CN102093198B - Method for producing acetic acid - Google Patents
Method for producing acetic acid Download PDFInfo
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- CN102093198B CN102093198B CN 200910201102 CN200910201102A CN102093198B CN 102093198 B CN102093198 B CN 102093198B CN 200910201102 CN200910201102 CN 200910201102 CN 200910201102 A CN200910201102 A CN 200910201102A CN 102093198 B CN102093198 B CN 102093198B
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Abstract
The invention discloses a method for producing acetic acid, which comprises the following steps of: reacting methanol and CO feed in a liquid reaction medium containing iridium catalyst, rhodium catalyst, metal accelerant, stabilizer, methyl iodide, water, methyl acetate and acetic acid, and then reclaiming the acetic acid, wherein the content of iridium is 500 to 4,000ppm; the content of rhodium is 50 to 400ppm; the metal accelerant is one or more of zinc, cadmium, mercury, gallium and indium, and the molar ratio of the metal accelerant to the iridium is 1-10; the stabilizer is a metal iodide, and the metal of the metal iodide is one or more of corrosive iron metal, chromium, nickel and molybdenum; and the content of the metal iodide enables the iodine ion concentration of the reaction system to be 2 to 20 mass percent. The catalyst has good stability; the metal accelerant has low cost and low volatility; and meanwhile, the catalyst has high catalytic reaction activity, good catalytic activity under the condition of low ester and/or low water content, and low cost.
Description
Technical field
The present invention relates to a kind of method of producing acetate.
Background technology
The catalysis methanol carbonylation prepares in the method for acetate, and the catalyst system that uses single rhodium catalytic system, single iridium catalyst systems and the coupling of rhodium iridium is arranged.The system that relates to rhodium basically all uses the basic metal salt compounded of iodine as stablizer, and the system that relates to iridium further improves activity of such catalysts with noble ruthenium as promotor.For example catalyst system is the iridium ruthenium system among the patent CN97120807.7 of BP company application; Wherein the mol ratio of ruthenium iridium is 0.5: 1～15: 1; But in use iridium and ruthenium have certain volatility for they; When particularly ruthenium concentration was higher, ruthenium was more because of volatilization loss, thereby had increased the unit consumption of catalyzer.European patent EP 752406 is pointed out, in the catalyst reaction system, should make corroding metal, and especially nickel, iron and chromium are few as far as possible, because these ions can make iridium catalyst systems poison.And catalyzer is an iridium rhodium coupling system among the international Zantrel patent CN99812415.X, adopts basic metal or the earth alkali metal salt compounded of iodine stablizer as catalyzer, also uses noble ruthenium to promote catalyzed reaction as metallic promoter agent simultaneously.
Summary of the invention
Technical problem to be solved by this invention is to have overcome existing iridium catalyst systems or iridium rhodium coupling catalyst system; Need corrosion metals siderochrome nickel molybdenum is removed; Perhaps use defectives such as the higher and volatile loss of noble metal promoted agent cost, provide the carbonylation of a kind of methyl alcohol and/or its reactive derivative to prepare the method for acetate.Method reaction system catalyst stability of the present invention is good, and rate of catalysis reaction is higher, has catalytic activity preferably under low ester and/or the low water content condition, and the catalyzer volatility is low, and catalyzer and metallic promoter agent cost obviously reduce.
Among the present invention; Contriver research attempts to use the compound of the noble ruthenium that the compound of comparatively cheap metals such as zinc, cadmium, mercury, gallium and indium replaces using in the prior art etc. to promote rate of catalysis reaction as metallic promoter agent; But experiment finds, in the catalystic converter system of rhodium iridium coupling, when adding compound such as zinc as metallic promoter agent; Can not play function of stabilizer, deposited phenomenon can take place in rhodium catalyst.Finally find through making great efforts untiringly pleasantly surprisedly; In the catalystic converter system of rhodium iridium coupling, when using compound such as zinc, use corrosion metals iodide (comprising siderochrome nickel molybdenum) as stablizer as metallic promoter agent; Can be used for stablizing rhodium catalyst; The stability of catalyzer is significantly increased, and the corrosion metals that produces because of equipment corrosion in the commercial process does not so need extra removing, and can be used as stablizer on the contrary and is used for stably catalyzed reaction system; Used metallic promoter agent is comparatively cheap base metal simultaneously, and the catalyzer cost is further reduced.
The present invention solves the problems of the technologies described above through following technical proposals.
The method of production acetate of the present invention; It is in the liquid reaction medium that contains iridium catalyst, rhodium catalyst, metallic promoter agent, stablizer, methyl-iodide, water, methyl acetate and acetate; With methyl alcohol and carbon monoxide charging reaction, from the reaction product that obtains, reclaim acetate then, wherein; The content of described iridium is 500～4000ppm, and that preferable is 1000～2000ppm; The content of described rhodium is 50～400ppm, and that preferable is 100～300ppm; Described metallic promoter agent is one or more in zinc, cadmium, mercury, gallium and the indium, and preferable is zinc; The mol ratio of said metallic promoter agent and iridium is 1～10, and preferable is 2～5; Described stablizer is a metal iodide, and wherein, the metal of described metal iodide is one or more in corrosion metals iron, chromium, nickel and the molybdenum; The content of described metal iodide is that to make the iodide ion concentration of reaction system be mass percent 2～20%, and preferable is 5～10%.
Wherein, The precursor of described iridium catalyst is the conventional iridium salt catalyst precursor that uses in this area, and that preferable is iridium acetate, iridium metals, iodate iridium, hydration iodate iridium, bromination iridium, hydration bromination iridium, iridium chloride, chloro-iridic acid, hydration iridium chloride, oxalic acid iridium, etheric acid iridium, iridium oxide, iridous oxide, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2, [Ir (CO)
2Br]
2, Ir
4(CO)
12, [Ir (CO)
2I
2]
-H
+, [Ir (CO)
2Br
2]
-H
+, [Ir (CO)
2I
4]
-H
+[Ir (CH
3) (CO)
2I
3]
-H
+In one or more, the better iridium catalyst precursor that preferably is dissolvable in water carbonylation reaction component such as water, alcohol and carboxylic acid is like in iridium acetate, oxalic acid iridium and the etheric acid iridium one or more.
Wherein, The precursor of described rhodium catalyst is the conventional rhodium salt catalyst precursor that uses in this area; The preferable rhodium salt catalyst precursor that is applicable to single rhodium catalystsystem that is selected from, that better is rhodium chloride, three hydration rhodium chlorides, bromination rhodium, iodate rhodium, rhodium acetate, dicarbonyl rhodium acetylacetonate, [Rh (CO)
2Cl]
2[Rh (CO)
2I]
2In one or more.The content of catalyst rhodium of the present invention in rhodium iridium catalystic converter system is lower, has reduced the catalyzer cost.
Wherein, The existence form of described metallic promoter agent is the conventional metallic promoter agent salt existence form in existing this area; Generally can be any appropriate form and join the salt that dissolves or be converted into soluble form in the liquid reaction medium; Preferable metal iodide or acetic acid compound are like zinc iodide, zinc acetate etc.
Wherein, the content of described methyl-iodide is this area conventional amount used, and preferable is 5～30%, and better is 10～20%, and per-cent is mass percent.
Wherein, the content of described water is this area conventional amount used, and preferable is 0.5～16%, and better is 0.5～14%, and best is 2～8%, and per-cent is mass percent.Applicable high water of catalystic converter system of the present invention or low aqueous systems, and in low aqueous systems, still can keep advantages of high catalytic activity, and lower water-content also makes, and the lock out operation difficulty and the cost of water and acetic acid product significantly reduces in the follow-up step.
Wherein, the content of described methyl acetate is this area conventional amount used, and preferable is 0.5～40%, and better is 0.5～5%, and best is 2～5%, and per-cent is mass percent.Wherein, the content of preferred methyl acetate belongs to low ester content scope, and catalystic converter system of the present invention still has catalytic activity preferably under low ester condition, should hang down the operation easier that ester content also reduces the subsequent recovery methyl-iodide simultaneously.
Wherein, the content of described acetate is this area conventional amount used, is generally the amount of replenishing liquid reaction medium mass percent 100% among the present invention.
Among the present invention, described methyl alcohol and/or its reactive derivative such as ether, ester, halogenide etc. are used for carbonylation reaction and produce acetate, and better is methyl alcohol.
The described content of above-mentioned each component is in the catalytic reaction process each components contents in the real reaction system among the present invention.
Among the present invention, on the basis that meets this area general knowledge, the optimum condition of each above-mentioned technical characterictic can arbitrary combination, obtains preferred embodiment of the present invention.
The suitable device of method of the present invention is this area conventional equipment, generally can adopt the typical reaction system, and the reactive system that the catalysis methanol carbonylation prepares acetate generally comprises liquid-phase carbonylation reactor drum, flash tank and separated from acetic acid tower.Carbonylation reactor generally is a stirred autoclave that can automatically the reaction liquid presented higher be held in constant level, in this reactor drum, can introduce alkanol and/or its reactive derivative, water continuously, from the alkyl iodide and the methyl acetate of recycling catalyst solution at the bottom of the flash tank and recycle.Carbon monoxide is carbonylate reactor drum and fully disperseing therein continuously also, and the top of reactor drum can emit steam state and dispel logistics simultaneously, with the accumulation of avoiding gaseous by-product and under given total reactor pressure, keep predetermined carbon monoxide pressure of tension.The control method of the temperature and pressure of carbonylation reactor is with this area ordinary method among the present invention.Flash tank receives the liquid crude product from the carbonylation reactor discharging.Through the flash tank flash distillation, catalyst solution goes out to return carbonylation reactor as the bottoms materials flow, and the top goes out the mixture that the condensation material comprises crude product acetate and alkyl iodide, water and methyl acetate, and the gaseous feed at top is gaseous by-product methane, carbonic acid gas etc.The separated from acetic acid tower is accepted the condensation material of flashing tower, separating acetic acid and alkyl iodide and methyl acetate.Product acetate can carry out follow-up refining purification afterwards from the knockout tower bottom discharge; Alkyl iodide and methyl acetate are looped back in the carbonylation reactor by the discharging of knockout tower cat head.
Agents useful for same of the present invention and raw material are all commercially available to be got.
Positive progressive effect of the present invention is: the invention provides a kind of method of producing acetate.Method reaction system catalyzer of the present invention and metallic promoter agent cost obviously reduce, good stability, and volatility is low, and rate of catalysis reaction is higher, has catalytic activity preferably under low ester and/or the low water content condition.
Embodiment
Mode through embodiment further specifies the present invention below, but does not therefore limit the present invention among the described scope of embodiments.
Catalyzed reaction when embodiment 1 different iridium rhodiums, stablizer and metal promoted agent content
In the zirconium material autoclave of a 200ml, add entry, acetate, methyl acetate, methyl-iodide, Trichlororhodium and iridous chloride.Experiment numbers is 1～6 and to contrast the weight percentage of each reactant feed that adds in 1～7 the reaction system mesohigh reaction kettle following: water 8%, methyl acetate 20%, methyl-iodide 14%; All the other are acetate, and the situation of iridium rhodium, stablizer and metallic promoter agent is as shown in table 1.After adding reaction solution 120 grams of above prescription in the autoclave, operate as follows:
(1) off-response still carries out leakage detection with nitrogen to reaction unit.After confirming that reaction unit does not have leakage point,, with CO 0.5MPa is arrived in the reactive system pressurising then with slowly displacement twice of CO;
(2) start stirring, rotating speed is about 850 rev/mins, and setting temperature controlling system is 190 ℃, heating;
(3) along with the rising of temperature, the pressure of reactive system constantly increases, and when treating that temperature is raised to 190 ℃, opens the pressurising gas circuit of CO, and the reactive system pressurising to 2.8Mpa, is closed the valve of pressurising gas circuit afterwards; Open the CO constant voltage source of the gas gas circuit that the CO flow control is housed again, its pressure is 2.8Mpa; Beginning carbonylation reaction timing, keeping temperature of reaction is 195 ± 1 ℃, reaction pressure 2.8Mpa (gauge pressure), whenever instantaneous delivery and the cumulative throughflow of CO under 1 second and computer record that reactive system links to each other;
When (4) the question response system does not absorb CO, " Quench " carried out in reaction handle termination reaction;
(5) treat that temperature reduces to room temperature,, open reaction kettle, pour out reaction solution and weigh, sampling analysis with nitrogen replacement twice.
The instantaneous delivery of CO when from record, accessing the CO cumulative throughflow and be 5.2 liters; The content of methyl acetate is about 3wt% in the reactive system at this moment; Water-content is about 4wt%, and the content of iridium, rhodium, stablizer and metallic promoter agent sees that (corresponding mass ratio was 2.5: 1: 2.5 to table 1 when wherein, stablizer was siderochrome nickel molybdenum: 1; Corresponding mass ratio was 2.5: 1: 2.5 when stablizer was siderochrome nickel; Corresponding mass ratio was 1: 1 when stablizer was iron nickel, and corresponding mass ratio was 2.5: 1 when stablizer was the nickel molybdenum, and corresponding mass ratio was 2.5: 1 when stablizer was siderochrome).Therefore, when methyl acetate content was 3wt% in reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represented speed of reaction, and the result lists in the table 1.
Rate of catalysis reaction when the different iridium of table 1, rhodium and stabiliser content and reaction system stability
Visible by last table data; Comparison test is numbered 2 and can knows with contrast 4～6 catalystic converter system: embodiment and Comparative Examples are under rhodium, iridium and the metallic promoter agent kind situation identical with content; Has only the content that stablizer and stablizer ought be contained in content range of the present invention; Catalyzer generation deposited phenomenon is comparatively stablized, do not had to catalyzer in the catalystic converter system, and rate of catalysis reaction is higher; If do not contain the then easy deposition of rhodium catalyst of stablizer; If stabiliser content is very few, then can't reach the stabilising effect catalyzer still has deposition; If stabiliser content is too much, although catalyzer does not precipitate, too much stablizer has suppressed rate of catalysis reaction on the contrary.Simultaneously, the consumption that metallic promoter agent has also been investigated in experiment is to the influence to catalystic converter system, and comparative experiments numbering 4 can't reach the effect that promotes catalyzed reaction with contrast 7, very few metallic promoter agent.To sum up show; Catalystic converter system of the present invention; In the stablizer of the content range of iridium rhodium, specific metallic promoter agent kind and content and particular types and content; When having kept higher catalytic reaction activity and rate of catalysis reaction, catalyzer also has stability preferably, and catalyzer and metallic promoter agent cost obviously reduce.
The rate of catalysis reaction and the stability of embodiment 2 different methyl-iodide content
Operation steps is with embodiment 1; Wherein the weight percentage of each component of autoclave internal reaction system is following: experiment numbers is that the add-on of each raw material of reaction system of 7～11 is: water 8%, methyl acetate 20%, iridium 1500ppm, rhodium 250ppm; Stablizer is a molysite, I
-Concentration is 3%, and the mol ratio of metallic promoter agent zinc and iridium is 5, and the methyl-iodide consumption sees the following form 2, and all the other are acetate, and per-cent is mass percent; Reaction solution 120 grams that add above prescription in the autoclave.
From record, access when the content of methyl acetate is about 5wt% in the reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured representes speed of reaction; This moment reaction system in water 4wt%, the result lists in the table 2.
The rate of catalysis reaction and the stability of the iridium rhodium catalytic system of the methyl-iodide of table 2 different content
| Numbering | Methyl-iodide consumption wt% | STY (5% methyl acetate mol/L.h) | Stability |
| 7 | 5 | 13 | There is not deposition |
| 8 | 10 | 15 | There is not deposition |
| 9 | 15 | 20 | There is not deposition |
| 10 | 20 | 24 | There is not deposition |
| 11 | 30 | 26 | There is not deposition |
Visible by last table data; Routine is suitable for content range to methyl-iodide in this area in the catalyst system of the present invention; The stability of catalyzer better simultaneously also has rate of catalysis reaction preferably, and its rate of catalysis reaction is generally along with the increase of concentrationofmethyiodide iodide increases gradually.
The rate of catalysis reaction and the stability of embodiment 3 different water content
Operation steps is with embodiment 1; Wherein the weight percentage of each component of autoclave internal reaction system is following: experiment numbers be 12～15 and the add-on that contrasts each raw material of reaction system of 5 be: methyl acetate 20%, methyl-iodide 14%, iridium 1500ppm, rhodium 200ppm, stablizer are iron, nickel salt (the corresponding mass ratio of iron nickel is 1: 1), I
-Concentration is 10%, and the mol ratio of metallic promoter agent zinc and iridium is 5, and the consumption that the concentration of water reaches sees the following form 2, and all the other are acetate, and per-cent is mass percent, and water-content sees the following form; Reaction solution 120 grams that add above prescription in the autoclave.
From record, access when the content of methyl acetate is about 5wt% in the reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured representes speed of reaction, and the result lists in the table 2.
The rate of catalysis reaction and the stability of the iridium rhodium catalytic system during table 3 different water content
| Numbering | The concentration wt% of water | STY (5% methyl acetate mol/L.h) | Stability |
| 12 | 0.5 | 11 | There is not deposition |
| 13 | 2 | 17 | There is not deposition |
| 14 | 8 | 21 | There is not deposition |
| 15 | 14 | 13 | There is not deposition |
Visible by last table data; Catalyst system of the present invention is applicable to high water or low aqueous systems; And catalyst body of the present invention ties up in the low aqueous systems still has advantages of high catalytic activity, also makes that the lock out operation difficulty and the cost of water and acetic acid product significantly reduces in the follow-up step simultaneously.
Rate of catalysis reaction and stability during the different methyl acetate content of embodiment 4
Operation steps is with embodiment 1; Wherein the weight percentage of each component of autoclave internal reaction system is following: experiment numbers is that the add-on of each raw material of reaction system of 16 is: water 8%, methyl acetate 20%, methyl-iodide 14%, iridium 1800ppm, rhodium 300ppm, stablizer are nickel molybdenum salt (the corresponding mass ratio of nickel molybdenum is 2.5: 1), I
-Concentration is 5%, and the mol ratio of metallic promoter agent zinc and iridium is 2, and all the other are acetate, and per-cent is mass percent; Reaction solution 120 grams that add above prescription in the autoclave.
From record, access when the content of methyl acetate is about the following table data in the reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured representes speed of reaction, and the result lists in the table 3.
The rate of catalysis reaction and the stability of the iridium rhodium catalytic system during the different methyl acetate content of table 4
Visible by last table data; Catalyst system of the present invention is applicable to high ester or low ester system; Although rate of catalysis reaction is along with the increase of methyl acetate concentration increases gradually; But the stability that catalyst body of the present invention ties up in the low ester system is also better, have advantages of high catalytic activity simultaneously, and low ester condition can also make the lock out operation difficulty and the cost of alkyl iodide in the follow-up step significantly reduce.
Claims (13)
1. method of producing acetate; It is in the liquid reaction medium that contains iridium catalyst, rhodium catalyst, metallic promoter agent, stablizer, methyl-iodide, water, methyl acetate and acetate; With methyl alcohol and carbon monoxide charging reaction; From the reaction product that obtains, reclaim acetate then, wherein, the content of described iridium is 500～4000ppm; The content of described rhodium is 50～400ppm; Described metallic promoter agent is one or more in zinc, cadmium, mercury, gallium and the indium, and the mol ratio of said metallic promoter agent and iridium is 1～10; Described stablizer is a metal iodide, and wherein, the metal of described metal iodide is one or more in corrosion metals iron, chromium, nickel and the molybdenum; The content of described metal iodide is that to make the iodide ion concentration of reaction system be mass percent 2～20%.
2. the method for claim 1, it is characterized in that: the molar ratio of described metallic promoter agent and iridium is 2～5.
3. like each described method of claim 1～2, it is characterized in that: the content of described metal iodide is that to make the iodide ion concentration of reaction system be mass percent 5～10%.
4. like each described method of claim 1～2, it is characterized in that: the content of described iridium catalyst is 1000～2000ppm.
5. like each described method of claim 1～2, it is characterized in that: the content of described rhodium catalyst is 100～300ppm.
6. like each described method of claim 1～2, it is characterized in that: the precursor of described iridium catalyst is iridium acetate, iridium metals, iodate iridium, hydration iodate iridium, bromination iridium, hydration bromination iridium, iridium chloride, chloro-iridic acid, hydration iridium chloride, oxalic acid iridium, etheric acid iridium, iridium oxide, iridous oxide, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2, [Ir (CO)
2Br]
2, Ir
4(CO)
12, [Ir (CO)
2I
2]
-H
+, [Ir (CO)
2Br
2]
-H
+, [Ir (CO)
2I
4]
-H
+[Ir (CH
3) (CO)
2I
3]
-H
+In one or more.
7. like each described method of claim 1～2, it is characterized in that: the precursor of described rhodium catalyst is rhodium chloride, three hydration rhodium chlorides, bromination rhodium, iodate rhodium, rhodium acetate, dicarbonyl rhodium acetylacetonate, [Rh (CO)
2Cl]
2[Rh (CO)
2I]
2In one or more.
8. like each described method of claim 1～2, it is characterized in that: the content of described methyl-iodide is 5～30%, and per-cent is mass percent.
9. method as claimed in claim 8 is characterized in that: the content of described methyl-iodide is 10～20%; Per-cent is mass percent.
10. like each described method of claim 1～2, it is characterized in that: the content of described water is 0.5～14%, and per-cent is mass percent.
11. method as claimed in claim 10 is characterized in that: the content of described water is 2～8%, and per-cent is mass percent.
12. like each described method of claim 1～2, it is characterized in that: the content of described methyl acetate is 0.5～5%, per-cent is mass percent.
13. method as claimed in claim 12 is characterized in that: the content of described methyl acetate is 2～5%, and per-cent is mass percent.
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|---|---|---|---|
| CN 200910201102 CN102093198B (en) | 2009-12-15 | 2009-12-15 | Method for producing acetic acid |
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|---|---|---|---|
| CN 200910201102 CN102093198B (en) | 2009-12-15 | 2009-12-15 | Method for producing acetic acid |
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| CN102093198B true CN102093198B (en) | 2012-12-05 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187482A (en) * | 1996-12-19 | 1998-07-15 | 英国石油化学品有限公司 | Iridium-catalysed carbonylation 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 |
| CN1491198A (en) * | 2001-02-08 | 2004-04-21 | ��ɪ����˹��ѧ��˾ | Modification of catalytic system in industrial process for making acetic and/or methyl acetate acid |
| WO2009134333A1 (en) * | 2008-04-29 | 2009-11-05 | Celanese International Corporation | Method and apparatus for carbonylating methanol with acetic acid enriched flash stream |
-
2009
- 2009-12-15 CN CN 200910201102 patent/CN102093198B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187482A (en) * | 1996-12-19 | 1998-07-15 | 英国石油化学品有限公司 | Iridium-catalysed carbonylation 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 |
| CN1491198A (en) * | 2001-02-08 | 2004-04-21 | ��ɪ����˹��ѧ��˾ | Modification of catalytic system in industrial process for making acetic and/or methyl acetate acid |
| WO2009134333A1 (en) * | 2008-04-29 | 2009-11-05 | Celanese International Corporation | Method and apparatus for carbonylating methanol with acetic acid enriched flash stream |
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