CN102167663A - Method for synthesizing acetic acid through iridium catalysis and carbonylation - Google Patents
Method for synthesizing acetic acid through iridium catalysis and carbonylation Download PDFInfo
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- CN102167663A CN102167663A CN201010114116XA CN201010114116A CN102167663A CN 102167663 A CN102167663 A CN 102167663A CN 201010114116X A CN201010114116X A CN 201010114116XA CN 201010114116 A CN201010114116 A CN 201010114116A CN 102167663 A CN102167663 A CN 102167663A
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Abstract
The invention discloses a method for synthesizing acetic acid through carbonylation. The method comprise the following step of: reacting a liquid phase medium containing methanol, methyl acetate, acetic acid and water with carbon monoxide to generate acetic acid, wherein a catalyst system used in the reaction is that: an iridium compound of a VIII family is taken as a main catalyst, methyl iodide is taken as an auxiliary catalyst, and an indium-containing compound is taken as a metal promoting agent. The method has the advantages: indium taken as the metal promoting agent is added, so that the reacting rate of the system is greatly increased and the generation of byproduct, namely, propionic acid is reduced; the water content of the system is reduced and the energy consumption of the refining process is lowered; the dosage of the acetic acid is reduced while the reacting rate is increased, and delamination through a decanter is convenient; the stability of iridium taken as the main catalyst is improved, the dissolving of iridium is facilitated, the effective concentration of iridium is increased, the loss of noble metal iridium is reduced, and the production cost is lowered; and compared with a pure iridium system, an iridium-indium system has the advantages: the required iodomethane concentration is increased, byproducts are reduced, and an aqueous phase and an iodomethane phase are easy to separate at the acetic acid recycling stage.
Description
Technical field
The present invention relates to a kind of method of oxonation, specifically relate to a kind of method of iridium catalytic carbonylation synthesis of acetic acid.
Background technology
Acetic acid is a kind of important Organic Chemicals, can derive hundreds of kind derived product by it, as Vinyl Acetate Monomer, cellulose acetate, aceticanhydride, acetic ester, Mono Chloro Acetic Acid, terephthalic acid (FFA), polyvinyl alcohol and metal acetate salt etc.Acetic acid is widely used in basic organic synthesis, medicine, agricultural chemicals, printing and dyeing, light textile, food, makes industries such as lacquer, tackiness agent.
Carbonylation of methanol is the main method of producing acetic acid at present, and iridium is catalyst based to be the catalyzer that the most promising methanol carbonylation prepares acetic acid.In recent years more about the patent of the catalyst based preparation acetate of iridium aspect, CN94115261.8 is by improving catalyst system with ruthenium and osmium; CN96110366.3 discloses wherein a kind of promotor of interpolation ruthenium, osmium, rhenium, chromium, tungsten, gallium, indium and has improved reactivity worth; CN97120825.5 has reported the response situation that exists under metallic promoter agent and the ionic iodide secondary accelerator; CN99812415 improves reactivity worth by adding transition metal and lithium salts; CN03813777.1 has reported to add and has been selected from alkaline metal iodide, and alkaline earth metal iodide can generate the salt of iodide ion metal complex and iodide ion.CN03822190.X provides and has added the method that stablizer improves oxonation; CN200480020623 reaches and improves reactivity worth by adding at least a non-haloid acid.
EP-A-0752406, EP-A-0849248, EP-A-0849249, EP-A-1002785 disclose the method for passing through carbonylation methanol production acetate in the presence of iridium catalyst and ruthenium promotor.EP-A-0643034, EP-A-0749948 provides and added a kind of as promotor in zinc, chromium, mercury, indium, gallium, the tungsten at least in Primary Catalysts iridium, a kind of work under the cocatalyst effect by carbon monoxide carbonylation methyl alcohol or/and its derivative prepares the process of acetate in ruthenium, rhenium, the osmium.
GB-A-1234121, US-A-3772380, DE-A-1767150, WO-A-96/11179 and CN97120825.5 have reported the iridium catalytic carbonylation system acetic acid process of not adding promotor, but reactive behavior is relatively poor.
Among the WO-A-96/237757, related to the especially purposes in carbonylation reaction of the method for preparing carboxylic acid iridium and they, not mentioned use promotor, opposite with WO-A-95/314326, think and preferably remove basic metal and alkaline-earth metal ions, because their existence is that the subsequent reaction kinetics and the selectivity of catalyzer has disadvantageous effect to wherein adopting carboxylic acid iridium.
Having many good qualities aspect the carbonylation system acetate though iridium is catalyst based, but in actual application, also there are problems, do not preponderate as pure iridium catalyst speed of reaction, oxonation speed increases along with methyl acetate concentration and accelerates, but too high methyl acetate concentration is unfavorable for follow-up decanting vessel layering; Pure iridium system requires methyl iodide concentration very low, is unfavorable for being separated at acetate recovery stage water and methyl iodide; Pure iridium catalyst is too responsive to corroding metal, requires the corroding metal amount very low; Pure iridium catalyst is too harsh to the reactive component composition requirement; Pure iridium catalyst precipitates under certain condition easily; By product increases when carbon monoxide pressure of tension is high; The adding of basic metal or alkaline earth metal iodide stablizer makes that iodine content is too high in the acetate, influences product quality of acetic acid or the like.
Summary of the invention
The method that the purpose of this invention is to provide a kind of iridium catalytic carbonylation synthesis of acetic acid is to overcome the deficiencies in the prior art.
The present invention adds indium compound in catalyst system, can be used as metallic promoter agent on the one hand and accelerate oxonation speed, improves catalytic activity; Can be used as the solubleness of stablizer increase iridium on the other hand, reduce the precipitation of Primary Catalysts iridium, reduce the precious metal iridium loss; In addition, the effect that improves the reaction of iridium catalytic carbonylation has also been played in the interpolation of indium compound.
The method of synthesizing acetic acid by carbonylation of the present invention, its process comprises: make the liquid phase medium and the carbon monoxide that comprise methyl alcohol, methyl acetate, acetate and water react generation acetate; The catalyst system that uses in the reaction is: the iridic compound with the 8th family is Primary Catalysts, is promotor with the methyl iodide, is metallic promoter agent and stablizer with the compound that contains indium.
Preferable, in the catalyst system of described synthesizing acetic acid by carbonylation, the described compound that contains indium is the soluble salt that contains indium.The described soluble salt that contains indium comprises indium acetate, Indium sesquioxide, indium chloride, indium iodide, the inferior indium of iodate, indium hydroxide or Indium Tris acetylacetonate.Preferably dissolve in the indium compound of one or more carbonylation reaction components such as water, acid, alcohol, as Indium sesquioxide, indium acetate, indium hydroxide.
Preferable, the consumption of described indium compound is pressed in the catalyst system mol ratio of elemental indium and element indium and calculated, and the mol ratio of elemental indium and indium is 1: (1～20) is preferably 1: (2～15), more preferably 1: (2～10) most preferably are 1: (2～5).
In the method for iridium catalytic carbonylation synthesis of acetic acid of the present invention, iridium catalyst systems is improved a kind of advantage that is produced is: the introducing that contains indium compound can be used as promotor on the one hand and has accelerated oxonation speed greatly, make iridium concentration obtaining than high reaction activity under the lower concentration very much, reduced cost, than the speed of reaction height of CN03822190 report; Indium compound has played function of stabilizer on the other hand, and when carbon monoxide pressure of tension was low, iridium catalyst was easily separated out with precipitation forms, and the adding of indium has promoted the iridium dissolving, has increased the effective concentration of iridium catalyst, has reduced precious metal losses, reduces cost.
In the iridium catalyst systems of the present invention, the further advantages that adding produced of indium compound are: do not need to add alkaline metal iodide or alkaline earth metal iodide in the catalyst system, reduced iodine negative ion so on the one hand to the speed of reaction detrimental action, guarantee the purity of acetic acid product on the other hand, reduced operation easier and expense aspect the acetate recovery.
In the iridium catalyst systems of the present invention, the adding of indium compound has also improved the solvability of iridium catalyst: iridium catalyst is added in the acetic acid solvent, and iridium catalyst can not dissolve fully; If after wherein adding indium compound of the present invention, insoluble iridium catalyst can dissolve rapidly again; Thereby make the effective concentration of iridium in oxonation liquid increase, and then improved speed of reaction.Be embodied in:
Described iridic compound is not molten entirely in acetic acid solution, and wherein, the amount of iridium is 0.02～0.5mmol in the described iridic compound, and the amount of described acetate is 0.2～3.0g; In this solution, add the described compound that contains indium again, can make the dissolving rapidly in acetate of described iridic compound; The described amount that contains the compound of indium is 0.01～2.00mmol.
Because the iodine title complex of iron, nickel, chromium and the molybdenum of separating out from conversion unit has catalysis toxicity to iridium is catalyst based, so must guarantee they will be reduced in iridium base catalyst system minimum; Usually adopt resin to remove corroding metals such as these iron of from conversion unit, separating out, nickel, chromium and molybdenum in process of production.The present invention is in the corroding metal compound that removes iron, nickel, chromium or the molybdenum of separating out with resin from conversion unit, and the indium compound that is added can be by resin absorption; Being added in of indium compound also guaranteed homeostasis when having stablized Primary Catalysts iridium.
Because it is pure iridium catalyst is very responsive to corroding metal, therefore very harsh to the content requirement of corroding metal.The present invention in iridium catalyst systems, add indium compound more further advantage be: the adding of indium compound makes that iridium is catalyst based the corroding metal content requirement is reduced.
Among the present invention, in the catalyst system of described synthesizing acetic acid by carbonylation, based on the reaction solution gross weight: the mass concentration of iridic compound in mixed reaction solution is that benchmark is calculated as 500～2000ppm with iridium, and preferred 600～1800ppm most preferably is 600～1500ppm;
The precursor that is applicable to iridium catalyst of the present invention 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 (OAc)
3, Ir (acac) (CO)
2, [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
+Preferred Ir (OAc)
3, preferably dissolve in the complex of iridium of one or more carbonylation reaction components such as water, acid, alcohol, but described iridic compound catalyst precursor need not be confined to above-claimed cpd.
In the liquid phase medium of synthesizing acetic acid by carbonylation of the present invention, based on the reaction solution gross weight: the weight percent concentration of methyl acetate is greater than 0 and smaller or equal to 30%, preferred 5～16%; The weight percent concentration of water is greater than 0 and smaller or equal to 10%, preferred 2～6%; The weight percent concentration of methyl iodide is 3～18%, preferred 5～15%; All the other are solvent acetic acid.
The methyl alcohol that adds in the reaction system, with acetic acidreaction very fast change into methyl acetate, so the content of methyl alcohol is very low in the reaction system.
In the reaction system of synthesizing acetic acid by carbonylation described in the present invention, range of reaction temperature is: 170～230 ℃, and preferred 175～200 ℃; The reaction total pressure is 20～50bar, preferred 25～40bar.
The CO (carbon monoxide converter) gas of using in the described reaction system can be a respective pure form, also can contain a certain amount of hydrogen.
The reaction method of synthesizing acetic acid by carbonylation of the present invention can intermittently or carry out in a continuous manner.In the successive production method, can be in an operation steps solution of described catalyzer for preparing or catalyst precursor compound and reaction solvent etc. be joined in the reactor 1, successive feeds CO and methyl alcohol then, the reactor heating, control reaction temperature is after 185～200 ℃, reactor pressure is controlled at 20～50bar, and the reaction solution 7 that contains catalyzer, promotor, partial reaction raw material, acetate, methyl acetate enters flasher 2, and flashing pressure is 1～3bar.Shift out by flash distillation gas phase part 8 and to contain acetate, methyl acetate, water, methyl iodide and a small amount of trace impurity, and remove the part heat, the liquid phase part 9 that contains catalyzer and stablizer indium compound thereof is recycled reactor, and the pump circulation cooling system that can rely on reactor simultaneously according to the situation of exothermic heat of reaction is removed remaining reaction heat.The gas phase part 8 that flash separation is come out enters lights column 3 and further separates, can obtain the thick product 12 of acetate, flasher is returned in lights column bottommost logistics 10, to reclaim on a small quantity the catalyzer that may volatilize away from decanting vessel, the methyl acetate of separating in the lights column, water, components such as methyl iodide are allowed to condition at by condensation carries out layering in the decanting vessel 11, the light phase component of partially aqueous is through logistics 13 lights column that refluxes back, part is light by mutually 14 and mainly contain the heavy phase logistics 14 direct circulation Returning reactors of methyl iodide and methyl acetate in addition, also can turn back to mixing tank recirculation earlier and return reactor, the logistics of coming out from reactor further absorbs by methyl alcohol after condensation, non-condensable gas 6 enters the vent gas treatment district, the direct Returning reactor of methanol solution that contains light constituents such as methyl iodide after the absorption, or reactor is returned in recirculation after returning mixing tank earlier.
Method of the present invention needs regularly or the above each component concentrations of continuous monitoring the reaction system of moving, catalyst concentration particularly, be lower than the adding value if find to measure catalyst concn, then may cause the loss of catalyzer owing to reasons such as precipitation or volatilizations, this moment can be by adding catalyzer in reaction solution.
Compare with the technology of the carbonylation system acetate of prior art, beneficial effect of the present invention is: (1) by adding the promotor indium, has improved catalytic activity greatly in the iridium catalyst system, accelerated speed of reaction; (2) adding indium compound in reaction system makes reaction can keep activity preferably under lower methyl acetate concentration; Because the concentration of methyl acetate can maintain low concentration, under higher relatively methyl iodide concentration, the easier layering of the decanting vessel of lights column; (3) further reduce the concentration of iridium catalyst, thereby reduce the catalyzer cost, more economically, and it is higher to obtain the purity of product; (4) stablize Primary Catalysts iridium, reduced the loss of catalyzer in the whole flow process; (5) promote the iridium dissolving, make the effective concentration of iridium in oxonation liquid increase, and then improve speed of reaction; (6) do not need basic metal or alkaline earth metal iodide to make stablizer, reduced the disadvantageous effect of iodide ion, reduced iodine content in the product acetate, increase the purity of product acetate oxonation.(7) add indium after, iridium reduces dissolved corroding metal content requirement such as the iron that gets off, nickel, chromium, molybdenum by reactor, can keep reactive behavior preferably in the finite concentration scope.(8) when removing by corroding metals such as the iron under the reactor dissolving, nickel, chromium, molybdenums with resin, indium is not adsorbed, and the adsorptive capacity of iridium is littler.
Description of drawings
Fig. 1 is a kind of reacting flow chart of rhodium iridium associating synthesizing acetic acid by carbonylation.
Wherein P1, P2 are recycle pump, and M is an agitator motor, and E is a condenser, 1 is reactor, and 2 is flasher, and 3 is lights column, 4 is methanol stream, 5 is the CO logistics, and 6 is the emptying of tail gas high pressure, and 7 is the reaction solution logistics, 8 for the light constituent logistics at flash distillation top, the heavy constituent logistics of 9 flash distillations bottom contains catalyzer in 10 lights column, 11 decanting vessels; The thick product stream of 12 acetate; 13 decanting vessels gently come out to return the logistics of lights column mutually; The 14 decanting vessel heavy constituent logistics of coming out; Gently come out the mutually logistics of Returning reactor of 15 decanting vessels; 16 absorption towers; Logistics after 17 absorption towers absorb; The logistics of coming out in 18 lights column tops.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The general experimental technique of batch experiment is as follows: all being reflected at is equipped with in the high pressure resistant zirconium material of the 250ml reactor of being with the electric mixer that tests the speed and carried out, and reacts to be outer heating, and zirconium material spiral coil cooling tube is arranged in the reactor.Catalyzer, methyl acetate or methyl alcohol, methyl iodide, water, acetate that weighing is certain, reactor is put in the initial charge that above component constitutes, gross weight 125 grams.With the air in the CO replacement reaction kettle, be stamped into 6bar at every turn, emptying slowly is to prevent the loss of volatile matters such as methyl iodide again.With CO reactor is stamped into 30bar, pressurize 1h confirms all right nothing leakage of sealing, emptying slowly then, pressure drops to 6bar, begins to stir heating, and by temperature in the thermocouple measurement reactor, be warmed up to 190 ℃, feed CO gas then, regulate the flooding quantity of spiral coil cooling tube, keep 190 ℃ ± 1 ℃ of the interior temperature of reaction, write down the cumulative throughflow and the instantaneous delivery in each stage by mass-flow gas meter.After reaction proceeds to certain phase, close the CO inlet mouth, stop heating, strengthen the spiral coil cooling tube flooding quantity, the reactor outer wall is further used water quench, quick cooling.After the cooling, slowly bleed off remaining gas, and use N
2Replace 3 times.Reactor liquid is by its composition of gas chromatographic analysis.Stability is by observing final reacting mixture at cool to room temperature and be vented in the atmosphere, places to observe after for some time to have or not metal deposit or metal black to exist and determine, and can pass through the content of iridium metals in the ICP assaying reaction liquid.
The successive mode of production is carried out in device as shown in Figure 1, squeeze into iridic compound by pump toward reactor 1, squeeze into the compound that contains indium in addition, methyl iodide, acetate, methyl acetate, the water of reactor 1 simultaneously, after the catalyzer of reactive system needs comprises that promotor, stablizer and methyl iodide, acetate meet production requirement, reactor 1 charge into CO to reactor pressure at 10bar, reactor and flasher are set up catalyst recirculation then, and reactor 1 heats up, and charges into CO again to 20-50bar.After temperature of reaction, reaction pressure satisfy the production technique index, formally drop into material benzenemethanol.The logistics 8 of coming out by flash distillation separates through lights column, logistics 10 is returned flash drum to a spot of catalyzer bottom, light constituent logistics 18 such as moisture, the methyl iodide of separating from lights column upper end, acetate, methyl acetate are through layering decanting vessel after the condensation, the logistics 13 that light part is mutually the come out fractionate that refluxes back, heavy phase logistics 15 turns back to reactor with the logistics 14 that part is gently come out mutually, and 12 of the logistics of coming out from lights column are the thick product of acetate.
The speed that the gas sometime that carries out with reaction absorbs is calculated instantaneous carbonylation rate, the accumulation gas of a certain section time response consumption calculates average carbonylation rate, suppose that equimolar CO consumes equimolar methyl acetate, methyl alcohol, can calculate sometime the mole number STY (mol/Lh) of the reactant that every liter instantaneous or average reaction solution down per hour consumes.
Embodiment 1
Under air atmosphere, be equipped with in the manometric zirconium material autoclave and add Ir (OAc) to 250ml
3237mg, iridium concentration in system is 900ppm, methyl iodide 8.75g, initial concentration is 7%, and distilled water 10.00g, initial concentration are 8%, methyl acetate 37.50g, initial concentration is 30%, and all the other are acetic acid solvent 68.52g, keeps 190 ℃ of temperature of reaction, reaction pressure 30bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, corresponding oxonation speed 8.55mol/Lh.
Embodiment 2
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 360mg in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 1500ppm, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, all the other are acetic acid solvent 68.39g, keep 190 ℃ of temperature of reaction, reaction pressure 30bar is reacted to the certain phase Quench, and the methyl acetate weight ratio is 15% in the reaction solution at this moment, quality concentration is 5.1%, and corresponding carbonylation speed is 16.50mol/Lh.
Embodiment 3
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.1627g, elemental indium indium mol ratio is 1: 2, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, all the other are acetic acid solvent 72.16g, keep 190 ℃ of temperature of reaction, reaction pressure 30bar is reacted to the certain phase Quench, and the methyl acetate weight ratio is 15% in the reaction solution at this moment, the mass concentration of water is 4.8%, and corresponding carbonylation speed is 16.54mol/Lh.
Embodiment 4
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.4062g, elemental indium indium mol ratio is 1: 5, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, all the other are acetic acid solvent 72.16g, keep 190 ℃ of temperature of reaction, reaction pressure 30bar is reacted to the certain phase Quench, and the methyl acetate weight ratio is 15% in the reaction solution at this moment, the mass concentration of water is 4.5%, and corresponding carbonylation speed is 18.50mol/Lh.
Embodiment 1 and 3,4 more as can be known, in the Primary Catalysts iridium of same concentrations, add the small amounts indium after, the oxonation activity improves greatly under same reaction conditions, speed of reaction has improved twice.Embodiment 2 and 3 more as can be known, identical during pure iridium mass concentration 1500ppm with oxonation speed after iridium concentration 900ppm adds small amount of indium, this that is to say and will obtain same reaction speed, can reduce Primary Catalysts precious metal iridium content greatly by adding the promotor indium, has reduced production cost.
Embodiment 2,3,4 more as can be known, the catalyst based reactive behavior of iridium of adding indium is very good, can reach more considerable oxonation speed by adjusting the amount of adding indium.Iridium concentration 900ppm adds the pure iridium catalyst that 1: 5 indium speed of reaction of iridium indium mol ratio has surpassed 1500ppm.
Embodiment 5
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.1627g, elemental indium indium mol ratio is 1: 2, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 12.50g, initial mass concentration 10%, methyl acetate 37.50g, initial mass concentration is 30%, all the other are acetic acid solvent 65.86g, keep 190 ℃ of temperature of reaction, reaction pressure 30bar is reacted to the certain phase Quench, and the methyl acetate weight ratio is 15% in the reaction solution at this moment, the mass percent of water is 4.6%, and corresponding carbonylation speed is 14.14mol/Lh.
By embodiment 1,3,4,5 more as can be known, pure iridium catalyst itself is less demanding to water-content, in the iridium that adds indium is catalyst based, water-content high reactive behavior bad on the contrary, the adding of promotor indium has further reduced the water-content requirement, and the separation of further part water has been reduced a large amount of energy consumptions.
Embodiment 6
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.4062g, elemental indium indium mol ratio is 1: 5, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 72.16g, keeps 190 ℃ of temperature of reaction, reaction pressure 30bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 14% in the reaction solution at this moment, and corresponding carbonylation speed is 17.83mol/Lh.
Embodiment 7
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.4062g, elemental indium indium mol ratio is 1: 5, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 31.25g, initial mass concentration is 25%, and all the other are acetic acid solvent 74.36g, keeps 190 ℃ of temperature of reaction, reaction pressure 30bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 14% in the reaction solution at this moment, and corresponding carbonylation speed is 14.70mol/Lh.
By embodiment 1,6,7 contrasts as can be seen, obviously high a lot of when methyl acetate concentration is low behind the interpolation metallic promoter agent indium than the speed of reaction under the pure iridium system high-concentration acetic acid methyl esters.The iridium System Catalyst is along with methyl acetate concentration increases reaction rate accelerates, so pure iridium system requires methyl acetate concentration higher, but too high methyl acetate concentration can have a negative impact separating mutually to water in the acetate removal process and methyl iodide.Above embodiment has illustrated that the adding of metallic promoter agent indium not only improves oxonation speed greatly, and has reduced the concentration requirement of reaction pair methyl acetate, is convenient to the decanting vessel layering of back.
Embodiment 8
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, methyl iodide 6.25g, initial mass concentration is 5%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 71.02g, keeps 190 ℃ of temperature of reaction, reaction pressure 30bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 8.53mol/Lh.
Embodiment 9
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.4062g, elemental indium indium mol ratio is 1: 5, methyl iodide 11.25g, initial mass concentration is 9%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 65.61g, keeps 190 ℃ of temperature of reaction, reaction pressure 30bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 13.11mol/Lh.
Embodiment 10
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.4062g, elemental indium indium mol ratio is 1: 5, methyl iodide 13.75g, initial mass concentration is 11%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 63.01g, keeps 190 ℃ of temperature of reaction, reaction pressure 30bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 17.50mol/Lh.
Embodiment 11
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.4062g, elemental indium indium mol ratio is 1: 5, methyl iodide 16.25g, initial mass concentration is 13%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 60.51g, keeps 190 ℃ of temperature of reaction, reaction pressure 30bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 13.92mol/Lh.
The iridium System Catalyst of adding the metallic promoter agent indium as can be seen by embodiment 1,8,9,10,11 contrasts has improved than pure iridium system promotor methyl iodide concentration demand, but also obtains than high reaction rate.Along with methyl iodide concentration increases by product propionic acid, carbonic acid gas, the reduction of methane generating rate, by increasing methyl iodide concentration oxonation speed is accelerated, more remarkable when more higher than water concentration when water concentration is low, the reduction of water concentration has reduced in process of production and has been used for the dried up required a large amount of energy consumptions of branch.And along with methyl iodide concentration raises, easier separating mutually at acetate recovery stage water and methyl iodide.
Embodiment 12
Under air atmosphere, be equipped with in the manometric zirconium material autoclave and add Ir (OAc) to 250ml
3237mg, iridium concentration in system is 900ppm, methyl iodide 8.75g, initial concentration is 7%, and distilled water 10.00g, initial concentration are 8%, methyl acetate 37.50g, initial concentration is 30%, and all the other are acetic acid solvent 68.52g, keeps 190 ℃ of temperature of reaction, reaction pressure 32bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, corresponding oxonation speed 11.38mol/Lh.
Embodiment 13
Under air atmosphere, be equipped with in the manometric zirconium material autoclave and add Ir (OAc) to 250ml
3237mg, iridium concentration in system is 900ppm, methyl iodide 8.75g, initial concentration is 7%, and distilled water 10.00g, initial concentration are 8%, methyl acetate 37.50g, initial concentration is 30%, and all the other are acetic acid solvent 68.52g, keeps 190 ℃ of temperature of reaction, reaction pressure 35bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, corresponding oxonation speed 13.87mol/Lh.
Embodiment 14
Under air atmosphere, be equipped with in the manometric zirconium material autoclave and add Ir (OAc) to 250ml
3237mg, iridium concentration in system is 900ppm, methyl iodide 8.75g, initial concentration is 7%, and distilled water 10.00g, initial concentration are 8%, methyl acetate 37.50g, initial concentration is 30%, and all the other are acetic acid solvent 68.52g, keeps 190 ℃ of temperature of reaction, reaction pressure 38bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, corresponding oxonation speed 14.39mol/Lh.
Embodiment 15
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.4062g, elemental indium indium mol ratio is 1: 5, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 72.16g, keeps 190 ℃ of temperature of reaction, reaction pressure 25bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 3.00mol/Lh.
Embodiment 16
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.4062g, elemental indium indium mol ratio is 1: 5, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 72.16g, keeps 190 ℃ of temperature of reaction, reaction pressure 28bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 11.87mol/Lh.
Embodiment 17
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.4062g, elemental indium indium mol ratio is 1: 5, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 72.16g, keeps 190 ℃ of temperature of reaction, reaction pressure 32bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 19.20mol/Lh.
Embodiment 18
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.4062g, elemental indium indium mol ratio is 1: 5, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 72.16g, keeps 190 ℃ of temperature of reaction, reaction pressure 35bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 19.05mol/Lh.
Embodiment 19
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.4062g, elemental indium indium mol ratio is 1: 5, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 72.16g, keeps 190 ℃ of temperature of reaction, reaction pressure 38bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 18.56mol/Lh.
By between embodiment 1, the 12-14 more as can be known, in the pure iridium catalyst system of synthesizing acetic acid by carbonylation, along with reaction pressure augmenting response speed speeds, speed of reaction is faster during more than 30bar such as reaction pressure 38bar.
By embodiment 4,15-19 more as can be seen, the adding of metallic promoter agent indium makes oxonation to obtain than high reaction rate under the relatively mild like this operational condition of stagnation pressure 30bar in the catalyst system.The reaction system stagnation pressure is different from pure iridium catalyst system to the reaction influence in adding the indium catalyst system, in iridium indium catalyst system when the system stagnation pressure rises to 30bar by 28bar, it is fast that speed of reaction is carried nice and high, what speed of reaction improved when improving reaction pressure again is few, when rising to 32bar by 30bar, speed of reaction changes little.And when continue increasing system pressure on the contrary speed of reaction downtrending appears.Phenomenon above having occurred when reaching 38bar as increasing by 32bar.The interpolation that this shows indium in the iridium catalyst system makes that reaction pressure is tending towards relaxing more, under the such high pressure of 35bar, 38bar with the 30bar low pressure under the speed of reaction that obtains close, so indium can relax such as operational conditions such as pressure.
The acetic acid iridium sample of getting three parts of different manufacturers productions is marked respectively and is 1#, 2#, 3#, carries out the solubility experiment in acetic acid solution, specifically implements as follows.
Embodiment 20
Get 1# acetic acid iridium 0.05g and be put in the small test tube, in this test tube, add the 0.21g acetic acid solution, sway and leave standstill, have precipitation to separate out; Add the 0.25g acetic acid solution again, not molten entirely; Continue to drip 0.28g acetate in the mixture upward, shake up, all be dissolved as green solution.
Embodiment 21
Get 1# acetic acid iridium 0.05g and be put in the small test tube, in this test tube, add the 0.21g acetic acid solution, sway and leave standstill, have precipitation to separate out; Add the 0.25g acetic acid solution again, not molten entirely; Add the 0.02g Indium sesquioxide in the mixture upward again, shake up, all be dissolved as green solution.
Embodiment 22
Get 2# acetic acid iridium 0.05g and be put in the small test tube, in this test tube, add the 0.21g acetic acid solution, sway and leave standstill, can not all dissolve; Add the 0.26g acetic acid solution again, not molten entirely; Continue to add the 0.60g acetic acid solution in the mixture upward, shake up, still have small amount of precipitate, add the 1.00g acetic acid solution in the mixture upward again, shake up, all dissolving.
Embodiment 23
Get 2# acetic acid iridium 0.05g and be put in the small test tube, in this test tube, add the 0.21g acetic acid solution, sway and leave standstill, can not all dissolve; Add the 0.26g acetic acid solution again, not molten entirely; Continue to add the 0.60g acetic acid solution in the mixture upward, shake up, still have small amount of precipitate, add the 0.02g Indium sesquioxide in the mixture upward again, shake up, basic dissolving.
Embodiment 24
Get 3# acetic acid iridium 0.05g and be put in the small test tube, in this test tube, add the 0.20g acetic acid solution, sway and leave standstill, can not all dissolve; Add the 0.50g acetic acid solution again, not molten entirely; Continue to add the 0.50g acetic acid solution in the mixture upward, shake up, still have small amount of precipitate, add the 1.00g acetic acid solution in the mixture upward again, shake up, basic dissolving.
Embodiment 25
Get 3# acetic acid iridium 0.05g and be put in the small test tube, in this test tube, add the 0.20g acetic acid solution, sway and leave standstill, can not all dissolve; Add the 0.50g acetic acid solution again, not molten entirely; Continue to add the 0.50g acetic acid solution in the mixture upward, shake up, still have small amount of precipitate, add the 0.02g Indium sesquioxide in the mixture upward again, shake up, basic dissolving.
As can be seen, acetic acid iridium needs a large amount of acetate be dissolved as solution from embodiment 20-25, and when acetic acid iridium when molten, is not added the small amounts indium by complete, acetic acid iridium all dissolves, and required solvent acetic acid amount can be still less.A spot of thus Indium sesquioxide can promote the dissolving of acetic acid iridium in acetic acid solution really.
Embodiment 26
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Anhydrous Ferric Chloride 0.0362g, the content of iron in system is 100ppm, nickel acetate 0.0318g, the nickel content in system is 60ppm, chromium acetate aqueous solution 0.0660g, chromium content in system is 60ppm, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, all the other are acetic acid solvent 68.39g, keep 190 ℃ of temperature of reaction, reaction pressure 30bar is reacted to the certain phase Quench, and the methyl acetate weight ratio is 15% in the reaction solution at this moment, the mass concentration of water is 4.5%, and corresponding carbonylation speed is 4.82mol/Lh.
Embodiment 27
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, Indium sesquioxide 0.4062g, elemental indium indium mol ratio is 1: 5, Anhydrous Ferric Chloride 0.0362g, the content of iron in system is 100ppm, nickel acetate 0.0318g, the nickel content in system is 60ppm, chromium acetate aqueous solution 0.0660g, chromium content in system is 60ppm, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, all the other are acetic acid solvent 67.98g, keep 190 ℃ of temperature of reaction, reaction pressure 30bar is reacted to the certain phase Quench, and the methyl acetate weight ratio is 15% in the reaction solution at this moment, the mass concentration of water is 4.5%, and corresponding carbonylation speed is 15.36mol/Lh.
Contrast by embodiment 1 and 26, embodiment 4 and 27 contrast are as can be known, add equivalent corroding metal iron, nickel, chromium respectively to pure iridium catalyst system and iridium indium catalyst system, to oxonation speed influence degree difference, comparatively speaking, the catalyst system of interpolation indium is influenced greatly by corroding metal than pure iridium catalyst system.So the iridium System Catalyst of adding indium has reduced the susceptibility of the corroding metal that is dissolved out from conversion unit, has enlarged the scope of operational condition.
Embodiment 28
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, indium hydroxide 0.1941g, elemental indium indium mol ratio is 1: 2, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 68.33g, keeps 190 ℃ of temperature of reaction, reaction pressure 30bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 15.35mol/Lh.
Embodiment 29
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, indium hydroxide 0.4852g, elemental indium indium mol ratio is 1: 5, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 68.03g, keeps 190 ℃ of temperature of reaction, reaction pressure 30bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 18.49mol/Lh.
Embodiment 30
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, indium acetate 0.3416g, elemental indium indium mol ratio is 1: 2, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 68.18g, keeps 190 ℃ of temperature of reaction, reaction pressure 30bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 14.27mol/Lh.
Embodiment 31
Under air atmosphere, be equipped with and add iridium acetate (iridium content 48%) 0.2307g in the manometric zirconium material autoclave to 250ml, the content of iridium in system is 900ppm, indium acetate 0.8540g, elemental indium indium mol ratio is 1: 5, methyl iodide 8.75g, initial mass concentration is 7%, distilled water 10.00g, initial mass concentration 8%, methyl acetate 37.50g, initial mass concentration is 30%, and all the other are acetic acid solvent 67.66g, keeps 190 ℃ of temperature of reaction, reaction pressure 30bar, be reacted to the certain phase Quench, the methyl acetate weight ratio is 15% in the reaction solution at this moment, and corresponding carbonylation speed is 17.14mol/Lh.
Contrast by embodiment 1,2 and embodiment 28-31 as can be seen, in the Primary Catalysts iridium of same concentrations, added the compound of other indium such as indium hydroxide, indium acetate has been accelerated speed of reaction too greatly, than pure iridium catalyst oxonation speed is significantly improved.Even in iridium concentration 900ppm, add the catalyst system speed of reaction that iridium 1: 5 indium hydroxide of indium mol ratio or the resulting speed of reaction of indium acetate are almost caught up with pure iridium concentration 1500ppm.
Claims (10)
1. the method for an iridium catalytic carbonylation synthesis of acetic acid, its process comprises: make the liquid phase medium and the carbon monoxide that comprise methyl alcohol, methyl acetate, acetate and water react generation acetate; The catalyst system that uses in the reaction is promotor with the methyl iodide for the iridic compound with group VIII is Primary Catalysts, is metallic promoter agent and stablizer with the compound that contains indium.
2. the method for synthesizing acetic acid by carbonylation as claimed in claim 1 is characterized in that, the described effect that contains the compound of indium is to promote the dissolving of described Primary Catalysts iridic compound in catalyst system, is embodied in:
Described iridic compound is not molten entirely in acetic acid solution, and wherein, the amount of iridium is 0.02～0.5mmol in the described iridic compound, and the amount of described acetate is 0.2～3.0g; In this solution, add the described compound that contains indium again, can make the dissolving rapidly in acetate of described iridic compound; The described amount that contains the compound of indium is 0.01～2.00mmol.
3. the method for synthesizing acetic acid by carbonylation as claimed in claim 1 is characterized in that, the compound that contains indium is the soluble salt that contains indium.
4. the method for synthesizing acetic acid by carbonylation as claimed in claim 1 is characterized in that, the described compound that contains indium is selected from indium acetate, Indium sesquioxide, indium chloride, indium iodide, the inferior indium of iodate, indium hydroxide or Indium Tris acetylacetonate.
5. the method for synthesizing acetic acid by carbonylation as claimed in claim 1 is characterized in that, in the described catalyst system, the mol ratio of elemental indium and indium is 1: (1～20).
6. the method for synthesizing acetic acid by carbonylation as claimed in claim 5 is characterized in that, in the described catalyst system, the mol ratio of elemental indium and indium is 1: (2～15).
7. the method for synthesizing acetic acid by carbonylation as claimed in claim 1 is characterized in that, in the described catalyst system, does not need to add alkaline metal iodide or alkaline earth metal iodide.
8. as the method for the described synthesizing acetic acid by carbonylation of arbitrary claim among the claim 1-7, it is characterized in that in the catalyst system of described synthesizing acetic acid by carbonylation, the mass concentration of iridic compound in mixed reaction solution is that benchmark is calculated as 500～2000ppm with iridium.
9. as the method for the described synthesizing acetic acid by carbonylation of arbitrary claim among the claim 1-7, it is characterized in that, in the described liquid phase medium, based on the reaction solution gross weight, the weight percent concentration of methyl acetate is greater than 0 and smaller or equal to 30%, the weight percent concentration of water is greater than 0 and smaller or equal to 10%, and the weight percent concentration of methyl iodide is 3～18%.
10. as the method for the described synthesizing acetic acid by carbonylation of arbitrary claim among the claim 1-7, it is characterized in that described temperature of reaction is 170～250 ℃, the stagnation pressure of reaction is 20～50bar.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2327420A (en) * | 1997-07-22 | 1999-01-27 | Bp Chem Int Ltd | Production of oxygenated compounds |
| CN1681764A (en) * | 2002-09-19 | 2005-10-12 | 英国石油化学品有限公司 | Process for the production of acetic acid |
| CN101374795A (en) * | 2006-01-30 | 2009-02-25 | 英国石油化学品有限公司 | Process for the production of acetic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2327420A (en) * | 1997-07-22 | 1999-01-27 | Bp Chem Int Ltd | Production of oxygenated compounds |
| CN1681764A (en) * | 2002-09-19 | 2005-10-12 | 英国石油化学品有限公司 | Process for the production of acetic acid |
| CN101374795A (en) * | 2006-01-30 | 2009-02-25 | 英国石油化学品有限公司 | Process for the production of acetic acid |
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