CN103084214B - Iridium catalyst system - Google Patents
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- CN103084214B CN103084214B CN201110341568.6A CN201110341568A CN103084214B CN 103084214 B CN103084214 B CN 103084214B CN 201110341568 A CN201110341568 A CN 201110341568A CN 103084214 B CN103084214 B CN 103084214B
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides an iridium catalyst system comprising an iridium-containing compound, a halogen cocatalyst, an accelerant containing ruthenium and/or osmium, and rare earth oxide. According to the iridium catalyst system, the rare earth oxide is added into the iridium catalyst system, such that methanol carbonylation rate is improved, catalyst system stability is good, and the catalyst system can be recycled.
Description
Technical field
The present invention relates to a kind of iridium catalyst systems.
Background technology
Acetic acid, as a kind of important basic organic chemical raw material, is widely used in the multiple fields such as fiber, plasticizer, paint, adhesive, copolymer resins, is production capacity increase recent years a kind of chemical products faster.The main method of producing in the world acetic acid at present has acetaldehyde oxidation, butane and light oil oxidizing process and methanol carbonylation.Wherein methanol carbonylation is produced the more than 70% of acetic acid Yi Zhan world 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.As far back as Monsanto company, carrying out rhodium is carbonylating catalyst exploitation time, to iridium, is that carbonylating catalyst has launched research.It is carbonylating catalyst that researcher discloses a kind of iridium in US3772380.The complex of halide, carbonylic halide or other iridium of employing iridium is as catalyst; Br
2, I
2or other compounds are as promoter, are 50-300 ℃ in reaction temperature, carry out methanol carbonylation under pressure 10-1000psi, reaction rate is starkly lower than rhodium catalytic system, so industrialization methanol carbonylation process has at that time adopted rhodium catalytic system.
But rhodium exists obvious shortcoming as the activated centre of catalyst system, 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 irreversibility inactivation.The effective ways of head it off comprise raising system water content and add stabilizing agent, but the increase of water content means the raising of energy consumption, unfavorable for producing.Current classic catalyst stabilizer is iodate alkali 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 operating cost.Iridium catalyst systems is because the dissolubility 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 researchers' attention, and the reaction rate that improves iridium and be carbonylation of methanol catalyst is the emphasis of research.
A kind of iridium and platinum in CN1325374A, have been announced as the method for preparing acetic acid and/or methyl acetate of catalyst.Researcher finds to add platinum can increase the throughput rate of acetic acid in the catalyst system that iridium or iridium and rhodium is matrix to take, and the metal total mole number of use still remains unchanged simultaneously.Even when reaction system reduced water content, platinum add still can sizable reinforcement iridium stability.But the bullion content needing in the method is higher, catalyst cost is large.
The method that adopts ruthenium and osmium catalysis methanol carbonylation to produce acetic acid is also known, in GB1234641 and GB1234642, disclose a kind of compound that is selected from palladium, platinum, iridium, ruthenium or osmium as catalyst, helping of halogen or halogen compounds, under catalysis, carried out alcohol, halides or ether etc. and as raw material, produce the method for carboxylic acid or its ester class.GB20209409A discloses a kind of compound of ruthenium or ruthenium that adopts as catalyst, halogen-containing, especially under the promoting catalysis of iodine, by alcohol and reaction of carbon monoxide, prepares carboxylic acid and corresponding ester thereof.
British Petroleum Company (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 one in iridium catalyst, methyl iodide and ruthenium or osmium.Thereby the existence of ruthenium can reduce the volatility of iridium catalyst and improve catalyst stability energy.In addition, the use of ruthenium or osmium can improve carbonylation of methanol speed, and reaction can be carried out under lower water content, is conducive to reduce the generation of accessory substance.CN1681764A discloses a kind of method that acetic acid is prepared in improved carbonylation of methanol.The caltalyst using in the method is iridium, comprises at least one co-catalyst that is selected from ruthenium, osmium and rhenium and at least one is selected from the stabilizing agent of indium, cadmium, mercury, gallium and zinc.Carbonylation rate has been accelerated in adding of co-catalyst, but uses the co-catalyst of higher concentration may make catalyst system produce precipitation and inactivation.Can improve the adding of stabilizing agent catalyst stability energy and carbonylation rate constant or increase.In order to improve the carbonylation rate of iridium catalyst systems, researcher has carried out a large amount of research, and CN1823031A discloses a kind of methyl alcohol and/or its reactive derivative is prepared the Catalyst And Method of acetic acid by carbonylation.This catalyst system comprises a kind of iridium carbonylating catalyst, methyl iodide co-catalyst, ruthenium, osmium, rhenium, indium, cadmium, mercury, gallium and zinc at least one and at least one can be the non-halogen acids promoter of oxyacid, super acid and/or heteropoly acid.Promoter can be improved the carbonylation rate of iridium catalyst systems, but may produce potential adverse effect to consersion 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 catalyst, alkyl halide are that co-catalyst, ruthenium are promoter that the method has adopted iridium, also needs in addition to comprise to be a kind ofly selected from alkaline metal iodide, alkaline earth metal iodide, can to produce I in liquid reaction mixture
-metal complex, can produce I
-salt or its mixture as kicker.
In prior art, use iridium catalyst systems catalysis methanol carbonylation to prepare acetic acid, when carbon monoxide content is low while for example reacting complete or after completion of the reaction during flash distillation acetic acid, because iridium catalyst systems becomes unstable, make to occur precipitating in liquid reaction mixture, this liquid reaction mixture cannot recycling, causes production cost to improve.The present inventor is surprised to find that, the oxide to adding rare earth metal in iridium catalyst systems, can make aforesaid liquid reactant mixture in the situation that carbon monoxide content is low, there will not be precipitation, thereby can recycle.
Iridium catalyst systems provided by the invention, wherein, this catalyst system contains containing iridic compound, halogen catalyst, contains ruthenium and/or the promoter of osmium and the oxide of rare earth element.
Adopt iridium catalyst systems provided by the invention, owing to having added the oxide of rare earth element in iridium catalyst systems, so improved carbonylation of methanol speed, and do not occurred precipitation in liquid reaction mixture, catalyst system good stability has been described, can recycles.For example, in embodiment 1, add cerium oxide, in liquid reaction mixture, do not occurred precipitation; And all there is precipitation in liquid reaction mixture in the comparative example 2 of not adding the comparative example 1 of cerium oxide and having added cerous acetate; And the carbonylation rate of embodiment 1 is apparently higher than comparative example 1.
Summary of the invention
The present invention is directed to the problems referred to above, a kind of good stability of catalyst system is provided and can improves the iridium catalyst systems of carbonylation of methanol speed.
The specific embodiment
The invention provides a kind of iridium catalyst systems, wherein, this catalyst system contains containing iridic compound, halogen catalyst, contains ruthenium and/or the promoter of osmium and the oxide of rare earth element.
According to iridium catalyst systems of the present invention, wherein, in described iridium catalyst systems, in mole, containing the iridium in iridic compound: the halogen in halogen catalyst: the ruthenium in promoter 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, containing the iridium in iridic compound: the halogen in halogen catalyst: the ruthenium in promoter and/or osmium: rare earth element=1: 30-100: 0.5-3: 0.5-2.5.Within the scope of aforementioned proportion, iridium catalyst systems of the present invention can improve the reaction rate of being prepared corresponding carboxylic acid by alcohol carbonylation, and described iridium catalyst systems good stability, in last handling process (as low in carbon monoxide content in flash distillation acetic acid, this process), do not produce precipitation, can recycle, at this, the present invention is so that be example with the reaction that above-mentioned iridium catalyst systems catalysis methanol and/or methyl acetate are prepared acetic acid, described in result, iridium catalyst systems has improved methanol carbonylation speed effectively, and this iridium catalyst systems good stability.At this, need explanation, when the oxide that simultaneously contains ruthenium and osmium, rare earth element when promoter is multiple, with the total mole number of ruthenium and osmium, the total mole number of rare earth element calculates aforementioned proportion.
According to iridium catalyst systems of the present invention, wherein, the oxide of described rare earth element can be one or more of the oxide of the rare earth element for catalyst.In the preferred case, the oxide of described rare earth element is selected from one or more in lanthana, cerium oxide, praseodymium oxide, neodymia, samarium oxide.More preferably, the oxide of described rare earth element is selected from two or more in lanthana, cerium oxide, praseodymium oxide, neodymia, samarium oxide.Use the oxide of rare earth element can make iridium catalyst systems stability improve, especially when using the oxide of two or more rare earth elements can further improve carbonylation rate.
According to iridium catalyst systems of the present invention, wherein, described can be the various iridic compounds that contain for catalytic alcohol preparing carboxylic acid by carbonylation containing iridic compound, should comprise the oxide of iridium salt, iridium, the complex of iridium etc. containing iridic compound, the described iridic compound that contains can be dissolved in reaction system, should can list but be not limited to following material containing iridic compound, 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 hetero atom, reduce I
-content and raw material sources widely viewpoint set out, and preferably described is H containing iridic compound
2irCl
6.
According to iridium catalyst systems of the present invention, wherein, promoter containing ruthenium and/or osmium can be the various promoter containing ruthenium and/or osmium for alcohol preparing carboxylic acid by carbonylation, should comprise containing the promoter of ruthenium and/or osmium the salt containing ruthenium and/or osmium, oxide containing ruthenium and/or osmium, contain the complex of ruthenium and/or osmium etc., the described promoter containing ruthenium and/or osmium can be dissolved in reaction system, should can list but be not limited to following material containing the promoter of ruthenium and/or osmium, for example: ruthenium trichloride, ruthenic 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, osmium tetroxide, 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, preferably the described promoter containing ruthenium and/or osmium is selected from ruthenium trichloride, osmium trichloride, ruthenium-oxide, osmium tetroxide, diiodo-four carbonyls and closes ruthenium (II), diiodo-four carbonyls and close one or more in osmium (II).
According to iridium catalyst systems of the present invention, wherein, described halogen catalyst can be the various halogen catalysts for alcohol preparing carboxylic acid by carbonylation, for example, described halogen catalyst is that carbon number is the halogenated alkane of 1-3, can be one or more in the carbon number chloralkane that is 1-3, brominated alkanes that carbon number is 1-3 and the carbon number alkane iodide that is 1-3, be preferably carbon number and be one or more in the alkane iodide that a chloralkane of 1-3, bromoalkanes hydrocarbon that carbon number is 1-3 and carbon number are 1-3.In the preferred case, described halogen catalyst is iodomethane.
Iridium catalyst systems of the present invention is for being prepared the process of acetic acid by methyl alcohol and/or acetate carbonyl, usually, the gross weight of iridium catalyst systems, water, organic solvent and methyl acetate of take is benchmark, the content of described iridium catalyst systems can be 3-20 % by weight, the content of described water can be 0.1-15 % by weight, the content of organic solvent can be 30-80 % by weight, and the content of methyl acetate can be 1-40 % by weight.
According to iridium catalyst systems of the present invention, in above-mentioned preferred situation, owing to less using and containing I
-catalytic component, can reduce the corrosion of liquid reaction mixture to reaction unit, reduce the requirement that reaction unit is adopted to material; And be reduced to and remove I
-and the energy consuming.
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 example, material used all can be commercially available.
The amount of substance of the product acetic acid that the carbonylation rate described in the present invention is produced with the reaction liquid under every liter of room temperature per hour represents, unit is mol/ (Lhr).
In embodiment 1-8 and comparative example 1-2, the content of methyl acetate and water is when consuming 1 mole of CO according to hypothesis, will consume the methyl acetate of 1 mole and the water of 1 mole is determined.The organic component 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 under carbon monoxide atmosphere, be kept at refrigerator in stand-by.(this synthetic method reference literature J.Am.Chem.Soc., 2004,126,2847)
The intermittent reaction adopting in embodiment 1-8 and comparative example 1-2 all carries out in a 300ml zirconium material autoclave with magnetic stirring apparatus and liquid feeding device, with a gas cylinder, by pressure-reducing valve, to reactor, provide stable carbon monoxide raw material, make the gas pressure in autoclave keep constant, by precision digital Pressure gauge, read the pressure data in gas cylinder.
During in embodiment 1-8 and comparative example 1-2, each carbonylation is tested, to be dissolved in part water and acetic acid and adding in liquid feeding device containing iridic compound, the oxide of methyl acetate, iodomethane, rare earth element and remaining water and acetic acid will be joined in autoclave.Enclosed high pressure still, with the nitrogen of about 3.0MPa, autoclave is carried out to pressure testing, then use carbon monoxide (3 * 1.0MPa, " 3 " representative displacement number of times) nitrogen or the air in displacement autoclave and liquid feeding device be finally filled with the carbon monoxide of 0.6MPa, passes into carbon monoxide to about 2.5MPa and stablizes 30 minutes after then liquid reaction composition being heated to 190 ℃ under the condition of 750 revs/min of stir speed (S.S.)s.With the CO gas of 3.0MPa, the iridic compound that contains that is dissolved in acetic acid and water in liquid injection system is joined in autoclave and starts reaction, 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.In finding 5 minutes inner high voltage gas cylinders, carbon monoxide pressure does not disconnect source of the gas after not declining, and stops reacting and lowering the temperature.
In addition, in embodiment 1-8 and comparative example 1-2, after carbonylation completes, immediately by cooling coil by reaction solution cool to room temperature, after emptying, take out 50 milliliters of reacted solution and put into withstand voltage glass reaction tube, with the carbon monoxide dissolving in nitrogen replacement solution be finally pressurized to 0.02MPa, be heated to 130 ℃ and keep 24 hours.Cooling rear observation solution has determined whether that precipitation generates.
Embodiment 1
To contain acetic acid 60g, iodomethane 12g, methyl acetate 45g, water 7.5g, Ru (CO)
4i
21.05g (being equivalent to Ru content is 1500ppm), CeO
2the mixture of 0.18g (being equivalent to Ce content is 1000ppm) joins in 300ml zirconium material autoclave, by acetic acid 18g, water 3.6g and H
2irCl
60.72g (being equivalent to Ir content 2000ppm) joins in liquid injection system.After pressure testing slowly displaced air, pass into the CO of 0.6MPa, be heated to 190 ℃ under the stirring of 750 revs/min after, pass into CO to about 2.5MPa and stablize 30 minutes, with the CO gas of 3.0MPa, the catalyst solution in liquid injection system joined in autoclave and start reaction.In corresponding to liquid reaction mixture, contain 20wt%MeOAc and 6.26wt%H
2during O, recording carbonylation rate is 34.2mol/ (Lhr); In corresponding to liquid reaction mixture, contain 15wt%MeOAc and 5.05wt%H
2during O, recording carbonylation rate is 24.5mol/ (Lhr); In corresponding to liquid reaction mixture, contain 10wt%MeOAc and 3.87wt%H
2during O, recording carbonylation rate is 13.4mol/ (Lhr).In finding 5 minutes inner high voltage gas cylinders, carbon monoxide pressure does not disconnect source of the gas after not declining, and stops reacting and lowering the temperature.Negate afterwards fluid sample is tested, and acetic acid is selectively 99.8% in product.Visual observations reaction tube, does not find deposited phenomenon.
Comparative example 1
According to the method for embodiment 1, carry out catalysis methyl acetate and prepare acetic acid, different is not add CeO
2.In corresponding to liquid reaction mixture, contain 20wt%MeOAc and 6.26wt%H
2during O, recording carbonylation rate is 17.2mol/ (Lhr); In corresponding to liquid reaction mixture, contain 15wt%MeOAc and 5.05wt%H
2during O, recording carbonylation rate is 10.7mol/ (Lhr); In corresponding to liquid reaction mixture, contain 10wt%MeOAc and 3.87wt%H
2during O, recording carbonylation rate is 8.0mol/ (Lhr).Negate afterwards fluid sample is tested, and acetic acid is selectively 99.7% in product.Visual observations reaction tube, has precipitation to produce.
Comparative example 2
According to the method for embodiment 1, carry out catalysis methyl acetate and prepare acetic acid, different is to replace 0.18g CeO with 0.21g cerous acetate (being equivalent to Ce content is 1000ppm)
2.In corresponding to liquid reaction mixture, contain 20wt%MeOAc and 6.26wt%H
2during O, recording carbonylation rate is 30.1mol/ (Lhr); In corresponding to liquid reaction mixture, contain 15wt%MeOAc and 5.05wt%H
2during O, recording carbonylation rate is 20.5mol/ (Lhr); In corresponding to liquid reaction mixture, contain 10wt%MeOAc and 3.87wt%H
2during O, recording carbonylation rate is 12.3mol/ (Lhr).Negate afterwards fluid sample is tested, and acetic acid is selectively 99.9% in product.Visual observations reaction tube, has precipitation to produce.
Embodiment 2
To contain acetic acid 60g, iodomethane 12g, methyl acetate 45g, water 7.5g, Ru (CO)
4i
22.10g (being equivalent to Ru content is 3000ppm), CeO
2the mixture of 0.36g (being equivalent to Ce content is 2000ppm) joins in 300ml zirconium material autoclave, by acetic acid 18g, water 3.6g and H
2irCl
60.72g (being equivalent to Ir content 2000ppm) joins in liquid injection system.After pressure testing slowly displaced air, pass into the CO of 0.6MPa, be heated to 190 ℃ under the stirring of 750 revs/min after, pass into CO to about 2.5MPa and stablize 30 minutes, with the CO gas of 3.0MPa, the catalyst solution in liquid injection system joined in autoclave and start reaction.In corresponding to liquid reaction mixture, contain 20wt%MeOAc and 6.26wt%H
2during O, recording carbonylation rate is 38.7mol/ (Lhr); In corresponding to liquid reaction mixture, contain 15wt%MeOAc and 5.05wt%H
2during O, recording carbonylation rate is 29.1mol/ (Lhr); In corresponding to liquid reaction mixture, contain 10wt%MeOAc and 3.87wt%H
2during O, recording carbonylation rate is 16.8mol/ (Lhr).In finding 5 minutes inner high voltage gas cylinders, carbon monoxide pressure does not disconnect source of the gas after not declining, and stops reacting and lowering the temperature.Negate afterwards fluid sample is tested, and acetic acid is selectively 99.8% in product.Visual observations reaction tube, does not find deposited phenomenon.
Embodiment 3
According to the method for embodiment 1, carry out catalysis methyl acetate and prepare acetic acid, different is to use CeO
20.09g (being equivalent to Ce content is 500ppm), Sm
2o
30.08g (being equivalent to Sm content is 500ppm) replaces 0.18g CeO
2.In corresponding to liquid reaction mixture, contain 20wt%MeOAc and 6.26wt%H
2during O, recording carbonylation rate is 35.6mol/ (Lhr); In corresponding to liquid reaction mixture, contain 15wt%MeOAc and 5.05wt%H
2during O, recording carbonylation rate is 26.2mol/ (Lhr); In corresponding to liquid reaction mixture, contain 10wt%MeOAc and 3.87wt%H
2during O, recording carbonylation rate is 14.7mol/ (Lhr).Negate afterwards fluid sample is tested, and acetic acid is selectively 99.9% in product.Visual observations reaction tube, does not find deposited phenomenon.
Embodiment 4
According to the method for embodiment 1, carry out catalysis methyl acetate 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
2.In corresponding to liquid reaction mixture, contain 20wt%MeOAc and 6.26wt%H
2during O, recording carbonylation rate is 28.4mol/ (Lhr); In corresponding to liquid reaction mixture, contain 15wt%MeOAc and 5.05wt%H
2during O, recording carbonylation rate is 19.1mol/ (Lhr); In corresponding to liquid reaction mixture, contain 10wt%MeOAc and 3.87wt%H
2during O, recording carbonylation rate is 11.2mol/ (Lhr).Negate afterwards fluid sample is tested, and acetic acid is selectively 99.9% in product.Visual observations reaction tube, does not find deposited phenomenon.
Embodiment 5
According to the method for embodiment 1, carry out catalysis methyl acetate and prepare acetic acid, different is to use 0.17g Pr
6o
11(being equivalent to Pr content is 1000ppm) replaces 0.18g CeO
2.In corresponding to liquid reaction mixture, contain 20wt%MeOAc and 6.26wt%H
2during O, recording carbonylation rate is 32.5mol/ (Lhr); In corresponding to liquid reaction mixture, contain 15wt%MeOAc and 5.05wt%H
2during O, recording carbonylation rate is 22.8mol/ (Lhr); In corresponding to liquid reaction mixture, contain 10wt%MeOAc and 3.87wt%H
2during O, recording carbonylation rate is 14.8mol/ (Lhr).Negate afterwards fluid sample is tested, and acetic acid is selectively 99.9% in product.Visual observations reaction tube, does not find deposited phenomenon.
Embodiment 6
According to the method for embodiment 1, carry out catalysis methyl acetate and prepare acetic acid, different is to use 0.18gNd
2o
3(being equivalent to Nd content is 1000ppm) replaces 0.18g CeO
2.In corresponding to liquid reaction mixture, contain 20wt%MeOAc and 6.26wt%H
2during O, recording carbonylation rate is 36.4mol/ (Lhr); In corresponding to liquid reaction mixture, contain 15wt%MeOAc and 5.05wt%H
2during O, recording carbonylation rate is 29.9mol/ (Lhr); In corresponding to liquid reaction mixture, contain 10wt%MeOAc and 3.87wt%H
2during O, recording carbonylation rate is 18.4mol/ (Lhr).Negate afterwards fluid sample is tested, and acetic acid is selectively 99.7% in product.Visual observations reaction tube, does not find deposited phenomenon.
Embodiment 7
According to the method for embodiment 1, carry out catalysis methyl acetate and prepare acetic acid, different is to use 0.17g Sm
2o
3(being equivalent to Sm content is 1000ppm) replaces 0.18g CeO
2.In corresponding to liquid reaction mixture, contain 20wt%MeOAc and 6.26wt%H
2during O, recording carbonylation rate is 36.4mol/ (Lhr); In corresponding to liquid reaction mixture, contain 15wt%MeOAc and 5.05wt%H
2during O, recording carbonylation rate is 29.9mol/ (Lhr); In corresponding to liquid reaction mixture, contain 10wt%MeOAc and 3.87wt%H
2during O, recording carbonylation rate is 15.5mol/ (Lhr).Negate afterwards fluid sample is tested, and acetic acid is selectively 99.8% in product.Visual observations reaction tube, does not find deposited phenomenon.
Embodiment 8
According to the method for embodiment 1, carry out catalysis methyl acetate and prepare acetic acid, different is to use 0.70gLa
2o
3(being equivalent to La content is 2000ppm) replaces 0.18g CeO
2.In corresponding to liquid reaction mixture, contain 20wt%MeOAc and 6.26wt%H
2during O, recording carbonylation rate is 27.9mol/ (Lhr); In corresponding to liquid reaction mixture, contain 15wt%MeOAc and 5.05wt%H
2during O, recording carbonylation rate is 20.1mol/ (Lhr); In corresponding to liquid reaction mixture, contain 10wt%MeOAc and 3.87wt%H
2during O, recording carbonylation rate is 11.7mol/ (Lhr).Negate afterwards fluid sample is tested, and acetic acid is selectively 99.9% in product.Visual observations reaction tube, does not find deposited phenomenon.
By the data comparison of embodiment 1-8 and comparative example 1, can find out the oxide of iridium catalyst systems interpolation rare earth element, can significantly improve carbonylation rate.By the data comparison of embodiment 1 and comparative example 2, than the organic salt that adds rare earth element in iridium catalyst systems, can find out that the oxide of interpolation rare earth element can improve the stability of iridium catalyst systems.By the data comparison of embodiment 3 and embodiment 1, can find out that the oxide that adds two or more rare earth elements can further improve carbonylation rate.
Claims (7)
1. an iridium catalyst systems, is characterized in that, this caltalyst is containing iridic compound, halogen catalyst, contains ruthenium and/or the promoter of osmium and the oxide of rare earth element; In described iridium catalyst systems, in mole, containing the iridium in iridic compound: the halogen in halogen catalyst: the ruthenium in promoter and/or osmium: rare earth element=1:10-200:0.2-5:0.2-5; Described halogen catalyst is that carbon number is the halogenated alkane of 1-3.
2. iridium catalyst systems according to claim 1, wherein, in described iridium catalyst systems, in mole, containing the iridium in iridic compound: the halogen in halogen catalyst: the ruthenium in promoter and/or osmium: rare earth element=1:30-100:0.5-3:0.5-2.5.
3. iridium catalyst systems according to claim 1 and 2, wherein, the oxide of described rare earth element is selected from one or more in lanthana, cerium oxide, praseodymium oxide, neodymia, samarium oxide.
4. iridium catalyst systems according to claim 3, wherein, the oxide of described rare earth element is selected from two or more in lanthana, cerium oxide, praseodymium oxide, neodymia, samarium oxide.
5. iridium catalyst systems according to claim 1 and 2, wherein, described is H containing iridic compound
2irCl
6.
6. iridium catalyst systems according to claim 1 and 2, wherein, is selected from ruthenium trichloride, osmium trichloride, ruthenium-oxide, osmium tetroxide, diiodo-four carbonyls containing the promoter of ruthenium and/or osmium and closes ruthenium, diiodo-four carbonyls and close one or more in osmium.
7. iridium catalyst systems according to claim 1, wherein, described halogen catalyst is iodomethane.
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| US3772380A (en) * | 1970-03-12 | 1973-11-13 | Monsanto Co | Production of carboxylic acids and esters |
| CN1107460A (en) * | 1993-09-10 | 1995-08-30 | 英国石油化学品有限公司 | Process for the production of acetic acid |
| CN1334790A (en) * | 1999-02-16 | 2002-02-06 | 伊斯曼化学公司 | Iridium catalyst for carbonylation of lower aliphatic alcohols |
| CN1334789A (en) * | 1999-02-16 | 2002-02-06 | 伊斯曼化学公司 | Method for carbonylation of lower aliphatic alcohols |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772380A (en) * | 1970-03-12 | 1973-11-13 | Monsanto Co | Production of carboxylic acids and esters |
| CN1107460A (en) * | 1993-09-10 | 1995-08-30 | 英国石油化学品有限公司 | Process for the production of acetic acid |
| CN1210760A (en) * | 1993-09-10 | 1999-03-17 | 英国石油化学品有限公司 | Catalyst system used in process for production of acetic acid |
| CN1334790A (en) * | 1999-02-16 | 2002-02-06 | 伊斯曼化学公司 | Iridium catalyst for carbonylation of lower aliphatic alcohols |
| CN1334789A (en) * | 1999-02-16 | 2002-02-06 | 伊斯曼化学公司 | Method for carbonylation of lower aliphatic alcohols |
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