CN102093196B - Method for preparing carboxylic acid by carbonylation of alkanol and/or active derivative thereof - Google Patents
Method for preparing carboxylic acid by carbonylation of alkanol and/or active derivative thereof Download PDFInfo
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- CN102093196B CN102093196B CN 200910201100 CN200910201100A CN102093196B CN 102093196 B CN102093196 B CN 102093196B CN 200910201100 CN200910201100 CN 200910201100 CN 200910201100 A CN200910201100 A CN 200910201100A CN 102093196 B CN102093196 B CN 102093196B
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Abstract
The invention discloses a method for preparing carboxylic acid by carbonylation of alkanol and/or active derivative thereof, which comprises the following steps of: reacting the alkanol and/or the active derivative thereof and carbon monoxide feed in a liquid reaction medium containing iridium catalyst, rhodium catalyst, stabilizer, alkyl iodide, water, methyl acetate and acetic acid, and then reclaiming the carboxylic acid from the obtained reaction product, wherein the content of iridium is 500 to 4,000ppm; the content of rhodium is 50 to 400ppm; and the stabilizer is one or more of iron, chromium, nickel and molybdenum, and the content of the stabilizer is 200 to 600ppm. The reaction system catalyst for the method has good stability in the presence of one or more of iron, chromium, nickel and molybdenum; and meanwhile, the catalyst has high catalytic reaction rate, good catalytic activity under the condition of low ester and/or low water content, and low cost.
Description
Technical field
The present invention relates to the method for the preparing carboxylic acid by carbonylation of a kind of alkanol and/or its reactive derivative.
Background technology
The catalysis methanol carbonylation prepares the method for acetic acid, and the catalyst system that uses single rhodium catalytic system, single iridium catalyst systems and the coupling of rhodium iridium is arranged.Although the catalyzer that above-mentioned catalyst system uses is not quite similar, in Industrial Catalysis carbonylation of methanol manufacture acetic acid process, all relate to the stability problem of catalyzer.Because rhodium and iridium belong to precious metal, cost is expensive, if can increase the stability of catalyzer, then can effectively reduce cost.Many researchists endeavour to study the stability that carbonylation of methanol prepares acetic acid catalyst.The people's such as Simith US5001259, US5026908 and US5144068 disclose a kind of unsettled problem of catalyzer can solve single rhodium system water content and be lower than 14% time, it is by using the method for soluble alkali metal or alkaline-earth metal salt compounded of iodine such as lithium iodide, perhaps by using the method rugged catalyst of solubility quaternary ammonium-Huo quaternary phosphine salt compounded of iodine, but all needing to consume a large amount of iodide salts, these methods are unfavorable for the operations such as later stage product purification and solvent recuperation.Point out in the European patent EP 752406, in the catalyst reaction system, should make corroding metal, especially nickel, iron and chromium are as far as possible few, because these ions can make iridium catalyst systems poison.And catalyzer is iridium rhodium coupling system among the international artificial silk patent CN99812415.X, adopts basic metal or alkaline-earth metal salt compounded of iodine as the stablizer of catalyzer.
Summary of the invention
Technical problem to be solved by this invention is that the catalyzer less stable that has overcome in the catalyst system of existing preparing carboxylic acid by carbonylation often need to be added catalyzer, perhaps the existence because of the corrosion metals ion causes the defectives such as poisoning of catalyst or catalytic activity reduction, and the method for the preparing carboxylic acid by carbonylation of a kind of alkanol and/or its reactive derivative is provided.In iron, chromium, nickel and molybdenum one or more of method reaction system catalyzer of the present invention exist stability inferior good, and rate of catalysis reaction is higher simultaneously, have preferably catalytic activity under low ester and/or the low water content condition, and the catalyzer cost is lower.
The method of the preparing carboxylic acid by carbonylation of alkanol of the present invention and/or its reactive derivative, it is in the liquid reaction medium that contains iridium catalyst, rhodium catalyst, stablizer, alkyl iodide, water, methyl acetate and acetic acid, with alkanol and/or its reactive derivative and carbon monoxide charging reaction, then from the reaction product that obtains, reclaim carboxylic acid, wherein, the content of described iridium is 500～4000ppm, and that better is 1000～2000ppm; The content of described rhodium is 50～400ppm, and that better is 100～300ppm; Described stablizer is one or more in iron, chromium, nickel and the molybdenum, and the content of described stablizer is 200～600ppm, and that better is 300～400ppm.
Wherein, the better metallic promoter agent that also contains is used for promoting rate of catalysis reaction in the described liquid reaction medium.What the molar ratio of described metallic promoter agent and iridium was better is 1～15, and better is 6～15, and best is 5～10.Described metallic promoter agent is the conventional metallic promoter agent of using in this area, one or more that better is in ruthenium, osmium and the rhenium, and better is ruthenium.The existence form of described metallic promoter agent is the salt of the metal catalyst of existing this area routine, generally can be any appropriate form and join the salt that dissolves or be converted into soluble form in the liquid reaction medium, that better is ruthenium chloride, ruthenium bromide, ruthenium metal, ruthenium oxide, ruthenium acetate, propionic acid ruthenium, butyric acid ruthenium, pentacarbonyl ruthenium, hydration osmium chloride, anhydrous chlorides of rase osmium, osmium metal, perosmic anhydride, ten dicarbapentaborane, three osmiums, Re
2(CO)
10, Re (CO)
5Cl, Re (CO)
5Br, Re (CO)
5I, ReCl
3XH
2O and ReCl
5YH
2Among the O one or more.
Reaction system of the present invention adopts the coupling system of iridium catalyst and rhodium catalyst.Although existing document is often reported for rhodium, iridium or rhodium iridium coupling catalyst system, iron, chromium, in nickel and the molybdenum one or more are impurity to the catalyst reaction system mostly, can make the catalytic activity reduction even make poisoning of catalyst, but the inventor gropes research through great many of experiments to be found, in the rhodium iridium catalyst coupling system, the iron that contains certain content, chromium, in nickel and the molybdenum one or more, and in the content range of the iridium rhodium of above-mentioned special selection, the proportioning of while or complexed metal promotor and iridium, can so that reaction when guaranteeing preferably catalytic reaction activity and speed, the larger raising that the stability of catalyzer itself also obtains, particularly reduce the number of times of adding of catalyzer in the commercial process, greatly reduced the catalyzer cost; The catalytic activity of reaction system of the present invention under low ester, low water condition is still better simultaneously, and the saving resource cost reduces energy consumption.
Wherein, the adding form of one or more in described iron, chromium, nickel and the molybdenum is the metallic salt of existing this area routine, generally can be any appropriate form and join the salt that dissolves or be converted into soluble form in the liquid reaction medium, better is metal iodide and/or oxyhydroxide.
Wherein, the precursor of described iridium catalyst is the conventional iridium salt catalyst precursor that uses in this area, and that better is iridium acetate, iridium metals, iodate iridium, hydration iodate iridium, bromination iridium, hydration bromination iridium, iridium chloride, chloro-iridic acid, hydration iridium chloride, oxalic acid iridium, etheric acid iridium, iridium oxide, iridous oxide, [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
+[Ir (CH
3) (CO)
2I
3]
-H
+In one or more, the better iridium catalyst precursor that preferably is dissolvable in water carbonylation reaction component such as water, alcohol and carboxylic acid is such as in iridium acetate, oxalic acid iridium and the etheric acid iridium one or more.
Wherein, the precursor of described rhodium catalyst is the conventional rhodium salt catalyst precursor that uses in this area, the better rhodium salt catalyst precursor that is applicable to single rhodium catalyst system that is selected from, that better is rhodium chloride, three hydration rhodium chlorides, bromination rhodium, iodate rhodium, rhodium acetate, dicarbonyl rhodium acetylacetonate, [Rh (CO)
2Cl]
2[Rh (CO)
2I]
2In one or more.The content of catalyst rhodium of the present invention in rhodium iridium catalystic converter system is lower, has reduced the catalyzer cost.
Wherein, described alkyl iodide is the conventional alkyl iodide that uses in this area, considers the length of carbochain to the impact of alkyl iodide activity, and what alkyl iodide was better is methyl-iodide and/or iodoethane; The content of described alkyl iodide is this area conventional amount used, and better is 5～30%, and better is 10～20%, and per-cent is mass percent.
Wherein, the content of described water is this area conventional amount used, and better is 0.5～16%, and better is 0.5～14%, and best is 2～8%, and per-cent is mass percent.The applicable high water of catalystic converter system of the present invention or low aqueous systems, and in low aqueous systems, still can keep higher catalytic activity, and lower water-content also makes, and lock out operation difficulty and the cost of water and acetic acid product significantly reduces in the follow-up step.
Wherein, the content of described methyl acetate is this area conventional amount used, and better is 0.5～40%, and better is 0.5～5%, and best is 2～5%, and per-cent is mass percent.Wherein, the content of preferred methyl acetate belongs to low ester content scope, and catalystic converter system of the present invention still has preferably catalytic activity under low ester condition, should hang down the operation easier that ester content also reduces the subsequent recovery alkyl iodide simultaneously.
Wherein, the content of described acetic acid is this area conventional amount used, is generally the amount of replenishing liquid reaction medium mass percent 100% among the present invention.
Among the present invention, described alkanol and/or its reactive derivative such as ether, ester, halogenide etc. are used for carbonylation reaction and produce carboxylic acid.Described alkanol better for carbonatoms is 1～5 alcohols, better is methyl alcohol.What described carboxylic acid was better is acetic acid.
The described content of above-mentioned each component is in the catalytic reaction process content of each component in the real reaction system among the present invention.
Among the present invention, on the basis that meets this area general knowledge, the optimum condition of each above-mentioned technical characterictic can arbitrary combination, obtains preferred embodiment of the present invention.
The suitable device of method of the present invention is this area conventional equipment, generally can adopt typical reactive system, and the reactive system that the catalysis methanol carbonylation prepares acetic acid generally comprises liquid-phase carbonylation reactor, flash tank and separated from acetic acid tower.Carbonylation reactor generally is a stirred autoclave that can automatically the reaction liquid capacity dimension be held in constant level, can introduce continuously alkanol and/or its reactive derivative, water in this reactor, from alkyl iodide and the methyl acetate of the recycling catalyst solution at the bottom of the flash tank and recycle.Carbon monoxide is continuous carbonylate reactor and fully disperseing therein also, and the top of simultaneous reactions device can emit steam state and dispel logistics, with the accumulation of avoiding gaseous by-product and keep predetermined carbon monoxide pressure of tension under given total reactor pressure.The control method of the temperature and pressure of carbonylation reactor is with this area ordinary method among the present invention.Flash tank receives the liquid crude product from the carbonylation reactor discharging.Through the flash tank flash distillation, catalyst solution flows out as the bottom material and returns carbonylation reactor, and the top goes out the mixture that the condensation material comprises crude product acetic acid and alkyl iodide, water and methyl acetate, and the gaseous feed at top is gaseous by-product methane, carbonic acid gas etc.The separated from acetic acid tower is accepted the condensation material of flashing tower, separating acetic acid and alkyl iodide and methyl acetate.Product acetic acid can carry out follow-up refining purification afterwards from the knockout tower bottom discharge; Alkyl iodide and methyl acetate are looped back in the carbonylation reactor by the discharging of knockout tower cat head.
Agents useful for same of the present invention and raw material be commercially available getting all.
Positive progressive effect of the present invention is: the method that the invention provides the preparing carboxylic acid by carbonylation of a kind of alkanol and/or its reactive derivative.In iron, chromium, nickel and molybdenum one or more of method reaction system catalyzer of the present invention exist stability inferior good, and rate of catalysis reaction is higher simultaneously, have preferably catalytic activity under low ester and/or the low water content condition, and the catalyzer cost is lower.
Embodiment
Mode below by embodiment further specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.
Catalyzed reaction when the content of embodiment 1 different iridium rhodiums and stabiliser content
In the zirconium material autoclave of a 200ml, add entry, acetic acid, methyl acetate, methyl-iodide, Trichlororhodium and iridous chloride.Experiment numbers is 1～9 and to contrast the weight percentage of each reactant feed that adds in 1～4 the reaction system mesohigh reactor as follows: water 8%, methyl acetate 20%, methyl-iodide 14%, all the other are acetic acid, and the consumption of iridium rhodium, stablizer and metallic promoter agent is as shown in table 1.After adding reaction solution 120 grams of above prescription in the autoclave, operate as follows:
(1) off-response still carries out leakage detection with nitrogen to reaction unit.After determining that reaction unit is without leakage point, with slowly displacement twice of CO, then with CO 0.5MPa is arrived in the reactive system pressurising;
(2) start stirring, rotating speed is about 850 rev/mins, and setting temperature controlling system is 190 ℃, heating;
(3) along with the rising of temperature, the pressure of reactive system constantly increases, and when treating that temperature is raised to 190 ℃, opens the pressurising gas circuit of CO, and the reactive system pressurising to 2.8Mpa, is closed the valve of pressurising gas circuit afterwards; Open the CO constant voltage source of the gas gas circuit that the CO flow control is housed, its pressure is 2.8Mpa again; Beginning carbonylation reaction timing, keeping temperature of reaction is 190 ± 1 ℃, reaction pressure 2.8Mpa (gauge pressure), instantaneous delivery and the cumulative throughflow of CO under 1 second and computer record that reactive system links to each other;
When (4) the question response system does not absorb CO, " Quench " carried out in reaction process termination reaction;
(5) treat that temperature is down to room temperature, with nitrogen replacement twice, open reactor, pour out reaction solution and weigh, sampling analysis.
The instantaneous delivery of CO when from record, accessing the CO cumulative throughflow and be 5.2 liters, the content of methyl acetate is about 3wt% in the reactive system at this moment, water-content is about 4wt%, methyl-iodide content 14wt%, iridium, rhodium, the content of stablizer and metallic promoter agent sees Table 1 (wherein, corresponding mass ratio was 2.5: 1: 2.5 when stablizer was siderochrome nickel molybdenum: 1, corresponding mass ratio was 2.5: 1: 2.5 when stablizer was siderochrome nickel, corresponding mass ratio was 1: 1 when stablizer was iron nickel, corresponding mass ratio was 2.5: 1 when stablizer was the nickel molybdenum, and corresponding mass ratio was 2.5: 1 when stablizer was siderochrome).Therefore, when methyl acetate content was 3wt% in reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represented speed of reaction, and the results are shown in Table 1.
Rate of catalysis reaction when the different iridium of table 1, rhodium and stabiliser content and reaction system stability
By upper table data as seen, the contrast experiment be numbered 2 with contrast 2 and experiment numbers be 3 with contrast 1 catalystic converter system as can be known: at two Comparative Examples and embodiment under iridium rhodium content same case, experiment numbers of the present invention is that 2 and 3 catalystic converter system contains stablizer, thereby catalyzer is more stable, there is not catalyzer generation deposited phenomenon, and rate of catalysis reaction higher (in this area, namely belonging to larger raising if speed of reaction STY can improve 2 unit values).Simultaneously, the contrast experiment be numbered 2 with contrast 4 and experiment numbers be 3 with contrast 3 catalystic converter system as can be known: under iridium rhodium content same case, the content of stablizer cross low then can't the rugged catalyst system, cause rate of catalysis reaction lower; And the too high levels of stablizer, although deposited phenomenon does not occur catalyzer, too much corrosion metals ion has suppressed rate of catalysis reaction on the contrary.In addition, the catalystic converter system of the embodiment of experiment numbers 7～9 has wherein added a certain amount of metallic promoter agent, has further improved thus rate of catalysis reaction.Show thus, catalystic converter system of the present invention, when the stablizer of the content range of iridium rhodium and certain content, when having kept higher catalytic reaction activity and rate of catalysis reaction, catalyzer also has preferably stability, simultaneously, can also further improve rate of catalysis reaction if can add a certain amount of metallic promoter agent.Therefore, the present invention has reduced the number of times of adding catalyzer in the actual industrial flow process significantly, has reduced significantly the catalyzer cost.
Rate of catalysis reaction and the stability of the alkyl iodide of embodiment 2 different sortses and content
Operation steps is with embodiment 1, wherein the weight percentage of each component of autoclave internal reaction system is as follows: experiment numbers is that the add-on of each raw material of reaction system of 10～17 is: water 8%, methyl acetate 20%, iridium 1500ppm, rhodium 200ppm, the content of stablizer is that 300ppm (is comprised of iron, nickel, iron: the nickel mass ratio is 1: 1), the consumption of alkyl iodide and metallic promoter agent ruthenium sees the following form 2, all the other are acetic acid, and per-cent is mass percent; Reaction solution 120 grams that add above prescription in the autoclave.
Access from record when the content of methyl acetate is about 5wt% in the reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represents speed of reaction; This moment reaction system in water 4wt%, the results are shown in Table 2.
Rate of catalysis reaction and the stability of the iridium rhodium catalytic system of the alkyl iodide of table 2 different sorts and content
| Numbering | The alkyl iodide kind | Alkyl iodide consumption wt% | Ruthenium/iridium mol ratio | STY (@5wt% methyl acetate, mol/L.h) | Stability |
| 10 | Methyl-iodide | 10 | / | 15 | Without precipitation |
| 11 | Methyl-iodide | 20 | / | 21 | Without precipitation |
| 12 | Iodoethane | 5 | / | 11 | Without precipitation |
| 13 | Iodoethane | 30 | / | 17 | Without precipitation |
| 14 | Methyl-iodide | 10 | 5 | 18 | Without precipitation |
| 15 | Methyl-iodide | 20 | 5 | 23 | Without precipitation |
| 16 | Iodoethane | 5 | 5 | 15 | Without precipitation |
| 17 | Iodoethane | 30 | 5 | 20 | Without precipitation |
By upper table data as seen, alkyl iodide is at the applicable content range of this area routine in the catalyst system of the present invention, the stability of catalyzer better, also has simultaneously preferably rate of catalysis reaction, its rate of catalysis reaction is generally along with the increase of alkyl iodide concentration increases gradually, and, add a certain amount of metallic promoter agent and can also further improve rate of catalysis reaction.
Rate of catalysis reaction and the stability of embodiment 3 different water-contents
Operation steps is with embodiment 1, wherein the weight percentage of each component of autoclave internal reaction system is as follows: experiment numbers be 18～25 and the add-on that contrasts each raw material of reaction system of 5 be: the concentration of methyl acetate 20%, methyl-iodide 14%, iridium 1500ppm, rhodium 200ppm, stablizer is that 500ppm (is comprised of siderochrome nickel, the mass ratio of siderochrome nickel is 2.5: 1: 2.5), the consumption of the concentration of water and metallic promoter agent rhenium sees the following form 3, all the other are acetic acid, per-cent is mass percent, and water-content sees the following form; Reaction solution 120 grams that add above prescription in the autoclave.
Access from record when the content of methyl acetate is about 5wt% in the reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represents speed of reaction, and the results are shown in Table 3.
Rate of catalysis reaction and the stability of the iridium rhodium catalytic system during the different water-content of table 3
By upper table data as seen, catalyst system of the present invention is applicable to high water or low aqueous systems, although the catalystic converter system of experiment numbers 18 and 22 contains the precipitation of minute quantity, but compare with simultaneous test 5, obviously the adding of stablizer has obviously improved the catalyzer wild effect, the simultaneous test 5 that does not contain stablizer has a large amount of obvious sediment, although and add metallic promoter agent, its rate of catalysis reaction is far below the rate of catalysis reaction of experiment numbers 22.In addition, data show, add a certain amount of metallic promoter agent and can further improve rate of catalysis reaction.
Rate of catalysis reaction and stability during embodiment 4 different methyl acetate content
Operation steps is with embodiment 1, wherein the weight percentage of each component of autoclave internal reaction system is as follows: experiment numbers is that the add-on of each raw material of reaction system of 26～27 is: the content of water 8%, methyl acetate 20%, methyl-iodide 14%, iridium 1800ppm, rhodium 300ppm, stablizer is 400ppm (being comprised of iron), all the other are acetic acid, and per-cent is mass percent; Reaction solution 120 grams that add above prescription in the autoclave.
Access from record when the content of methyl acetate is about the following table data in the reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represents speed of reaction, and the results are shown in Table 4.
Rate of catalysis reaction and the stability of the iridium rhodium catalytic system during the different methyl acetate content of table 4
By upper table data as seen, catalyst system of the present invention is applicable to high ester or low ester system, although rate of catalysis reaction is along with the increase of methyl acetate concentration increases gradually, but the stability that catalyst body of the present invention ties up in the low ester system is also better, have simultaneously higher catalytic activity, and low ester condition can also make lock out operation difficulty and the cost of alkyl iodide in the follow-up step significantly reduce.In addition, add a certain amount of metallic promoter agent and can also further improve rate of catalysis reaction.
Rate of catalysis reaction and the stability of the metallic promoter agent of embodiment 5 different sortses and content
Operation steps is with embodiment 1, wherein the weight percentage of each component of autoclave internal reaction system is as follows: experiment numbers is that the add-on of 28～35 each raw material of reaction system is: water 5%, methyl acetate 20%, methyl-iodide 14%, iridium 1500ppm, rhodium 200ppm, the concentration of stablizer is that 300ppm (is comprised of the nickel molybdenum, the mass ratio of nickel molybdenum is 2.5: 1), all the other are acetic acid, and per-cent is mass percent; The content of metallic promoter agent sees the following form; Reaction solution 120 grams that add above prescription in the autoclave.
The content of methyl acetate is about 3wt% in the instantaneous delivery of CO when accessing the CO cumulative throughflow and be 5.2 liters from record, this moment reactive system, and water-content is about 2wt%, and the results are shown in Table 4.
Rate of catalysis reaction and the stability of the iridium rhodium catalytic system of the metallic promoter agent of table 5 different sorts and content
By upper table data as seen, adding a certain amount of metallic promoter agent in the catalyst system of the present invention can also the Effective Raise rate of catalysis reaction.
In comparative example's 1 single iridium system, one or more in iron, chromium, nickel and the molybdenum are on the rate of catalysis reaction of catalystic converter system and the impact of stability
Operation steps is with embodiment 1, and wherein the add-on of each raw material of autoclave internal reaction system is that weight percentage is as follows: water 5%, methyl acetate 20%, methyl-iodide 14%, and all the other are acetic acid, the consumption of iridium is as shown in table 6; Reaction solution 120 grams that add above prescription in the autoclave.
Access from record when the content of methyl acetate is about 3wt% in the reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represents speed of reaction; This moment reaction system in water 2wt%, the results are shown in Table 6.
In table 6 iron, chromium, nickel and the molybdenum one or more are on the rate of catalysis reaction of single iridium catalyst systems and the impact of stability
| Numbering | Ir (ppm) | Metal species | Stabiliser content (ppm) | STY (@3wt% methyl acetate, mol/L.h) | Stability |
| 1 | 2000 | / | / | 6.0 | Without precipitation |
| 2 | 1500 | / | / | 4.6 | Without precipitation |
| 3 | 2000 | Iron | 500 | 3.5 | Without precipitation |
| 4 | 1500 | Chromium | 600 | 2.0 | Without precipitation |
By upper table data as seen, with the consumption of similar iridium in the embodiment of the invention 1, in the catalyst system of single iridium, although under the existence of one or more in a certain amount of iron, chromium, nickel and the molybdenum, catalyzer is not observed precipitation, but its rate of catalysis reaction obtains obviously strong compacting.
In comparative example's 2 single rhodium systems, one or more in iron, chromium, nickel and the molybdenum are on the rate of catalysis reaction of catalystic converter system and the impact of stability
Operation steps is with embodiment 1, and wherein the add-on of each raw material of autoclave internal reaction system is that weight percentage is as follows: water 5%, methyl acetate 20%, methyl-iodide 14%, and all the other are acetic acid, the consumption of rhodium is as shown in table 7; Reaction solution 120 grams that add above prescription in the autoclave.
Access from record when the content of methyl acetate is about 3wt% in the reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represents speed of reaction; This moment reaction system in water 2wt%, the results are shown in Table 6.
In table 7 iron, chromium, nickel and the molybdenum one or more are on the rate of catalysis reaction of single rhodium catalytic system and the impact of stability
| Numbering | Rh (ppm) | Metal species | Metal content (ppm) | STY (@3wt% methyl acetate, mol/L.h) | Stability |
| 1 | 300 | / | / | 6.0 | Obvious sediment |
| 2 | 400 | / | / | 8.0 | Obvious sediment |
| 3 | 300 | Iron | 500 | 5.8 | Obvious sediment |
| 4 | 400 | Chromium | 600 | 7.5 | Obvious sediment |
By upper table data as seen, consumption with similar rhodium in the embodiment of the invention 1, in the catalyst system of single rhodium, the rhodium catalyst instability generation precipitates in a large number, during in adding a certain amount of iron, chromium, nickel and molybdenum one or more, the situation that catalyzer contains obvious sediment does not improve, and its rate of catalysis reaction but has certain compacting simultaneously.
Claims (17)
1. the method for the preparing carboxylic acid by carbonylation of an alkanol and/or its reactive derivative, it is in the liquid reaction medium that contains iridium catalyst, rhodium catalyst, stablizer, alkyl iodide, water, methyl acetate and acetic acid, with alkanol and/or its reactive derivative and carbon monoxide charging reaction, then from the reaction product that obtains, reclaim carboxylic acid, wherein, the content 500～4000ppm of described iridium; The content of described rhodium is 50～400ppm; Described stablizer is one or more in iron, chromium, nickel and the molybdenum, and the content of described stablizer is 200～600ppm; Wherein, described reactive derivative is ether, ester or halogenide.
2. the method for claim 1, it is characterized in that: also contain metallic promoter agent in the described liquid reaction medium, the molar ratio of described metallic promoter agent and iridium is 1～15.
3. method as claimed in claim 2, it is characterized in that: the molar ratio of described metallic promoter agent and iridium is 6～15.
4. method as claimed in claim 2 or claim 3, it is characterized in that: described metallic promoter agent is one or more in ruthenium, osmium and the rhenium.
5. such as each described method of claim 1～3, it is characterized in that: the content of described stablizer is 300～400ppm.
6. such as each described method of claim 1～3, it is characterized in that: the content of described iridium catalyst is 1000～2000ppm.
7. such as each described method of claim 1～3, it is characterized in that: the content of described rhodium catalyst is 100～300ppm.
8. such as each described method of claim 1～3, it is characterized in that: the precursor of described iridium catalyst is iridium acetate, iridium metals, iodate iridium, hydration iodate iridium, bromination iridium, hydration bromination iridium, iridium chloride, chloro-iridic acid, hydration iridium chloride, oxalic acid iridium, etheric acid iridium, iridium oxide, iridous oxide, [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
+[Ir (CH
3) (CO)
2I
3]
-H
+In one or more.
9. such as each described method of claim 1～3, it is characterized in that: the precursor of described rhodium catalyst is rhodium chloride, three hydration rhodium chlorides, bromination rhodium, iodate rhodium, rhodium acetate, dicarbonyl rhodium acetylacetonate, [Rh (CO)
2Cl]
2[Rh (CO)
2I]
2In one or more.
10. such as each described method of claim 1～3, it is characterized in that: described alkyl iodide is methyl-iodide and/or iodoethane, and the content of described alkyl iodide is 5～30%, and per-cent is mass percent.
11. method as claimed in claim 10 is characterized in that: the content of described alkyl iodide is 10～20%; Per-cent is mass percent.
12. such as each described method of claim 1～3, it is characterized in that: the content of described water is 0.5～14%, per-cent is mass percent.
13. method as claimed in claim 12 is characterized in that: the content of described water is 2～8%, and per-cent is mass percent.
14. such as each described method of claim 1～3, it is characterized in that: the content of described methyl acetate is 0.5～5%, per-cent is mass percent.
15. method as claimed in claim 14 is characterized in that: the content of described methyl acetate is 2～5%, and per-cent is mass percent.
16. such as each described method of claim 1～3, it is characterized in that: described alkanol is that carbonatoms is 1～5 alcohols.
17. such as each described method of claim 1～3, it is characterized in that: described alkanol is methyl alcohol; Described carboxylic acid is acetic acid.
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|---|---|---|---|
| CN 200910201100 CN102093196B (en) | 2009-12-15 | 2009-12-15 | Method for preparing carboxylic acid by carbonylation of alkanol and/or active derivative thereof |
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|---|---|---|---|
| CN 200910201100 CN102093196B (en) | 2009-12-15 | 2009-12-15 | Method for preparing carboxylic acid by carbonylation of alkanol and/or active derivative thereof |
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| Publication Number | Publication Date |
|---|---|
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| CN102093196B true CN102093196B (en) | 2013-03-06 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187482A (en) * | 1996-12-19 | 1998-07-15 | 英国石油化学品有限公司 | Iridium-catalysed carbonylation process for production of acetic acid |
| CN1324341A (en) * | 1998-10-23 | 2001-11-28 | 国际人造丝公司 | Carbonylation of methanol in the presence of a rhodium/iridium/iodide ion catalytic system |
| CN1491198A (en) * | 2001-02-08 | 2004-04-21 | ��ɪ����˹��ѧ��˾ | Modification of catalytic system in industrial process for making acetic and/or methyl acetate acid |
| WO2009134333A1 (en) * | 2008-04-29 | 2009-11-05 | Celanese International Corporation | Method and apparatus for carbonylating methanol with acetic acid enriched flash stream |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187482A (en) * | 1996-12-19 | 1998-07-15 | 英国石油化学品有限公司 | Iridium-catalysed carbonylation process for production of acetic acid |
| CN1324341A (en) * | 1998-10-23 | 2001-11-28 | 国际人造丝公司 | Carbonylation of methanol in the presence of a rhodium/iridium/iodide ion catalytic system |
| CN1491198A (en) * | 2001-02-08 | 2004-04-21 | ��ɪ����˹��ѧ��˾ | Modification of catalytic system in industrial process for making acetic and/or methyl acetate acid |
| WO2009134333A1 (en) * | 2008-04-29 | 2009-11-05 | Celanese International Corporation | Method and apparatus for carbonylating methanol with acetic acid enriched flash stream |
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