CN102442897B - Method for preparing acetic acid through hydroformylation reaction - Google Patents
Method for preparing acetic acid through hydroformylation reaction Download PDFInfo
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Abstract
The invention provides a method for preparing acetic acid through hydroformylation reaction, which is characterized by enabling carbon monoxide to be in contact with methyl acetate in the presence of water, a rhodium catalyst system and an organic solvent, wherein the rhodium catalyst system comprises a rhodium source, a halogen promoter, an iodide of alkali metal and/or alkaline earth metal and a platinum source; the rhodium source is a rhodium iodide and/or a rhodium complex; and the platinum source is one or more of platinum, a platinum salt and a platinum complex. By using the method to prepare acetic acid, the hydroformylation reaction rate can be obviously increased; and especially in case of a low water content of 0.3-5wt% in the acetic acid preparation reaction system, the reaction rate in the acetic acid preparation process based on methanol hydroformylation can still be increased greatly.
Description
Technical field
The present invention relates to a kind of carbonylation reaction and prepare the method for acetic acid.
Background technology
Acetic acid, as a kind of important basic organic chemical raw material, is widely used in the multiple fields such as fiber, softening agent, paint, tackiness agent and copolymer resins, is production capacity increase recent years a kind of Chemicals faster.The main method of producing in the world acetic acid at present has acetaldehyde oxidation, butane and lightweight oil oxidation style and methanol carbonylation.Wherein methanol carbonylation is produced the more than 70% of acetic acid Yi Zhan world yield of acetic acid.
US3,769,329 disclose the technique of a kind of low pressure methanol carbonylation acetic acid processed, this process using rhodium carbonyl-iodine catalyst system of solubility, can under gentle reaction conditions, obtain higher carbonylation rate.But in the reaction system that this technique adopts, need to comprise the have an appointment water of 14wt% and could keep higher carbonylation rate.
Chemistry circular, in " the promoting catalysis research of inorganic phosphor-contained salt additives on formic acid carbonylation reaction " of the 5th phase 390-393 page in 2005, the impact of inorganic phosphate salt pair catalyzer is studied, finds that inorganic phosphor-contained salt has good catalytic activity as the rhodium catalyst system of additive in methanol carbonylation.The promoting catalysis of ammonium phosphate and zinc phosphate is more approaching, reacts 15min left and right under same reaction conditions, and the pure Rh catalytic body of its carbonylation productivity ratio can improve 30% left and right.The catalytic activity of sodium phosphate catalyst system is in the reaction starting stage a little less than pure Rh catalyst system, and along with the carrying out of reaction, its promoting catalysis also embodies rapidly.Sodium phosphomolybdate and Tungstophosphoric acid, sodium salt also have more significant promoting catalysis, and when reaction 18min, the pure Rh system of carbonylation productivity ratio of this catalyst system improves nearly 15%.But be not exactly that what reason is made an explanation.
CN1134397C provides a kind of method of the Studies of Producing Acetic Acid by Carbonylation of Methanol under rhodium/iridium/iodide ion catalyst system exists.The method, for to add iridium to improve catalyst reaction speed and stable center atom rhodium in rhodium/iodine catalyst system, also contains the lithium metal-salt of the 10wt% that has an appointment as promotor and stablizer in this catalyst system.195 ℃ of temperature of reaction, under the condition of pressure 2.8MPa, carry out intermittent reaction, in the catalyzer that is 600ppm at rhodium content, add the iridium of 1000ppm, can make speed of reaction improve significantly to 22mol/L/hr from 18mol/L/hr, and the growing amount of impurity, particularly unsaturates is improved.
Although the disclosed method of CN1134397C has obtained obvious improvement in carbonylation rate, carbonylation rate still has the space of further raising, and in low water content situation, the carbonylation rate of the method is still lower especially.
Therefore, reduce system water content, obtain higher carbonylation rate, improve the throughput (the acetic acid amount that the throughput of carbonylation reactor can generate with the reaction liquid of unit volume or unit weight is calculated) of current Studies of Producing Acetic Acid by Carbonylation of Methanol industrialization reactor, adapt to Production requirement, reducing energy consumption of unit product level is a technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to overcome carbonylation rate in prior art, the particularly lower problem of carbonylation rate under the condition of low water content, provide a kind of carbonylation to prepare the method for acetic acid, use the method under compared with the condition of low water content, significantly to improve the speed of reaction that acetic acid is prepared in carbonylation of methanol, and can in comprises low-water carbonylation environment, improve catalyst stability energy.
The invention provides a kind of carbonylation and prepare the method for acetic acid, it is characterized in that, under water, rhodium catalytic system and carboxylic acid exist, carbon monoxide is contacted with methyl acetate, described rhodium catalytic system is made up of iodide and the platinum source of rhodium source, halogen promotor, basic metal and/or alkaline-earth metal, the iodide of described rhodium source selected from rhodium and/or the title complex of rhodium, described platinum source is selected from one or more in the title complex of platinum, platinum salt and platinum.
The present inventor finds, while using method of the present invention to prepare acetic acid, can significantly accelerate carbonylation rate, particularly, in the reaction system of preparing acetic acid of the present invention, under the low water content that water-content is 0.3-5wt%, still can significantly improve the speed of reaction that acetic acid is prepared in carbonylation of methanol.Meanwhile, in this rhodium catalytic system, platinic compound can also be served as stablizer, and improved catalyst stability energy can be provided in low water content carbonylation of methanol environment.The reduction of water-content can improve carbonylation reactor useful volume, improves reactor utilization ratio, increases single covering device production capacity; The reduction of water-content significantly reduces the energy consumption of flash stage in technique in addition, as the larger step of energy consumption in whole technique, reduces water-content and has obvious economic worth, also has very large meaning for saving energy and reduce the cost of complete assembly.In addition, the existence of the metal-salt of platinum has reduced the amount that in acetic acid preparation and catalyst recirculation process, the rhodium in catalyst system is precipitated out from solution.Rhodium catalyst is in catalyst recirculation process, and particularly flash stage is unstable especially, causes rhodium catalyst finally as RhI
3be deposited in device or pipeline.Rhodium itself is expensive, affects the work-ing life of catalyzer and the steady running of device will bring disadvantageous effect economically to acetic acid production because rhodium loss.
Embodiment
The invention provides a kind of carbonylation and prepare the method for acetic acid, it is characterized in that, under water, rhodium catalytic system and carboxylic acid exist, carbon monoxide is contacted with methyl acetate, described rhodium catalytic system is made up of iodide and the platinum source of rhodium source, halogen promotor, basic metal and/or alkaline-earth metal, the iodide of described rhodium source selected from rhodium and/or the title complex of rhodium, described platinum source is selected from one or more in the title complex of platinum, platinum salt and platinum.
In the present invention, described rhodium source can be selected from the various rhodium source dissolving in the reaction system of preparing acetic acid of the present invention known in the field, and this is because rhodium compound all can be converted into the material [Rh (CO) of catalytic activity under reaction conditions
2i
2]
-negative ion.The present invention is preferably the iodide of rhodium and/or the title complex of rhodium; But consider and do not wish introducing hetero-atoms, more preferably iodate rhodium.
In addition, in the reaction system of preparing acetic acid of the present invention, take the total amount of rhodium catalytic system, water, organic solvent and methyl acetate as benchmark, the content of rhodium can be 100-2000ppm, is preferably 300-1000ppm.
In the present invention, described platinum source can be various platinum known in the field sources, particularly, can be for being dissolved in the reaction system of preparing acetic acid of the present invention arbitrarily or can generating the various containing platinic compound of solvend in the reaction system of preparing acetic acid of the present invention, can be for example one or more in the title complex of platinum, platinum salt and platinum, be preferably Platinic chloride, platinum chloride and solubility containing one or more in platinum complex, more preferably Platinic chloride.
In addition, in the present invention, above-mentioned platinic compound has the effect of stablizer.The use of stablizer in the prior art need to be used under water-content higher strip part, and in catalyst system of the present invention, above-mentioned platinic compound can significantly improve catalyst stability energy in comprises low-water carbonylation environment.
In rhodium catalytic system of the present invention, the mol ratio of platinum and rhodium can in very large range change, particularly, in platinum in platinum source and rhodium source, the mol ratio of rhodium can be 0.01-10, preferably in the platinum in platinum source and rhodium source, the mol ratio of rhodium is 0.1-5, more preferably in the platinum in platinum source and rhodium source, the mol ratio of rhodium is 0.2-2, and the mol ratio that most preferably is rhodium in platinum in platinum source and rhodium source is 0.3-1.
In the present invention, described alkyl halide promoter can be various alkyl halide promoter known in the field, particularly, can be selected from the halogenated alkane that carbonatoms is 1-3, is preferably methyl iodide.
In the reaction system of preparing acetic acid of the present invention, take the total amount of rhodium catalytic system, water, organic solvent and methyl acetate as benchmark, above-mentioned alkyl halide promoter can be 3-25wt%, is preferably 8-20wt%.
In the present invention, can select various basic metal in the reaction system of preparing acetic acid of the present invention and/or the iodide of alkaline-earth metal of may be dissolved in arbitrarily known in the field as the iodine compound of common promotor, be preferably lithium iodide.
In the reaction system of preparing acetic acid of the present invention, take the total amount of rhodium catalytic system, water, organic solvent and methyl acetate as benchmark, the content of the iodide of above-mentioned basic metal and/or alkaline-earth metal can be 3-25wt%, is preferably 10-20wt%.
In the present invention, water can be by adding in carbonylation reactor together with response composite; Can also water be separated with other components in reaction system by tripping device, and return to reaction unit according to manipulated variable, to keep water-content in carbonylation reaction liquid phase in certain level.In the prior art, in catalyst system, need in the higher carbonylation reaction environment of water-content, could keep higher carbonylation rate, and in the reaction system of preparing acetic acid of the present invention, even under low water content, still can significantly improve the speed of reaction that acetic acid is prepared in carbonylation of methanol.Particularly, in the reaction system of preparing acetic acid of the present invention, take the total amount of rhodium catalytic system, water, organic solvent and methyl acetate as benchmark, the content of water can be 0.2wt%-6wt%, is preferably 0.3wt%-5wt%.
In the reaction system of preparing acetic acid of the present invention, the content of methyl acetate can be 1-20wt%, is preferably 2-10wt%.
In the present invention, described organic solvent can be the various solvents that can be used in carbonylation reaction known in the field, is preferably organic carboxyl acid, the organic carboxyl acid that more preferably carbonatoms is 2-5.Because the target product of the carbonylation reaction of methyl acetate is acetic acid, while therefore using acetic acid as reaction solvent, the product of acquisition can not need to isolate organic solvent, thus in the present invention most preferably organic solvent be acetic acid.
Organic solvent can be to join together with liquid reaction composition in carbonylation reactor, and amount that also can be by returning to control after separating with liquid reaction composition is to keep in liquid phase other component concentrations constant.The content of organic solvent is not had to special requirement, as long as keep the content of other each components in this reaction liquid phase constant by adjusting organic solvent content, particularly, in the reaction system of preparing acetic acid of the present invention, take the total amount of rhodium catalytic system, water, organic solvent and methyl acetate as benchmark, the content of organic solvent can be 30-80wt%, is preferably 40-70wt%.
In the present invention, described carbonylation reaction condition can be various reaction conditions known in the field, the present invention be preferably carbon monoxide dividing potential drop be 0.5-10MPa, the temperature of reaction is 140-250 ℃, anti-more preferably carbon monoxide dividing potential drop be 1-5MPa, the temperature of reaction is 170-210 ℃.In addition, carbonylation reaction both can carry out in mode intermittently, also can carry out in a continuous manner, was preferably in a continuous manner and carried out.
Below by specific embodiment, the present invention is further detailed, but the present invention is not limited in following embodiment.
The amount of substance of the product acetic acid that the carbonylation rate described in the present invention is produced with the reaction liquid volume under every liter of room temperature per hour represents, unit is mol/L/hr.
In embodiment 1-5 and comparative example 1-2, the content of methyl acetate and water is will consume the methyl acetate of 1 mole and the water of 1 mole when consuming 1 mole of CO according to hypothesis.The organic constituent that the upper sheaf space of reactor exists is ignored.
The intermittent reaction adopting in embodiment 1-5 and comparative example 1-2 all carries out in a 300ml zirconium material autoclave with magnetic stirring apparatus and liquid feeding device, provide stable carbon monoxide raw material by reducing valve to reactor with a gas cylinder, make the gaseous tension in autoclave keep constant, read the pressure data in gas cylinder by precision digital tensimeter.
In embodiment 1-5 and comparative example 1-2, in each carbonylation reaction experiment, the total overall reaction composition except raw acetic acid methyl esters is joined in autoclave, raw acetic acid methyl esters joins in fluid infusion apparatus.Enclosed high pressure still, autoclave is carried out to pressure testing with the nitrogen of about 3.0MPa, then use nitrogen or the air in carbon monoxide (3 × 0.5MPa) displacement autoclave and liquid feeding device and be finally filled with the carbon monoxide of 0.6MPa, pass into carbon monoxide to about 2.5MPa and stablize 30 minutes after then liquid reaction composition being heated to 190 ℃ under the condition of 750 revs/min of stir speed (S.S.)s.Raw acetic acid methyl esters in liquid injection system is joined in autoclave and start by the CO (carbon monoxide converter) gas of 3.0MPa and react, by gas cylinder, to supply raw materials carbon monoxide keep autoclave internal pressure 3.0MPa of reactor, the Pressure Drop of a gas cylinder of every 30 seconds records also calculates carbonylation rate accordingly.When finding that in 5 minutes inner high voltage gas cylinders, carbon monoxide pressure disconnects source of the gas after not declining, stopped reaction cooling.
In addition, in embodiment 6-7 and comparative example 3, under nitrogen atmosphere, carry out rhodium catalyst stability test with withstand voltage Glass tubing simulation flash tank.Adopt the rhodium content in atomic absorption spectrometry solution.
Methyl iodide in following examples is purchased from Shenyang chemical reagent company limited, and lithium iodide is purchased from ACROS ORGANICS company, and iodate rhodium is purchased from STREM CHEMICALS company, and six water Platinic chlorides are purchased from ACROS ORGANICS company.
Embodiment 1
Rhodium catalytic system is made up of methyl iodide 21g, lithium iodide 22.5g, iodate rhodium 0.28g, six water Platinic chloride 0.20g.
The solution that contains acetic acid 73g, methyl iodide 21g, lithium iodide 22.5g, water 6.7g, iodate rhodium 0.28g (being equivalent to Rh content 400ppm), six water Platinic chloride 0.20g (mol ratio that is equivalent to platinum and rhodium is 0.66) is joined in 300ml zirconium material autoclave, raw acetic acid methyl esters 26.5g is joined in liquid injection system.After pressure testing displaced air, pass into the CO of 0.6MPa, join 190 ℃ under the stirring of 750 revs/min after, pass into CO to about 2.5MPa and stablize 30 minutes, the raw acetic acid methyl esters in liquid injection system being joined in autoclave and start by the CO (carbon monoxide converter) gas of 3.0MPa and react.Containing 10wt%MeOAc and 5.5wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 15.6mol/L/hr; Containing 5wt%MeOAc and 4.2wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 9.8mol/L/hr.
Embodiment 2
Rhodium catalytic system is made up of methyl iodide 21g, lithium iodide 22.5g, iodate rhodium 0.28g, six water Platinic chloride 0.39g.
The solution that contains acetic acid 73g, methyl iodide 21g, lithium iodide 22.5g, water 6.7g, iodate rhodium 0.28g (being equivalent to Rh content 400ppm), six water Platinic chloride 0.39g (mol ratio that is equivalent to platinum and rhodium is 1.32) is joined in 300ml zirconium material autoclave, raw acetic acid methyl esters 26.5g is joined in liquid injection system.After pressure testing displaced air, pass into the CO of 0.6MPa, join 190 ℃ under the stirring of 750 revs/min after, pass into CO to about 2.5MPa and stablize 30 minutes, the raw acetic acid methyl esters in liquid injection system being joined in autoclave and start by the CO (carbon monoxide converter) gas of 3.0MPa and react.Containing 10wt%MeOAc and 5.5wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 16.8mol/L/hr; Containing 5wt%MeOAc and 4.2wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 10.2mol/L/hr.
Embodiment 3
Rhodium catalytic system is made up of methyl iodide 21g, lithium iodide 22.5g, iodate rhodium 0.56g, six water Platinic chloride 0.20g.
The solution that contains acetic acid 73g, methyl iodide 21g, lithium iodide 22.5g, water 6.7g, iodate rhodium 0.56g (being equivalent to Rh content 800ppm), six water Platinic chloride 0.20g (mol ratio that is equivalent to platinum and rhodium is 0.33) is joined in 300ml zirconium material autoclave, raw acetic acid methyl esters 26.5g is joined in liquid injection system.After pressure testing displaced air, pass into the CO of 0.6MPa, join 190 ℃ under the stirring of 750 revs/min after, pass into CO to about 2.5MPa and stablize 30 minutes, the raw acetic acid methyl esters in liquid injection system being joined in autoclave and start by the CO (carbon monoxide converter) gas of 3.0MPa and react.Containing 10wt%MeOAc and 5.5wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 23.6mol/L/hr; Containing 5wt%MeOAc and 4.2wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 13.4mol/L/hr.
Embodiment 4
Rhodium catalytic system is made up of methyl iodide 21g, lithium iodide 22.5g, iodate rhodium 0.56g, six water Platinic chloride 0.39g.
The solution that contains acetic acid 73g, methyl iodide 21g, lithium iodide 22.5g, water 6.7g, iodate rhodium 0.56g (being equivalent to Rh content 800ppm), six water Platinic chloride 0.39g (mol ratio that is equivalent to platinum and rhodium is 0.66) is joined in 300ml zirconium material autoclave, raw acetic acid methyl esters 26.5g is joined in liquid injection system.After pressure testing displaced air, pass into the CO of 0.6MPa, join 190 ℃ under the stirring of 750 revs/min after, pass into CO to about 2.5MPa and stablize 30 minutes, the raw acetic acid methyl esters in liquid injection system being joined in autoclave and start by the CO (carbon monoxide converter) gas of 3.0MPa and react.Containing 10wt%MeOAc and 5.5wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 32.1mol/L/hr; Containing 5wt%MeOAc and 4.2wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 17.6mol/L/hr.
Embodiment 5
Rhodium catalytic system is made up of methyl iodide 21g, lithium iodide 22.5g, iodate rhodium 0.56g, six water Platinic chloride 0.61g.
The solution that contains acetic acid 73g, methyl iodide 21g, lithium iodide 22.5g, water 6.7g, iodate rhodium 0.56g (being equivalent to Rh content 800ppm), six water Platinic chloride 0.61g (mol ratio that is equivalent to platinum and rhodium is 0.99) is joined in 300ml zirconium material autoclave, raw acetic acid methyl esters 26.5g is joined in liquid injection system.After pressure testing displaced air, pass into the CO of 0.6MPa, join 190 ℃ under the stirring of 750 revs/min after, pass into CO to about 2.5MPa and stablize 30 minutes, the raw acetic acid methyl esters in liquid injection system being joined in autoclave and start by the CO (carbon monoxide converter) gas of 3.0MPa and react.Containing 10wt%MeOAc and 5.5wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 22.8mol/L/hr; Containing 5wt%MeOAc and 4.2wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 12.9mol/L/hr.
Comparative example 1
Rhodium catalytic system is by methyl iodide 21g, lithium iodide 22.5g, iodate rhodium 0.28g.
Do not add platinum promotor altogether, the solution that contains acetic acid 73g, methyl iodide 21g, lithium iodide 22.5g, water 6.7g, iodate rhodium 0.28g (being equivalent to Rh content 400ppm) is joined in 300ml zirconium material autoclave, raw acetic acid methyl esters 26.5g is joined in liquid injection system.After pressure testing displaced air, pass into the CO of 0.6MPa, join 190 ℃ under the stirring of 750 revs/min after, pass into CO to about 2.5MPa and stablize 30 minutes, the raw acetic acid methyl esters in liquid injection system being joined in autoclave and start by the CO (carbon monoxide converter) gas of 3.0MPa and react.Containing 10wt%MeOAc and 5.5wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 14.3mol/L/hr; Containing 5wt%MeOAc and 4.2wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 9.1mol/L/hr.
Comparative example 2
Rhodium catalytic system is by methyl iodide 21g, lithium iodide 22.5g, iodate rhodium 0.56g.
Do not add platinum promotor altogether, the solution that contains acetic acid 73g, methyl iodide 21g, lithium iodide 22.5g, water 6.7g, iodate rhodium 0.56g (being equivalent to Rh content 800ppm) is joined in 300ml zirconium material autoclave, raw acetic acid methyl esters 26.5g is joined in liquid injection system.After pressure testing displaced air, pass into the CO of 0.6MPa, join 190 ℃ under the stirring of 750 revs/min after, pass into CO to about 2.5MPa and stablize 30 minutes, the raw acetic acid methyl esters in liquid injection system being joined in autoclave and start by the CO (carbon monoxide converter) gas of 3.0MPa and react.Containing 10wt%MeOAc and 5.5wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 19.5mol/L/hr; Containing 5wt%MeOAc and 4.2wt%H corresponding to liquid combination reaction species
2when O, recording carbonylation rate is 10.3mol/L/hr.
Embodiment 6
Rhodium catalytic system is made up of methyl iodide 5.6g, lithium iodide 6.0g, iodate rhodium 0.15g, six water Platinic chloride 0.11g.
In the withstand voltage Glass tubing with stirring and heating system, add 0.15g RhI
3(being equivalent to rhodium content 800ppm), six water Platinic chloride 0.11g (mol ratio that is equivalent to platinum and rhodium is 0.66), 5.6g methyl iodide, 6.0g lithium iodide, 1.6g methyl acetate, 0.2g water and 26.5g acetic acid.With airtight after carbon monoxide replacement(metathesis)reaction air in tube three times, at 150 ℃, under the condition of stirring, continue to pass into carbon monoxide catalyzer is dissolved completely.Prepared solution is cold to be gone to after room temperature with nitrogen replacement solution 1 hour, removes the carbon monoxide being dissolved in liquid.Airtight Glass tubing reactor, heated solution to 135 ℃ also keeps 96 hours.At 24 hours, 48 hours, 72 hours with within 96 hours, sample and measure the rhodium concentration of solution.Measurement result is as shown in table 1.
Embodiment 7
Rhodium catalytic system is made up of methyl iodide 5.6g, lithium iodide 6.0g, iodate rhodium 0.15g, six water Platinic chloride 0.22g.
In the withstand voltage Glass tubing with stirring and heating system, add 0.15g RhI
3(being equivalent to rhodium content 800ppm), six water Platinic chloride 0.22g (mol ratio that is equivalent to platinum and rhodium is 1.32), 5.6g methyl iodide, 6.0g lithium iodide, 1.6g methyl acetate, 0.2g water and 26.5g acetic acid.With airtight after carbon monoxide replacement(metathesis)reaction air in tube three times, at 150 ℃, under the condition of stirring, continue to pass into carbon monoxide catalyzer is dissolved completely.Prepared solution is cold to be gone to after room temperature with nitrogen replacement solution 1 hour, removes the carbon monoxide being dissolved in liquid.Airtight Glass tubing reactor, heated solution to 135 ℃ also keeps 96 hours.At 24 hours, 48 hours, 72 hours with within 96 hours, sample and measure the rhodium concentration of solution.Measurement result is as shown in table 1.
Comparative example 3
Rhodium catalytic system is by methyl iodide 5.6g, lithium iodide 6.0g, iodate rhodium 0.15g.
In the withstand voltage Glass tubing with stirring and heating system, add 0.15g RhI
3(being equivalent to rhodium content 800ppm), 5.6g methyl iodide, 6.0g lithium iodide, 1.6g methyl acetate, 0.2g water and 26.5g acetic acid.With airtight after carbon monoxide replacement(metathesis)reaction air in tube three times, at 150 ℃, under the condition of stirring, continue to pass into carbon monoxide catalyzer is dissolved completely.Prepared solution is cold to be gone to after room temperature with nitrogen replacement solution 1 hour, removes the carbon monoxide being dissolved in liquid.Airtight Glass tubing reactor, heated solution to 135 ℃ also keeps 96 hours.At 24 hours, 48 hours, 72 hours with within 96 hours, sample and measure the rhodium concentration of solution.Measurement result is as shown in table 1.
Table 1.
Note: reaction conditions: 135 ℃, nitrogen atmosphere.
Known according to table 1, in reaction liquid phase, add platinum salt and obviously reduced RhI as stablizer
3settling rate.Under simulation flash evaporation unit operational condition, after 96 hours, do not add Rh content in the reaction soln of stablizer to decline 29.6%, and added platinum salt as stablizer, in the time that platinum/rhodium (mol ratio) is 0.66, after 96 hours, in reaction soln, rhodium content drops to 12.7%, and in the time that platinum/rhodium (mol ratio) is 1.32, after 96 hours, in reaction soln, rhodium content drops to 12.3%.
Claims (8)
1. a carbonylation reaction is prepared the method for acetic acid, it is characterized in that, at water, under rhodium catalytic system and organic solvent exist, carbon monoxide is contacted with methyl acetate, described rhodium catalytic system is by rhodium source, halogen promotor, the iodide of basic metal and/or alkaline-earth metal and platinum source composition, the iodide of described rhodium source selected from rhodium and/or the title complex of rhodium, described platinum source is selected from platinum, one or more in the title complex of platinum salt and platinum, the mol ratio of the rhodium in the platinum in platinum source and rhodium source is 0.3-1, wherein, with rhodium catalytic system, water, the total amount of organic solvent and methyl acetate is benchmark, the content of water is 0.3wt%-5wt%.
2. method according to claim 1, wherein, described rhodium source is iodate rhodium.
3. method according to claim 1, wherein, take the total amount of rhodium catalytic system, water, organic solvent and methyl acetate as benchmark, in described rhodium source, the content of rhodium is 100-2000ppm, the content of described halogen promotor is 3-25wt%, the content of the iodide of described basic metal and/or alkaline-earth metal is 3-25wt%, and the content of described methyl acetate is 1-20wt%, and the content of described organic solvent is 30-80wt%.
4. method according to claim 3, wherein, take the total amount of rhodium catalytic system, water, organic solvent and methyl acetate as benchmark, in described rhodium source, the content of rhodium is 300-1000ppm, the content of described halogen promotor is 8-20wt%, the content of the iodide of described basic metal and/or alkaline-earth metal is 10-20wt%, and the content of described methyl acetate is 2-10wt%, and the content of described organic solvent is 40-70wt%.
5. method according to claim 3, wherein, described platinum source is one or more in the title complex of Platinic chloride, platinum chloride and solubility platinum, and described halogen promotor is that carbonatoms is the halogenated alkane of 1-3, described alkali-metal iodide are lithium iodide, and described organic solvent is organic carboxyl acid.
6. wherein, described organic solvent is acetic acid to method according to claim 5, and described halogen promotor is methyl iodide.
7. method according to claim 1, wherein, the dividing potential drop that described carbonylation reaction condition is carbon monoxide is 0.1-10Mpa, the temperature of reaction is 150-250 ℃.
8. method according to claim 7, wherein, the dividing potential drop that described carbonylation reaction condition is carbon monoxide is 1-5Mpa, the temperature of reaction is 170-210 ℃.
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| US5883295A (en) * | 1996-12-19 | 1999-03-16 | Bp Chemicals Limited | Iridium catalyzed carbonylation process for the production of acetic acid |
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