CN103721751A - Catalyst used for preparing acetate by carbonylation - Google Patents
Catalyst used for preparing acetate by carbonylation Download PDFInfo
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- CN103721751A CN103721751A CN201210384747.2A CN201210384747A CN103721751A CN 103721751 A CN103721751 A CN 103721751A CN 201210384747 A CN201210384747 A CN 201210384747A CN 103721751 A CN103721751 A CN 103721751A
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- iridium
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Abstract
A disclosed catalyst used for preparing acetate by carbonylation comprises an iridium-containing compound, a halogen-containing cocatalyst, a promoter and a manganese-containing compound, wherein the promoter is selected from ruthenium-containing compounds and osmium-containing compounds. Due to the fact that the iridium catalyst comprises manganese, by applying the catalyst provided by the invention to prepare acetate by carbonylation, the catalyst activity and the selectivity are relatively high, and also in subsequent flash evaporation and circulation steps, no precipitate is easy to generate even the content of carbon monoxide is low; and the catalyst is high in stability, so that the service life of the catalyst is prolonged.
Description
Technical field
The present invention relates to a kind of catalyst, specifically, relate to a kind of carbonylation acetic acid catalyst processed.
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.
In CN1325374A, announced a kind of iridium and the platinum method of preparing acetic acid and/or methyl acetate as catalyst.Researcher finds to add platinum to the throughput rate that can increase acetic acid take iridium or iridium and rhodium in the catalyst system of matrix, 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 produce as raw material 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 and be 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 are prepared acetic acid Catalyst And Method 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 that one is selected from alkaline metal iodide, alkaline earth metal iodide, can produces I in liquid reaction mixture
-metal complex, can produce I
-salt or its mixture as kicker.
But, using iridium catalyst systems catalysis methanol carbonylation to prepare in the prior art of acetic acid, when carbon monoxide content is low, because iridium catalyst systems becomes unstable, make to occur precipitating in liquid reaction mixture; In addition, in treatment process after carbonylation, for separating catalyst need to carry out flash distillation by liquid reaction mixture, due to the existence of a large amount of co-catalysts, promoter, and carbon monoxide pressure of tension now significantly reduces, the flash stage of separating catalyst and catalyst circulation are returned in the pipeline of reactor can relatively large appearance precipitation and cause catalysqt deactivation, causes production cost to improve.
Summary of the invention
For deficiency of the prior art, the invention provides a kind of catalyst, it is for carbonylation acetic acid processed, not only there is higher carbonylation rate and selective, and can make at flash distillation or carbon monoxide content low in the situation that, also there will not be precipitation, the extending catalyst inactivation time, improved catalyst stability and life-span.
According to an aspect of the present invention, provide a kind of carbonylation acetic acid catalyst processed, it comprises: contain iridic compound, halogen-containing co-catalyst, promoter and contain manganese compound, wherein said promoter is selected from containing ruthenium compound with containing osmium compound.
In above-mentioned catalyst, in described catalyst, containing iridic compound, promoter and the mass ratio containing manganese compound, with the metallic element/manganese in iridium/promoter, count 1:0.2-5:0.2-5.Preferably, in described catalyst, containing iridic compound, promoter and the mass ratio containing manganese compound, with the metallic element/manganese in iridium/promoter, count 1:0.5-2:0.5-2.Within the scope of aforementioned proportion, the amplitude that catalyst can improve carbonylation rate is large, and described iridium catalyst systems stability is better.
In above-mentioned catalyst, the described manganese compound that contains is selected from manganese salt, Mn oxide and manganese complex.The described manganese compound that contains can be dissolved in reaction system, should can include, but are not limited to following material containing manganese compound, for example: MnCl
2xH
2o, MnBr
2xH
2o, MnI
2xH
2o, Mn
2(CO)
10, MnSO
4, MnSxH
2o, MnS, MnCO
3, Mn
3(PO
4)
2, KMnO4, K
2mnO
4, K
2[MnF
6], Mn
2o
7.
In above-mentioned catalyst, described can be the various iridic compounds that contain for catalytic alcohol preparing carboxylic acid by carbonylation containing iridic compound, as this is selected from iridium salt, iridium oxide and 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.
In above-mentioned catalyst, described promoter can be the various promoter containing ruthenium and/or osmium for alcohol preparing carboxylic acid by carbonylation, comprises salt, oxide, complex etc.Described promoter can be dissolved in reaction system.Described promoter can include, but are not limited to following material, for example: ruthenium trichloride, ruthenic chloride (IV), ruthenium bromide (III), ruthenium acetate (III), propionic acid ruthenium (III), pentacarbonyl close ruthenium, ten dicarbapentaborane and close three rutheniums, diiodo-four carbonyls and close ruthenium (II), osmium trichloride, osmium tetroxide, ten dicarbapentaborane and close three osmiums, diiodo-four carbonyls and close one or more in osmium (II).Extensive or the simple viewpoint of synthetic method from raw material sources, preferred described promoter is selected from ruthenium trichloride, osmium trichloride, ruthenium-oxide, osmium tetroxide, diiodo-four carbonyls close ruthenium and diiodo-four carbonyls close ruthenium.It is that diiodo-four carbonyls close ruthenium (II) that the carbonyl of diiodo-four described in the present invention closes ruthenium, and it is that diiodo-four carbonyls close osmium (II) that described diiodo-four carbonyls close ruthenium.
In above-mentioned catalyst, described halogen-containing co-catalyst is the various halogen catalysts for alcohol preparing carboxylic acid by carbonylation, its consumption is the known consumption of those skilled in the art, as itself and the mol ratio containing iridic compound can be 10 ~ 200:1 in halogen/iridium.In one embodiment, the halogenated alkane that described halogen-containing co-catalyst is C1 ~ C3; In the preferred case, described halogen catalyst is iodomethane.
According to another aspect of the present invention, provide the method for a kind of carbonylation acetic acid processed, it comprises that methyl alcohol and/or carbinol derivatives react with carbon monoxide under the existence of above-mentioned catalyst.
In said method, described carbinol derivatives is preferably methyl acetate.
In an embodiment of said method, described reaction is carried out in solvent, the preferred acetic acid of described solvent.
According to catalyst provided by the invention, in iridium catalyst, comprise manganese element, for carbonylation, prepare acetic acid, not only there is higher catalyst activity and selectivity, and in follow-up flash distillation and circulation step, even when carbon monoxide content is low, also there will not be precipitation, the stability of catalyst is high, thus service life that can extending catalyst.
The specific embodiment
Below by specific embodiment, the present invention is further detailed, but does not form any limitation of the invention.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 volume under every liter of room temperature per hour represents, unit is mol/ (Lhr).
In embodiment and comparative example, 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 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.
The intermittent reaction adopting in embodiment and comparative example all carries out in a 300ml zirconium material autoclave with magnetic stirring apparatus and liquid feeding device, by pressure-reducing valve, to reactor, provide stable carbon monoxide raw material with a gas cylinder, make the gas pressure in autoclave keep constant, by precision digital Pressure gauge, read the pressure data in gas cylinder.
In embodiment and comparative example, in each carbonylation experiment, will be dissolved in part water and acetic acid and adding in liquid feeding device containing iridic compound, methyl acetate, iodomethane, promoter and remaining water and acetic acid will be joined in autoclave.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 × 1.0MPa) 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.To in liquid injection system, be dissolved in joining in autoclave and start reaction containing iridic compound of acetic acid and water with the CO gas of 3.0MPa, 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, stop reacting and lowering the temperature.
In addition, in embodiment and comparative example, after carbonylation completes, immediately by cooling coil by reaction solution cool to room temperature, after emptying, taking out 50 milliliters of reacted solution puts into withstand voltage glass reaction tube and carries out carbonylating catalyst estimation of stability, 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
2it is 1500ppm that 1.05g(is equivalent to Ru content), MnI
24H
2the solution of O 1.04g (being equivalent to Mn content is 1000ppm) joins in 300ml zirconium material autoclave, by acetic acid 18g, water 3.6g and H
2irCl
60.72g(is equivalent to Ir content 2000ppm) join in liquid injection system.After pressure testing slowly displacement nitrogen, pass into the CO of 0.6MPa, be heated to 185 ℃ under the stirring of 750 revs/min after, pass into CO to about 2.5MPa and stablize 30 minutes, with the CO gas of 2.8MPa, the catalyst solution in liquid injection system being joined in autoclave and start and react.In corresponding to liquid combination reactant, contain 20wt%MeOAc and 6.26wt%H
2during O, recording carbonylation rate is 25.5mol/ (Lhr); In corresponding to liquid combination reactant, contain 15wt%MeOAc and 5.05wt%H
2during O, recording carbonylation rate is 21.1mol/ (Lhr); In corresponding to liquid combination reactant, 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.Investigate carbonylating catalyst stability, visual observations reaction tube, does not find deposited phenomenon.
Embodiment 2
Step is with embodiment 1, and difference is to add MnI
24H
2o 2.08g (being equivalent to Mn content is 2000ppm).Data are in Table 1.
Embodiment 3
Step is with embodiment 1, and difference is to add OsCl
33H
2it is 1500ppm that O0.42g(is equivalent to Os content) and MnI
24H
2o 3.12g (being equivalent to Mn content is 3000ppm).Data are in Table 1.
Embodiment 4
Step is with embodiment 1, and difference is to add OsCl
33H
2it is 1500ppm that O0.42g(is equivalent to Os content) and MnI
24H
2o 4.16g (being equivalent to Mn content is 4000ppm).Data are in Table 1.
Embodiment 5
With embodiment 1, difference is to add MnCl
24H
2o 0.54g (being equivalent to Mn content is 1000ppm).Data are in Table 1.
Embodiment 6
Step is with embodiment 1, and difference is to add H
2irCl
60.54g(is equivalent to Ir content 15000ppm), add MnI
24H
2o 2.08g (being equivalent to Mn content is 2000ppm).Data are in Table 1.
Embodiment 7
Step is with embodiment 1, and difference is to add Ru (CO)
4i
2it is 1000ppm that 0.7g(is equivalent to Ru content), MnI
24H
2o 2.08g (being equivalent to Mn content is 2000ppm).Data are in Table 1.
Embodiment 8
Step is with embodiment 1, and difference is to add Ru (CO)
4i
2it is 2000ppm that 1.4g(is equivalent to Ru content), MnI
24H
2o 2.08g (being equivalent to Mn content is 2000ppm).Data are in Table 1.
Comparative example 1
Step is with embodiment 1, and difference is, does not add containing manganese compound.In data in Table 1.
From table 1, data can be found out, utilize catalyst provided by the invention to prepare acetic acid for carbonylation, not only have higher carbonylation rate, and higher is selective, and in course of reaction, without precipitation, occur the stable height of catalyst, long service life.
It should be noted in the discussion above that above-described embodiment, only for explaining the present invention, does not form any limitation of the invention.By with reference to exemplary embodiments, invention has been described, but should be understood to word wherein used, be descriptive and explanatory vocabulary, rather than limited vocabulary.Can in the scope of the claims in the present invention, to the present invention, modify in accordance with regulations, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention who wherein describes relates to specific method, material and embodiment, and does not mean that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention can extend to other all methods and applications with identical function.
Table 1
Claims (10)
1. a carbonylation acetic acid catalyst processed, it comprises: contain iridic compound, halogen-containing co-catalyst, promoter and contain manganese compound, wherein said promoter is selected from containing ruthenium compound with containing osmium compound.
2. catalyst according to claim 1, is characterized in that, in described catalyst, containing iridic compound, promoter and the mass ratio containing manganese compound, with the metallic element/manganese in iridium/promoter, counts 1:0.2-5:0.2-5.
3. catalyst according to claim 1 and 2, is characterized in that, in described catalyst, containing iridic compound, promoter and the mass ratio containing manganese compound, with the metallic element/manganese in iridium/promoter, counts 1:0.5-2:0.5-2.
4. according to the catalyst described in any one in claim 1 ~ 3, it is characterized in that, the described manganese compound that contains is selected from manganese salt, Mn oxide and manganese complex.
5. according to the catalyst described in any one in claim 1 ~ 4, it is characterized in that, the described iridic compound that contains is selected from iridium salt, iridium oxide and complex of iridium, is preferably H
2irCl
6.
6. according to the catalyst described in any one in claim 1 ~ 5, it is characterized in that, described promoter is selected from ruthenium trichloride, osmium trichloride, ruthenium-oxide, osmium tetroxide, diiodo-four carbonyls close ruthenium and diiodo-four carbonyls close osmium.
7. according to the catalyst described in any one in claim 1 ~ 6, it is characterized in that, described halogen-containing co-catalyst is C
1~ C
3halogenated alkane, preferably iodomethane.
8. a method for carbonylation acetic acid processed, it comprises that methyl alcohol and/or carbinol derivatives react with carbon monoxide under the existence of catalyst described in any one in claim 1 ~ 7.
9. method according to claim 8, is characterized in that, described carbinol derivatives is methyl acetate.
10. method according to claim 8 or claim 9, is characterized in that, described reaction is carried out in solvent, the preferred acetic acid of described solvent.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003011A (en) * | 2016-10-31 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of method of imurity-removal metal ion |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1324341A (en) * | 1998-10-23 | 2001-11-28 | 国际人造丝公司 | Carbonylation of methanol in the presence of a rhodium/iridium/iodide ion catalytic system |
| WO2009077723A1 (en) * | 2007-12-17 | 2009-06-25 | Bp P.I.C. | Process for the conversion of hydrocarbons into ethanol |
-
2012
- 2012-10-11 CN CN201210384747.2A patent/CN103721751B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1324341A (en) * | 1998-10-23 | 2001-11-28 | 国际人造丝公司 | Carbonylation of methanol in the presence of a rhodium/iridium/iodide ion catalytic system |
| WO2009077723A1 (en) * | 2007-12-17 | 2009-06-25 | Bp P.I.C. | Process for the conversion of hydrocarbons into ethanol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003011A (en) * | 2016-10-31 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of method of imurity-removal metal ion |
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