CN103086868A - Method for preparing acetic acid through carbonylation reaction - Google Patents
Method for preparing acetic acid through carbonylation reaction Download PDFInfo
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- CN103086868A CN103086868A CN2011103415648A CN201110341564A CN103086868A CN 103086868 A CN103086868 A CN 103086868A CN 2011103415648 A CN2011103415648 A CN 2011103415648A CN 201110341564 A CN201110341564 A CN 201110341564A CN 103086868 A CN103086868 A CN 103086868A
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Abstract
The invention provides a method for preparing acetic acid through a carbonylation reaction. Under the existences of water, an iridium catalyst system, and an organic solvent, methanol and/or methyl acetate contact carbon monoxide. The iridium catalyst system comprises an iridium-containing compound, a halogen cocatalyst, an accelerant containing ruthenium and/or osmium, and a rare earth oxide. With the method provided by the invention for preparing acetic acid through a carbonylation reaction, the adopted iridium catalyst system comprises the rare earth oxide, such that carbonylation reaction speed can be increased. When the content of carbon monoxide is low, no precipitate is formed in a liquid reaction mixture. Therefore, when the liquid reaction mixture is subjected to flash evaporation and acetic acid is separated, the mixture can be utilized as a catalyst system again.
Description
Technical field
The present invention relates to a kind of method that carbonylation reaction prepares acetic acid.
Background technology
Acetic acid is widely used in the multiple fields such as fiber, softening agent, paint, tackiness agent, copolymer resins as a kind of important basic organic chemical raw material, 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 acetic acid and has been accounted for more than 70% of world's yield of acetic acid.
The method that adopts iridium catalyst systems catalysis methanol carbonylation to produce acetic acid is known, and has been applied in the middle of suitability for industrialized production.Carrying out rhodium when being the carbonylating catalyst exploitation as far back as Monsanto company, is that carbonylating catalyst has launched research to iridium.The researchist discloses a kind of iridium in US3772380 be carbonylating catalyst.The title complex of halogenide, carbonylic halide or other iridium of employing iridium is as catalyzer; Br
2, I
2Or other compounds are 50-300 ℃ as promotor in temperature of reaction, carry out methanol carbonylation under pressure 10-1000psi, and speed of reaction is starkly lower than rhodium catalytic system, so industrialization methanol carbonylation process has at that time adopted rhodium catalytic system.
But there is obvious shortcoming in rhodium as the active centre of catalyst system, and for having relatively high expectations of water-content in reaction system and carbon monoxide pressure of tension, when reduced water content or carbon monoxide pressure of tension reduction, rhodium may the non-reversibility inactivation.The effective ways of head it off comprise raising system water content and add stablizer, but the increase of water-content means the raising of energy consumption, and are unfavorable for producing.Present classic catalyst stabilizer is iodate basic metal, especially lithium iodide, but the interpolation of a large amount of lithium iodides can cause post-processing step loaded down with trivial details, increases plant construction and produces originally and running cost.Iridium catalyst systems is because the solvability in liquid reaction mixture (comprising catalyst system, solvent acetic acid, material benzenemethanol and/or methyl acetate and water) is better, stability is high and be subject to numerous researchists' attention, and the speed of reaction that improves iridium and be the carbonylation of methanol catalyzer is the emphasis of research.
A kind of iridium and platinum have been announced in CN1325374A as the method for preparing acetic acid and/or methyl acetate of catalyzer.The researchist finds to add the throughput rate that platinum can increase acetic acid in take iridium or iridium and rhodium as the catalyst system of matrix, and the metal total mole number of use still remains unchanged simultaneously.Even when the reactive system reduced water content, platinum add still can sizable reinforcement iridium stability.But the bullion content that needs in this method is higher, and the catalyzer cost is large.
The method that adopts ruthenium and osmium catalysis methanol carbonylation to produce acetic acid is also known, disclose a kind of compound that is selected from palladium, platinum, iridium, ruthenium or osmium in GB1234641 and GB1234642 as catalyzer, carried out alcohol, halides or ether etc. under catalysis as the method for raw material production carboxylic acid or its ester class helping of halogen or halogen compounds.GB20209409A discloses a kind of compound that adopts ruthenium or ruthenium as catalyzer, halogen-containing, especially prepares carboxylic acid and corresponding ester thereof by alcohol and reaction of carbon monoxide under the promoting catalysis of iodine.
British Petroleum Company p.l.c. (BP) discloses a kind of method of methyl alcohol and/or its reactive derivative production acetic acid in CN1107460A.In the method, disclosed catalyst system comprises at least a in iridium catalyst, methyl-iodide and ruthenium or osmium.Thereby the existence of ruthenium can reduce the volatility of iridium catalyst and improve the catalyst stability energy.In addition, the use of ruthenium or osmium can improve carbonylation of methanol speed, makes reaction to carry out under lower water-content, is conducive to reduce the generation of by product.CN1681764A discloses a kind of method that improved carbonylation of methanol prepares acetic acid.The catalyst body that uses in the method is iridium, comprises at least a promotor and at least a stablizer that is selected from indium, cadmium, mercury, gallium and zinc that is selected from ruthenium, osmium and rhenium.Carbonylation rate has been accelerated in adding of promotor, but uses the promotor of higher concentration may make catalyst system produce precipitation and inactivation.To improve the adding of stablizer catalyst stability energy and carbonylation rate constant or increase.In order to improve the carbonylation rate of iridium catalyst systems, the researchist has carried out a large amount of research, and CN1823031A discloses a kind of methyl alcohol and/or its reactive derivative prepares the Catalyst And Method of acetic acid by carbonylation.This catalyst system comprises a kind of iridium carbonylating catalyst, the methyl-iodide promotor, and at least a and at least a of ruthenium, osmium, rhenium, indium, cadmium, mercury, gallium and zinc can be the non-haloid acid promotor of oxygen acid, super acid and/or heteropolyacid.Promotor can be improved the carbonylation rate of iridium catalyst systems, but may produce potential disadvantageous effect to the conversion unit material simultaneously.
The method of the synthetic acetic acid of a kind of methyl alcohol and/or its reactive derivative and carbon monoxide carbonylation is disclosed in CN1187482A.It is that catalyzer, haloalkane are that promotor, ruthenium are promotor that the method has adopted iridium, also needs in addition to comprise in liquid reaction mixture a kind ofly to be selected from alkaline metal iodide, alkaline earth metal iodide, can to produce I
-Metal complexes, can produce I
-Salt or its mixture as secondary accelerator.
Summary of the invention
The present invention is directed to the problems referred to above, provide a kind of and used iridium catalyst systems catalysis methanol and/or methyl acetate and carbon monoxide contact preparation acetic acid, improved the method that carbonylation reaction that carbonylation rate and this iridium catalyst systems can be recycled after by the aftertreatment separating acetic acid prepares acetic acid.
Use iridium catalyst systems catalysis methanol carbonylation to prepare acetic acid in prior art, when carbon monoxide content is low when for example reacting complete or react complete rear flash distillation acetic acid, because iridium catalyst systems becomes unstable, make and occur precipitation in liquid reaction mixture, this liquid reaction mixture can't recycling, causes production cost to improve.The present inventor is surprised to find that, adds the oxide compound of rare earth metal in the iridium catalyst systems, can make the aforesaid liquid reaction mixture in the situation that carbon monoxide content is low, precipitation can not occur, thereby can recycle.
Carbonylation reaction provided by the invention prepares the method for acetic acid, wherein, the method is included under water, iridium catalyst systems and organic solvent existence, methyl alcohol and/or methyl acetate are contacted with carbon monoxide, and described iridium catalyst systems contains iridic compound, halogen catalyst, contains the promotor of ruthenium and/or osmium and the oxide compound of rare earth element.
Adopt carbonylation reaction provided by the invention to prepare the method for acetic acid, because the iridium catalyst systems of using contains the oxide compound of rare earth element, so can improve carbonylation rate; When carbon monoxide content was low, liquid reaction mixture can not produce precipitation, with can be again as the catalyst system utilization after liquid reaction mixture flash separation acetic acid.For example, add cerium oxide in embodiment 1, do not occurred precipitation in liquid reaction mixture; And precipitation all appears in the Comparative Examples 2 of not adding the Comparative Examples 1 of cerium oxide and having added cerous acetate in liquid reaction mixture; And the carbonylation rate of embodiment 1 is apparently higher than Comparative Examples 1.
Embodiment
The invention provides a kind of method that carbonylation reaction prepares acetic acid, wherein, under water, iridium catalyst systems and organic solvent exist, methyl alcohol and/or methyl acetate are contacted with carbon monoxide, and described iridium catalyst systems contains iridic compound, halogen catalyst, contains the promotor of ruthenium and/or osmium and the oxide compound of rare earth element.
The method according to this invention, wherein, take the gross weight of iridium catalyst systems, water, organic solvent and methyl acetate as benchmark, the content of described iridium catalyst systems can be the 3-20 % by weight, the content of described water can be the 0.1-15 % by weight, the content of organic solvent can be the 30-80 % by weight, and the content of methyl acetate can be the 1-40 % by weight.In the preferred case, take the gross weight of iridium catalyst systems, water, organic solvent and methyl acetate as benchmark, the content of described iridium catalyst systems is the 5-15 % by weight, the content of described water is the 0.5-10 % by weight, the content of organic solvent is the 50-70 % by weight, and the content of methyl acetate is the 5-35 % by weight.More preferably, the content of described water is the 2-7 % by weight.
The method according to this invention, wherein, in described iridium catalyst systems, in mole, contain the iridium in iridic compound: the halogen in halogen catalyst: the ruthenium in promotor and/or osmium: rare earth element=1: 10-200: 0.2-5: 0.2-5.In the preferred case, in described iridium catalyst systems, in mole, contain the iridium in iridic compound: the halogen in halogen catalyst: the ruthenium in promotor and/or osmium: rare earth element=1: 30-100: 0.5-3: 0.5-2.5.In the aforementioned proportion scope, described iridium catalyst systems can improve methanol carbonylation speed, and this iridium catalyst systems good stability.Need explanation at this, when the oxide compound that contains simultaneously ruthenium and osmium, rare earth element when promotor is multiple, calculate aforementioned proportion with the total mole number of ruthenium and osmium, the total mole number of rare earth element.
The oxide compound of described rare earth element can be one or more of the oxide compound of the rare earth element that is used for catalyzer.In the preferred case, the oxide compound of described rare earth element is selected from one or more in lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide.More preferably, the oxide compound of described rare earth element is selected from two or more in lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide.Use the oxide compound of rare earth element that iridium catalyst systems stability is improved, especially the oxide compound when the two or more rare earth element of use can further improve carbonylation rate.
The method according to this invention, wherein, the described iridic compound that contains can be the various iridic compounds that contain for the catalytic alcohol preparing carboxylic acid by carbonylation, this contains the oxide compound that iridic compound comprises iridium salt, iridium, title complex of iridium etc., the described iridic compound that contains can be dissolved in reaction system, this contains iridic compound and can list but be not limited to following material, for example: IrCl
3, IrI
3, IrBr
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2, [Ir (CO)
2Br]
2, [Ir (CO)
4I
2]
-H
+, [Ir (CO)
2Br
2]
-H
+, [Ir (CO)
2I
4]
-H
+, [Ir (CH
3) I
3(CO)
2]
-H
+, Ir
4(CO)
12, IrCl
33H
2O, Ir
2O
3, IrO
2, iridium acetate, H
2IrCl
6In one or more.Never introduce multiple heteroatoms, reduce I
-Content and raw material sources viewpoint widely set out, and the preferred described iridic compound that contains is H
2IrCl
6
the method according to this invention, wherein, the promotor that contains ruthenium and/or osmium can be the various promotor that contain ruthenium and/or osmium for pure preparing carboxylic acid by carbonylation, contain the salt of ruthenium and/or osmium this promotor comprising that contains ruthenium and/or osmium, the oxide compound that contains ruthenium and/or osmium, contain the title complex of ruthenium and/or osmium etc., the described promotor that contains ruthenium and/or osmium can be dissolved in reaction system, this promotor that contains ruthenium and/or osmium can list but be not limited to following material, for example: ruthenium trichloride, ruthenium chloride (IV), ruthenium bromide (III), ruthenium acetate (III), propionic acid ruthenium (III), ruthenium oxide, pentacarbonyl closes ruthenium, ten dicarbapentaborane close three rutheniums, diiodo-four carbonyls close ruthenium (II), osmium trichloride, perosmic anhydride, ten dicarbapentaborane close three osmiums, diiodo-four carbonyls close one or more in osmium (II).Extensive or the simple viewpoint of synthetic method from raw material sources, the preferred described promotor that contains ruthenium and/or osmium are selected from ruthenium trichloride, osmium trichloride, ruthenium oxide, perosmic anhydride, diiodo-four carbonyls and close ruthenium (II), diiodo-four carbonyls and close one or more in osmium (II).
The method according to this invention, wherein, described halogen catalyst can be various halogen catalysts for pure preparing carboxylic acid by carbonylation, for example, described halogen catalyst is that carbonatoms is the halogenated alkane of 1-3, can for carbonatoms be the chloroparaffin of 1-3, brominated alkanes that carbonatoms is 1-3 and carbonatoms be 1-3 alkane iodide in one or more, be preferably carbonatoms and be one or more in the alkane iodide that the chloroparaffin of 1-3, bromoalkanes hydrocarbon that carbonatoms is 1-3 and carbonatoms be 1-3.In preferred situation, described halogen catalyst is methyl iodide.
The method according to this invention in above-mentioned preferred situation, contains I owing to less using
-Catalyst component, can reduce liquid reaction mixture to the corrosion of reaction unit, reduce the requirement of reaction unit being adopted material; And be reduced to the energy that removes I-and consume.
In the present invention, described organic solvent can be preferably organic carboxyl acid for the various solvents that can be used in carbonylation reaction known in the field, and more preferably carbonatoms is the organic carboxyl acid of 2-5.Because the target product of the carbonylation reaction of methyl acetate is acetic acid, when 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.
In the present invention, described carbonylation reaction condition can be various reaction conditionss known in the field, the dividing potential drop that the preferred described carbonylation reaction condition of the present invention is carbon monoxide is 0.5-10MPa, the temperature of reaction is 140-250 ℃, more preferably, the dividing potential drop that described carbonylation reaction condition is carbon monoxide is 1-5MPa, and 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.Unless specified otherwise, in the following example and Comparative Examples, material used all can be commercially available.
Carbonylation rate described in the present invention represents with the amount of substance of the product acetic acid that the reaction liquid under every liter of room temperature is per hour produced, and unit is mol/ (Lhr).
In embodiment 1-8 and Comparative Examples 1-2, the content of methyl acetate and water is will consume the methyl acetate of 1 mole when consuming 1 mole of CO according to hypothesis and the water of 1 mole is determined.The organic constituent that the upper sheaf space of reactor exists is ignored.
Diiodo-four carbonyls close ruthenium (II) and close three rutheniums and I by ten dicarbapentaborane
2Synthetic and be kept at refrigerator under carbon monoxide atmosphere in stand-by.(this synthetic method is with reference to civilian J.Am.Chem.Soc., 2004,126,2847)
The intermittent reaction that adopts in embodiment 1-8 and Comparative Examples 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 pressure data in gas cylinder by the precision digital tensimeter.
During in embodiment 1-8 and Comparative Examples 1-2, each carbonylation reaction is tested, to contain iridic compound and be dissolved in part water and acetic acid and adding in liquid feeding device, the oxide compound of methyl acetate, methyl iodide, rare earth element and remaining water and acetic acid will be joined in autoclave.The enclosed high pressure still, with the about nitrogen of 3.0MPa, autoclave is carried out pressure testing, then use carbon monoxide (3 * 1.0MPa, " 3 " representative displacement number of times) then nitrogen or the air in displacement autoclave and liquid feeding device and be filled with at last the carbon monoxide of 0.6MPa pass into carbon monoxide to about 2.5MPa and stablized 30 minutes after under the condition of 750 rev/mins of stir speed (S.S.)s, liquid reaction composition being heated to 190 ℃.CO (carbon monoxide converter) gas with 3.0MPa joins the iridic compound that contains that is dissolved in acetic acid and water in liquid injection system in autoclave and begins reaction, to supply raw materials carbon monoxide and 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 by gas cylinder.Disconnection source of the gas, stopped reaction and cooling after carbon monoxide pressure does not descend in finding 5 minutes inner high voltage gas cylinders.
In addition, in embodiment 1-8 and Comparative Examples 1-2, after carbonylation reaction is completed, immediately by spiral coil cooling tube with the reaction soln cool to room temperature, take out 50 milliliters of reacted solution after emptying and put into withstand voltage glass reaction tube, with the carbon monoxide that dissolves in nitrogen replacement solution and finally be pressurized to 0.02MPa, be heated to 130 ℃ and kept 24 hours.Cooling rear observation solution has determined whether that precipitation generates.
Embodiment 1
To contain acetic acid 60g, methyl iodide 12g, methyl acetate 45g, water 7.5g, Ru (CO)
4I
2(1.05g being equivalent to Ru content is 1500ppm), CeO
20.18g the mixture of (being equivalent to Ce content is 1000ppm) joins in 300ml zirconium material autoclave, with acetic acid 18g, water 3.6g and H
2IrCl
60.72g (being equivalent to Ir content 2000ppm) joins in liquid injection system.Pass into the CO of 0.6MPa after pressure testing and slow displaced air, pass into CO to about 2.5MPa after being heated to 190 ℃ under the stirring of 750 rev/mins and stablized 30 minutes, join the catalyst solution in liquid injection system in autoclave and begin reaction with the CO (carbon monoxide converter) gas of 3.0MPa.Contain 20wt%MeOAc and 6.26wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 34.2mol/ (Lhr); Contain 15wt%MeOAc and 5.05wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 24.5mol/ (Lhr); Contain 10wt%MeOAc and 3.87wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 13.4mol/ (Lhr).Disconnection source of the gas, stopped reaction and cooling after carbon monoxide pressure does not descend in finding 5 minutes inner high voltage gas cylinders.Negate liquid sample is afterwards tested, and the selectivity of acetic acid in product is 99.8%.The visual observations reaction tubes is not found deposited phenomenon.
Comparative Examples 1
Carry out the catalysis methyl acetate according to the method for embodiment 1 and prepare acetic acid, different is not add CeO
2Contain 20wt%MeOAc and 6.26wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 17.2mol/ (Lhr); Contain 15wt%MeOAc and 5.05wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 10.7mol/ (Lhr); Contain 10wt%MeOAc and 3.87wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 8.0mol/ (Lhr).Negate liquid sample is afterwards tested, and the selectivity of acetic acid in product is 99.7%.The visual observations reaction tubes has precipitation to produce.
Comparative Examples 2
Carry out the catalysis methyl acetate according to the method for embodiment 1 and prepare acetic acid, different is to replace 0.18g CeO with 0.21g cerous acetate (being equivalent to Ce content is 1000ppm)
2Contain 20wt%MeOAc and 6.26wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 30.1mol/ (Lhr); Contain 15wt%MeOAc and 5.05wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 20.5mol/ (Lhr); Contain 10wt%MeOAc and 3.87wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 12.3mol/ (Lhr).Negate liquid sample is afterwards tested, and the selectivity of acetic acid in product is 99.9%.The visual observations reaction tubes has precipitation to produce.
Embodiment 2
To contain acetic acid 60g, methyl iodide 12g, methyl acetate 45g, water 7.5g, Ru (CO)
4I
2(2.10g being equivalent to Ru content is 3000ppm), CeO
20.36g the mixture of (being equivalent to Ce content is 2000ppm) joins in 300ml zirconium material autoclave, with acetic acid 18g, water 3.6g and H
2IrCl
60.72g (being equivalent to Ir content 2000ppm) joins in liquid injection system.Pass into the CO of 0.6MPa after pressure testing and slow displaced air, pass into CO to about 2.5MPa after being heated to 190 ℃ under the stirring of 750 rev/mins and stablized 30 minutes, join the catalyst solution in liquid injection system in autoclave and begin reaction with the CO (carbon monoxide converter) gas of 3.0MPa.Contain 20wt%MeOAc and 6.26wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 38.7mol/ (Lhr); Contain 15wt%MeOAc and 5.05wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 29.1mol/ (Lhr); Contain 10wt%MeOAc and 3.87wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 16.8mol/ (Lhr).Disconnection source of the gas, stopped reaction and cooling after carbon monoxide pressure does not descend in finding 5 minutes inner high voltage gas cylinders.Negate liquid sample is afterwards tested, and the selectivity of acetic acid in product is 99.8%.The visual observations reaction tubes is not found deposited phenomenon.
Embodiment 3
Carry out the catalysis methyl acetate according to the method for embodiment 1 and prepare acetic acid, different is to use CeO
2(0.09g being equivalent to Ce content is 500ppm), Sm
2O
30.08g (being equivalent to Sm content is 500ppm) replaces 0.18g CeO
2Contain 20wt%MeOAc and 6.26wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 35.6mol/ (Lhr); Contain 15wt%MeOAc and 5.05wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 26.2mol/ (Lhr); Contain 10wt%MeOAc and 3.87wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 14.7mol/ (Lhr).Negate liquid sample is afterwards tested, and the selectivity of acetic acid in product is 99.9%.The visual observations reaction tubes is not found deposited phenomenon.
Embodiment 4
Carry out the catalysis methyl acetate according to the method for embodiment 1 and prepare acetic acid, that different is 0.42g OsCl
33H
2O (being equivalent to Os content is 1500ppm) replaces 1.05g Ru (CO)
4I
2Contain 20wt%MeOAc and 6.26wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 28.4mol/ (Lhr); Contain 15wt%MeOAc and 5.05wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 19.1mol/ (Lhr); Contain 10wt%MeOAc and 3.87wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 11.2mol/ (Lhr).Negate liquid sample is afterwards tested, and the selectivity of acetic acid in product is 99.9%.The visual observations reaction tubes is not found deposited phenomenon.
Embodiment 5
Carry out the catalysis methyl acetate according to the method for embodiment 1 and prepare acetic acid, different is to use 0.17g Pr
6O
11(being equivalent to Pr content is 1000ppm) replaces 0.18g CeO
2Contain 20wt%MeOAc and 6.26wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 32.5mol/ (Lhr); Contain 15wt%MeOAc and 5.05wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 22.8mol/ (Lhr); Contain 10wt%MeOAc and 3.87wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 14.8mol/ (Lhr).Negate liquid sample is afterwards tested, and the selectivity of acetic acid in product is 99.9%.The visual observations reaction tubes is not found deposited phenomenon.
Embodiment 6
Carry out the catalysis methyl acetate according to the method for embodiment 1 and prepare acetic acid, different is to use 0.18g Nd
2O
3(being equivalent to Nd content is 1000ppm) replaces 0.18g CeO
2Contain 20wt%MeOAc and 6.26wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 36.4mol/ (Lhr); Contain 15wt%MeOAc and 5.05wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 29.9mol/ (Lhr); Contain 10wt%MeOAc and 3.87wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 18.4mol/ (Lhr).Negate liquid sample is afterwards tested, and the selectivity of acetic acid in product is 99.7%.The visual observations reaction tubes is not found deposited phenomenon.
Embodiment 7
Carry out the catalysis methyl acetate according to the method for embodiment 1 and prepare acetic acid, different is to use 0.17g Sm
2O
3(being equivalent to Sm content is 1000ppm) replaces 0.18g CeO
2Contain 20wt%MeOAc and 6.26wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 36.4mol/ (Lhr); Contain 15wt%MeOAc and 5.05wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 29.9mol/ (Lhr); Contain 10wt%MeOAc and 3.87wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 15.5mol/ (Lhr).Negate liquid sample is afterwards tested, and the selectivity of acetic acid in product is 99.8%.The visual observations reaction tubes is not found deposited phenomenon.
Embodiment 8
Carry out the catalysis methyl acetate according to the method for embodiment 1 and prepare acetic acid, different is to use 0.70g La
2O
3(being equivalent to La content is 2000ppm) replaces 0.18g CeO
2Contain 20wt%MeOAc and 6.26wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 27.9mol/ (Lhr); Contain 15wt%MeOAc and 5.05wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 20.1mol/ (Lhr); Contain 10wt%MeOAc and 3.87wt%H in corresponding to liquid reaction mixture
2During O, recording carbonylation rate is 11.7mol/ (Lhr).Negate liquid sample is afterwards tested, and the selectivity of acetic acid in product is 99.9%.The visual observations reaction tubes is not found deposited phenomenon.
Data by embodiment 1-8 and Comparative Examples 1 compare, and can find out the oxide compound of iridium catalyst systems interpolation rare earth element, can significantly improve carbonylation rate.Data by embodiment 1 and Comparative Examples 2 compare, and than add the organic salt of rare earth element in iridium catalyst systems, can find out that the oxide compound that adds rare earth element can improve the stability of iridium catalyst systems.Data by embodiment 3 and embodiment 1 compare, and can find out that the oxide compound that adds two or more rare earth elements can further improve carbonylation rate.Due to the good stability of the iridium catalyst systems of embodiment 1-8, thereby after through the aftertreatment separating acetic acid, this iridium catalyst systems can also be recycled for carbonylation reaction.
Claims (9)
1. a carbonylation reaction prepares the method for acetic acid, it is characterized in that, the method is included under water, iridium catalyst systems and organic solvent existence, methyl alcohol and/or methyl acetate are contacted with carbon monoxide, and described iridium catalyst systems contains iridic compound, halogen catalyst, contains the promotor of ruthenium and/or osmium and the oxide compound of rare earth element.
2. method according to claim 1, wherein, take the gross weight of iridium catalyst systems, water, organic solvent and methyl acetate as benchmark, the content of described iridium catalyst systems is the 3-20 % by weight, the content of described water is the 0.1-15 % by weight, the content of organic solvent is the 30-80 % by weight, and the content of methyl acetate is the 1-40 % by weight; Preferably, take the gross weight of iridium catalyst systems, water, organic solvent and methyl acetate as benchmark, the content of described iridium catalyst systems is the 5-15 % by weight, and the content of described water is the 0.5-10 % by weight, the content of organic solvent is the 50-70 % by weight, and the content of methyl acetate is the 5-35 % by weight.
3. method according to claim 2, wherein, in described iridium catalyst systems, in mole, contain the iridium in iridic compound: the halogen in halogen catalyst: the ruthenium in promotor and/or osmium: rare earth element=1: 10-200: 0.2-5: 0.2-5; Preferably, contain iridium in iridic compound: the halogen in halogen catalyst: the ruthenium in promotor and/or osmium: rare earth element=1: 30-100: 0.5-3: 0.5-2.5.
4. method according to claim 3, wherein, the oxide compound of described rare earth element is selected from one or more in lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide, preferably, the oxide compound of described rare earth element is selected from two or more in lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide.
5. the described method of any one according to claim 1-4, wherein, the described iridic compound that contains is H
2IrCl
6
6. the described method of any one according to claim 1-4, wherein, the promotor that contains ruthenium and/or osmium is selected from ruthenium trichloride, osmium trichloride, ruthenium oxide, perosmic anhydride, diiodo-four carbonyls and closes ruthenium, diiodo-four carbonyls and close one or more in osmium.
7. the described method of any one according to claim 1-4, wherein, described halogen catalyst is that carbonatoms is the halogenated alkane of 1-3, preferably, described halogen catalyst is methyl iodide.
8. method according to claim 1 and 2, wherein, described organic solvent is acetic acid.
9. method according to claim 1 and 2, wherein, the dividing potential drop that described carbonylation reaction condition is carbon monoxide is 0.5-10MPa, the temperature of reaction is 140-250 ℃, preferably, the dividing potential drop that described carbonylation reaction condition is carbon monoxide is 1-5MPa, and the temperature of reaction is 170-210 ℃.
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