CN101153002A - Method for producing carboxylic acid - Google Patents
Method for producing carboxylic acid Download PDFInfo
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- CN101153002A CN101153002A CNA2006101396891A CN200610139689A CN101153002A CN 101153002 A CN101153002 A CN 101153002A CN A2006101396891 A CNA2006101396891 A CN A2006101396891A CN 200610139689 A CN200610139689 A CN 200610139689A CN 101153002 A CN101153002 A CN 101153002A
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Abstract
The present invention provides a production method of carboxylic acid. The alcohol compounds and derivatives react in a liquid reaction medium for carbonylation reaction to prepare carboxylic acid under the condition with carbon monoxide as the catalyst. The reaction medium comprises rhodium catalyst, water, organic halide, carboxylate, hydrohalogenic acid, catalytic additive and carboxylic acid; wherein, the catalyst additive has a structure as shown in MnYz, and M comes from IIIA-IVA metal, IB-VIIIB metal and lanthanide metal compounds and salts; Y is chosen from single or composite anion of hydroxide, carbonate, oxalate, acetate, nitrate, halogen oxygenate, sulfate, phosphate, halogen and oxygen atoms; n and z are integer to balance positive and negative charges. The catalyst system of the method uses specific catalytic additives, so that the carbonylation does not have a great deal of catalyst deposition under low-humidity conditions.
Description
Technical field
The present invention relates to utilize alcohol compound and carbon monoxide to carry out the method that oxonation is made carboxylic acid, particularly utilize methyl alcohol and carbon monoxide to carry out the method that oxonation is made acetic acid.
Background technology
Utilize oxonation to make carboxylic acid and be widely used for various chemical techniquees, for example under the condition that catalyzer exists, utilize alcohol compound and carbon monoxide to react the organic carboxyl acid that manufacturing has n+1 carbon atom with n carbon atom.
The U.S. the 3rd, 769, No. 329 patents disclose a kind of rhodium catalyst system, can be under relatively low temperature and pressure condition, for example below 300 ℃ and 15, the 000psig carbon monoxide pressure of tension carries out the methyl alcohol oxonation and forms acetic acid.The U.S. the 4th, 690, No. 912 patent further discloses, and uses the promotion composition contain halogen can be under relatively low temperature and pressure condition, increase selectivity, reactivity, and the stability of oxonation, and help the separation of product and the recovery of catalyzer.
The rhodium catalyst catalysis system that above-mentioned patent disclosed, though can under relatively low temperature and pressure condition, react, and have the advantage of high reaction preference.Yet, use rhodium catalyst to carry out the methyl alcohol oxonation when making acetic acid, under the lower operational condition of carbon monoxide pressure of tension and water-content, rhodium catalyst can change insoluble trivalent rhodium into and precipitate.Therefore, reactive system must carry out under the water content conditions of higher, to keep catalyst activity and high reaction rate.But the reactive system that this water content is higher can cause a large amount of energy cost of process consumption of subsequent purification acetate products.
No. 0055618 patent in Europe discloses a kind of sedimentary method of rhodium catalyst of avoiding, and comprises adding containing the organic compound of one or more nitrogen-atoms, phosphorus atom or COOH base as catalyst stabilizer.The U.S. the 4th, 733, No. 006 patent further discloses the alkali metal acetate class, and for example Lithium Acetate can be used as and avoids the sedimentary stablizer of rhodium catalyst.Yet the cognation of all not mentioned catalyst stabilizer of above-mentioned patent and methyl alcohol oxonation speed.
The U.S. the 5th, 001, No. 259 patent discloses, in methyl alcohol oxonation system, use the stablizer of the quaternary ammonium salt of the IA of 10～20 weight % and IIA family iodide salt and iodide as rhodium catalyst, can be under the condition of water-content 1～4 weight %, improve the deposited phenomenon of rhodium catalyst, and reach the speed of reaction almost close with high water content.Yet document points out, iodide quaternary ammonium salt N-methyl Pi Kao Lin iodide (N-methyl-picolinium Iodide) easily and rhodium (Rh) form insoluble complex compound, from solution, be precipitated out, and cause the loss of rhodium catalyst.Moreover this patent points out that also even if under the high water content condition, high density acetic acid methyl esters still can be poisoned rhodium catalyst stability.
On the other hand, No. 153834 patent in Europe discloses and can use mercaptan and the imidazolium compounds rhodium catalyst stablizer as the oxonation system.The U.S. the 5th, 442, No. 107 patents then further disclose uses the catalyst stabilizer of several heterocyclic nitrogen compoundss as the methyl alcohol oxonation of low water content, comprises 2-ethyl-4-methylimidazole, 4-methylimidazole, 4-tert .-butylpyridine, 2 hydroxy pyrimidine, 3-pyridone, reaches the 4-pyridone.Yet above-mentioned patent does not disclose the influence to speed of reaction under low water content of employed catalyst stabilizer, and the catalyst stabilizer that is disclosed is also easy and rhodium forms insoluble complex compound, and is precipitated out from solution.
Therefore, still need a kind ofly can under harsh oxonation condition, effectively stablize rhodium catalyst, reduce the rhodium catalyst precipitation, keep high reaction rate simultaneously, and can reduce the carboxylic acid manufacture method of the energy that the isolation and purification acetic acid product consumed.
Summary of the invention
Main purpose of the present invention is to provide a kind of and makes carboxylic acid at water-content than under the low condition, and can not cause a large amount of sedimentary method of catalyzer.
Another object of the present invention is to provide a kind of and under the low part of water-content, make carboxylic acid, and can keep the method for high reaction rate.
For reaching above-mentioned and other purpose, the invention provides a kind of manufacture method of carboxylic acid, by alcohol compound or derivatives thereof and carbon monoxide under the catalyzer existence condition, carry out oxonation and form carboxylic acid in liquid reaction medium, this reaction medium comprises rhodium catalyst, water, Organohalogen compounds, carboxylicesters, haloid acid, catalyst aid and carboxylic acid; Wherein, this catalyst aid has the structure shown in the formula (I)
MnYz (I)
In the formula, M is selected from IIIA-IVA metal, IB-VIIIB metal, reaches the cohort that lanthanide metal compound and salt constituted; Y is selected from hydroxide radical, carbonate, oxalate, acetate, nitrate radical, oxyhalogen acid group, sulfate radical, phosphate radical, halogen and Sauerstoffatom and constitutes single or composite anion in the cohort; N and z are the integer that makes balance positive and negative charges.This method is used specific catalyst aid complexing haloid acid in catalyst system, oxonation is operated under low moisture content condition, keeps high reaction rate, and can not cause a large amount of precipitations of catalyzer.
Embodiment
Below further specify characteristics of the present invention and effect with particular specific embodiment, but can not be used to limit category of the present invention.
The present invention makes the method for carboxylic acid under the catalyzer existence condition, for example under the rhodium catalyst existence condition, alcohol compound or derivatives thereof and carbon monoxide is fed to reactive tank carries out oxonation to make carboxylic acid.The example of this alcohol compound and derivative thereof comprises having 1 to 20 carbon atom, is preferably the fatty alcohol compounds with 1 to 6 carbon atom, for example methyl alcohol, ethanol, propyl alcohol, Virahol, isopropylcarbinol, and sec-butyl alcohol etc.; Aromatic series or alicyclic oxy-compound with 6 to 20 carbon atoms; Have 2 to 20 former polyalcohols of carbon, for example 1, ammediol, 1,4-butyleneglycol; Or similar alcohol compound deutero-ether compound and ester compound etc.
In a specific examples, use methyl alcohol and carbon monoxide in reactive tank, to carry out oxonation and make acetic acid.The reaction medium that carries out in the reactive tank of oxonation has been kept rhodium catalyst, for example water; With respect to the Organohalogen compounds of raw alcohol, for example methyl-iodide; Raw alcohol and sour formed carboxylicesters, for example ritalin; Haloid acid, for example hydroiodic acid HI; Catalyst aid and carboxylic acid with structure shown in the formula (I):
MnYz (I)
In the formula, M is selected from IIIA-IVA metal, IB-VIIIB metal, reaches the cohort that lanthanide metal compound and salt constituted; Y is selected from the single or composite anion of hydroxide radical, carbonate, oxalate, acetate, nitrate radical, oxyhalogen acid group, sulfate radical, phosphate radical, halogen and cohort that Sauerstoffatom constitutes; N and z are the integer that makes balance positive and negative charges.The example of this IIIA-IVA metal comprises aluminium, tin, reaches lead, is preferably aluminium, reaches lead.The example of IB-VIIIB metal comprises copper, zinc, yttrium, titanium, zirconium, vanadium, chromium, molybdenum, manganese, cobalt, nickel, reaches palladium, is preferably copper, zinc, yttrium, zirconium, vanadium, molybdenum, manganese, cobalt, reaches nickel.The example of lanthanide series metal comprises lanthanum, cerium, reaches ytterbium.
In this specific examples, with methyl alcohol or ritalin and acetic acid, together with carbon monoxide, methyl-iodide, hydroiodic acid HI, and formula (I) shown in catalyst aid be fed to the reactive tank of oxonation.Because the esterification of methyl alcohol and carboxylic acid is quite quick, in reactive tank, only contain a spot of free alcohol.Correspond to the reactive tank of continuously feeding, include product acetic acid, corresponding ritalin, rhodium catalyst, and halogen derivative in the reaction product effluent liquid.Liquid reaction product is continued to export to the sudden strain of a muscleization device, and acetic acid and light composition are discharged by sudden strain of a muscleization groove top through gasification, further separating acetic acid and moisture content in the zone purification, and the sudden strain of a muscleization trench bottom comprises that the heavy ingredient of catalyzer is back to reactor.After the acetic acid finished product is isolated in the zone purification, water, part acetic acid, and other composition (comprising methyl-iodide, ritalin etc.) be back to reactor.In reaction process, methyl-iodide, hydroiodic acid HI, and formula (I) shown in catalyst aid can't be consumed, and can be circulated back to reactive tank from sudden strain of a muscleization groove or zone purification continuously.Those skilled in the art can optionally add the component content of adjusting reaction medium as one feels fit according to the actually operating situation.
The method according to this invention, the reaction medium at the oxonation that is used for carrying out carbon monoxide contains 200 to 5000ppm rhodium catalyst usually, is preferably 500 to 2000ppm rhodium catalyst; The water of 1 to 14 weight % is preferably the water of 7 to 10 weight %; The Organohalogen compounds of 5 to 30 weight % are preferably the Organohalogen compounds of 10 to 30 weight %; 0.1, be preferably the carboxylicesters of 0.1 to 5 weight % to the carboxylicesters of 30 weight %; 0.1 the catalyst aid metal concentration to shown in the 5 weight % formulas (I) is preferably the catalyst aid metal concentration shown in 0.5 to the 2 weight % formula (I); And surplus is carboxylic acid and small amount of impurities.Haloid acid is to be enough to the providing capacity of specified quantitative halide-ions to be added in the reaction medium, and the part of not dissociating still is present in the reaction medium with the haloid acid form.With the hydroiodic acid HI is example, so that this reaction medium 1 weight % to be provided above iodide ion, is preferably the above iodide ion of 2.5 weight % usually, the above iodide ion of 3 weight % more preferably, and the capacity that most preferably is the above iodide ion of 5 weight % is added in the reaction medium; If in addition, preferably add the hydroiodic acid HI of 1 to 20 weight %, more preferably add the hydroiodic acid HI of 2 to 10 weight %.This oxonation can in 100 to 220 ℃, are preferable over 140 to 200 ℃ temperature condition, and 10 to 80atm, are preferably under 10 to 50atm the carbon monoxide pressure of tension condition to carry out.
Compared with the past, the water-content in the reaction medium of oxonation is maintained more than the 14 weight %, with solubleness that improves rhodium catalyst and the catalytic activity of keeping catalyzer.The catalyst aid that method of the present invention uses the haloid acid complexing to have structure shown in the formula (I) can form stable complex compound with rhodium catalyst, to avoid reducing the catalyst precipitation phenomenon that the reaction medium water-content is caused.Generally speaking, the catalyst aid content in the reaction medium reduces and increases along with the water-content in the reactive system.After the catalyst aid concentration in the reaction medium increases to a certain degree, can make the rhodium catalyst in this reaction medium, under the condition of low water content, keep the concentration that is equivalent to the high water content reactive system.Therefore, method of the present invention, can the low CO dividing potential drop, and the critical conditions of low water content under, keep high reaction rate, effectively promote time and space productive rate STY, keep the stability of rhodium catalyst, reduce the situation of catalyst precipitation, have the advantage that reduces the purifying cost.
Embodiment
The employed main technique equipment of the inventive method comprises reactor and carbon monoxide storagetank.This reactor configurations has the variable speed motor of rotation rate-controllable, and in order to adjusting suitable rotating speed, keeping good gas-liquid mixed effect, and the inside and outside layer of this reactor adds water coolant coiled pipe and electricradiator respectively, with control and keep stable temperature of reaction.Between this reactor and CO (carbon monoxide converter) gas carbon storage tank, be equiped with the Regulation Control valve, to keep the also pressure of controlling reactor.
In the operation of reaction, carry out the test experiments of catalyst stability and speed of reaction, with reactant directly adding comprise rhodium catalyst, Organohalogen compounds, moisture content, haloid acid and have in the mixed solution of the catalyst aid of structure shown in the formula (I).Reactor all maintains the condition of 185 ℃ of pressure 27atm, temperature, remains under constant temperature and the level pressure and reacts.Add an amount of reactant and carbon monoxide in initial reaction stage, under the situation of suitable control ratio, after reaction finishes, still can possess a spot of ester class in the reaction medium and exist, increase the unstable of catalyzer, in the hope of observing the sedimentary changing condition of rhodium catalyst at short notice.
In operating process, get the analysis that an amount of reaction soln carries out iodometric titration, gas chromatograph, reaches atomic absorption spectrum in the reactor thief hole, observe the sedimentary situation of rhodium by the data of being analyzed, and calculate the usefulness of judging haloid acid complex catalysis auxiliary agent.Among the embodiment of this specification sheets, all about the rhodium concentration data that atomic absorption spectrum analyzed, the standard method of analysis that is to use Meng Shan all to analyze the dissolving rhodium in the technology obtains, and unit is all hundred concentration (ppm) very much.
Embodiment 1 to 10, comparative example 1
(adding the lifting benefit of the different catalyst aids of hydroiodic acid HI complexing) to oxonation speed (STY)
Use the dicarbapentaborane diiodo-rhodium solution of 15 grams 2%, each component content (or addition) in the reaction medium of reactor is listed as table 1, and the hydroiodic acid HI addition is 4 weight %, and all the other are the acetic acid of an amount of difference.Methyl alcohol is imported reactor, feed reaction of carbon monoxide after 30 minutes, record carbon monoxide consumption, composition analysis is carried out in sampling, calculate acetic acid unit time space productive rate (STY) value (unit: mole/kilogram/hour), and with outcome record in table 1, comparative example is a blank assay.
Table 1
| Catalyst aid/metal concentration (ppm) | Moisture content (weight %) | Methyl-iodide (weight %) | The STY value | ||
| Embodiment 1 | Aluminium hydroxide | 10000 | 10 | 14 | 16.00 |
| Embodiment 2 | Plumbic acetate | 10000 | 10 | 14 | 15.80 |
| Embodiment 3 | Copper hydroxide | 10000 | 10 | 14 | 14.05 |
| Embodiment 4 | Yttrium oxide | 10000 | 10 | 14 | 14.44 |
| Embodiment 5 | Lanthanum trichloride | 10000 | 10 | 14 | 14.83 |
| Embodiment 6 | Zirconium hydroxide | 10000 | 10 | 14 | 16.58 |
| Embodiment 7 | Vanadium oxide | 10000 | 10 | 14 | 14.24 |
| Embodiment 8 | Molybdenum oxide | 10000 | 10 | 14 | 16.78 |
| Embodiment 9 | Cerium oxide | 10000 | 10 | 14 | 14.24 |
| Embodiment 10 | Ytterbium oxide | 10000 | 10 | 14 | 14.83 |
| Comparative example 1 | - | 10 | 14 | 13.65 | |
By table 1 experimental data, STY value 13.65 compared to comparative example 1, embodiment 1 to 10 experimentizes to add hydroiodic acid HI and complexing 10000ppm different sorts catalyst aid, its STY value all has lifting in various degree, wherein with kind catalyst aids such as aluminium, lead, zirconium, molybdenums preferable effect is arranged, signify hydrogen acid iodide complex catalysis auxiliary agent can effectively promote methyl alcohol oxonation speed.
Embodiment 11 to 14, comparative example 2
(the different catalyst aids of hydroiodic acid HI complexing are to stablizing rhodium catalyst and the benefit that promotes iodide ion concentration)
Repeat the step of embodiment 1, except that increasing the different catalyst aids of part, all the other moisture content, methyl-iodide, hydroiodic acid HI add proportion of composing and operational reaction conditions is kept identical.Behind the oxonation, be that index compares with rhodium catalyst concentration (ppm) with iodide ion concentration (I-) weight %, and the result is embedded in table 2.
Table 2
| Catalyst aid/metal concentration (ppm) | Reaction back Rh (ppm) | Reaction back (I-) weight % | ||
| Embodiment 1 | Aluminium hydroxide | 10000 | 633 | 3.89 |
| Embodiment 4 | Yttrium oxide | 10000 | 532 | 2.32 |
| Embodiment 5 | Lanthanum trichloride | 10000 | 700 | 1.48 |
| Embodiment 11 | Zinc acetate | 10000 | 462 | 3.70 |
| Embodiment 12 | Cobaltous diacetate | 10000 | 563 | 3.44 |
| Embodiment 13 | Manganese acetate | 10000 | 510 | 3.67 |
| Embodiment 14 | Nickel acetate | 10000 | 750 | 3.25 |
| Comparative example 2 | - | 450 | 0.74 | |
By table 2 experimental data, the result who does not add catalyst aid with comparative example 2 compares, other embodiment carries out oxonation with the catalyst aid of the different metal kinds such as aluminium, yttrium, lanthanum, zinc, cobalt, manganese or nickel salt of the hydroiodic acid HI complexing 10000ppm of 4 weight %, can effectively promote iodide ion concentration and rhodium catalyst concentration in the reactive system, it acts on along with the metal species difference difference to some extent, really have the iodide ion concentration of lifting and stablize the effect of rhodium catalyst so demonstrate hydroiodic acid HI complex catalysis auxiliary agent, and help the carrying out of methyl alcohol oxonation.
Embodiment 6,8,15 to 18
(changing hydroiodic acid HI and catalyst aid adding proportion lifting benefit) to oxonation speed (STY)
Repeat the step of embodiment 1, except that table 3 listed hydroiodic acid HI concentration and catalyst aid kind and addition, all the other proportion of composing and operational condition are all identical.Calculate acetic acid unit time space productive rate (STY) value (unit: mole/kilogram/hour), and the result is embedded in table 3.
Table 3
| Hydroiodic acid HI addition (weight %) | Catalyst aid/metal concentration (ppm) | Moisture content (weight %) | The STY value | ||
| Embodiment 15 | 4 | Molybdenum oxide | 5000 | 10 | 16.19 |
| Embodiment 8 | 4 | 10000 | 10 | 16.78 | |
| Embodiment 16 | 6 | 15000 | 10 | 17.79 | |
| Embodiment 17 | 4 | Zirconium hydroxide | 5000 | 10 | 16.0 |
| Embodiment 6 | 4 | 10000 | 10 | 16.58 | |
| Embodiment 18 | 6 | 15000 | 10 | 18.05 | |
As shown in Table 3, (embodiment 8﹠amp under the condition of adding hydroiodic acid HI concentration fixed 4 weight %; 15, embodiment 6﹠amp; 17), when the catalyst aid metal concentration increases to 10000ppm by 5000ppm, can make the STY of reaction have the lifting benefit, illustrate that the increase of catalyst aid amount can bring into play the effect that promotes oxonation really.Moreover, when adding hydroiodic acid HI concentration (embodiment 16﹠amp when increasing to 6 weight % and catalyst aid metal concentration and increasing to 15000ppm; 18), bigger to the lifting amplitude of advancing oxonation STY value.So if can promote the amount of hydroiodic acid HI and catalyst aid simultaneously, can be more remarkable to the lifting benefit of methyl alcohol oxonation.
Claims (21)
1. the preparation method of a carboxylic acid, its by alcohol compound or derivatives thereof and carbon monoxide under the catalyzer existence condition, carry out oxonation and form carboxylic acid in liquid reaction medium, this reaction medium comprises rhodium catalyst, water, Organohalogen compounds, carboxylicesters, haloid acid, catalyst aid and carboxylic acid; Wherein, this catalyst aid has the structure shown in the formula (I)
MnYz(I)
In the formula, M is selected from IIIA-IVA metal, IB-VIIIB metal, reaches lanthanide metal compound and salt; Y is selected from the single or composite anion of hydroxide radical, carbonate, oxalate, acetate, nitrate radical, oxyhalogen acid group, sulfate radical, phosphate radical, halogen and Sauerstoffatom; N and z are the integer that makes balance positive and negative charges.
2. method according to claim 1, wherein alcohol compound is a methyl alcohol, this carboxylic acid is an acetic acid.
3. method according to claim 1, wherein reaction medium contains 1000 to 50000ppm catalyst aid metal concentration.
4. method according to claim 3, wherein reaction medium contains 5000 to 20000ppm catalyst aid metal concentration.
5. method according to claim 1, wherein the IIIA-IVA metal comprises aluminium, tin, reaches lead.
6. method according to claim 1, wherein the IB-VIIIB metal comprises copper, zinc, yttrium, titanium, zirconium, vanadium, chromium, molybdenum, manganese, cobalt, nickel, reaches palladium.
7. method according to claim 1, wherein lanthanide series metal comprises lanthanum, cerium, reaches ytterbium.
8. method according to claim 1, wherein haloid acid is a hydroiodic acid HI.
9. method according to claim 8, wherein capacity is added hydroiodic acid HI to reaction medium, so that this reaction medium 1 weight % to be provided above iodide ion.
10. method according to claim 9, wherein capacity is added hydroiodic acid HI to reaction medium, so that this reaction medium 3 weight % to be provided above iodide ion.
11. method according to claim 10, wherein capacity is added hydroiodic acid HI to reaction medium, so that this reaction medium 5 weight % to be provided above iodide ion.
12. method according to claim 1 wherein contains the carboxylicesters of 0.1 to 30 weight % in the reaction medium.
13. method according to claim 12 wherein contains the carboxylicesters of 0.1 to 5 weight % in the reaction medium.
14. method according to claim 1, wherein carboxylicesters is a ritalin.
15. method according to claim 1 wherein contains the Organohalogen compounds of 5 to 30 weight % in the reaction medium.
16. method according to claim 15 wherein contains the Organohalogen compounds of 10 to 30 weight % in the reaction medium.
17. method according to claim 1, wherein Organohalogen compounds are methyl-iodide.
18. method according to claim 1 wherein contains the water of 1 to 14 weight % in the reaction medium.
19. method according to claim 18 wherein contains the water of 7 to 10 weight % in the reaction medium.
20. method according to claim 1, wherein reaction medium contains 200 to 5000ppm rhodium catalyst.
21. method according to claim 20, wherein reaction medium contains 500 to 2000ppm rhodium catalyst.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954295A (en) * | 2010-09-26 | 2011-01-26 | 华陆工程科技有限责任公司 | Catalyst system for methanol low-pressure carbonyl synthesis of acetic acid and application thereof |
| CN103086868A (en) * | 2011-11-02 | 2013-05-08 | 中国石油化工股份有限公司 | Method for preparing acetic acid through carbonylation reaction |
| CN103084214A (en) * | 2011-11-02 | 2013-05-08 | 中国石油化工股份有限公司 | Iridium catalyst system |
| CN103724179A (en) * | 2012-10-11 | 2014-04-16 | 中国石油化工股份有限公司 | Method for preparing acetic acid |
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| US5144068A (en) * | 1984-05-03 | 1992-09-01 | Hoechst Celanese Corporation | Methanol carbonylation process |
| US5218143A (en) * | 1989-02-23 | 1993-06-08 | The British Petroleum Company P.L.C. | Process for preparing carboxylic acids |
| GB9503382D0 (en) * | 1995-02-21 | 1995-04-12 | Bp Chem Int Ltd | Process |
| US5760279A (en) * | 1995-06-19 | 1998-06-02 | Bp Chemicals Limited | Process for the carbonylation of alkyl alcohols |
| GB9712601D0 (en) * | 1997-06-16 | 1997-08-20 | Bp Chem Int Ltd | Chemical process |
| CN1166615C (en) * | 2002-01-21 | 2004-09-15 | 中国石油化学工业开发股份有限公司 | Process for preparing carboxylic acid |
| US7005541B2 (en) * | 2002-12-23 | 2006-02-28 | Celanese International Corporation | Low water methanol carbonylation process for high acetic acid production and for water balance control |
| CN100337750C (en) * | 2004-09-24 | 2007-09-19 | 中国科学院化学研究所 | Catalyst system for carbonylation of methanol for synthesizing ethanol, and application |
| CN100443173C (en) * | 2004-11-22 | 2008-12-17 | 中国科学院化学研究所 | Catalyst system for synthetizing acetic acid from methanol or synthetizing ethylanhydride from methyl acetate and use thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954295A (en) * | 2010-09-26 | 2011-01-26 | 华陆工程科技有限责任公司 | Catalyst system for methanol low-pressure carbonyl synthesis of acetic acid and application thereof |
| CN103086868A (en) * | 2011-11-02 | 2013-05-08 | 中国石油化工股份有限公司 | Method for preparing acetic acid through carbonylation reaction |
| CN103084214A (en) * | 2011-11-02 | 2013-05-08 | 中国石油化工股份有限公司 | Iridium catalyst system |
| CN103086868B (en) * | 2011-11-02 | 2015-06-17 | 中国石油化工股份有限公司 | Method for preparing acetic acid through carbonylation reaction |
| CN103724179A (en) * | 2012-10-11 | 2014-04-16 | 中国石油化工股份有限公司 | Method for preparing acetic acid |
| CN103724179B (en) * | 2012-10-11 | 2015-07-22 | 中国石油化工股份有限公司 | Method for preparing acetic acid |
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