CN101659607A - Method for preparing acetic acid and acetic anhydride respectively or synchronously - Google Patents
Method for preparing acetic acid and acetic anhydride respectively or synchronously Download PDFInfo
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- CN101659607A CN101659607A CN 200810042294 CN200810042294A CN101659607A CN 101659607 A CN101659607 A CN 101659607A CN 200810042294 CN200810042294 CN 200810042294 CN 200810042294 A CN200810042294 A CN 200810042294A CN 101659607 A CN101659607 A CN 101659607A
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- diacetyl oxide
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Abstract
The invention discloses a method for preparing an acetic acid and an acetic anhydride respectively and synchronously, which is characterized in that: a methanol, a methylacetate or a mixture of the methanol and the methylacetate and a mixed gas of carbon monoxide and hydrogen are reacted at 150 to 250 DEG C and 2.0 to 6.0 MPa; and a catalyst system used in the reaction comprises a mixture of rhodium or one of rhodium compounds and iridium or one of iridium compounds, a methyl iodide, at least one selected from mixtures of an amino acid and an amino acid derivative, the amino acid or the aminoacid derivative, and an accelerant. The method for preparing the acetic acid and the acetic anhydride in the invention has the advantages of: (1) reducing the generated tar, (2) reducing substance content of the acetic anhydride product, and (3) improving the stability of the catalyst system in the invention and avoiding the precipitation phenomenon. Due to the fact that the reaction system has nowater, the corrosion to devices is also reduced.
Description
Technical field
The present invention relates to a kind of method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously.
Background technology
As the important basic Organic Chemicals of a class, acetate and diacetyl oxide and downstream derived product thereof are widely used in the synthetic of medicine, synthon, light industry, weaving, leather, agricultural chemicals, explosive, rubber and metal processing, food and Fine Organic Chemical product.At present, the market outlook of world's acetate and diacetyl oxide are quite had an optimistic view of.
Producing the method for acetate and diacetyl oxide in the prior art, is to take the successive production equipment, is made by methyl alcohol and methyl acetate or dme and methyl alcohol and reaction of carbon monoxide.
Catalyst system by oxo process acetate or diacetyl oxide has experienced 3 stages, fs is the cobaltous iodide catalyzer, the earliest be nineteen sixty BASF AG on the research basis of Reppe etc., what develop first is that catalyzer, methyl iodide are the cobalt series catalyst of promotor with the cobalt-carbonyl, this catalyst system shortcomings such as condition harshness (65MPa, 250 ℃), acetic acid selectivity low (counting 87% with methyl alcohol), by product are many that respond fail to realize industrialization.Subordinate phase is that U.S. Monsanto company in 1970 has succeeded in developing rhodium base catalyst, and its technology relies on advantages such as reaction conditions gentle relatively (3～4MPa, 175 ℃), acetic acid selectivity higher (counting 99% with methyl alcohol), by product are few to realize industrialization rapidly.But rhodium base catalyst exists water-gas reforming reaction, by product propionic acid content high relatively, ethanoyl iodide and hydrogen iodide effect generation acetaldehyde takes place, and is settled out RhI
3Make defectives such as catalyst deactivation.Rhodium base catalyst is used for then synthesis of acetic acid acid anhydride of methyl acetate carbonylation, improves oxonation speed, exist equally also that reaction system tar formation speed is fast, rhodium catalyst is separated out sedimentary defective by adding auxiliary agent LiI or lithium acetate.Phase III is Britain BP company succeeded in developing, realized in 1996 industrial application in nineteen ninety a kind of novel carbinol carbonylation system acetic acid process, this process using iridium catalyst based (Cativa catalyzer), compare with rhodium base catalyst, have higher speed of reaction, higher catalyst stability, carbonylation reaction 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 oxo process diacetyl oxide with regard to iridium base catalyst system is the GB2333773 of BP company.As seen it is less relatively that the iridium catalyst system is used for the research of methyl acetate synthesizing acetic acid by carbonylation acid anhydride, reason is that the diacetyl oxide itself that (1) generates is a good part, diacetyl oxide and rhodium have certain weak coordination ability, the coordination ability of iridium is higher than rhodium, so diacetyl oxide and iridium are stablized coordination and then formed the inertia species; (2) diacetyl oxide can carry out the oxidation addition reaction with the species of iridium, forms the inertia species; (3) in the rhodium system, produce diacetyl oxide and need add a certain amount of an alkali metal salt, as LiI or Li (OAc), help methyl acetate and LiI effect on the one hand, form methyl iodide, Li of Sheng Chenging (OAc) and acetyliodide effect help the generation of diacetyl oxide on the other hand, but in the iridium system, add too much lithium salts, can cause more I
-Ion is free, causes the inertia species to generate.Because severe reaction conditions, catalyst levels are big, replace rhodium production diacetyl oxide difficulty bigger with the iridium catalyst system.
With rhodium as the patent of the catalyzer of preparation acetate and diacetyl oxide 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, mineral compound (as an alkali metal salt: promotor lithium iodide), the content of methyl iodide account for the reaction solution 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 diacetyl oxide product liquid that obtains of this carbonylation method is the mixture that contains diacetyl oxide and acetate.
There are following three problems in the mixture that adopts this rhodium base catalyst carbonylation method to prepare diacetyl oxide or acetate, diacetyl oxide: can produce tar (mixture of macromole organic polymer) in the time of (1) reaction; (2) acetate and the diacetyl oxide 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 diacetyl oxide 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 diacetyl oxide new catalyst does not have very big breakthrough.
Be still rhodium base catalyst and the carbonylation reaction device of world production acetate associating diacetyl oxide adopts, production cost is still in continuous rising.Novel thus catalyzer 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 diacetyl oxide cheaply according to deficiency of the prior art.
For achieving the above object, the present invention is achieved through the following technical solutions:
Prepare acetate, diacetyl oxide or prepare the method for acetate and diacetyl oxide simultaneously, it is characterized in that, the mixed gas that makes the mixture of methyl alcohol, methyl acetate or methyl alcohol and methyl acetate and carbon monoxide and hydrogen reacts under 150～250 ℃ and 2.0～6.0MPa, and the catalyst body that uses in the reaction is:
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;
Methyl iodide;
Amino acid and amino acid derivative mixture, amino acid or amino acid derivative;
And promotor.
Wherein, the mass concentration of the compound of rhodium or rhodium in mixed reaction solution is 200～1000ppm; The mass concentration of the compound of iridium or iridium in mixed reaction solution is 500～2000ppm.
Wherein, the consumption of methyl iodide is 5～16% of a mixed reaction solution weight.
Wherein, the mass concentration of lithium salts in mixed reaction solution is 50～500ppm.
Wherein, amino acid or amino acid derivative consumption be iridium or iridic compound mole number 0.1～3.0.
Wherein, hydrogen usage be carbon monoxide mole number 1～10%.
Wherein, the weight ratio of methyl acetate in mixed reaction solution is 5～30%.
Wherein, described rhodium compound selected from rhodium metal, iodate rhodium, hydration iodate rhodium, bromination rhodium, hydration bromination rhodium, rhodium chloride, hydration rhodium 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, etheric acid iridium, iridium 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, described amino acid is selected from glycine, L-Ala, proline(Pro), Threonine, tryptophane, leucine or tyrosine.
Wherein, described amino acid derivative is selected from N, N-N-methylsarcosine, N-methylalanine, leucine benzyl ester, tyrosine tert-butyl ester, glycine methyl ester or cyclopropyl alanine.
Wherein, described promotor is selected from lithium salts.
Wherein, described lithium salts is selected from lithium iodide, lithiumbromide, lithium chloride or lithium acetate.
Wherein, described catalyst system also comprises one or both in nickel salt and the platinum salt.
Catalyst system among the present invention, add in the reactor together by precursor, amino acid or amino acid whose derivative, acetate, methyl iodide and a spot of water with rhodium and iridium, under 150～250 ℃ and 2.0～6.0MPa, stir, the catalyst precursor of rhodium and iridium, by with I
-The rhodium that ion, CO reaction promptly form and the coordination compound [Rh (CO) of iridium
2I
2]
-[Ir (CO)
2I
2]
-
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 diacetyl oxide on the other hand.
The method for preparing acetate and diacetyl oxide among the present invention, solved that rhodium base catalyst produces that the coal-tar middle oil generation of reaction solution that acetate and diacetyl oxide exist is 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, diacetyl oxide mix product, the tar of generation is lower than 0.0002kg; (2) reducing substances content is low in the diacetyl oxide product, by the method among the present invention, not needing increases the device of handling reducing substances, and the permanganate indices of the diacetyl oxide product that can obtain just can reach the requirement of premium grads 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 diacetyl oxide.In the iridium catalyst system, add lithium salts and make I
-Stable existence, I
-With CO competition and the coordination of iridium central atom, thereby restrain speed of response, thereby be called as catalyzer influential " poisonous " reagent.Thereby make acetyliodide and the easier generation diacetyl oxide of lithium acetate promote oxonation but in the rhodium catalyst system, add lithium salts, improve speed of response.By adding a certain amount of amino acid or amino acid derivative, make the amino cationic moiety of amino acid and amino acid derivative and the hydrogen bond action of amino acid whose-COOH group come complexing I jointly in the iridium catalyst system
-Ion, thus part I reduced
-Free, weaken influence to speed of response.
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 stabilising 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 derivative thereof contain oxynitrides, the amino of amino acid and amino acid derivative and the H in the system
+Or Me
+Form positively charged ion, 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
-Ionic is free, thereby has further stablized iridium catalyst.
The ratio that the content that method of the present invention in addition can change material benzenemethanol and methyl acetate is regulated acetate and diacetyl oxide is to satisfy specific economic needs.
Description of drawings
Fig. 1 is the process flow sheet of preparation acetate and diacetyl oxide.
Embodiment
The present invention further specifies below in conjunction with accompanying drawing.
As shown in Figure 1, use present method to prepare acetate and the diacetyl oxide 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 disengaging zone of reaction mixture, generally include one or two flasher 2, at this, catalyzer separates with reaction solution, light constituent methyl acetate, methyl iodide and a part of acetate, diacetyl oxide enter the 3rd district as gas phase, return reaction zone and carry catalyzer, promotor, stablizer, just first district as acetate, the diacetyl oxide of heavy constituent.The 3rd district is a rectification zone, and the realization product separates with light constituent methyl acetate, methyl iodide, and light constituent 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 methyl iodide, acetate, diacetyl oxide, the lithium salts in addition of reactor 1 simultaneously.The purpose that adds diacetyl oxide is to consume the water of bringing into when Preparation of Catalyst.After the catalyzer of reactive system needs comprises that promotor, stablizer and methyl iodide, acetate meet production requirement, reactor 1 charge into CO and an amount of hydrogen to reactor pressure at 1.0MPa, reactor and flasher are set up catalyst recirculation then, and reactor 1 heats up, charges into CO and a certain proportion of hydrogen.After temperature of reaction, reaction pressure satisfy the production technique index, formally drop into material benzenemethanol and methyl acetate.
Catalyst system among the present invention, in the time of can or preparing acetate and diacetyl oxide simultaneously at preparation acetate, diacetyl oxide each raw material is joined in the reaction solution, it is suitable that temperature and pressure is adjusted to, and gets final product catalytic preparation acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously.In order to save time, also can before preparing acetate, diacetyl oxide or preparing acetate and diacetyl oxide simultaneously, make each raw material reaction for some 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 reaction solution relatively stable, and carry out macrocyclic test, the generating rate that the test reaction system is coal-tar middle oil, the permanganate indices of diacetyl oxide product.Need to prove that there are three rectifying tower in the 3rd district shown in the accompanying drawing 1, first rectifying tower is a lights column, separating acetic acid methyl esters, methyl iodide and acetate, diacetyl oxide, the methyl acetate of cat head, methyl iodide Returning reactor; Second rectifying tower separating acetic acid and diacetyl oxide, cat head or side line obtain purified acetate; The 3rd rectifying tower is the diacetyl oxide rectifying tower, and acetate described in this specification sheets and diacetyl oxide mixing prod are light constituent rectifying tower 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 and iridium molfraction 1: 1 N-methylalanine and water; Add the methyl iodide, the solvent acetic acid that meet production technique; Feed CO then, 150 ℃ of temperature of reaction, 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
In the reactor of Preparation of Catalyst, add rhodium precursor iodate rhodium, add amount, the solvent acetic acid of the methyl iodide that meets production technique again, feed CO then, 150 ℃ of temperature of reaction, pressure 3.0MPa reacted 2 hours down, prepared the coordination compound of rhodium, and this coordination compound is the solution shape.
This embodiment is not embodiments of the invention, because do not have amino acid or amino acid derivative stablizer in this catalyst system.
In the continuous apparatus of flow process such as accompanying drawing 1, the product of embodiment A preparation is added in the reactor together with methyl iodide, acetate, diacetyl oxide, lithium acetate, the add-on visual response of methyl iodide, acetate, diacetyl oxide need be determined, the water that adds in the purpose spent catalyst preparation of diacetyl oxide.In temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm, iridium mass concentration 1000ppm in the control reaction solution, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide 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 mole number.Device moves 500 hours continuously, the about 8.9mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00015kg, permanganate indices is 35mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide 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 methyl iodide content is: before (1) reaction beginning, drop into the methyl acetate and the methyl iodide of desired component concentration to reactor; (2) after the reaction beginning, (such as one hour) extracts reaction solution analysis at regular intervals, calculates speed of reaction, requires to adjust corresponding raw material according to reaction process and drops into ratio, to guarantee the requirement of reaction solution component.
It should be noted that also the mass concentration of reacting back acetate and diacetyl oxide only refers to acetate and the diacetyl oxide that generates, and does not comprise the concentration of the solvent acetic acid that contains in the reactive 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 methyl iodide, acetate, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, in temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, the methyl iodide 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 mole number.Operation is 500 hours continuously, the about 6.7mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00032kg, permanganate indices is 75mg/100ml, product acetate and diacetyl oxide are brown liquid after placing for some time, and the acetate of generation and diacetyl oxide 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 diacetyl oxide process, a part of catalyzer has been wrapped up in the generation of tar, causes catalyst precipitation to be separated out, and the reactive system catalyst concn descends.
Embodiment C
Repeat the method for Preparation of Catalyst embodiment A, change the processing condition of preparation, adopt 200 ℃ of temperature of reaction, pressure 4.5MPa stirs 5 hours prepared rhodium and iridium mixed ligand complex down.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.
Adopt the method for preparing catalyst of Embodiment C, 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 methyl iodide, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 150 ℃, pressure is 2.0MPa, the rhodium mass concentration is 200ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 50ppm, the mol ratio of N-methylalanine and iridium is 1.0, and the methyl iodide 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 mole number.Operation is 500 hours continuously, the about 5.3mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00003kg, permanganate indices is 40mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide 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, making the rhodium mass concentration is 200ppm.In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 150 ℃, pressure is 2.0MPa, the rhodium mass concentration is 200ppm in the control reaction solution, the lithium mass concentration is 50ppm, the methyl iodide consumption is 12% of a mixed reaction solution weight, methyl acetate is 15% of a mixed reaction solution weight, and reaction raw materials is 43% methyl alcohol and 57% methyl acetate of calculating by weight, 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 mole number.Continuously operation is 500 hours, the about 0.55mol/lh of speed of reaction, and average every kilogram of diacetyl oxide product correspondence generates to such an extent that tar content is 0.00001kg, and permanganate indices is 65mg/100ml, and product after placement for some time is faint yellow.Because the speed of reaction of oxo process acetate or diacetyl oxide is directly relevant with the concentration of rhodium catalyst, rhodium content is low, and speed of response is slow.So after the successive reaction 500 hours, reaction solution tar formation speed is slower, the reaction solution rhodium content does not obviously descend.
Embodiment 3
Repeat Embodiment C, only change the iodate rhodium of adding and the consumption of iodate iridium, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 250 ℃, pressure is 6.0MPa, the rhodium mass concentration is 200ppm in the control reaction solution, iridium mass concentration 500ppm, the lithium mass concentration is 500ppm, the mol ratio of N-methylalanine and iridium is 1.0, and the methyl iodide 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 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 mole number.Operation is 500 hours continuously, the about 3.9mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00019kg, permanganate indices is 48mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide 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 200ppm.In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 250 ℃, pressure is 6.0MPa, the rhodium mass concentration is 1000ppm in the control reaction solution, the lithium mass concentration is 500ppm, the methyl iodide 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 mole number.Operation is 500 hours continuously, the about 0.59mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00003kg, permanganate indices is 70mg/100ml, product acetate and diacetyl oxide are weak yellow liquid after placing for some time, and the acetate of generation and diacetyl oxide account for 26.8% and 26.2% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 850ppm.。
Embodiment 4
Repeat embodiment A, changing the precursor that adds rhodium is Rh (acac)
3, the iridium precursor is Ir (acac)
3In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, the small amount of acetic acid acid anhydride, lithium chloride adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 3.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide 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 mole number.Operation is 500 hours continuously, the about 8.8mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00014kg, permanganate indices is 32mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide 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, the rhodium mass concentration is 800ppm.In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, lithium chloride adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 3.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, the methyl iodide 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 42% methyl alcohol and 58% 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 mole number.Operation is 500 hours continuously, the about 6.6mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00031kg, permanganate indices is 70mg/100ml, product acetate and diacetyl oxide are brown liquid after placing for some time, and the acetate of generation and diacetyl oxide 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 processing condition of preparation, adopt 250 ℃ of temperature of reaction, pressure 6.0MPa stirs 8 hours prepared rhodium and iridium mixed ligand complex down.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
Adopt the method for preparing catalyst of embodiment D, changing the precursor that adds rhodium is Rh
4(CO)
12, changing the iridium precursor is Ir
4(CO)
12In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 5.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide 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 mole number.Operation is 500 hours continuously, the about 8.9mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00019kg, permanganate indices is 35mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide 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 Embodiment B, changing the rhodium precursor that adds is Rh
4(CO)
12, 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 methyl iodide, acetate, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 5.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, the methyl iodide consumption is 15% 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 42% methyl alcohol and 58% 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 mole number.Operation is 500 hours continuously, the about 4.1mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00035kg, permanganate indices is 80mg/100ml, product acetate and diacetyl oxide are brown liquid after placing for some time, and the acetate of generation and diacetyl oxide account for 26.8% and 26.2% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 650ppm.
Embodiment 6
Repeat embodiment D, changing the precursor that adds rhodium is Rh
2O
3, changing 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 methyl iodide, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 200 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0,12% of methyl iodide consumption 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 mole number.Operation is 500 hours continuously, the about 9.1mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00017kg, permanganate indices is 45mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide 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
3In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 200 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, the methyl iodide 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 mole number.Operation is 500 hours continuously, the about 4.0mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00036kg, permanganate indices is 82mg/100ml, product acetate and diacetyl oxide are brown liquid after placing for some time, and the acetate of generation and diacetyl oxide account for 26.8% and 26.2% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 670ppm.
Embodiment 7
Repeat embodiment A, change the iodate rhodium and the iodate one ground amount that add, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 170 ℃, pressure is 4.0MPa, the rhodium mass concentration is 1000ppm in the control reaction solution, iridium mass concentration 2000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, and the methyl iodide 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 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 mole number.Operation is 500 hours continuously, the about 9.2mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00013kg, permanganate indices is 30mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide 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 methyl iodide, acetate, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 170 ℃, pressure is 4.0MPa, the rhodium mass concentration is 1000ppm in the control reaction solution, the lithium mass concentration is 250ppm, the methyl iodide 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 mole number.Operation is 500 hours continuously, the about 7.1mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00041kg, permanganate indices is 68mg/100ml, product acetate and diacetyl oxide are weak yellow liquid after placing for some time, and the acetate of generation and diacetyl oxide account for 26.8% and 26.2% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 690ppm.
Embodiment 8
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, the small amount of acetic acid acid anhydride, lithium iodide adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide 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 mole number.Device moves 500 hours continuously, the about 8.6mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00011kg, permanganate indices is 30mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide 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 methyl iodide, acetate, lithium iodide adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, and the methyl iodide 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 mole number.Operation is 500 hours continuously, the about 3.2mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00024kg, permanganate indices is 55mg/100ml, product acetate and diacetyl oxide are colourless transparent liquid, and the acetate of generation and diacetyl oxide account for 30.4% and 29.% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 750ppm.
Embodiment 9
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 16% 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 mole number.Device moves 500 hours continuously, the about 9.2mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00017kg, permanganate indices is 45mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide account for 24.8% and 24.2% 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.
Comparative Examples 9
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, and the methyl iodide consumption is 16% 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 mole number.Operation is 500 hours continuously, the about 7.0mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00038kg, permanganate indices is 85mg/100ml, product acetate and diacetyl oxide are light brown liquid after placing for some time, and the acetate of generation and diacetyl oxide account for 24.8% and 24.2% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 650ppm.
Embodiment 10
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 12% of a mixed reaction solution weight, methyl acetate is 5% 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 mole number.Device moves 500 hours continuously, the about 5.5mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00010kg, permanganate indices is 35mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide account for 31.9% and 31.1% 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 10
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, and the methyl iodide consumption is 12% of a mixed reaction solution weight, and methyl acetate is 5% 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 mole number.Operation is 500 hours continuously, the about 3.5mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00023kg, permanganate indices is 75mg/100ml, product acetate and diacetyl oxide are brown liquid after placing for some time, and the acetate of generation and diacetyl oxide account for 31.9% and 31.1% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 760ppm.
Embodiment 11
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 50ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 12% of a mixed reaction solution weight, methyl acetate is 30% 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 mole number.Device moves 500 hours continuously, the about 9.2mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00017kg, permanganate indices is 35mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide account for 19.2% and 18.8% 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 11
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 50ppm, and the methyl iodide consumption is 12% of a mixed reaction solution weight, and methyl acetate is 30% 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 mole number.Operation is 500 hours continuously, the about 5.1mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00036kg, permanganate indices is 75mg/100ml, product acetate and diacetyl oxide are brown liquid after placing for some time, and the acetate of generation and diacetyl oxide account for 19.2% and 18.8% of entire reaction liquid respectively.The rhodium concentration of 500 hours afterreaction liquid is 650ppm.
Embodiment 12
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 16% 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 1% of a carbon monoxide mole number.Device moves 200 hours continuously, the about 4.9mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00017kg, permanganate indices is 35mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide account for 26.8% and 26.2% of entire reaction liquid respectively., extract reaction solution and make rhodium, iridium content analysis after 200 hours in the continuous apparatus operation, find that content does not descend.
Comparative Examples 12
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, and the methyl iodide consumption is 16% of a mixed reaction solution weight, and 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, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 1% of a carbon monoxide mole number.Operation is 200 hours continuously, the about 4.3mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00041kg, permanganate indices is 75mg/100ml, product acetate and diacetyl oxide are brown liquid after placing for some time, and the acetate of generation and diacetyl oxide account for 26.8% and 26.2% of entire reaction liquid respectively.The rhodium concentration of 200 hours afterreaction liquid is 550ppm.
Embodiment 13
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, the small amount of acetic acid acid anhydride, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 500ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide 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 10% of a carbon monoxide mole number.Device moves 200 hours continuously, the about 9.1mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00021kg, permanganate indices is 38mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide account for 26.8% and 26.2% of entire reaction liquid respectively., extract reaction solution and make rhodium, iridium content analysis after 200 hours in the continuous apparatus operation, find that content does not descend.
Comparative Examples 13
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetate, lithium acetate adds in the reactor together, methyl iodide, acetate, the add-on visual response of diacetyl oxide need be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 500ppm, and the methyl iodide consumption is 12% of a mixed reaction solution weight, and 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, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 10% of a carbon monoxide mole number.Operation is 200 hours continuously, the about 7.7mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00033kg, permanganate indices is 46mg/100ml, product acetate and diacetyl oxide are colourless transparent liquid, and the acetate of generation and diacetyl oxide account for 25.8% and 25.2% of entire reaction liquid respectively.Also there is 2% EDA in the reaction solution simultaneously.The rhodium concentration of 200 hours afterreaction liquid is 750ppm.
Result from above embodiment and Comparative Examples thereof, when in reaction solution, adding a certain amount of iridium catalyst and amino acid stabilizers, in any case change temperature of reaction, reaction pressure, rhodium concentration, lithium concentration, methyl iodide content, the hydrogen ratio, methyl acetate content, the result is that the speed of response 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 reaction solution did not significantly descend.
Embodiment's spirit of the present invention 14～25 is listed in the table below in order better to illustrate.Embodiment 14～25, and method for preparing catalyst provides according to embodiment A, and wherein the kind of the mass concentration of rhodium and iridium, amino acid or amino acid derivative stablizer and add-on add by embodiment 14～25 requirements.Reaction conditions is identical, 190 ℃ of temperature of reaction, pressure is 4.0MPa, lithium mass concentration 250ppm, the methyl iodide consumption is 8% of a mixed reaction solution weight, the methyl acetate consumption is 15% of a mixed reaction solution weight, variation be rhodium and iridium concentration, amino acid or amino acid derivative stabilizer types with and with the mass ratio of mol ratio, material benzenemethanol and the methyl acetate of iridium catalyst.
| Embodiment | Methanol/methyl acetate w/w | Rhodium content ppm | Iridium content ppm | Amino acid stabilizers | Stablizer/iridium mol ratio | ??STY ??mol/l·h | Acetic acid/acetic anhydride w/w | Tar generating rate Kg/Kg | Permanganate indices mg/100ml |
| ??14 | ??10/90 | ??400 | ??1000 | The N-methylalanine | ??1.0 | ??6.4 | ??7.5/49.5 | ??0.00011 | ??35 |
| ??15 | ??43/57 | ??400 | ??1000 | The N-methylalanine | ??1.0 | ??9.1 | ??28.9/28.1 | ??0.00009 | ??35 |
| ??16 | ??83/17 | ??400 | ??1000 | The N-methylalanine | ??1.0 | ??12.3 | ??49.5/7.5 | ??0.00007 | ??30 |
| ??17 | ??43/57 | ??400 | ??1000 | Glycine | ??1.0 | ??8.9 | ??28.9/28.1 | ??0.00010 | ??35 |
| ??18 | ??43/57 | ??400 | ??1000 | Proline(Pro) | ??1.0 | ??8.4 | ??28.9/28.1 | ??0.00012 | ??40 |
| ??19 | ??43/57 | ??400 | ??1000 | Tyrosine | ??1.0 | ??7.9 | ??28.9/28.1 | ??0.00013 | ??35 |
| ??20 | ??43/57 | ??400 | ??1000 | Cyclopropyl alanine | ??1.0 | ??8.3 | ??28.9/28.1 | ??0.00015 | ??38 |
| ??21 | ??43/57 | ??400 | ??1000 | The N-methylalanine | ??0.5 | ??8.1 | ??28.9/28.1 | ??0.00013 | ??45 |
| ??22 | ??43/57 | ??400 | ??1000 | The N-methyl-prop | ??2.0 | ??9.0 | ??28.9/28.1 | ??0.00011 | ??40 |
| Propylhomoserin | |||||||||
| ??23 | ??43/57 | ??200 | ??2000 | The N-methylalanine | ??1.0 | ??8.7 | ??28.9/28.1 | ??0.00005 | ??30 |
| ??24 | ??43/57 | ??1000 | ??500 | The N-methylalanine | ??1.0 | ??9.1 | ??28.9/28.1 | ??0.00021 | ??65 |
| ??25 | ??43/57 | ??800 | ??1200 | The N-methylalanine | ??1.0 | ??9.2 | ??28.9/28.1 | ??0.00014 | ??40 |
Embodiment 14～25, after for some 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
Add rhodium precursor iodate rhodium in the Preparation of Catalyst reactor, making the rhodium mass concentration is 800ppm; Add iridium precursor iodate iridium, make iridium mass concentration 1000ppm; Add platinum precursor acetate platinum, making the platinum mass concentration is 500ppm; Add and iridium molfraction 1: 1 N-methylalanine and water; The amount, the solvent acetic acid that add the methyl iodide that meets production technique.Feed CO then, 150 ℃ of temperature of reaction, pressure 3.0MPa reacted 1 hour down, prepared the coordination compound of rhodium and iridium, and this coordination compound is the solution shape.
Embodiment 26
In the continuous apparatus of flow process such as accompanying drawing 1, the product that Embodiment C is prepared adds in the reactor together with methyl iodide, acetate, small amount of acetic acid acid anhydride, lithium acetate.In temperature of reaction is 190 ℃, pressure is 5.0MPa, the rhodium mass concentration is 800ppm, iridium mass concentration 1000ppm in the control reaction solution, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide 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 mole number.Device moves 500 hours continuously, the about 8.4mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00016kg, permanganate indices is 40mg/100ml, product acetate and diacetyl oxide are water white transparency, and the acetate of generation and diacetyl oxide 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 27
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 methyl iodide, acetate, lithium acetate, water.In temperature of reaction is 190 ℃, pressure is 3.0MPa, the rhodium mass concentration is 800ppm, iridium mass concentration 1000ppm in the control reaction solution, and the lithium mass concentration is 250ppm, and the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide 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 mixed gas of carbon monoxide or carbon monoxide and hydrogen.Device moves 500 hours continuously, the about 15.0mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide 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 28
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 methyl iodide, acetate, lithium acetate, small amount of acetic acid acid anhydride, and the purpose of diacetyl oxide is the water that spent catalyst is brought reaction system into.In temperature of reaction is 190 ℃, pressure is 5.0MPa, the rhodium mass concentration is 800ppm, iridium mass concentration 1000ppm in the control reaction solution, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide 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 mole number.Device moves 500 hours continuously, the about 4.5mol/lh of speed of reaction, average every kilogram of acetate and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00019kg, and permanganate indices is 35mg/100ml, the product diacetyl oxide is a water white transparency, and the diacetyl oxide 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 present invention, the content of used rhodium compound all is to be benchmark with the rhodium content, and the content of used iridic compound all is that the content with iridium is benchmark, and the amount of used lithium salts all is that the content with lithium is benchmark.
Among the embodiment 1-28, described catalyst system also can not use the product of embodiment A or C preparation, but change into directly the raw material of catalyst system is added in the reaction vessel with preparation acetate, diacetyl oxide or the raw material for preparing acetate and diacetyl oxide simultaneously, under the reaction conditions of each embodiment, can play same katalysis.
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 (14)
1. prepare acetate, diacetyl oxide or prepare the method for acetate and diacetyl oxide simultaneously, it is characterized in that, the mixed gas that makes the mixture of methyl alcohol, methyl acetate or methyl alcohol and methyl acetate and carbon monoxide and hydrogen reacts under 150～250 ℃ and 2.0～6.0MPa, and the catalyst body that uses in the reaction is:
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;
Methyl iodide;
Amino acid and amino acid derivative mixture, amino acid or amino acid derivative;
And promotor.
2. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously according to claim 1 is characterized in that the mass concentration of the compound of rhodium or rhodium in mixed reaction solution is 200～1000ppm; The mass concentration of the compound of iridium or iridium in mixed reaction solution is 500～2000ppm.
3. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously according to claim 1 is characterized in that the consumption of methyl iodide is 5～16% of a mixed reaction solution weight.
4. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously according to claim 1 is characterized in that the mass concentration of lithium salts in mixed reaction solution is 50～500ppm.
5. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously according to claim 1 is characterized in that, amino acid or amino acid derivative consumption be iridium or iridic compound mole number 0.1～3.0.
6. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously according to claim 1 is characterized in that, hydrogen usage be carbon monoxide mole number 1～10%.
7. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously according to claim 1 is characterized in that the weight ratio of methyl acetate in mixed reaction solution is 5～30%.
8. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide 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, rhodium chloride, hydration rhodium 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
9. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide 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, etheric acid iridium, iridium 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) 1
2, [Ir (CO)
2I
2]
-H
+, [Ir (CO)
2Br
2]
-H
+, [Ir (CO)
2I
4]
-H
+Or [Ir (CH
3) (CO)
2I
3]
-H
+
10. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously according to claim 1 is characterized in that described amino acid is selected from glycine, L-Ala, proline(Pro), Threonine, tryptophane, leucine or tyrosine.
11. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously according to claim 1, it is characterized in that, described amino acid derivative is selected from N, N-N-methylsarcosine, N-methylalanine, leucine benzyl ester, tyrosine tert-butyl ester, glycine methyl ester or cyclopropyl alanine.
12. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously according to claim 1 is characterized in that described promotor is selected from lithium salts.
13. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously according to claim 12 is characterized in that described lithium salts is selected from lithium iodide, lithiumbromide, lithium chloride or lithium acetate.
14. the method for preparing acetate, diacetyl oxide or prepare acetate and diacetyl oxide simultaneously according to claim 1 is characterized in that described catalyst system also comprises one or both in nickel salt and the platinum salt.
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| CN 200810042294 CN101659607B (en) | 2008-08-29 | 2008-08-29 | Method for preparing acetic acid and acetic anhydride respectively or synchronously |
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| CN101659607B CN101659607B (en) | 2013-04-10 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320950A (en) * | 2011-09-28 | 2012-01-18 | 上海华谊（集团）公司 | Method for synthesizing acetic acid through carbonylation |
| CN102381956A (en) * | 2011-09-06 | 2012-03-21 | 安徽皖维高新材料股份有限公司 | Method for preparation of acetic anhydride and acetic acid by means of carbonyl synthesis of methyl acetate and methanol azeotrope and method for separation |
| CN104250209A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Method for production of acetic acid by methanol carbonylation |
| CN104250210A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Method for production of acetic acid by methanol carbonylation |
| CN104250208A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Production method for preparing acetic acid through carbonylation of methanol |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2703351A1 (en) * | 1993-03-31 | 1994-10-07 | Rhone Poulenc Chimie | Process for the preparation of carboxylic acids or the corresponding esters in the presence of a catalyst based on rhodium and iridium. |
| US6211405B1 (en) * | 1998-10-23 | 2001-04-03 | Celanese International Corporation | Addition of iridium to the rhodium/inorganic iodide catalyst system |
| CN1166615C (en) * | 2002-01-21 | 2004-09-15 | 中国石油化学工业开发股份有限公司 | Process for preparing carboxylic acid |
| US7737298B2 (en) * | 2006-06-09 | 2010-06-15 | Eastman Chemical Company | Production of acetic acid and mixtures of acetic acid and acetic anhydride |
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2008
- 2008-08-29 CN CN 200810042294 patent/CN101659607B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381956A (en) * | 2011-09-06 | 2012-03-21 | 安徽皖维高新材料股份有限公司 | Method for preparation of acetic anhydride and acetic acid by means of carbonyl synthesis of methyl acetate and methanol azeotrope and method for separation |
| CN102381956B (en) * | 2011-09-06 | 2013-08-21 | 安徽皖维高新材料股份有限公司 | Method for preparation of acetic anhydride and acetic acid by means of carbonyl synthesis of methyl acetate and methanol azeotrope and method for separation |
| CN102320950A (en) * | 2011-09-28 | 2012-01-18 | 上海华谊（集团）公司 | Method for synthesizing acetic acid through carbonylation |
| CN102320950B (en) * | 2011-09-28 | 2015-05-13 | 上海华谊（集团）公司 | Method for synthesizing acetic acid through carbonylation |
| CN104250209A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Method for production of acetic acid by methanol carbonylation |
| CN104250210A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Method for production of acetic acid by methanol carbonylation |
| CN104250208A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Production method for preparing acetic acid through carbonylation of methanol |
| CN104250209B (en) * | 2013-06-28 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of production method of Production of Acetic Acid by Methanol Carbonylation |
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|---|---|
| CN101659607B (en) | 2013-04-10 |
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