CN102476988A - Method for preparing carboxyl anhydride - Google Patents
Method for preparing carboxyl anhydride Download PDFInfo
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- CN102476988A CN102476988A CN2010105572687A CN201010557268A CN102476988A CN 102476988 A CN102476988 A CN 102476988A CN 2010105572687 A CN2010105572687 A CN 2010105572687A CN 201010557268 A CN201010557268 A CN 201010557268A CN 102476988 A CN102476988 A CN 102476988A
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Abstract
The present invention relates to a method for preparing carboxyl anhydride. The method comprises adopting carboxylate derived from alcohol and carboxylic acid and carbon monoxide containing a small amount of hydrogen gas as raw material, and allowing oxonation in a liquid reaction medium in the presence of group VIIIB catalyst to produce carboxyl anhydride. The liquid reaction medium includes the group VIIIB catalyst, organic halide, carboxylate, alkali metal salt, carboxyl anhydride, carboxylic acid, a protectant N-acetylimidazole, and an organic additive ethylidene diacetate (EDA). The method avoids reaction of metal ions and EDA and decreases insoluble tar generated during reaction by using the protectant N-acetylimidazole, and improves whole oxonation rate by maintaining the content of the organic additive EDA at a constant level.
Description
Technical field
The present invention relates to utilize the verivate of alcohols and carboxylic acid and carbon monoxide to carry out the method that oxonation is made carboxylic acid anhydride, particularly utilize ritalin and carbon monoxide to carry out the method that oxonation is made acetic anhydride.
Background technology
Acetic anhydride is a kind of chemical industry raw material of knowing commonly used, and its main application is the chemical substance of manufacturing FM, and is the important source material of chemical such as synthetic drugs, spices, dyestuff.Industrial technology is made acetic anhydride at present has three kinds of methods; Be respectively ketene process, acetaldehyde oxidation and ritalin carbonyl process; Wherein with belong to old technology, scale is less, the manufacturer is numerous ketene process is a main flow; But, make that the method for present maximum-norm commercial prodn acetic anhydride is the ritalin carbonyl process because its energy consumption is high and many shortcomings.
Ketene process is a raw material with acetic acid or acetone, at high temperature removes a water molecules or methane and generates ketene, generates acetic anhydride with acetic acid reaction more afterwards.This technology because of temperature of reaction up to 750 ℃, its demand for high energy consumption will make this technology be eliminated gradually in the epoch of paying attention to the energy future.
Acetaldehyde oxidation is a catalyzer with metals such as manganese, cobalt, nickel, copper; Oxidation of acetaldehyde is become Peracetic Acid; Further generate acetic anhydride and water byproduct with the acetaldehyde reaction again; But acetic anhydride can further be hydrolyzed into acetic acid, thereby final product is the miscellany of acetic anhydride and acetic acid, reduces the productive rate of acetic anhydride.
It is the expanded application that the methyl alcohol carbonyl process is made acetic acid that the ritalin carbonyl process is produced acetic anhydride, and it is a raw material with ritalin and carbon monoxide, in the presence of transition-metal catalyst (as: rhodium, nickel, cobalt, iridium) and iodide promoters, produces acetic anhydride.The difference of ritalin carbonyl process production acetic anhydride and two kinds of technologies of methyl alcohol carbonyl process manufacturing acetic acid is the water cut of reaction solution.The former reaction solution must remain under the anhydrous state and carry out, and can there be the moisture of 1～20wt% in latter's reaction solution.Moisture is very big to the stability influence of catalyzer, and high-moisture helps the stable of catalyzer, thereby the stability of ritalin carbonyl process catalyzer under no water system then becomes the matter of utmost importance that must overcome.Want head it off, interpolation promotor capable of using or co-catalyst, like basic metal, phosphonium salt, ammonium salt and transition-metal catalyst, the stability that promotes catalyst system is with active.In addition, the ritalin carbonyl process is produced acetic anhydride must add small quantity of hydrogen in the carbon monoxide charging, to keep the activity of rhodium catalyst.
In catalystsystem, add one or more promotor to improve the catalysis efficiency of catalyzer, for this type of studies most important problem.No. 4002678 Patent publish of the U.S. is catalyzer with nickel, chromium under anhydrous state, and carbon monoxide, ritalin or dme are raw material, in the presence of halogenide and trivalent organonitrogen or phosphorus compound, carry out oxonation.Europe EP 0391680 A1 Patent publish is a kind of makes the method for carboxylic acid with alcohol or its ester class under aqueous conditions, and with the stablizer of level Four ammonium iodide (quaternary ammonium iodide) as rhodium catalyst.No. 4115444 a kind of method of making acetic anhydride of Patent publish of the U.S.; It is a catalyzer with VIIIB family precious metal, cooperates at least a IVB of being selected from family, VB family, group vib or VIIIB family non-noble metal compound and the multiple promotor that contains trivalent organonitrogen or organo phosphorous compounds; Its catalyzer is rhodium and iridium, and metallic promoter agent is iron, cobalt, nickel, chromium etc., and it has disclosed organic nitrogen compound promotor and has been selected from compounds such as amine, imidazoles, imide, acid amides, oximes.China 1876239A and 1778468A patent all disclose with rhodium compound as catalyzer; With alkyl iodide, heteropolyacid salt and the alkali-metal salt compounded of iodine of different content catalystsystem as promotor; Be used for ritalin oxo process anhydride reaction; This catalystsystem produces synergy through heteropolyacid salt and catalyzer, can improve the performance of catalystsystem.No. 7553991 patent of the U.S. used different nitrogen heterocyclic ring organic promoters in carbonylation process; Make itself and rhodium catalyst form stable complex compound (complex; Title complex, mixture), have the effect that promotes oxonation speed; Add this type of organic promoter and can reduce temperature of reaction or reduction lithium iodide addition and can keep original speed of reaction, have the effect of saving the energy, reducing production costs.No. 4430273 patent of No. 5298586 patent of the U.S. and the U.S. is all clear to be disclosed in the technology of carrying out rhodium catalyst catalytic carbonylation reacted carboxylic acid anhydride under the anhydrous condition, adds stability and solvability that the ionic iodide that contains level Four nitrogen can effectively improve rhodium catalyst.Taiwan is applied for that No. 97147075 patent mentioned and in carbonylation process, is added the ionic liquid with nitrogen heterocyclic ring structural cation; Can improve oxonation speed; Simultaneously, ionic liquid has the characteristic of thermostability, chemicalstability and low-vapor pressure, easily separated and recovery in catalysis system.
In the industrial technology of the synthetic acetic anhydride of ritalin carbonylation; The general catalysis system that adopts precious metal and iodide; But regular meeting in carbonylation process of this system produces insoluble tar thing, and people such as the Cao Yu of Shanghai Jiaohua Co., Ltd then analyze and inquire into reaction mechanism [Shanghai Chemical, 2006 years that the tar thing generates to the moity of the tar thing that is generated in the acetic anhydride technology; The 31st volume; The 07th phase], find in the process of carbonylation successive reaction, to generate by products such as acetaldehyde, vinyl-acetic ester, two acetic acid ethyls simultaneously, and these by products be prone to reactor drum in the metals ion effect; Precious metal ion particularly, and form insoluble tar thing.Because the tar thing can reduce catalyst activity; Even iodine and noble metal catalyst sealed, make catalyst deactivation and cause carbonylation reaction to stop, and then oxonation speed is descended; Therefore, grasping and control the tar generation is one of improved key of carbonylating process.
In many prior art patent; Mention ester class and ethers oxonation are made has the tar resistates in the technology of acetic anhydride and two acetic acid ethyls generation; And the tar resistates be prone to coat rhodium metal and makes the rhodium catalyst loss, so the patented technology that has disclosed at present all focuses on the tar resistates is removed and with the method for rhodium recycling.The rhodium recovery technology can be divided into extraction process, the precipitator method, combustion method and adsorption method of separation haply.After the 4340569th, 4340570 and No. 4341741 patents of the U.S. all disclose the pre-treatment and evaporation concentration through alcohols, through the extraction of amine processing and haloid acid, just can the precious metal that comprise rhodium be reclaimed again.No. 1171879 Patent publish of Canada extracts the precious metal that comprises rhodium by means of being prone to tar thing dissolved solvent, and this solvent comprises alkanes, naphthenic, alkyl halide class and aromatic hydrocarbon solvent, particularly hexanaphthene, toluene and carbon tetrachloride solvent.No. 3920449 Patent publish resistates of the U.S. reclaims rhodium metal through the mode of Pintsch process.No. 3978148 Patent publish of the U.S. is adsorbed in rhodium metal on the activated carbon, reaches the effect that reclaims rhodium metal.The carbonyl that No. 3560539 Patent publish of the U.S. uses hydrogen and hydrogenate to reduce in the tar thing forms hydroxy, thus with the release of rhodium misfit thing and with its recovery.
Therefore, develop and a kind ofly can effectively prolong rhodium catalyst work-ing life, reduce the complicacy that the tar thing generated and then reduced technology, and can improve the space-time output of carboxylic acid anhydride simultaneously, make this technology have more economic rationality, be still following main research topic.
Summary of the invention
Main purpose of the present invention is to provide a kind of method of manufacture of under anhydrous condition, keeping high reaction rate, reducing the carboxylic acid anhydride of tar thing formation simultaneously.
For reaching above-mentioned and other purpose; The method of manufacture of carboxylic acid anhydride of the present invention is to be raw material with carboxylic acid institute deutero-carboxylicesters with the carbon monoxide that contains small quantity of hydrogen with alcohol; In the presence of VIII B family catalyzer, in liquid reaction medium, carry out oxonation and form carboxylic acid anhydride.
Mainly comprise in this reaction medium VIII B family catalyzer, Organohalogen compounds, carboxylicesters, an alkali metal salt, organic additive two acetic acid ethyls (Ethylidene diacetate, EDA), protective material N-acetyl imidazole (N-acetylimidazole), carboxylic acid anhydride, carboxylic acid and a small amount of impurity (impurity).Particularly; In this liquid reaction medium, contain 300 to 3000ppm VIII B family catalyzer, the Organohalogen compounds of 5 to 30 weight %, an alkali metal salt of 1 to 15 weight %, the two acetic acid ethyls of 0.5 to 20 weight %, N-acetyl imidazole and carboxylicesters, carboxylic acid anhydride, carboxylic acid and a small amount of impurity of 0.5 to 20 weight % usually.These organic additive two acetic acid ethyls need be kept certain content in system, can keep its content in system through the generation of the side reaction in the system or by the mode of extra interpolation.
Employed alcohol is the fatty alcohol compounds with 1 to 6 carbon atom among the present invention, and carboxylic acid is the carboxylic acid with 1 to 6 carbon atom, then contains an amount of hydrogen in the CO gas of participation oxonation, can help keeping of catalyst activity.Preferably, the hydrogen that contains concentration 0.1 to 10% in the carbon monoxide feed gas.In addition, this VIII B family catalyzer can be one or more the catalyzer that is selected from the group of being made up of rhodium, nickel, cobalt, iridium; These Organohalogen compounds can be methyl halogenide, for example methyl-iodide; And this an alkali metal salt can be the iodide salt of IA/IIA family, lithium iodide for example, and in this liquid reaction medium, then can contain 500 to 8000ppm IA/IIA family metals ion provides relative iodide ion content.
In one embodiment, carboxylicesters used in the present invention is a ritalin; Carboxylic acid is an acetic acid; Carboxylic acid anhydride is an acetic anhydride.
Manufacturing method according to the invention, oxonation can in 160 to 240 ℃ and with carbon monoxide control reaction pressure between 20 to 60kg/cm
2Condition under carry out.
In catalyst system of the VIII of oxonation of the present invention B family; Reduce the formation that indissoluble is separated the tar thing through protective material N-acetyl imidazole; And improve the space-time output of carboxylic acid anhydride with organic additive two acetic acid ethyls; Expand the operation scope thus, reaction can be carried out under relatively mild condition.
Description of drawings
Fig. 1 is the infrared spectrogram of embodiment 1 to 3.
Fig. 2 is the infrared spectrogram of embodiment 4 to 6.
Embodiment
Below further specify characteristics of the present invention and effect through particular specific embodiment, but non-ly be used to limit scope of the present invention.
The present invention can be applicable to batch wise processes, and wherein employed major equipment comprises, for example, and one liter of reactor drum that anticorrosive material is processed and carbon monoxide storage tanks.Reactor drum itself is with the variable speed motor of rotation rate-controllable, and it can adjust suitable rotating speed to keep good gas-liquid mixed effect; The reactor drum ectonexine installs cooling coil and electric heating piece respectively additional, to control and to keep stable temperature of reaction; One Regulation Control valve is installed, to keep and to control the pressure of main reactor between reactor drum and hydrogen, carbon monoxide storage tanks.
According to of the present invention one preferred specific embodiment, use ritalin and the carbon monoxide that contains small quantity of hydrogen, in reactive tank, carry out oxonation and make acetic anhydride.The reaction medium that carries out in the reactive tank of oxonation has been kept VIII B family catalyzer, for example rhodium catalyst; Alcohol and the formed carboxylicesters of carboxylic acid, for example ritalin, or alcohol compound deutero-ethers, for example dme; With respect to the Organohalogen compounds of raw alcohol, for example methyl-iodide; An alkali metal salt, for example lithium iodide; Carboxylic acid anhydride, for example acetic anhydride; Carboxylic acid, for example acetic acid; Organic additive two acetic acid ethyls and protective material N-acetyl imidazole.
In addition, also can be in continuous process embodiment of the present invention.According to another preferred specific embodiment of the present invention; With the ritalin raw material together with the carbon monoxide that contains small quantity of hydrogen; Continuously feeding to oxonation groove; Ritalin and reaction of carbon monoxide are changed into acetic anhydride, and wherein the reactive tank liquid reaction medium contains rhodium catalyst, ritalin, acetic acid, acetic anhydride, methyl-iodide, basic metal, organic additive two acetic acid ethyls and protective material N-acetyl imidazole.Corresponding to the reactive tank of continuously feeding, comprise product acetic anhydride, unreacted ritalin, acetic acid, methyl-iodide, rhodium catalyst, an alkali metal salt, organic additive two acetic acid ethyls and protective material N-acetyl imidazole in the reaction product effluent.Continue dispensing liquid reaction product to sudden strain of a muscleization groove (or evaporating pot); The liquid reactant light composition is through gasification and by discharging at sudden strain of a muscleization groove top; Further separating acetic acid and acetic anhydride to the zone purification, the rhodium catalyst that the sudden strain of a muscleization trench bottom comprises and other heavy ingredient are back to reactor drum.After the acetic anhydride finished product was isolated in the zone purification, acetic acid and other composition (comprising methyl-iodide, ritalin etc.) then were back to reactor drum.In reaction process, methyl-iodide, an alkali metal salt, and above-mentioned organic additive and protective material can't be consumed, and can be circulated back to reactive tank from sudden strain of a muscleization groove or zone purification continuously.Be familiar with those skilled in the art of the present invention and can suitably add the component content of adjustment reaction medium as required according to the actually operating situation.
Can prevent metals ion, particularly precious metal ion (for example, the rhodium metal catalyzer) through the following example 1-6 explanation N-acetyl imidazole, with two acetic acid ethyl effects, and then formed indissoluble is separated the tar thing in the reduction reaction process.
(embodiment 1)
With the two acetic acid ethyls of 0.29g, the IrCl of 0.37g
3XH
2The ethanol of O (wherein the Ir atom accounts for 52.5%) and 100 milliliters adds in the reaction flask, be heated to 100 degrees centigrade after back flow reaction 20 hours.Filter after cooling to room temperature, black precipitate solid and brown solution, with brown solution concentrate and with after the ether flushing again oven dry remove solvent, can measure the infrared spectrogram ((a) among Fig. 1) of this reaction after product, and as control experiment.
(embodiment 2)
With the N-acetyl imidazole of 0.22g, the IrCl of 0.37g
3XH
2The ethanol of O (wherein the Ir atom accounts for 52.5%) and 100 milliliters adds in the reaction flask, be heated to 100 degrees centigrade after back flow reaction 20 hours.Filter after cooling to room temperature, yellow solid and yellow solution, with yellow solution concentrate and with after the ether flushing again oven dry remove solvent, can measure the infrared spectrogram ((b) among Fig. 1) of this reaction after product, and as control experiment.
(embodiment 3)
With the two acetic acid ethyls of 0.29g, the N-acetyl imidazole of 0.22g, the IrCl of 0.37g
3XH
2The ethanol of O (wherein the Ir atom accounts for 52.5%) and 100 milliliters adds in the reaction flask, be heated to 100 degrees centigrade after back flow reaction 20 hours.Filter after cooling to room temperature, yellow solid and yellow solution, with yellow solution concentrate and with after the ether flushing again oven dry remove solvent, can measure the infrared spectrogram ((c) among Fig. 1) of this reaction after product.
Compare with the infrared spectrogram of embodiment 1 and embodiment 2 through embodiment 3, can obviously find out the spectrogram of embodiment 3 and the spectrogram signal similar of embodiment 2, promptly the coordination power of N-acetyl imidazole and iridium ion is preferable.Show that the present invention adds this type of protective material the effect that prevents two acetic acid ethyls and iridium metals ionization is arranged really.
(embodiment 4)
With the two acetic acid ethyls of 0.29g, the RhCl of 0.27g
3XH
2The ethanol of O (wherein the Rh atom accounts for 38%) and 100 milliliters adds in the reaction flask, be heated to 100 degrees centigrade after back flow reaction 20 hours.Filter after cooling to room temperature, black precipitate solid and yellow solution, with yellow solution concentrate and with after the ether flushing again oven dry remove solvent, can measure the infrared spectrogram ((a) among Fig. 2) of this reaction after product, and as control experiment.
(embodiment 5)
With the N-acetyl imidazole of 0.22g, the RhCl of 0.27g
3XH
2The ethanol of O (wherein the Rh atom accounts for 38%) and 100 milliliters adds in the reaction flask, be heated to 100 degrees centigrade after back flow reaction 20 hours.Filter after cooling to room temperature, a small amount of black precipitate solid and red solution, with red solution concentrate and with after the ether flushing again oven dry remove solvent, can measure the infrared spectrogram ((b) among Fig. 2) of this reaction after product, and as control experiment.
(embodiment 6)
With the two acetic acid ethyls of 0.29g, the N-acetyl imidazole of 0.22g, the RhCl of 0.27g
3XH
2The ethanol of O (wherein the Rh atom accounts for 38%) and 100 milliliters adds in the reaction flask, be heated to 100 degrees centigrade after back flow reaction 20 hours.Filter after cooling to room temperature, a small amount of black precipitate solid and red solution, with red solution concentrate and with after the ether flushing again oven dry remove solvent, can measure the infrared spectrogram ((c) among Fig. 2) of this reaction after product.
Compare with the infrared spectrogram of embodiment 4 and embodiment 5 through embodiment 6, can obviously find out the spectrogram of embodiment 6 and the spectrogram signal similar of embodiment 5, promptly the coordination power of N-acetyl imidazole and rhodium ion is preferable.Show that the present invention adds this type of protective material the effect that prevents two acetic acid ethyls and rhodium metal ionization is arranged really.
Through existing a certain amount of organic additive two acetic acid ethyls will help to improve the space-time output of acetic anhydride in following comparative example 1 and the embodiment 7-15 illustrative system.
(comparative example 1)
In this comparative example, adopt the batch type experiment method, under the situation of not adding promotor of the present invention, carry out oxonation, with as control experiment.Each composition charging content is respectively the rhodium catalyst of ritalin 43wt%, methyl iodide 18wt%, acetic anhydride 18wt%, lithium iodide (4000ppm iodide ion) and 1400ppm in the reactor drum, and the acetic acid of all the other an amount of difference is its solvent.This reaction mixture is inserted in the reactor drum, at first build and press 1kg/cm with hydrogen
2, import carbon monoxide again and build after the pressure and heat up gradually, reach the reaction design temperature after, additional carbon monoxide makes system's internal pressure reach 27kg/cm
2Along with the consumption of carbon monoxide, continue to replenish carbon monoxide and make pressure-stabilisation remain on 27kg/cm between the reaction period
2, record carbon monoxide consumption, and sampling analyzes calculates acetic anhydride unit time-space productive rate (STY) value (unit: mol * hour).
(embodiment 7 to 9: add the influence of organic additive to speed of reaction)
Under the reaction conditions identical, carry out oxonation with comparative example 1, and in initial reaction medium, add 1,3 respectively, the organic additive two acetic acid ethyls of 5wt% experimentize.The experimental result of embodiment 7～9 and comparative example 1 is recorded in table 1, and wherein comparative example 1 is not for adding the blank assay of organic additive.Can obviously find out by this table 1; The STY value of the oxonation of different organic additive two acetic acid ethyl additions all has raising in various degree; All reach more than the 7mol/L*h, show that the present invention adds this type of organic additive the effect that improves acetic anhydride unit time-space productive rate is arranged really.
Table 1: add the influence of organic additive to speed of reaction
(embodiment 10 to 13: temperature of reaction and organic additive are to the influence of speed of reaction)
Under the reaction conditions identical, carry out oxonation, and in initial reaction medium, add the organic additive two acetic acid ethyls of 3wt%, and change temperature of reaction and experimentize, experimental result is recorded in table 2 with comparative example 1.By can obviously finding out in this table 2, add organic additive and change temperature of reaction, still have the effect of the STY value that improves oxonation, show that the present invention adds this type of organic additive under the differential responses temperature, the effect that improves the acetic anhydride productive rate is arranged really.In addition, compare, add this type of organic additive and can reduce temperature of reaction and preferable speed of reaction is arranged, have the effect of saving the energy, reducing production costs by embodiment 10,11 and comparative example 1.
Table 2: temperature of reaction and organic additive are to the influence of speed of reaction
(embodiment 14 to 15: reaction pressure and organic additive are to the influence of speed of reaction)
Under the reaction conditions identical, carry out oxonation, and in initial reaction medium, add the organic additive two acetic acid ethyls of 3wt%, and change reaction pressure and experimentize, experimental result is recorded in table 3 with comparative example 1.Can obviously find out by table 3, add organic additive and increase reaction pressure, can improve the STY value of oxonation really.Show that the present invention adds this type of organic additive under differential responses pressure, the effect that improves the acetic anhydride productive rate is arranged really.
Table 3: reaction pressure and organic additive are to the influence of speed of reaction
Claims (10)
1. the method for manufacture of a carboxylic acid anhydride; Is raw material with carboxylic acid institute deutero-carboxylicesters with the carbon monoxide that contains small quantity of hydrogen with alcohol; In the presence of VIII B family catalyzer; In liquid reaction medium, carry out oxonation and form carboxylic acid anhydride; Said reaction medium comprises VIII B family catalyzer, Organohalogen compounds, carboxylicesters, an alkali metal salt, carboxylic acid anhydride, carboxylic acid, protective material N-acetyl imidazole and organic additive two acetic acid ethyls, and said organic additive can be kept its content in system by means of the generation of the side reaction in the system or with the mode of extra interpolation.
2. method of manufacture according to claim 1, wherein, said oxonation carries out under 160～240 ℃ temperature.
3. method of manufacture according to claim 1, wherein, said oxonation is at 20～60kg/cm
2Pressure under carry out.
4. method of manufacture according to claim 1, wherein, it is 300～3000ppm that said reaction medium contains VIIIB family catalyzer total concn.
5. method of manufacture according to claim 1, wherein, said reaction medium contains the Organohalogen compounds of 5 to 30 weight %.
6. method of manufacture according to claim 1, wherein, said carbon monoxide feed gas contains 0.1 to 10% density of hydrogen.
7. method of manufacture according to claim 1, wherein, said an alkali metal salt is the iodide salt of IA/IIA family.
8. method of manufacture according to claim 7, wherein, said reaction medium contains 500 to 8000ppm IA/IIA family metals ion so that relative iodide ion content to be provided.
9. method of manufacture according to claim 1, wherein, the content of said organic additive two acetic acid ethyls is maintained 0.5 to 20 weight %.
10. method of manufacture according to claim 1, wherein, the addition of said protective material N-acetyl imidazole is 0.5 to 20 weight %.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113636930A (en) * | 2021-09-09 | 2021-11-12 | 宁夏希贝化工有限公司 | Production process of acetic anhydride |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115444A (en) * | 1975-03-10 | 1978-09-19 | Halcon International, Inc. | Process for preparing carboxylic acid anhydrides |
| CN1105603A (en) * | 1994-01-21 | 1995-07-26 | 中国科学院化学研究所 | Methyl alcohol carbonylation homogeneous rhodium catalyst and its preparing method and use |
| CN1129690A (en) * | 1995-02-21 | 1996-08-28 | 英国石油化学品有限公司 | Process for the carbonylation of an alcohol |
| CN1843624A (en) * | 2006-04-13 | 2006-10-11 | 西南化工研究设计院 | Catalyst system for synthesizing acetic anhydride by carbonyl under low pressure |
| US7553991B1 (en) * | 2008-01-07 | 2009-06-30 | China Petrochemical Development Corporation | Process for producing carboxylic acid anhydrides |
-
2010
- 2010-11-22 CN CN2010105572687A patent/CN102476988A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115444A (en) * | 1975-03-10 | 1978-09-19 | Halcon International, Inc. | Process for preparing carboxylic acid anhydrides |
| CN1105603A (en) * | 1994-01-21 | 1995-07-26 | 中国科学院化学研究所 | Methyl alcohol carbonylation homogeneous rhodium catalyst and its preparing method and use |
| CN1129690A (en) * | 1995-02-21 | 1996-08-28 | 英国石油化学品有限公司 | Process for the carbonylation of an alcohol |
| CN1843624A (en) * | 2006-04-13 | 2006-10-11 | 西南化工研究设计院 | Catalyst system for synthesizing acetic anhydride by carbonyl under low pressure |
| US7553991B1 (en) * | 2008-01-07 | 2009-06-30 | China Petrochemical Development Corporation | Process for producing carboxylic acid anhydrides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113636930A (en) * | 2021-09-09 | 2021-11-12 | 宁夏希贝化工有限公司 | Production process of acetic anhydride |
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