CN101058537A - Method of preparing acetic anhydride under rhodium catalyst - Google Patents
Method of preparing acetic anhydride under rhodium catalyst Download PDFInfo
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- CN101058537A CN101058537A CN 200610025835 CN200610025835A CN101058537A CN 101058537 A CN101058537 A CN 101058537A CN 200610025835 CN200610025835 CN 200610025835 CN 200610025835 A CN200610025835 A CN 200610025835A CN 101058537 A CN101058537 A CN 101058537A
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Abstract
The invention discloses a making method of acetic anhydride acted by rhodium catalyst, which comprises the following steps: proceeding liquid phase carbonylation reaction for methyl acetate or dimethyl ether or the composition of methyl acetate and dimethyl ether in the first area; entering the composition into the second area to evaporate and separate; entering gas-phased fraction with acetic anhydride into the third area to separate and purify the acetic anhydride; entering the non-evaporated liquid-phased fraction with rhodium catalyst into the fourth area to contact hydrogen or the composition of hydrogen and carbon monoxide; inputting liquid phase fraction of non-evaporating liquid with rhodium catalyst into the first area to do carbonylation reaction; adding carbinol or water into methyl acetate or dimethyl ether and the composition of methyl acetate and dimethyl ether; fitting for preparing the composition of acetic anhydride and acetic acid; improving the entire productivity.
Description
Technical field
The present invention relates to a kind of preparation method of diacetyl oxide, relate to a kind of preparation method of acetic anhydride under rhodium catalyst in particular.
Background technology
Employing is that the carbonylation method that the soluble catalyst of main ingredient prepares diacetyl oxide is the method for knowing with the rhodium, and normally implement these methods in the equipment that includes three districts: first district is a reaction zone, comprises a pressurized reactor that carries out oxonation; Second district is the disengaging zone of reaction mixture, carries out in the mode of flash distillation usually, and realization product diacetyl oxide separates with rhodium catalyst; The 3rd district is the zone purification of product, and the gaseous component that is evaporated out through second district is sent to the 3rd district carries out diacetyl oxide in this district purifying, comprises various distillation towers in this district, wherein gained diacetyl oxide and acetate, reagent and separation of by-products.Usually, the unevaporated liquid phase in second district is for containing mixture of catalysts, and this mixture carries out oxonation by the pressurized reactor that pump is circulated back to first district.WO8201704A has announced a kind of representational method for preparing diacetyl oxide, acetate carbonylization prepares diacetyl oxide under rhodium catalyst, first district's reaction solution is methyl acetate and diacetyl oxide, acetate is made solvent, the catalyzer major ingredient is a rhodium, methyl iodide is as promotor, and lithium iodide is as promotor.Yet when stating the method for preparing diacetyl oxide under the rhodium catalyst on the implementation, the activity of such catalysts that reaction mixture contains after the flash distillation of second district in the not evaporated fraction of catalyzer can reduce greatly, and the production capacity that causes reacting whole descends.
Summary of the invention
Technical problem to be solved by this invention provides the method that a kind of improvement carbonylation reaction under rhodium catalyst prepares diacetyl oxide, and this method is used the reactivation of catalyst after a kind of simple and effective way makes flash distillation, thereby improves the whole production capacity of reaction.
The technical solution used in the present invention: a kind of preparation method of acetic anhydride under rhodium catalyst, be in the presence of the catalyzer of main ingredient with the rhodium, the mixture of methyl acetate or dme or methyl acetate and dme is that reaction zone carries out the liquid-phase carbonylation reaction in first district, it is that separation is evaporated in the disengaging zone that post reaction mixture enters second district, it is that the separation that the separation and purification district carries out the product diacetyl oxide is purified that the gas phase fraction that contains the product diacetyl oxide enters the 3rd district, containing the liquid fraction that do not evaporate of rhodium catalyst, to enter the 4th district be that the catalyst activation district contacts with the mixed gas of hydrogen or hydrogen and carbon monoxide with the activation rhodium catalyst, and the described not evaporation liquid fraction that contains rhodium catalyst is imported into first district after through the 4th district and carries out carbonylation reaction once more.Rhodium catalyst is the given indicative table of referenced patents US 3769329 specifically.
In described liquid-phase carbonylation reaction, use methyl halide to be promotor, use basic metal or alkaline earth salt to be promotor.
Described methyl halide is a methyl iodide, and described basic metal or alkaline earth salt are lithium iodide or lithium acetate.
The liquid fraction that do not evaporate that contains rhodium catalyst is 0.01～100 minute with mixture duration of contact of hydrogen or hydrogen and carbon monoxide in the 4th district.
The liquid fraction that do not evaporate that contains rhodium catalyst is 1～60 minute with mixture duration of contact of hydrogen or hydrogen and carbon monoxide in the 4th district.
Containing the liquid fraction that do not evaporate of rhodium catalyst, to contact temperature with the mixture of hydrogen or hydrogen and carbon monoxide in the 4th district be 30～250 ℃.
Containing the liquid fraction that do not evaporate of rhodium catalyst, to contact temperature with the mixture of hydrogen or hydrogen and carbon monoxide in the 4th district be 50～220 ℃.
The absolute pressure in described the 4th district is 1～100bar.
The absolute pressure in described the 4th district is 10～50bar, and the high 0.01～20bar of pressure in pressure ratio first district in the 4th district.
High 0.1～the 5bar of pressure in pressure ratio first district in the 4th district.
The molar weight of the mixed gas of hydrogen or hydrogen and carbon monoxide is 2～100,000 times of molar weight of rhodium in the rhodium catalyst.
The molar weight of the mixed gas of hydrogen or hydrogen and carbon monoxide is 100～5000 times of molar weight of rhodium in the rhodium catalyst.
Add methyl alcohol or water in the mixture of described methyl acetate or dme or methyl acetate and dme, the present invention can prepare the mixture of diacetyl oxide and acetate.
Can be the same with routine techniques, the oxonation in the present invention first district carries out in the presence of acetate, and the quality percentage composition of acetate in reactant is 1～60%.
Beneficial effect of the present invention: the not evaporation liquid fraction that contains rhodium catalyst among the present invention at first entered the 4th district before circulation enters first district, catalyzer is activated by the mixture of hydrogen or hydrogen and carbon monoxide, the catalyst deactivation that causes because of evaporation can be alleviated greatly, thereby has improved the overall throughput of reaction.The present invention should avoid being interpreted as the method that the mixture of hydrogen or hydrogen and carbon monoxide directly is sent to flasher, can avoid the loss of the mixture of hydrogen or hydrogen and carbon monoxide.In fact, if the mixture of hydrogen or hydrogen and carbon monoxide is introduced the flash zone in second district, because of the mixture of flash distillation effect hydrogen or hydrogen and carbon monoxide enters gas phase, then the mixture of hydrogen or hydrogen and carbon monoxide will lose in a large number.The mode that the mixture of hydrogen or hydrogen and carbon monoxide and unevaporated liquid fraction are circulated to first district among the present invention after the 4th district contacts can be avoided the loss of the mixture of hydrogen or hydrogen and carbon monoxide.The liquid fraction that do not evaporate that contains rhodium catalyst partly or entirely contacts with the mixture of carbon monoxide with hydrogen or hydrogen, does not evaporate decaying catalyst in the liquid fraction by part or all of being reduced by the mixture of hydrogen or hydrogen and carbon monoxide.The mixture of hydrogen or hydrogen and carbon monoxide is added into and the catalyst action that does not evaporate in the liquid fraction with gas form or the form in the liquid of being dissolved in the 4th district, enter into the reactor in first district then together, also do not need the mixture separation apparatus of special hydrogen or hydrogen and carbon monoxide.
Description of drawings
Fig. 1 is first kind of scheme synoptic diagram of the present invention;
Fig. 2 is second kind of scheme synoptic diagram of the present invention;
Fig. 3 is the third scheme synoptic diagram of the present invention;
Fig. 4 is the 4th a kind of scheme synoptic diagram of the present invention.
Embodiment
Below by embodiment the present invention is described in further detail: a kind of preparation method of acetic anhydride under rhodium catalyst, be in the presence of the catalyzer of main ingredient with the rhodium, reaction raw materials is the mixture of methyl acetate or dme or methyl acetate and dme, wherein preferred methyl acetate, the quality percentage composition of methyl acetate is 3～50%, reaction raw materials is that reaction zone carries out the liquid-phase carbonylation reaction in first district, it is that separation is evaporated in the disengaging zone that post reaction mixture enters second district, it is that the separation that the separation and purification district carries out the product diacetyl oxide is purified that the gas phase fraction that contains the product diacetyl oxide enters the 3rd district, containing the liquid fraction that do not evaporate of rhodium catalyst, to enter the 4th district be that the catalyst activation district contacts with the mixed gas of hydrogen or hydrogen and carbon monoxide with the activation rhodium catalyst, and the described not evaporation liquid fraction that contains rhodium catalyst is imported into first district after through the 4th district and proceeds carbonylation reaction.Rhodium catalyst is the given indicative table of referenced patents US 3769329 specifically.Can use methyl halide to be promotor in described liquid-phase carbonylation reaction, the quality percentage composition of promotor is 2～40%, uses basic metal or alkaline earth salt to be promotor.Described methyl halide is a methyl iodide, and described basic metal or alkaline earth salt are lithium iodide or lithium acetate, and its quality percentage composition is 1.5～20%.The liquid fraction that do not evaporate that contains rhodium catalyst is 0.01～100 minute with mixture duration of contact of hydrogen or hydrogen and carbon monoxide in the 4th district, preferred 1～60 minute.Containing the liquid fraction that do not evaporate of rhodium catalyst, to contact temperature with the mixture of hydrogen or hydrogen and carbon monoxide in the 4th district be 30～250 ℃, preferred 50～220 ℃.The absolute pressure in described the 4th district is 1～100bar.The absolute pressure in described the 4th district is 10～50bar, and the high 0.01～20bar of pressure in pressure ratio first district in the 4th district, the high 0.1～5bar of pressure in pressure ratio first district in preferred the 4th district.Add methyl alcohol or water in the mixture of methyl acetate or dme or methyl acetate and dme, the present invention can prepare the mixture of diacetyl oxide and acetate.The oxonation in first district can carry out in the presence of acetate, and the quality percentage composition of acetate in reactant is 1～60%, and the preferred quality percentage composition of acetate in reactant is 10～40%.Can add rare gas element in the mixed gas of hydrogen or hydrogen and carbon monoxide, as methane or nitrogen etc.The mixed gas of hydrogen or hydrogen and carbon monoxide and the volume ratio of rare gas element are 10%-99%.The molar weight of the mixed gas of hydrogen or hydrogen and carbon monoxide is 2～100,000 times of molar weight of rhodium in the rhodium catalyst, is preferably 100～5000 times.The described not evaporation liquid fraction that contains rhodium catalyst can make its cut purifying, the processing of for example removing corroding metal through any kind ground purification process before entering the 4th district.
Fig. 1 is first kind of embodiment of the present invention, wherein do not evaporate liquid fraction and reducing substances (reducing substances all refers to the mixture of hydrogen or hydrogen and carbon monoxide in the accompanying drawing) and contact, the mixture of hydrogen or hydrogen and carbon monoxide is the catalyst reduction and the activation of not evaporating in the liquid fraction.Therefore, hydrogen or hydrogen with the mixture of carbon monoxide and not evaporated fraction enter the reactor 1 that contains catalyst system, ester, acetate, diacetyl oxide, by product and stablizer.Mixture reacts in reactor, leaves reactor afterwards, and reaction mixture utilizes the valve puffing, and mixture is partly evaporated, and introduces flasher 2.The cut of condensation evaporation makes the diacetyl oxide of wanting purifying separate with uncooled product, and uncooled product is the gaseous by-product of carbon monoxide, hydrogen, reaction.Stay and contain the catalyzer cut from the circulation loop Returning reactor in the liquid.The mixture of hydrogen or hydrogen and carbon monoxide is introduced from being used for the downstream of pump of circulating liquid cut.
Fig. 2 is second kind of embodiment of the present invention, wherein a part not evaporated fraction contact with the mixture of carbon monoxide with hydrogen or hydrogen, the mixture of hydrogen or hydrogen and carbon monoxide also activates the catalyst reduction in the evaporated fraction not.Therefore, hydrogen or hydrogen with the mixture of carbon monoxide and not evaporated fraction enter the reactor 1 that contains catalyst system, ester, acetate, diacetyl oxide, by product and stablizer.Mixture reacts in reactor, leaves reactor afterwards, and reaction mixture utilizes the valve puffing, and mixture is partly evaporated, and introduces flasher 2.The cut of condensation evaporation makes the diacetyl oxide of wanting purifying separate with uncooled product, and uncooled product is the gaseous by-product of carbon monoxide, hydrogen, reaction.Stay and contain the catalyzer cut from the circulation loop Returning reactor in the liquid.From the circulation road, a part is drawn in this logistics, this part is incorporated in the jar 4 that the mixture that stirs or do not adorn stirring and introduce hydrogen or hydrogen and carbon monoxide is housed, after stopping certain hour, merge, enter reactor with the not evaporated fraction logistics of not introducing jar 4.
Fig. 3 is the third embodiment of the present invention, is a variation of embodiment shown in Figure 2.The difference of two embodiments is that in the present embodiment, a unevaporated whole rather than part that contains the catalyzer cut enters jar 4, uses a pump thus less.
Fig. 4 is the 4th a kind of embodiment of the present invention, is a variation of embodiment shown in Figure 3.The difference of two embodiments is, in the present embodiment, the mixture of hydrogen or hydrogen and carbon monoxide is dissolved in the liquid state with liquid and enters jars 4.
Pressure in following examples and the Comparative Examples refers to absolute pressure.
Fen Si district continuous carbonylation ester or ether, the preparation diacetyl oxide.First district is a reaction zone, comprises a pressurized reactor that carries out carbonylation.Second district is the disengaging zone of formed diacetyl oxide.Adopt heating flash evaporation, then, the gas phase that is evaporated is partly delivered to the 3rd district, carry out the purifying of gained diacetyl oxide in this district.Comprise various distillation towers in this district, wherein gained diacetyl oxide and acetate, methyl acetate, methyl iodide and separation of by-products.The unevaporated liquid phase in second district is for containing mixture of catalysts, by looping back reactor behind the 4th district.The Primary Catalysts of reaction solution is a rhodium, and the control rhodium concentration is 500ppm, and methyl iodide is a promotor, and lithium iodide is a promotor, and reaction raw materials is a methyl acetate, and temperature of reaction is 180 ℃, pressure 28bar.The set-up mode in the 4th district is seen the high 0.01bar of accompanying drawing 1, the four district's pressure ratio, first district's pressure, is 28.01bar.The mixed gas of hydrogen and carbon monoxide (hydrogen volume content is 50%, and the carbon monoxide volume content is 50%) enters pump outlet behind the flasher, and gas is circulated to the reactor in first district with after the not evaporated fraction that contains catalyzer contacts in pipeline.The control tube channel temp is 140 ℃, and the mixture of hydrogen and carbon monoxide is 0.01 minute with the duration of contact that contains the not evaporated fraction of catalyzer.The experiment continuously through 500 hours, the mensuration carbonylation rate is 1.98mol/l/h.
Reaction solution component and reaction conditions are with embodiment 1, and except that the set-up mode difference in the 4th district, method is similarly to Example 1 carried out carbonylation and prepared diacetyl oxide.The set-up mode in the 4th district is seen accompanying drawing 2, and hydrogen enters the set jar of pump outlet behind the flasher.After the not evaporated fraction that hydrogen and 50% contains catalyzer contacts in jar, be circulated to the reactor in first district, the 50% not evaporated fraction that contains catalyzer direct cycles to the reactor in first district with pump in addition.The temperature of controlling the set jar in the 4th district is 220 ℃, and pressure is 1bar, and hydrogen is 1 minute with the duration of contact that contains the not evaporated fraction of catalyzer.The experiment continuously through 500 hours, the mensuration carbonylation rate is 2.15mol/l/h.
Embodiment 3
Reaction solution component and reaction conditions are with embodiment 1, and except that the set-up mode difference in the 4th district, method is similarly to Example 1 carried out carbonylation and prepared diacetyl oxide.The set-up mode in the 4th district is seen accompanying drawing 3, and the mixed gas of hydrogen and carbon monoxide (hydrogen volume content is 50%, and the carbon monoxide volume content is 50%) enters the set jar of pump outlet behind the flasher.Gas is circulated to the reactor in first district with after the not evaporated fraction that all contains catalyzer contacts in jar 4.The temperature of controlling the set jar in the 4th district is 250 ℃, and pressure is 28.1bar, and than the high 0.1bar of first district's pressure, the mixture of hydrogen and carbon monoxide is 100 minutes with the duration of contact that contains the not evaporated fraction of catalyzer.The experiment continuously through 500 hours, the mensuration carbonylation rate is 2.55mol/l/h.
Reaction solution component and reaction conditions be with embodiment 1, and except that the set-up mode difference in the 4th district, method is similarly to Example 1 carried out carbonylation and prepared diacetyl oxide or diacetyl oxide, acetate mixture.The set-up mode in the 4th district is seen accompanying drawing 4, and hydrogen is dissolved in the methyl acetate, enters the set jar of pump outlet behind the flasher with the liquid of gas dissolved afterwards.Gas is circulated to the reactor in first district with after the not evaporated fraction that all contains catalyzer contacts in pipeline.The temperature of controlling the set jar in the 4th district is 30 ℃, and pressure is 33bar, and than the high 5bar of first district's pressure, the methyl acetate that is dissolved with hydrogen is 40 minutes with the duration of contact that contains the not evaporated fraction of catalyzer.The experiment continuously through 500 hours, the mensuration carbonylation rate is 2.11mol/l/h.
Embodiment 5
Reaction solution component and reaction conditions are with embodiment 1, and except that the set-up mode difference in the 4th district, method is similarly to Example 1 carried out carbonylation and prepared diacetyl oxide.The set-up mode in the 4th district is seen accompanying drawing 3, and the mixed gas of hydrogen and carbon monoxide (hydrogen volume content is 50%, and the carbon monoxide volume content is 50%) enters the set jar of pump outlet behind the flasher.Gas and the not evaporated fraction that all contains catalyzer are circulated to the reactor in first district after jar contacts.The temperature of controlling the set jar in the 4th district is 180 ℃, and pressure is 48bar, and than the high 20bar of first district's pressure, the mixture of hydrogen and carbon monoxide is 1 minute with the duration of contact that contains the not evaporated fraction of catalyzer.The experiment continuously through 500 hours, the mensuration carbonylation rate is 2.20mol/l/h.
Comparative Examples 1
By the method for knowing, Fen San district continuous carbonylation ester or ether prepare diacetyl oxide.First district is a reaction zone, comprises a pressurized reactor that carries out carbonylation.Second district is the disengaging zone of formed diacetyl oxide.Adopt heating flash evaporation, then, the gas phase that is evaporated is partly delivered to the 3rd district, carry out the purifying of gained diacetyl oxide in this district.Comprise various distillation towers in this district, wherein gained diacetyl oxide and acetate, methyl acetate, methyl iodide and separation of by-products.The unevaporated liquid phase in second district loops back reactor for containing mixture of catalysts by pump.The composition of reaction solution and reaction conditions are tested through 500 hours continuously with embodiment 1, and recording carbonylation rate is 1.9mol/l/h.
The reaction solution composition of other embodiment of the present invention and reaction conditions are with embodiment 1, and different is the set-up mode in the 4th district and the condition difference in the 4th district.Typical embodiment and Comparative Examples are listed in the table below.
Embodiment 6～15 tabulations
| Embodiment | Embodiment | Hydrogen: carbon monoxide (volume ratio) | The contact temperature (℃) | The 4th district's pressure (bar) | Duration of contact (branch) | Speed of reaction (mol/l/h) |
| 6 7 8 9 10 11 12 13 14 15 | 1 2 2 2 3 3 3 3 4 4 | 80∶20 50∶50 80∶20 20∶80 100∶0 10∶90 50∶50 80∶20 100∶0 20∶80 | 180 180 200 200 50 220 140 180 50 100 | 28.5 45 5 40 29 50 100 30 28.5 40 | 2 60 30 30 80 20 50 80 50 80 | 2.10 2.21 2.25 2.19 2.42 2.33 2.38 2.52 2.01 1.96 |
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (13)
1. the preparation method of an acetic anhydride under rhodium catalyst, be in the presence of the catalyzer of main ingredient with the rhodium, the mixture of methyl acetate or dme or methyl acetate and dme is that reaction zone carries out the liquid-phase carbonylation reaction in first district, it is that separation is evaporated in the disengaging zone that post reaction mixture enters second district, it is that the separation that the separation and purification district carries out the product diacetyl oxide is purified that the gas phase fraction that contains the product diacetyl oxide enters the 3rd district, containing the liquid fraction that do not evaporate of rhodium catalyst, to enter the 4th district be that the catalyst activation district contacts with the mixed gas of hydrogen or hydrogen and carbon monoxide with the activation rhodium catalyst, and the described not evaporation liquid fraction that contains rhodium catalyst is imported into first district after through the 4th district and proceeds carbonylation reaction.
2. according to the preparation method of the described a kind of acetic anhydride under rhodium catalyst of claim 1, it is characterized in that: in described liquid-phase carbonylation reaction, use methyl halide to be promotor, use basic metal or alkaline earth salt to be promotor.
3. according to the preparation method of the described a kind of acetic anhydride under rhodium catalyst of claim 2, it is characterized in that: described methyl halide is a methyl iodide, and described basic metal or alkaline earth salt are lithium iodide or lithium acetate.
4. according to the preparation method of the described a kind of acetic anhydride under rhodium catalyst of claim 1, it is characterized in that: the liquid fraction that do not evaporate that contains rhodium catalyst is 0.01～100 minute with mixture duration of contact of hydrogen or hydrogen and carbon monoxide in the 4th district.
5. according to the preparation method of claim 1 or 4 described a kind of acetic anhydride under rhodium catalyst, it is characterized in that: the liquid fraction that do not evaporate that contains rhodium catalyst is 1～60 minute with mixture duration of contact of hydrogen or hydrogen and carbon monoxide in the 4th district.
6. according to the preparation method of the described a kind of acetic anhydride under rhodium catalyst of claim 1, it is characterized in that: containing the liquid fraction that do not evaporate of rhodium catalyst, to contact temperature with the mixture of hydrogen or hydrogen and carbon monoxide in the 4th district be 30～250 ℃.
7. according to the preparation method of claim 1 or 6 described a kind of acetic anhydride under rhodium catalyst, it is characterized in that: containing the liquid fraction that do not evaporate of rhodium catalyst, to contact temperature with the mixture of hydrogen or hydrogen and carbon monoxide in the 4th district be 50～220 ℃.
8. according to the preparation method of the described a kind of acetic anhydride under rhodium catalyst of claim 1, it is characterized in that: the absolute pressure in described the 4th district is 1～100bar.
9. according to the preparation method of claim 1 or 8 described a kind of acetic anhydride under rhodium catalyst, it is characterized in that: the absolute pressure in described the 4th district is 10～50bar, and the high 0.01～20bar of pressure in pressure ratio first district in the 4th district.
10. according to the preparation method of the described a kind of acetic anhydride under rhodium catalyst of claim 9, it is characterized in that: the high 0.1～5bar of pressure in pressure ratio first district in the 4th district.
11. the preparation method according to the described a kind of acetic anhydride under rhodium catalyst of claim 1 is characterized in that: the molar weight of the mixed gas of hydrogen or hydrogen and carbon monoxide is 2～100,000 times of molar weight of rhodium in the rhodium catalyst.
12. the preparation method according to the described a kind of acetic anhydride under rhodium catalyst of claim 11 is characterized in that: the molar weight of the mixed gas of hydrogen or hydrogen and carbon monoxide is 100～5000 times of molar weight of rhodium in the rhodium catalyst.
13. preparation method according to the described a kind of acetic anhydride under rhodium catalyst of claim 1, it is characterized in that: add methyl alcohol or water in the mixture of described methyl acetate or dme or methyl acetate and dme, the present invention can prepare the mixture of diacetyl oxide and acetate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721896B (en) * | 2009-12-10 | 2012-07-04 | 中国石化集团南京设计院 | Method for processing methyl iodide-contained combustible gas discharged into torch system by carbonylation compounding device |
| CN106140156A (en) * | 2015-04-20 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of activated carbon supported rhodium base catalyst and its preparation method and application |
| CN110845329A (en) * | 2019-10-23 | 2020-02-28 | 中石化南京工程有限公司 | Method for synthesizing acetic anhydride and co-producing propionic acid through carbonylation |
| CN114031492A (en) * | 2021-12-13 | 2022-02-11 | 上海簇睿低碳能源技术有限公司 | Process system for synthesizing acetic acid or acetic anhydride by using microchannel reactor and preparation method |
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2006
- 2006-04-19 CN CN200610025835A patent/CN100591655C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721896B (en) * | 2009-12-10 | 2012-07-04 | 中国石化集团南京设计院 | Method for processing methyl iodide-contained combustible gas discharged into torch system by carbonylation compounding device |
| CN106140156A (en) * | 2015-04-20 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of activated carbon supported rhodium base catalyst and its preparation method and application |
| CN110845329A (en) * | 2019-10-23 | 2020-02-28 | 中石化南京工程有限公司 | Method for synthesizing acetic anhydride and co-producing propionic acid through carbonylation |
| CN110845329B (en) * | 2019-10-23 | 2022-09-20 | 中石化南京工程有限公司 | Method for synthesizing acetic anhydride and co-producing propionic acid through carbonylation |
| CN114031492A (en) * | 2021-12-13 | 2022-02-11 | 上海簇睿低碳能源技术有限公司 | Process system for synthesizing acetic acid or acetic anhydride by using microchannel reactor and preparation method |
| CN114031492B (en) * | 2021-12-13 | 2023-08-29 | 上海簇睿低碳能源技术有限公司 | Process system for synthesizing acetic acid or acetic anhydride by adopting microchannel reactor and preparation method |
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