CN1288124C - Rhoaium/inorganic iodine compound catalyst system for reducing impurity in acetic acid production - Google Patents
Rhoaium/inorganic iodine compound catalyst system for reducing impurity in acetic acid production Download PDFInfo
- Publication number
- CN1288124C CN1288124C CN 03116492 CN03116492A CN1288124C CN 1288124 C CN1288124 C CN 1288124C CN 03116492 CN03116492 CN 03116492 CN 03116492 A CN03116492 A CN 03116492A CN 1288124 C CN1288124 C CN 1288124C
- Authority
- CN
- China
- Prior art keywords
- iodide
- acetic acid
- inorganic
- rhodium
- catalyst system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a method for preparing acetic acid, particularly to a rhodium / inorganic iodine compound catalyst system for decreasing impurities in acetic acid production. The present invention solves the problem that the impurities of the acetic acid in the existing methanol carbonylation production are difficult to control. The rhodium / inorganic iodine compound catalyst system for decreasing impurities in acetic acid production is the technical scheme. During acetic acid preparation, methanol and CO react in a liquid reaction medium, wherein the liquid reaction medium comprises rhodium, iodide, water, acetic acid and methyl acetate. The present invention is characterized in that the iodide is inorganic iodide; the media proportion of the liquid reaction medium can catalyze the rhodium with effective dose, the iodine ion concentration is from 2 to 15 wt%, the water is from 1 to 8 wt%, the methyl iodide is from 8 to 15 wt%, the methyl acetate is from 0.5 to 30 wt%, and the acetic acid accounts for the rest weight percentage. The content of water in the reaction liquid medium is decreased, and the formation of impurities of formic acid, propionic acid, etc. in the finished acetic acid is decreased.
Description
Technical field: the preparation method who the present invention relates to a kind of acetic acid, be particularly related to the rhodium/inorganic iodine compound catalyst system of the acetic acid production that reduces impurity, by reducing the content of water in the reaction solution medium, reduce the formation of impurity such as formic acid and propionic acid in the finished product acetic acid.
Background technology: the current method that is used to produce acetic acid has multiple, and the most widely the commercial run of Ying Yonging is the carbonylation reaction of methyl alcohol and CO, and this method is called the Monanto method.The method cited, this method wide range of industrial applications and obtain promoting and development worldwide at present as U.S. Pat 3769329.The US3769329 method has comprised dissolving or has been dispersed in rhodium catalyst and halogen-containing organic catalyst promotor (preferable methyl iodine) in the liquid reaction medium that it can be any solvent that mixes with catalyst system that this patent has been set forth the reaction solution medium.Carbonylation at methyl alcohol and CO generates in the preparation of acetic acid, and solvent can be methyl alcohol, vinyl acetic monomer and acetic acid, preferably acetic acid.Reaction medium has comprised: rhodium, methyl alcohol, methyl-iodide, methyl acetate, acetate, water and hydrogen iodide etc.Proposed to require the existence of big water gaging in the reaction medium mixture, so that make speed of response higher, catalyst stability is good.In addition, this patent has also proposed to reduce the formation that water-content in the reaction medium causes ester products, rather than carboxylic acid.In fact, use the water that has about 14-15% weight percentage in the reaction medium of common acetic acid factory of this technology.
European patent application EP 055618 points out that when catalyst system CO content in the sepn process descended, when water-content reduced in reaction medium, rhodium had the trend that is precipitated out from reaction medium.Therefore, US3769329 and EP055618 are stable for rhodium in the maintenance catalyst system, need the water that keeps a large amount of in reaction medium.At Chinese patent application CN85101460, people such as Celanese cloth Randt .L. Smith have proposed to add stablizer such as lithium iodide increases the stability of rhodium in the catalyst system, water-content in the catalyst system is reduced greatly, the trend that can not cause catalyzer to have precipitation to increase simultaneously.But these patents have also pointed out under the low excessively condition of water concentration, make that carbonyl forms the increase of impurity such as acetaldehyde or crotonic aldehyde in the reaction system, thereby influence the quality of acetate products.But the influence that the minimizing of all not mentioning water concentration in these patents generates impurity such as formic acid, propionic acid.
Summary of the invention: the technical issues that need to address of the present invention are: improve the speed of response of catalyzer, under the prerequisite of not sacrificing catalyst stability, need not the additional processing means, can reduce the generation of formic acid and propionic acid in the acetate products.
Technical scheme of the present invention is: the rhodium/inorganic iodine compound catalyst system that reduces the acetic acid production of impurity, the acetic acid preparation adopts methyl alcohol and CO to react in liquid reaction medium, liquid reaction medium comprises: rhodium, inorganic iodide, methyl-iodide, water, acetic acid, ritalin, described inorganic iodide, being the iodide of periodic table of elements IA family and IIA family, also can be the mixture of two or more inorganic iodides wherein.Concrete inorganic iodide is a kind of or two or more mixture in lithium iodide, hydrogen iodide, sodium iodide, potassiumiodide, the magnesium iodide.Inorganic iodide can be reacted to each other by corresponding acetate, carbonate or alkali and aqueous solution of hydrogen iodide and obtain.Preferred inorganic iodide is: lithium iodide, potassiumiodide or hydrogen iodide, and their mixture.Further preferred inorganic iodide is: the mixture of lithium iodide or lithium iodide and hydrogen iodide.The medium size composition of liquid reaction medium is: the rhodium of catalytically effective amount, the concentration 400mg/kg-5000mg/kg of rhodium in liquid reaction medium, generally at 400mg/kg-2000mg/kg, be preferably 650mg/kg-1500mg/kg, the concentration 2wt-15wt% of iodide ion, water 1wt-8wt%, preferred 3wt-7wt%, methyl-iodide 8wt-15wt%, ritalin 0.5wt-30wt%, all the other are acetic acid.
The invention has the beneficial effects as follows: of the present invention improving one's methods, make us having reduced impurity in the acetate products, especially formic acid and propionic acid unexpectedly.The present invention reduced the generation of formic acid and propionic acid rather than in reaction system additional means remove these impurity, neither be in product purification technology increase equipment and processing step after their form, remove them again.The present invention has also produced otherwise benefit naturally.Operating under the low regimen condition of formic acid carbonylation method operated, and rhodium catalyst concentration can significantly improve in the catalyst system, and catalyst reaction speed can significantly improve, but still does not sacrifice catalyst stability.Simultaneously, after the present invention has improved the reaction solution system, improved the bottleneck of the load reconciliation of factory's rectification step except rectification step.
Embodiment:
By the chemical process of front to carbonylation reaction, according to other patent reports, when water concentration reduced, acetaldehyde and acetaldehyde derivatives impurity increased, but the chemistry route that such impurity that do not know for sure generates.The generation of these impurity will exert an influence to quality product, be embodied in the reduction of product potassium permanganate oxidation time.
In fact, in process of the present invention, the concentration reduction along with water does not have the generation or the increase of tangible these impurity of discovery, is embodied in the variation of product potassium permanganate oxidation time with the concentration of water in the reaction medium, and the time does not reduce.On the contrary, according to the present invention, along with the concentration reduction of water, the turnout of impurity such as formic acid and propionic acid reduces.Think that tentatively wherein water-gas reaction reduces because reaction medium saliva concentration reduces, send out and answer process H (atomic state) to occur reducing, and H in the reaction gas phase
2Divide and reducing, the amount that has reduced formic acid and propionic acid production stage reduces.
About the reaction of formic acid and propionic acid generation several steps, the content that reduces water in the reaction medium will play influence to corresponding reaction from (1)～(5).Although it is multi-faceted influencing in reaction system that impurity such as formic acid propionic acid generates, the influence of other factors is sure existence.But the present invention has found that the generation of formic acid, propionic acid impurity has an influence that is subjected to water concentration in the reaction medium.The ionic inorganic iodide can be from any one acquisition of useful many solubility inorganic iodides.Should be realized that the concentration of the iodide ion in this catalyst system is important, rather than the relevant positively charged ion of inorganic iodide.Under the set volumetric molar concentration of iodide ion, cationic character has only determined the solubleness of iodide ion, especially solubleness and the degree of ionization in the medium of less water and the coexistence of a large amount of acetic acid, and this positively charged ion and acid group bonded stability, not to making vital role on the catalyst system performance.On this point, the present invention recognizes that this solubility inorganic iodide can be a kind of material, it also can be material more than two kinds, its source can be iodide, also can substitute with hydroiodic acid HI and solubility acetate, carbonate or corresponding alkali, after solubility acetate, carbonate or corresponding alkali and the hydroiodic acid HI effect, obtain the inorganic solubility iodate thing that the effect in reactor is equal to fully.
The invention process means have comprised: (1) reaction system, (2) separation system.Reaction system is made up of reactor, flash drum etc., and separation system has comprised: water, methyl-iodide and acetic acid separated tower, product purification tower.Reaction medium is under the concentration that test needs in the maintenance reactor, and CO and fresh methanol enters in the reactor continuously under 190 ℃ of temperature of reaction of maintenance, the reaction pressure～30MPa.Reaction product is extracted out from reactor continuously, extraction amount and methyl alcohol add-on fixed proportion.Reaction product flash distillation in flash drum of extracting out, gas-phase product advances separation system, and liquid product returns reactor.The water inlet of flash drum gas-phase product, methyl-iodide and acetic acid separated tower, the theoretical separation of knockout tower progression is 32 grades, the charging level is several the 15th grade from top to bottom, the thick product acetic acid of tower still output, divide two-phase behind the cat head vapor condensation, light part mutually is as the backflow of knockout tower, and part is returned reactor, and heavy phase all loops back reactor.It is refining that the thick product that produces from the tower still advances the product purification tower, remove reclaim qualified acetate products after, it is in the whole Returning reactors of material.The each operate continuously of this process is more than 12 hours.
Embodiment 1-5
Embodiment 1: be in the reaction solution except that hydrogen iodide, do not add other inorganic iodides, test-results under reaction medium water-content 13.6% condition.
Embodiment 2-9 be in the reaction solution except that adding hydrogen iodide, add other inorganic iodides simultaneously, water progressively descends in the reaction medium, obtained test-results.
Enforcement executes 10～12nd, only adds inorganic salt compounded of iodine in the reaction solution, does not add hydrogen iodide.More than said inorganic salt compounded of iodine be the mixture (ratio of quality) of 1 part of potassiumiodide and 10 parts of lithium iodides.
Embodiment 1～12 the results are shown in Table 1
Table 1 is implemented 1～12 test-results table
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | |
| Reaction conditions | ||||||||||||
| Inorganic iodide wt% is hydrogen iodide wt% wherein | 3.01 | 4.44 2.88 | 9.78 3.66 | 9.16 3.19 | 9.83 3.31 | 10.5 2.5 | 11.5 2.0 | 12.5 1.5 | 13.5 0.5 | 14.5 / | 15 / | 15.5 / |
| Rhmg/kg | 400 | 400 | 400 | 400 | 400 | 650 | 650 | 750 | 750 | 1000 | 1200 | 1500 |
| Water (wt%) | 13.69 | 12 | 9.56 | 8.04 | 7.6 | 7.0 | 6.0 | 5.0 | 4.5 | 4.2 | 4.0 | 3.0 |
| Ritalin (wt%) | 0.63 | 1.48 | 0.662 | 1.43 | 1.44 | 2.22 | 2.74 | 2.84 | 3.01 | 3.30 | 3.30 | 3.30 |
| Methyl-iodide (wt%) | 12.05 | 11.7 | 12.3 | 11.9 | 11.5 | 8.0 | 8.5 | 10.5 | 12.5 | 13.5 | 14.0 | 15 |
| Speed of reaction | ||||||||||||
| Mol/l.hr | 10.3 | 10.1 | 10.5 | 10.2 | 10.1 | 16.1 | 16.2 | 18.0 | 18.3 | 20.50 | 21.0 | 23.0 |
| Impurity concentration in the product | ||||||||||||
| Formic acid mg/kg | 325 | 277 | 250 | 203 | 63 | 58 | 55 | 53 | 52 | 52 | 54 | 55 |
| Propionic acid mg/kg | 150 | 150 | 129 | 112 | 39 | 35 | 33 | 32 | 33 | 33 | 31 | 32 |
| The product acetate concentration | ||||||||||||
| wt％ | 99.80 | 99.80 | 99.81 | 99.82 | 99.85 | 99.85 | 99.85 | 99.85 | 99.85 | 99.85 | 99.85 | 99.85 |
| Product potassium permanganate oxidation time min | ＞130 | ＞130 | ＞130 | ＞130 | ＞130 | ＞130 | ＞130 | ＞130 | ＞130 | ＞130 | ＞130 | ＞130 |
Claims (4)
1, reduce the rhodium/inorganic iodine compound catalyst system of the acetic acid production of impurity, the acetic acid preparation adopts methyl alcohol and CO to react in liquid reaction medium, liquid reaction medium comprises: rhodium, inorganic iodide, methyl-iodide, water, acetic acid, ritalin, it is characterized in that: described inorganic iodide is the mixture of the wherein two or more inorganic iodides of periodic table of elements IA family and IIA family, the medium size composition of liquid reaction medium is: the rhodium of catalytically effective amount, the concentration 2wt-15wt% of iodide ion, water 3wt-7wt%, methyl-iodide 8wt-15wt%, ritalin 0.5wt-30wt%, all the other are acetic acid.
2, the rhodium/inorganic iodine compound catalyst system of the acetic acid production of reduction impurity according to claim 1 is characterized in that, inorganic iodide is the two or more mixture in lithium iodide, hydrogen iodide, sodium iodide, potassiumiodide, the magnesium iodide.
3, the rhodium/inorganic iodine compound catalyst system of the acetic acid production of reduction impurity according to claim 2 is characterized in that inorganic iodide is: the mixture that lithium iodide, potassiumiodide or hydrogen iodide are two or more.
4, the rhodium/inorganic iodine compound catalyst system of the acetic acid production of reduction impurity according to claim 3 is characterized in that, inorganic iodide is the mixture of lithium iodide and hydrogen iodide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03116492 CN1288124C (en) | 2003-04-18 | 2003-04-18 | Rhoaium/inorganic iodine compound catalyst system for reducing impurity in acetic acid production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03116492 CN1288124C (en) | 2003-04-18 | 2003-04-18 | Rhoaium/inorganic iodine compound catalyst system for reducing impurity in acetic acid production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1537840A CN1537840A (en) | 2004-10-20 |
| CN1288124C true CN1288124C (en) | 2006-12-06 |
Family
ID=34320367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03116492 Ceased CN1288124C (en) | 2003-04-18 | 2003-04-18 | Rhoaium/inorganic iodine compound catalyst system for reducing impurity in acetic acid production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1288124C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954295B (en) * | 2010-09-26 | 2012-05-23 | 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 |
| US8877963B2 (en) | 2010-09-28 | 2014-11-04 | Celanese International Corporation | Production of acetic acid with high conversion rate |
| US8394988B2 (en) | 2010-09-28 | 2013-03-12 | Celanese International Corporation | Production of acetic acid with high conversion rate |
| CN102976919B (en) * | 2011-09-05 | 2015-04-22 | 上海吴泾化工有限公司 | Method for co-producing propionic acid during production of acetic acid |
| US9663437B2 (en) | 2011-09-13 | 2017-05-30 | Celanese International Corporation | Production of acetic acid with high conversion rate |
-
2003
- 2003-04-18 CN CN 03116492 patent/CN1288124C/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| CN1537840A (en) | 2004-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100341836C (en) | Low water methanol carbonylation process for high acetic acid production and for water balance control | |
| US7524988B2 (en) | Preparation of acetic acid | |
| US20080051601A1 (en) | Preparation of acetic acid | |
| AU2010271163A1 (en) | Acetic acid production by way of carbonylation with enhanced reaction and flashing | |
| CA2598766A1 (en) | Acetic acid production methods incorporating at least one metal salt as a catalyst stabilizer | |
| CN102612506A (en) | Preparation of acetic acid | |
| CN1288124C (en) | Rhoaium/inorganic iodine compound catalyst system for reducing impurity in acetic acid production | |
| JP2004536035A (en) | Modification of catalyst system in industrial process for producing acetic acid and / or methyl acetate | |
| CN115141093A (en) | Preparation method of ruthenium acetate | |
| CN1183080C (en) | Rhodium/inorganic iodide catalyst system for methanol carbonylation process with improved impurity profile | |
| CN110105173A (en) | A kind of purification process of efficient HPPO technique recycling design | |
| CN102218344B (en) | 3,5-dicarboxyl pyrazole iridium complex catalyst used for carbonylation synthesis of acetic acid as well as preparation method and application thereof | |
| CN1876239A (en) | Catalyst system for synthesizing acetic acid and acetic anhydride from carbonyl compound and its uses | |
| CN108976108A (en) | A method of synthesis pseudo ionone | |
| CN1032133C (en) | Continuous process for simultaneous preparation of acetic acid and acetic anhydride | |
| CN110878016B (en) | Process for preparing isooctanoic acid | |
| CN1260203C (en) | Process for synthesizing isopropyl acetate and method for preparing its catalyst | |
| CN1739852A (en) | Catalyst for preparing p-cyclodexanone dioxide | |
| JPH03291253A (en) | Purification of ether carboxylate | |
| CN1131110C (en) | Homogeneous carbonylation reaction catalyst and its preparation and application | |
| CN102001929B (en) | Method for co-producing formic acid and acetic acid | |
| CN114570375A (en) | Hydrotalcite-based catalyst, preparation method thereof and application of hydrotalcite-based catalyst in efficient catalytic preparation of vanillin | |
| CN115894215B (en) | Production method of neodymium iso-octoate | |
| CN113351199B (en) | Acidic heterogeneous catalyst, preparation method and one-step lactic acid preparation process | |
| CN112409179B (en) | Purification method of menthyl lactate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C35 | Partial or whole invalidation of patent or utility model | ||
| IW01 | Full invalidation of patent right |
Decision date of declaring invalidation: 20110429 Decision number of declaring invalidation: 16453 Granted publication date: 20061206 |
|
| C35 | Partial or whole invalidation of patent or utility model | ||
| IP01 | Partial invalidation of patent right |
Decision date of declaring invalidation: 20110429 Decision number of declaring invalidation: 16453 Granted publication date: 20061206 |