CN103724179B - Method for preparing acetic acid - Google Patents
Method for preparing acetic acid Download PDFInfo
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- CN103724179B CN103724179B CN201210384655.4A CN201210384655A CN103724179B CN 103724179 B CN103724179 B CN 103724179B CN 201210384655 A CN201210384655 A CN 201210384655A CN 103724179 B CN103724179 B CN 103724179B
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- promotor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
Abstract
A disclosed method for preparing acetic acid comprises: in the presence of water, a catalyst and a solvent, contacting methanol and/or a methanol derivative with carbon monoxide to obtain acetic acid, wherein the catalyst comprises an iridium compound, a halogen-containing cocatalyst, a promoter and a manganese-containing compound, and the promoter is selected from a ruthenium-containing compound and an osmium-containing compound. By utilizing the method provided by the invention for preparing acetic acid, 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 preparation method has relatively good application prospect.
Description
Technical field
The present invention relates to a kind of method of acetic acid processed.Specifically, the present invention relates to a kind of method utilizing carbonylation reaction to prepare acetic acid.
Background technology
Acetic acid is as a kind of important basic organic chemical raw material, and being widely used in the multiple fields such as fiber, softening agent, paint, tackiness agent, copolymer resins, is production capacity increase recent years a kind of Chemicals faster.The main method of producing acetic acid at present in the world has acetaldehyde oxidation, butane and lightweight oil oxidation style and methanol carbonylation.Wherein methanol carbonylation produces more than 70% of acetic acid Yi Zhan world yield of acetic acid.
The method adopting iridium catalyst systems catalysis methanol carbonylation to produce acetic acid is known, and has been applied in the middle of suitability for industrialized production.While Monsanto company carries out the carbonylating catalyst exploitation of rhodium system, research is expanded to iridium system carbonylating catalyst.Researchist discloses a kind of iridium system carbonylating catalyst in US3772380.Adopt the title complex of the halogenide of iridium, carbonylic halide or other iridium as catalyzer; Br
2, I
2or other compounds are as promotor, be 50-300 DEG C in temperature of reaction, carry out methanol carbonylation under pressure 10-1000psi, speed of reaction is starkly lower than rhodium catalytic system, so industrialization methanol carbonylation process at that time have employed rhodium catalytic system.
But rhodium exists obvious shortcoming as the active centre of catalyst system, the requirement for water-content in reaction system and carbon monoxide pressure of tension is higher, and when water-content reduces or carbon monoxide pressure of tension reduces, rhodium may 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, unfavorable for production.Current classic catalyst stabilizer is alkali metal iodides, 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 this and running cost.Iridium catalyst systems due to the solvability in liquid reaction mixture (comprising catalyst system, solvent acetic acid, material benzenemethanol and/or methyl acetate and water) better, stability is high and be subject to the attention of numerous researchists, and the speed of reaction improving iridium system carbonylation of methanol catalyzer is the emphasis of research.
A kind of iridium and the platinum method preparing acetic acid and/or methyl acetate as catalyzer is disclosed in CN1325374A.Researchist finds to add the throughput rate that can increase acetic acid in platinum to the catalyst system being matrix with iridium or iridium and rhodium, and the metal total mole number simultaneously used still remains unchanged.Even if when reactive system water-content reduces, adding of platinum still can the stability of sizable reinforcement iridium.But the bullion content needed in this method is higher, catalyzer cost is large.
The method adopting ruthenium and osmium catalysis methanol carbonylation to produce acetic acid is also known, disclose a kind of compound being selected from palladium, platinum, iridium, ruthenium or osmium in GB1234641 and GB1234642 as catalyzer, under the co catalysis of halogen or halogen compounds, carry out the method as raw material production carboxylic acid or its ester class such as alcohol, halides or ether.GB20209409A discloses a kind of compound of ruthenium or ruthenium that adopts as catalyzer, halogen-containing, prepares carboxylic acid and corresponding ester thereof under the promoting catalysis of especially iodine by alcohol and reaction of carbon monoxide.
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.Catalyst system disclosed in the method comprises at least one in iridium catalyst, methyl-iodide and ruthenium or osmium.The existence of ruthenium can reduce the volatility of iridium catalyst thus improve catalyst stabilization performance.In addition, the use of ruthenium or osmium can improve methanol carbonylation rates, and reaction can be carried out under lower water-content, is conducive to the generation reducing by product.The method of acetic acid is prepared in the carbonylation of methanol that CN1681764A discloses a kind of improvement.The catalyst body used in the method is iridium, comprises at least one and is selected from the stablizer that the promotor of ruthenium, osmium and rhenium and at least one are selected from indium, cadmium, mercury, gallium and zinc.Adding of promotor accelerates carbonylation rate, but uses the promotor of higher concentration that catalyst system generation may be made to precipitate and inactivation.The adding of stablizer can improve catalyst stabilization performance and carbonylation rate is constant or increase.In order to improve the carbonylation rate of iridium catalyst systems, researchist has carried out large quantifier elimination, 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, methyl iodide co-catalyst, and at least one of ruthenium, osmium, rhenium, indium, cadmium, mercury, gallium and zinc and at least one can be the non-haloid acid promotor of oxygen acid, super acid and/or heteropolyacid.Promotor can improve the carbonylation rate of iridium catalyst systems, but may produce potential disadvantageous effect to conversion unit material simultaneously.
A kind of method of methyl alcohol and/or its reactive derivative and carbon monoxide carbonylation synthesis of acetic acid is disclosed in CN1187482A.The process employs that iridium is catalyzer, haloalkane is promotor, ruthenium is promotor, in liquid reaction mixture, also need to comprise one be in addition selected from alkaline metal iodide, alkaline earth metal iodide, can I be produced
-metal complexes, can I be produced
-salt or its mixture as secondary accelerator.
Use iridium catalyst systems catalysis methanol carbonylation to prepare acetic acid in prior art, when carbon monoxide content is low, because iridium catalyst systems becomes unstable, make to occur precipitation in liquid reaction mixture; In addition, in treatment process after carbonylation reaction, in order to separating catalyst needs liquid reaction mixture to carry out flash distillation, due to the existence of a large amount of promotor, promotor, and carbon monoxide pressure of tension now significantly reduces, the flash stage of separating catalyst and catalyst recirculation are returned in the pipeline of reactor relatively large appearance to precipitate and cause catalyst deactivation, cause production cost to improve.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method preparing acetic acid, by method provided by the invention, not only carbonylation rate is high, and selectivity is high, and can solve the sedimentation problem existed in existing technique.
According to an aspect of the present invention, provide a kind of method preparing acetic acid, methyl alcohol and/or carbinol derivatives is made to contact to obtain acetic acid with carbon monoxide under being included in the existence of water, catalysts and solvents, wherein said catalyzer comprises containing iridic compound, halogen-containing promotor, promotor and contains manganic compound, and described promotor is selected from containing ruthenium compound with containing osmium compound.
In the above-mentioned methods, 1:0.2-5:0.2-5 is counted containing iridic compound, promotor and the mass ratio containing manganic compound with the metallic element/manganese in iridium/promotor in described catalyzer.Preferably, 1:0.5-2:0.5-2 is counted containing iridic compound, promotor and the mass ratio containing manganic compound with the metallic element/manganese in iridium/promotor in described catalyzer.Within the scope of aforementioned proportion, the amplitude that catalyzer can improve carbonylation rate is large, and described iridium catalyst systems stability is better.
In the above-mentioned methods, the described manganic compound that contains is selected from manganese salt, Mn oxide and manganese complex.The described manganic compound that contains can be dissolved in reaction system, should can include, but are not limited to following material, such as: MnCl containing manganic compound
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 the above-mentioned methods, described containing iridic compound can be various for catalytic alcohol preparing carboxylic acid by carbonylation contain iridic compound, as this can be 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 containing iridic compound but be not limited to following material, such as: 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 widely viewpoint set out, and preferably described is H containing iridic compound
2irCl
6.
In the above-mentioned methods, described halogen-containing promotor can be the various halogen catalyst 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, described halogen-containing promotor is C
1~ C
3halogenated alkane; In the preferred case, described halogen catalyst is methyl iodide.
In the above-mentioned methods, described can be the various promotor containing ruthenium and/or osmium for alcohol preparing carboxylic acid by carbonylation containing promotor, comprises salt, oxide compound, title complex etc.Described promotor can be dissolved in reaction system.Described promotor can include, but are not limited to following material, such as: ruthenium trichloride, ruthenium chloride (IV), ruthenium bromide (III), ruthenium acetate (III), propionic acid ruthenium (III), pentacarbonyl close that ruthenium, ten dicarbapentaborane close three rutheniums, diiodo-four carbonyl closes ruthenium, osmium trichloride, perosmic anhydride, duodenum tumor, diiodo-four carbonyl close in osmium one or more.Extensive or the simple viewpoint of synthetic method from raw material sources, preferred described promotor is selected from ruthenium trichloride, osmium trichloride, ruthenium oxide, perosmic anhydride, diiodo-four carbonyl closes ruthenium and diiodo-four carbonyl closes osmium.It is that diiodo-four carbonyl closes ruthenium (II) that wherein said diiodo-four carbonyl closes ruthenium, and diiodo-four carbonyl conjunction osmium is that diiodo-four carbonyl closes osmium (II).
In a specific embodiment of aforesaid method, described carbinol derivatives is methyl acetate, and with the gross weight of catalyzer, water, solvent and methyl acetate for benchmark, the content of described catalyzer is 3-20wt%, preferred 5-15wt%; The content of described water is 0.1-15wt%, preferred .5-10wt%, more preferably 2-7wt%; The content of described solvent is 30-80wt%, preferred 50-75%; The content of described methyl acetate is 1-40%, preferred 5-30%.
In the above-mentioned methods, described solvent can be the various solvent that can be used in carbonylation reaction known in the field, and be preferably organic carboxyl acid, more preferably carbonatoms is the organic carboxyl acid of 2-5.Target product due to the carbonylation reaction of methyl acetate is acetic acid, and when therefore using acetic acid as reaction solvent, the product of acquisition can not need to isolate organic solvent, therefore in the present invention, most preferred solvent is acetic acid.
In the above-mentioned methods, described carbonylation reaction condition can be various reaction conditions known in the field.The condition of preferred described reaction is, the dividing potential drop of carbon monoxide is 0.5-10Mpa, and temperature of reaction is 140-250 DEG C; Preferably, the dividing potential drop of carbon monoxide is 1-5Mpa, and temperature of reaction is 170-210 DEG C.In addition, carbonylation reaction both can carry out in an intermittent fashion, also can carry out in a continuous manner, preferably carried out in a continuous manner.
According to method provided by the invention, employ the iridium catalyst adding manganese.The method in the present invention is utilized to prepare acetic acid, not only there is higher catalyst activity and selectivity, the stability of catalyzer is high, in follow-up flash distillation and circulation step, even when carbon monoxide content is low, also there will not be precipitation, the long service life of catalyzer, therefore the method has broad application prospect.
Embodiment
Below by specific embodiment, the present invention is further detailed, but does not form any limitation of the invention.Unless specifically indicated, in the following example and comparative example, material used all can be commercially available.
Carbonylation rate described in the present invention amount of substance of the acetic acid product that the reaction liquid volume under often liter of room temperature per hour is produced represents, unit is mol/ (Lhr).
In embodiment and comparative example, the content of methyl acetate and water is according to consuming the methyl acetate of 1 mole and the water of 1 mole while of supposing consumption 1 mole of CO.The organic constituent that the upper sheaf space of reactor exists is ignored.
Diiodo-four carbonyl closes ruthenium (II) and closes three rutheniums and I by ten dicarbapentaborane
2synthesis is also kept in refrigerator stand-by under carbon monoxide atmosphere.
The intermittent reaction adopted in embodiment and comparative example all carries out in a 300ml zirconium material autoclave with magnetic stirring apparatus and liquid feeding device, stable carbon monoxide raw material is provided 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 and comparative example in each carbonylation reaction experiment, will be dissolved in part water and acetic acid containing iridic compound and add in liquid feeding device, methyl acetate, methyl iodide, promotor and remaining water and acetic acid will be joined in autoclave.Enclosed high pressure still, with the nitrogen of about 3.0MPa, pressure testing is carried out to autoclave, then use carbon monoxide (3 × 1.0MPa) to replace nitrogen in autoclave and liquid feeding device or air and be finally filled with the carbon monoxide of 0.6MPa, passing into carbon monoxide after then liquid reaction composition being heated to 190 DEG C under the condition of stir speed (S.S.) 750 revs/min to about 2.5MPa and stablize 30 minutes.Joining in autoclave containing iridic compound and starting reaction of acetic acid and water will be dissolved in liquid injection system by the CO (carbon monoxide converter) gas of 3.0MPa, to be supplied raw materials carbon monoxide keep autoclave internal pressure 3.0MPa to reactor by gas cylinder, the Pressure Drop of an every 30 seconds records gas cylinder also calculates carbonylation rate accordingly.When in discovery 5 minutes inner high voltage gas cylinders, carbon monoxide pressure disconnects source of the gas after not declining, stopped reaction is also lowered the temperature.
In addition, in embodiment and comparative example, after carbonylation reaction completes, immediately by spiral coil cooling tube by reaction soln cool to room temperature, take out reacted solution 50 milliliters after emptying to put into withstand voltage glass reaction tube and carry out carbonylating catalyst estimation of stability, also finally be pressurized to 0.02MPa with the carbon monoxide dissolved in nitrogen replacement solution, be heated to 130 DEG C and keep 24 hours.Observe solution after cooling and determined whether that precipitation generates.
Embodiment 1
Will containing acetic acid 60g, methyl iodide 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 O1.04g (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.Pressure testing passes into the CO of 0.6MPa after also slowly replacing nitrogen, passing into CO be heated to 185 DEG C under the stirring of 750 revs/min after to about 2.5MPa stablizes 30 minutes, to be joined by the catalyst solution in liquid injection system in autoclave and start reaction by the CO (carbon monoxide converter) gas of 2.8MPa.Corresponding in liquid combination reactant containing 20wt%MeOAc and 6.26wt%H
2during O, recording carbonylation rate is 25.5mol/ (Lhr); Corresponding in liquid combination reactant containing 15wt%MeOAc and 5.05wt%H
2during O, recording carbonylation rate is 21.1mol/ (Lhr); Corresponding in liquid combination reactant containing 10wt%MeOAc and 3.87wt%H
2during O, recording carbonylation rate is 12.3mol/ (Lhr).Negate should be tested by liquid sample afterwards, and acetic acid selectivity is in the product 99.9%.Investigate carbonylating catalyst stability, visual observations reaction tubes, does not find deposited phenomenon.
Embodiment 2
With embodiment 1, difference is to add MnI
24H
2o2.08g (being equivalent to Mn content is 2000ppm).Data are in table 1.
Embodiment 3
With embodiment 1, difference is to add OsCl
33H
2it is 1500ppm that O0.42g(is equivalent to Os content) and MnI
24H
2o3.12g (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
2o4.16g (being equivalent to Mn content is 4000ppm).Data are in table 1.
Embodiment 5
With embodiment 1, difference is to add MnCl
24H
2o0.54g (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
2o2.08g (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
2o2.08g (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
2o2.08g (being equivalent to Mn content is 2000ppm).Data are in table 1.
Comparative example 1
With embodiment 1, difference is not add containing manganic compound.Data are in table 1.
As can be seen from Table 1, prepare acetic acid according to method provided by the invention, not only carbonylation rate is high, and selectivity is high, and the stability of catalyzer is high, and produce without precipitation in reaction process, the long service life of catalyzer, has good application prospect.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Table 1
Claims (15)
1. prepare the method for acetic acid for one kind, methyl alcohol and/or carbinol derivatives is made to contact to obtain acetic acid with carbon monoxide under being included in the existence of water, catalysts and solvents, wherein said catalyzer comprises containing iridic compound, halogen-containing promotor, promotor and contains manganic compound, and described promotor is selected from containing ruthenium compound with containing osmium compound.
2. method according to claim 1, is characterized in that, counts 1:0.2-5:0.2-5 in described catalyzer containing iridic compound, promotor and the mass ratio containing manganic compound with the metallic element/manganese in iridium/promotor.
3. method according to claim 2, is characterized in that, counts 1:0.5-2:0.5-2 in described catalyzer containing iridic compound, promotor and the mass ratio containing manganic compound with the metallic element/manganese in iridium/promotor.
4. according to the method in claims 1 to 3 described in any one, it is characterized in that, the described manganic compound that contains is selected from manganese salt, Mn oxide and manganese complex.
5. according to the method in claims 1 to 3 described in any one, it is characterized in that, the described iridic compound that contains is selected from iridium salt, iridium oxide and complex of iridium.
6. method according to claim 5, is characterized in that, described is H containing iridic compound
2irCl
6.
7. according to the method in claims 1 to 3 described in any one, it is characterized in that, described halogen-containing promotor is C
1~ C
3halogenated alkane.
8. method according to claim 7, is characterized in that, described halogen-containing promotor is methyl iodide.
9. according to the method in claims 1 to 3 described in any one, it is characterized in that, described promotor is selected from ruthenium trichloride, osmium trichloride, ruthenium oxide, perosmic anhydride, diiodo-four carbonyl closes ruthenium and diiodo-four carbonyl closes osmium.
10. according to the method in claims 1 to 3 described in any one, it is characterized in that, described carbinol derivatives is methyl acetate, and with the gross weight of catalyzer, water, solvent and methyl acetate for benchmark, the content of described catalyzer is 3-20wt%; The content of described water is 0.1-15wt%; The content of described solvent is 30-80wt%; The content of methyl acetate is 1-40%.
11. methods according to claim 10, is characterized in that, described carbinol derivatives is methyl acetate, and with the gross weight of catalyzer, water, solvent and methyl acetate for benchmark, the content of described catalyzer is 5-15wt%; The content of described water is 0.5-10wt%; The content of described solvent is 50-75%; The content of methyl acetate is 5-30%.
12. methods according to claim 11, is characterized in that, described carbinol derivatives is methyl acetate, and with the gross weight of catalyzer, water, solvent and methyl acetate for benchmark, the content of described water is 2-7wt%.
13., according to the method in claims 1 to 3 described in any one, is characterized in that, described solvent is acetic acid.
14., according to the method in claims 1 to 3 described in any one, is characterized in that, the condition of described reaction is, the dividing potential drop of carbon monoxide is 0.5-10Mpa, and temperature of reaction is 140-250 DEG C.
15. methods according to claim 14, is characterized in that, the condition of described reaction is, the dividing potential drop of carbon monoxide is 1-5Mpa, and temperature of reaction is 170-210 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0752406A1 (en) * | 1995-06-21 | 1997-01-08 | BP Chemicals Limited | Process for the production of acetic acid by carbonylation |
| CN1681764A (en) * | 2002-09-19 | 2005-10-12 | 英国石油化学品有限公司 | Process for the production of acetic acid |
| CN101153002A (en) * | 2006-09-28 | 2008-04-02 | 中国石油化学工业开发股份有限公司 | Method for producing carboxylic acid |
-
2012
- 2012-10-11 CN CN201210384655.4A patent/CN103724179B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0752406A1 (en) * | 1995-06-21 | 1997-01-08 | BP Chemicals Limited | Process for the production of acetic acid by carbonylation |
| CN1681764A (en) * | 2002-09-19 | 2005-10-12 | 英国石油化学品有限公司 | Process for the production of acetic acid |
| CN101153002A (en) * | 2006-09-28 | 2008-04-02 | 中国石油化学工业开发股份有限公司 | Method for producing carboxylic acid |
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