying drawing 1, the product for preparing being added in the reactor together with iodomethane, acetate, lithium chloride, the addition visual response of iodomethane, acetate, acetic anhydride need determine that making the rhodium mass concentration is 800ppmppm.Reaction temperature is 190 ℃, pressure is 3.0MPa, the rhodium mass concentration is 800ppm in the control reactant liquor, the lithium mass concentration is 250ppm, and the iodomethane consumption is 12% of a mixed reaction solution weight, and the methyl acetate consumption is 15% of a mixed reaction solution weight, reaction raw materials is for calculating by weight 42% methyl alcohol and 58% methyl acetate, solvent is an acetate, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Operation is 500 hours continuously, the about 6.6mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00031kg, permanganate indices is 70mg/100ml, product acetate and acetic anhydride are brown liquid after placing a period of time, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 680ppm.
Embodiment D
Repeat the method for Preparation of Catalyst embodiment A, change the process conditions of preparation, adopt 250 ℃ of reaction temperatures, the technology that pressure 6.0MPa stirred 8 hours down prepares rhodium and iridium mixed ligand complex.The catalyst solution cooling back of preparation detects with infrared spectrometer, and rhodium is with [Rh (CO)
2I
2]
-Form exist, iridium is with [Ir (CO)
2I
2]
-Form exist.
Embodiment 5
Change the catalyst system proportioning
Each raw material consumption of catalyst system is: Rh
4(CO)
12, 8 weight portions; Ir
4(CO)
1210 weight portions; Iodomethane 1200 weight portions; The mol ratio of N-methylalanine and iridium is 1.0; Lithium acetate 2.5 weight portions.
Adopt the method for preparing catalyst of embodiment D, adopt embodiment 4 identical conditions to prepare acetate and acetic anhydride, operation is 500 hours continuously, the about 8.9mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00019kg, permanganate indices is 35mg/100ml, and product acetate and acetic anhydride are water white transparency, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.The device operation extracted reaction solution and makes rhodium, iridium content analysis after 500 hours, found that content does not obviously descend.
Comparative Examples 5
Repeat comparative example 4, changing the rhodium precursor that adds is Rh
4(CO)
12Other step is identical with comparative example 4, operation is 500 hours continuously, the about 4.1mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00035kg, permanganate indices is 80mg/100ml, and product acetate and acetic anhydride are brown liquid after placing a period of time, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 650ppm.
Embodiment 6
Each raw material consumption of catalyst system is: Rh
2O
38 weight portions; Iridous oxide 10 weight portions; Iodomethane 1200 weight portions; The mol ratio of N-methylalanine and iridium is 1.0; Lithium acetate 2.5 weight portions.
Repeat embodiment D, changing the precursor that adds rhodium is Rh
2O
3Changing the iridium precursor that adds is iridous oxide, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with iodomethane, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, iodomethane, acetate, the addition visual response of acetic anhydride need be determined, reaction temperature is 200 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reactant liquor, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0,12% of iodomethane consumption mixed reaction solution weight, and the methyl acetate consumption is 15% of a mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is an acetate, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Operation is 500 hours continuously, the about 9.1mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00017kg, permanganate indices is 45mg/100ml, product acetate and acetic anhydride are water white transparency, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.The device operation extracted reaction solution and makes rhodium, iridium content analysis after 500 hours, found that content does not obviously descend.
Comparative Examples 6
Repeat Embodiment B, changing the rhodium precursor that adds is Rh
2O
3, making the rhodium mass concentration is 800ppm.In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with iodomethane, acetate, lithium acetate adds in the reactor together, iodomethane, acetate, the addition visual response of acetic anhydride need be determined, reaction temperature is 200 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reactant liquor, the lithium mass concentration is 250ppm, the iodomethane consumption is 12% of a mixed reaction solution weight, the methyl acetate consumption is 15% of a mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is an acetate, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Operation is 500 hours continuously, the about 4.0mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00036kg, permanganate indices is 82mg/100ml, product acetate and acetic anhydride are brown liquid after placing a period of time, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 670ppm.
Embodiment 7
Each raw material consumption of catalyst system is: Rh
2O
310 weight portions; Iridous oxide 20 weight portions; Iodomethane 1600 weight portions; The mol ratio of N-methylalanine and iridium is 1.0; Lithium acetate 2.5 weight portions.
Repeat embodiment A, change the iodate rhodium of adding and the consumption of iodate iridium, making the rhodium mass concentration is that 1000ppm, iridium mass concentration are 2000ppm.In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with iodomethane, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, iodomethane, acetate, the addition visual response of acetic anhydride need be determined, reaction temperature is 170 ℃, pressure is 4.0MPa, the rhodium mass concentration is 1000ppm in the control reactant liquor, iridium mass concentration 2000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the iodomethane consumption is 16% of a mixed reaction solution weight, the methyl acetate consumption is 15% of a mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is an acetate, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Operation is 500 hours continuously, the about 9.2mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00013kg, permanganate indices is 30mg/100ml, product acetate and acetic anhydride are water white transparency, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.The device operation extracted reaction solution and makes rhodium, iridium content analysis after 500 hours, found that content does not obviously descend.
Comparative Examples 7
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with iodomethane, acetate, lithium acetate adds in the reactor together, iodomethane, acetate, the addition visual response of acetic anhydride need be determined, reaction temperature is 170 ℃, pressure is 4.0MPa, the rhodium mass concentration is 1000ppm in the control reactant liquor, the lithium mass concentration is 250ppm, the iodomethane consumption is 16% of a mixed reaction solution weight, the methyl acetate consumption is 15% of a mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is an acetate, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Operation is 500 hours continuously, the about 7.1mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00041kg, permanganate indices is 68mg/100ml, product acetate and acetic anhydride are weak yellow liquid after placing a period of time, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 690ppm.
Embodiment 8
Each raw material consumption of catalyst system is: iodate rhodium 8 weight portions; Iodate iridium 10 weight portions; Iodomethane 500 weight portions; The mol ratio of N-methylalanine and iridium is 1.0; Lithium iodide 2.5 weight portions.
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with iodomethane, acetate, the small amount of acetic acid acid anhydride, lithium iodide adds in the reactor together, iodomethane, acetate, the addition visual response of acetic anhydride need be determined, reaction temperature is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reactant liquor, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the iodomethane consumption is 5% of a mixed reaction solution weight, methyl acetate is 15% of a mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is an acetate, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Device moves 500 hours continuously, the about 8.6mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00011kg, permanganate indices is 30mg/100ml, product acetate and acetic anhydride are water white transparency, and the acetate of generation and acetic anhydride account for 30.4% and 29.6% of entire reaction liquid respectively., extract reaction solution and make rhodium, iridium content analysis after 500 hours in the continuous apparatus operation, find that content does not descend.
Comparative Examples 8
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with iodomethane, acetate, lithium iodide adds in the reactor together, iodomethane, acetate, the addition visual response of acetic anhydride need be determined, reaction temperature is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reactant liquor, the lithium mass concentration is 250ppm, and the iodomethane consumption is 5% of a mixed reaction solution weight, and methyl acetate is 12% of a mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is an acetate, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Operation is 500 hours continuously, the about 3.2mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00024kg, permanganate indices is 55mg/100ml, product acetate and acetic anhydride are colourless transparent liquid, and the acetate of generation and acetic anhydride account for 30.4% and 29.% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 750ppm.
Result from above embodiment and Comparative Examples thereof, when in reactant liquor, adding a certain amount of iridium catalyst and amino acid stabilizers, in any case change reaction temperature, reaction pressure, rhodium concentration, lithium concentration, iodomethane content, the hydrogen ratio, methyl acetate content, the result is that the reaction speed of carbonylation method of the production acetate of this invention and acetate mixture is fast, the tar formation speed, the permanganate indices of product is lower than the carbonylation method that adopts rhodium base catalyst production acetate and acetate mixture all the time, and after device moved continuously, the catalyst content of reactant liquor did not significantly descend.
Embodiment's spirit of the present invention 9～18 is listed in the table below in order better to illustrate.Embodiment 9～18, and method for preparing catalyst provides according to embodiment A, and wherein the kind of the parts by weight of rhodium and iridium, amino acid or amino acid derivativges stabilizing agent and addition add by embodiment 9～18 requirements.Reaction condition is identical, 190 ℃ of reaction temperatures, pressure is 4.0MPa, the lithium acetate consumption is 2.5 weight portions, the iodomethane consumption is 800 weight portions, the methyl acetate consumption is 15% of a mixed reaction solution weight, variation be rhodium and iridium consumption, amino acid or amino acid derivativges stabilizer types with and with the mol ratio of iridium catalyst.
| Embodiment | Rhodium content ppm | Iridium content ppm | Amino acid stabilizers | Stabilizing agent/iridium mol ratio | Tar generating rate Kg/Kg | Permanganate indices mg/100ml |
| 9 | 400 | 1000 | N-methylalanine | 1.0 | 0.00011 | 35 |
| 10 | 400 | 1000 | Glycine | 1.0 | 0.00010 | 35 |
| 11 | 400 | 1000 | Proline | 1.0 | 0.00012 | 40 |
| 12 | 400 | 1000 | Tyrosine | 1.0 | 0.00013 | 35 |
| 13 | 400 | 1000 | Cyclopropyl third ammonia | 1.0 | 0.00015 | 38 |
| Acid | ||||||
| 14 | 400 | 1000 | N-methylalanine | 0.5 | 0.00013 | 45 |
| 15 | 400 | 1000 | N-methylalanine | 2.0 | 0.00011 | 40 |
| 16 | 200 | 2000 | N-methylalanine | 1.0 | 0.00005 | 30 |
| 17 | 1000 | 500 | N-methylalanine | 1.0 | 0.00021 | 65 |
| 18 | 800 | 1200 | N-methylalanine | 1.0 | 0.00014 | 40 |
Embodiment 9～18, after a period of time is carried out in reaction, extract reaction solution and analyze rhodium and iridium concentration, and is consistent with the concentration of initial reaction stage.
Embodiment E
In the Preparation of Catalyst reactor, add rhodium precursor iodate rhodium 8 weight portions; Add iridium precursor iodate iridium 10 weight portions; Add acetate platinum 5 weight portions; Add N-methylalanine and water with iridium molfraction 1:1; Add iodomethane 1200 weight portions, solvent acetic acid.Feed CO then, 150 ℃ of reaction temperatures, pressure 3.0MPa reacted 1 hour down, prepared the complex of rhodium and iridium, and this complex is the solution shape.
Embodiment 19
In the continuous apparatus of flow process such as accompanying drawing 1, the product that embodiment E is prepared adds in the reactor together with iodomethane, acetate, small amount of acetic acid acid anhydride, lithium acetate.In reaction temperature is 190 ℃, pressure is 5.0MPa, the rhodium mass concentration is 800ppm, iridium mass concentration 1000ppm in the control reactant liquor, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the iodomethane consumption is 12% of a mixed reaction solution weight, methyl acetate is 15% of a mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is an acetate, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Device moves 500 hours continuously, the about 8.4mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00016kg, permanganate indices is 40mg/100ml, product acetate and acetic anhydride are water white transparency, and the acetate of generation and acetic anhydride account for 26.8% and 26.2% of entire reaction liquid respectively., extract reaction solution and make rhodium, iridium content analysis after 500 hours in the continuous apparatus operation, find that content does not descend.
Embodiment 20
In the continuous apparatus of flow process such as accompanying drawing 1, the product that embodiment A is prepared adds in the reactor together with iodomethane, acetate, lithium acetate, water.In reaction temperature is 190 ℃, pressure is 3.0MPa, the rhodium mass concentration is 800ppm, iridium mass concentration 1000ppm in the control reactant liquor, and the lithium mass concentration is 250ppm, and the mol ratio of N-methylalanine and iridium is 1.0, the iodomethane consumption is 12% of a mixed reaction solution weight, methyl acetate is 15% of a mixed reaction solution weight, and water is 4.5% of mixed reaction solution weight, and reaction raw materials is simple methyl alcohol, solvent is an acetate, and another raw material is the mist of carbon monoxide or carbon monoxide and hydrogen.Device moves 500 hours continuously, the about 15.0mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00005kg, permanganate indices is 30mg/100ml, product acetate is water white transparency, and the acetate of generation accounts for 78.5% (containing 20% acetic acid solvent) of entire reaction liquid., extract reaction solution and make rhodium, iridium content analysis after 500 hours in the continuous apparatus operation, find that content does not descend.
Embodiment 21
In the continuous apparatus of flow process such as accompanying drawing 1, the product that embodiment A is prepared adds in the reactor together with iodomethane, acetate, lithium acetate, small amount of acetic acid acid anhydride, and the purpose of acetic anhydride is the water that spent catalyst is brought reaction system into.In reaction temperature is 190 ℃, pressure is 5.0MPa, the rhodium mass concentration is 800ppm, iridium mass concentration 1000ppm in the control reactant liquor, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the iodomethane consumption is 12% of a mixed reaction solution weight, and methyl acetate is 15% of a mixed reaction solution weight, and solvent acetic acid is 25% of a mixed reaction solution weight.Reaction raw materials is simple methyl acetate, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of a carbon monoxide molal quantity.Device moves 500 hours continuously, the about 4.5mol/lh of reaction rate, average every kilogram of acetate and acetic anhydride product correspondence generate to such an extent that tar content is 0.00019kg, and permanganate indices is 35mg/100ml, the product acetic anhydride is a water white transparency, and the acetic anhydride of generation accounts for 48% of entire reaction liquid., extract reaction solution and make rhodium, iridium content analysis after 500 hours in the continuous apparatus operation, find that content does not descend.
Among the embodiment 1-21, described catalyst system also can change into directly the raw material of catalyst system is added in the reaction vessel with preparation acetate, acetic anhydride or the raw material for preparing acetate and acetic anhydride simultaneously, under the reaction condition of each embodiment, can play same catalytic action.
The foregoing description only is used for that the present invention will be described, does not constitute the restriction to the claim scope, and other substantial equivalence means that it may occur to persons skilled in the art that are all in claim scope of the present invention.
Claims (9)
1. a carbon monoxide-olefin polymeric that is used to prepare acetate, acetic anhydride or prepares acetate and acetic anhydride simultaneously is characterized in that, comprising:
In selected from rhodium or the rhodium compound one or more and one or more the mixture that is selected from iridium or the iridic compound;
Iodomethane;
Amino acid and amino acid derivativges mixture, amino acid or amino acid derivativges;
And promoter;
Wherein, each composition weight umber of described carbon monoxide-olefin polymeric is respectively:
In selected from rhodium or the rhodium compound one or more and one or more mixture 7～30 weight portions that are selected from iridium or the iridic compound;
Iodomethane 500～1600 weight portions;
Amino acid and amino acid derivativges mixture, amino acid or amino acid derivativges are with the molfraction of iridium or iridic compound
Be benchmark, 0.1～3;
With promoter 0.50～5 weight portion;
Described amino acid derivativges is selected from N, N-dimethylglycine, N-methylalanine, leucine benzyl ester, tyrosine tert-butyl ester, glycine methyl ester or cyclopropyl alanine.
2. the carbon monoxide-olefin polymeric that is used to prepare acetate, acetic anhydride or prepares acetate and acetic anhydride simultaneously according to claim 1, it is characterized in that described rhodium compound selected from rhodium metal, iodate rhodium, hydration iodate rhodium, bromination rhodium, hydration bromination rhodium, radium chloride, hydration radium chloride, [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, Rh (OAc)
3, Rh
2O
3, Rh (acac) (CO)
2, Rh
4(CO)
12Or Rh
6(CO)
16
3. the carbon monoxide-olefin polymeric that is used to prepare acetate, acetic anhydride or prepares acetate and acetic anhydride simultaneously according to claim 1, it is characterized in that described iridic compound is selected from iridium metals, iodate iridium, hydration iodate iridium, bromination iridium, hydration bromination iridium, iridium chloride, hydration iridium chloride, oxalic acid iridium, acetoacetate iridium, yttrium oxide, Ir (acac) (CO)
2, Ir (acac)
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2, [Ir (CO)
2Br]
2, Ir
4(CO)
12, [Ir (CO)
2I
2]
-H
+, [Ir (CO)
2Br
2]
-H
+, [Ir (CO)
2I
4]
-H
+Or [Ir (CH
3) (CO)
2I
3]
-H
+
4. the carbon monoxide-olefin polymeric that is used to prepare acetate, acetic anhydride or prepares acetate and acetic anhydride simultaneously according to claim 1, it is characterized in that, in a kind of and iridium or a kind of mixture in the iridic compound in rhodium or the rhodium compound, the weight ratio of rhodium and iridium is (2～10): (5～20).
5. the carbon monoxide-olefin polymeric that is used to prepare acetate, acetic anhydride or prepares acetate and acetic anhydride simultaneously according to claim 1, it is characterized in that described amino acid is selected from glycine, alanine, proline, threonine, tryptophan, leucine or tyrosine.
6. the carbon monoxide-olefin polymeric that is used to prepare acetate, acetic anhydride or prepares acetate and acetic anhydride simultaneously according to claim 1 is characterized in that described promoter is selected from lithium salts.
7. the carbon monoxide-olefin polymeric that is used to prepare acetate, acetic anhydride or prepares acetate and acetic anhydride simultaneously according to claim 6 is characterized in that described lithium salts is selected from lithium iodide, lithium bromide, lithium chloride or lithium acetate.
8. the carbon monoxide-olefin polymeric that is used to prepare acetate, acetic anhydride or prepares acetate and acetic anhydride simultaneously according to claim 1 is characterized in that described carbon monoxide-olefin polymeric also comprises one or both in nickel compound and the platinum compounds.
9. the described preparation method who is used to prepare acetate, acetic anhydride or prepares the carbon monoxide-olefin polymeric of acetate and acetic anhydride simultaneously of the arbitrary claim of claim 1-8, it is characterized in that, other raw material except that promoter is added in the reactor with acetate, water, under 150～250 ℃ and 2.0～6.0MPa, fully stir, react after 2～8 hours, add promoter again and can make described carbon monoxide-olefin polymeric.
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