CN100450621C - Catalyst system used in low pressure methanol carbonyl synthesizing acetic acid - Google Patents
Catalyst system used in low pressure methanol carbonyl synthesizing acetic acid Download PDFInfo
- Publication number
- CN100450621C CN100450621C CNB2006100277787A CN200610027778A CN100450621C CN 100450621 C CN100450621 C CN 100450621C CN B2006100277787 A CNB2006100277787 A CN B2006100277787A CN 200610027778 A CN200610027778 A CN 200610027778A CN 100450621 C CN100450621 C CN 100450621C
- Authority
- CN
- China
- Prior art keywords
- logistics
- catalyst
- acetic acid
- catalyst system
- decanter
- 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.)
- Active
Links
Images
Abstract
The present invention relates to a catalytic system for synthesizing acetic acid by methanol carbonyl at low pressure, which adopts halide of rhodium as a catalyst, methyl acetate and methyl iodide as cocatalysts, and inorganic c iodine salt as a stabilizer. The catalyst system comprises the concrete liquid reaction media of the mass concentration: 0.03 to 0.12 wt% of rhodium catalyst (measured by rhodium metal), 0.3 to 1.0 wt% of alkali metal ion, 3 to 15 wt% of iodine ion, 1 to 4 wt% of methyl acetate, 10 to 21 wt% of methyl iodide, 0.1 to 0.5 wt% of VIIIB and VIB-family metal element, 4 to 15 wt% of water and acetic acid as the rest. Compared with the production technology for synthesizing acetic acid at low pressure in the 'monsanto' company, the catalyst system for synthesizing acetic acid by methanol carbonyl at low pressure has higher activity and selectivity and fewer by-products of reaction. High-quality acetic acid products can be prepared by the combination of the catalyst formula and the purification technology of the present invention.
Description
Technical field
The present invention relates to the acetic acid preparing technical field, particularly a kind of catalyst system of acetic acid synthesized by low pressure methanol carbonylation, this catalyst system has higher activity and selectivity, and the less side products of reaction can the higher-quality acetate products of output.
Background technology
Developed the production technology of acetic acid synthesized by low pressure methanol carbonylation since U.S. Monsanto Company after, the acetic acid synthesized by low pressure methanol carbonylation technology becomes the main method of producing acetic acid in the world at present.
The technological process of production of known low-pressure methanol carbonyl synthesized acetic acid is seen " chemical encyclopedia ", and 4 editions second volumes were 719 pages in 1991.Add reactor 1 bottom with carbon monoxide, light fraction and the water-containing acetic acid that catalyst mother liquor, refining system return that contain that return after the methyl alcohol preheating, 175～200 ℃ of temperature, under stagnation pressure 3MPa (28.5atm), the carbon monoxide pressure of tension 1～1.5MPa, reactant liquor is drawn in the top of reactor 1 side line in the reaction back, flash distillation is decompressed to about 200kPa, product is separated, latter's Returning reactor 1 (reactor 1 gas of discharging contains carbon monoxide, iodomethane, hydrogen, methane sends into scrubbing tower 6) with the mother liquor that contains catalyst.The reaction mixture that contains thick acetic acid, light fraction enters first tower-lightness-removing column 2 of refining system with gas phase, deviates from light fraction, and the gas of cat head (containing iodomethane, methyl acetate, small amount of methanol) enters scrubbing tower through 7 of destilling tower condensation liquid baths.The still liquid of lightness-removing column 2 is moisture thick acetic acid, is sent second tower-dehydrating tower 3, the dry crude acetic acid of dehydrating tower 3 bottoms to be admitted to the 3rd Ta-Tuo heavy ends column 4 again.Draw finished acid from taking off heavy ends column 4 top side lines, this tower bottoms contains propionic acid 40% and other high carboxylic acids; Taking off acetic acid in heavy ends column 4 bottom fraction, to be sent to the 4th tower at last be spent acid destilling tower 5, to recycle.Discharging the heavy spent acid at the bottom of the tower is output 0.2%, can burn or reclaim.Consist of CO 40～80% after the gas that three towers and reactor 1 are discharged gathers, all the other 20～60% are H
2, CO
2, N
2, O
2And acetic acid, the iodomethane of trace, behind scrubbing tower 6 usefulness cold methanol washing and recycling iodine, burn emptying together.In order to guarantee that content of iodine is qualified in the finished product, in dehydrating tower 3, to add small amount of methanol and make HI be converted into CH
3I; Add a small amount of KOH iodide ion is shifted out at the bottom of still with the form of KI taking off heavy ends column 4 imports, can obtain containing the pure acetic acid of iodine 5～40ppb.
In this technology, adopting the halide of rhodium is that catalyst, iodomethane are co-catalyst, has realized methyl alcohol and carbon monoxide carbonyl synthesis acetic acid under 2.8-3.0MPa and 175-185 ℃.Because active component rhodium complex [Rh (CO) in the reaction system
2I
2]
-Unstability, make and from reactant liquor, to take out method based on the thick product of acetic acid, selected for use the recycle stock that is multiple times than methyl alcohol to carry out flash distillation, but its consumption of raw materials, energy consumption height.
Along with the development of associated production technology and technology, the synthetic acetic acid technology of low pressure methanol carbonylation there has been new improvement.Very big variation has taken place in the composition of catalyst in the reactant liquor.Wherein the raising of the content of co-catalyst methyl acetate and iodomethane, water content reduce in the catalyst, and this has clear and definite expression in patent CN8510146, CN95117948, CN93108283, CN99101723, CN03116492 or the like patent.In these patents, the composition of reactant liquor has had very big variation, as the reactant liquor in the production technology of the early stage acetic acid synthesized by low pressure methanol carbonylation of the concentration of methyl acetate, iodomethane in the catalyst system and Monsanto Company's exploitation very big variation has been arranged, methyl acetate concentration can be increased to 30%wt, the content of iodomethane (alkyl halide) also can rise to 30%wt, water content in the catalyst also drops to below 4% from 15%, or even anhydrous.Along with the variation that catalyst in this reactant liquor is formed, the purification of Dichlorodiphenyl Acetate also has requirement to change.This has increased the cost of product.
Composition change along with catalyst: water content in catalyst reduces on the one hand, and methyl acetate and iodomethane content in catalyst increases on the other hand.Moreover the inorganic iodine salt stabilizing agent suppresses evaporation of water in flash process, promotes the evaporation of acetic acid, methyl acetate and iodomethane.The effect of two aspects makes that into the content of lightness-removing column methyl acetate and iodomethane obviously increases, the effect of two aspects makes that into the content of lightness-removing column methyl acetate and iodomethane obviously increases, methyl acetate content is at 5-6% (wt), iodomethane content is at 35-50% (wt), make that methyl acetate and iodomethane concentration improve in the inner gas phase of this tower, methyl acetate and iodomethane also obviously increase in the fluid of overhead reflux, cause the head product acetic acid of extracting out from lightness-removing column, though moisture reduction but the amount of methyl acetate and iodomethane obviously increase, thereby caused containing methyl acetate in the discharging of dehydrating tower and the feed stream and iodomethane increases, especially methyl acetate and iodomethane content increase in the overhead reflux thing, caused this tower product to be polluted, therefore caused into lightness-removing column methyl acetate and the obvious increase of content of iodomethane and the head product acetic acid of extracting out from lightness-removing column about catalyst system changes by methyl acetate and iodomethane, the phenomenon that the content of methyl acetate and iodomethane obviously increases.
Summary of the invention
The technical problem that will solve of the present invention provides a kind of have higher activity and selectivity, the less side products of reaction, the catalyst system and catalyzing that is used for the acetic acid synthesized by low pressure methanol carbonylation production technology that can the higher-quality acetate products of output.
In order to address the above problem, the technical solution adopted in the present invention is:
A kind of catalyst system and catalyzing of acetic acid synthesized by low pressure methanol carbonylation, adopting the halide of rhodium is catalyst, methyl acetate, iodomethane are co-catalyst, inorganic salt compounded of iodine is a stabilizing agent, this catalyst system liquid reaction medium specifically comprises: mass concentration is 0.03-0.12wt% rhodium catalyst (in a rhodium metal), 0.3-1.0wt% alkali metal ion, 3-15wt% iodide ion, the 1-4wt% methyl acetate, 10-21wt% iodomethane, 0.1-0.5wt%VIIIB family and group vib metallic element, water 4-15wt%, remainder is an acetic acid.
With the composition of above-mentioned catalyst, in reactor, CO and methyl alcohol are under the catalyst condition, and carbonylation generates acetic acid, and reactor will contain the reactant liquor derivation of catalyst and acetic acid, carry out vacuum flashing in flash vessel.Become gas phase and liquid phase by flash separation, contain catalyst in the liquid phase, be recycled reactor.The gas phase that flash distillation is produced enters first rectifying column, just above said lightness-removing column (perhaps also being lights column), wet acetic acid is extracted out from the side of this tower in this tower, send into second rectifying column, just above said dehydrating tower (also being drying tower), main component is acetic acid and water in this wet acetic acid, and remainder also contains a spot of methyl acetate and iodomethane.Be divided into two liquid phases behind the cat head vapor condensation of first rectifying column in decanter, except the backflow of the first rectifying column action need, this two-phase is all returned reactor.Send into the wet acetic acid of second rectifying column (dehydrating tower) and deviate from water in this tower, the acetic acid of drying is sent into the 3rd rectifying column at the bottom of the tower, and the moisture acetic acid of cat head is condensed into Returning reactor after the liquid phase.Dry acetic acid is sent into the 3rd rectifying column (weight-removing column 4), sloughs heavy ends such as propionic acid, the product that output is qualified.
The catalyst system of acetic acid synthesized by low pressure methanol carbonylation of the present invention is compared with the catalyst of the production technology of the acetic acid synthesized by low pressure methanol carbonylation of previously described " Monsanto " company, has higher activity and selectivity, the less side products of reaction.Can the higher-quality acetate products of output under the combination of catalyst formulation of the present invention and purifying technique.
Description of drawings
Further specify the present invention below in conjunction with the drawings and specific embodiments.
Fig. 1 is applied to the schematic flow sheet of low pressure carbonylation system acetic acid for catalyst system of the present invention.
Among the figure: 1 is reaction system; 2 is lightness-removing column; 3 is dehydrating tower; 4 is weight-removing column; 5 is waste acid column; 6 is air-washing system; 7 is destilling tower condensation liquid bath; 8 is decanter; 9 is decanter; 39 is condenser; 40 is condenser.
The specific embodiment
For technological means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with the specific embodiment, further set forth the present invention.
Keeping catalyst to contain mass concentration is under the 0.03-0.12wt% rhodium catalyst condition (in rhodium metal); Keep the alkali metal ion of mass concentration at 0.3-1.0wt%; Keep the I of mass concentration at 3-15wt%
-Ion; Keep the methyl acetate of mass concentration at 1-4wt%; Keep mass concentration at the 10-21wt% iodomethane; Keep water any one concentration at mass concentration 4-15wt%; Keep containing mass concentration at the VIIIB of 0.1-0.5wt% family and group vib metallic element; VIIIB family and group vib metallic element form carbonyl complex with CO in catalyst; Remainder is an acetic acid.
Above-mentioned catalyst system contains the stabilizing agent that can stablize the major catalyst rhodium, and this stabilizing agent is to be become by multiple inorganic salt compounded of iodine combined group.As long as inorganic salt compounded of iodine can be dissolved in water and acetic acid mixed solution, and can provide enough I
-Ion can use as stabilizing agent.Because multiple alkali metal salt compounded of iodine can be dissolved in water and/or the acetum, and solubility is very big, therefore in catalyst system, preferably adopt the mixture of a kind of alkali metal salt compounded of iodine or two or more alkali metal salt compounded of iodine as stabilizing agent.As a kind of or two or more mixture in lithium iodide, sodium iodide, the KI.The alkali metal salt compounded of iodine can be reacted to each other by corresponding acetate, carbonate or alkali and aqueous solution of hydrogen iodide and obtain.Adopt the metallic atom amount of alkali metal salt compounded of iodine little, sufficient I can be provided like this
-Ion.For this reason, preferred scheme is lithium iodide, KI and their mixture in the above-mentioned catalyst system.
As long as lithium iodide is or/and the KI consumption makes K
+And Li
+Concentration maintains 0.3-1.0wt% in containing the reactant liquor of catalyst system, and reasonable is that concentration maintains 0.4-0.6wt%.And the ratio of these two kinds of alkali metal ions is by the decision of solubility separately, and not limited by other.
In the catalyst system of acetic acid synthesis from methanol carbonylation, add the alkali metal salt compounded of iodine,, can keep containing in the catalyst I of mass concentration at 8%-15% as stabilizing agent
-Ion particularly keeps I
-The mass concentration of ion in catalyst system just can make to keep containing 0.04-0.12wt% rhodium catalyst (in rhodium metal) in the catalyst at 8%-15%.And can keep containing the 0.06-0.09wt% rhodium catalyst better.
After adding the alkali metal salt compounded of iodine, can obtain the I of some
-Ion concentration, and can make in the catalyst and keep: mass concentration is in the methyl acetate concentration of 1-4wt%; Mass concentration is in 10-21wt% iodomethane concentration; Water is in any one concentration of mass concentration 4-15wt%, and when especially water quality concentration was reduced in 4%-8%, the major catalyst rhodium was still stable.
Found through experiments in addition, contain methyl acetate and surpass 2wt% in reactant liquor, the decanter middle-high density obviously increases mutually, and the phenomenon of layering is very obvious.
When methyl acetate content in reactant liquor is higher than certain concentration, the non-constant of the layered effect of decanter, the high density phase density that is embodied in the decanter descends rapidly, and experiment finds that methyl acetate this adverse influence when 4wt% is above is just apparent in view.Analyze reason, think that the density of methyl acetate is lower than water and acetic acid, methyl acetate solubility in water is very little and solubility in iodomethane is very big, after its concentration in decanter improves, be dissolved in during layering contain a large amount of iodomethane high density mutually in, make the density of high density phase reduce rapidly, and cause layered effect poor.
In addition when iodomethane content in reactant liquor is higher than certain concentration, the layered effect of decanter improves, and the high density phase density that is embodied in the decanter improves, and the layered effect of decanter improves, the middle mutually iodomethane concentration of high density that is embodied in the decanter improves, and water and acetate concentration reduce.Experiment finds that this iodomethane is favourable when concentration is higher than 10wt% in reactant liquor, and when iodomethane when concentration is higher than 13wt% in reactant liquor, this favourable effect is more obvious.
Certainly also find by experiment, when iodomethane content in reactant liquor is higher than certain concentration, the instability of catalyst rhodium in the liquid that can induce reaction.As the concentration of iodomethane in the reactant liquor near or surpass 18wt%, this adverse influence begins to have significantly and manifests, when the concentration of iodomethane in the reactant liquor during near 21wt%, this adverse effect is more obvious.
Therefore, above-mentioned methyl acetate mass concentration is preferably 2-4wt%, and the iodomethane mass concentration is preferably 13-18wt%.When the raising of inorganic iodine salinity, when iodide ion concentration improved, the stability of catalyst rhodium improved in the reactant liquor, makes rhodium under the concentration atmosphere of higher methyl acetate and iodomethane, can be stabilized in a high concentration like this.
In catalyst system, also contain mass concentration at 0.1-0.5%, particularly contain mass concentration at the VIIIB of 0.3-0.45wt% family and group vib metallic element; This VIIIB family element mainly comprises Fe, Ni, and this group vib element mainly comprises Cr, Mo, also can comprise other elements of this two family, and the tungsten of the iridium of VIIIB family, ruthenium, osmium and group vib for example, these elements form carbonyl complex with CO in catalyst.
Present invention is described below by embodiment, but should be understood that the following examples only constitute explanation of the present invention, and be not construed as limiting the invention.
In the following embodiments, reaction process is: in reactor, dispose catalyst as required and add acetic acid, prepare suitable reactant liquor, then with the reactor increasing temperature and pressure, when condition meets in reactor continuous feeding methyl alcohol 36 and CO37.The temperature of reaction is at 190-195 ℃, the pressure of reaction is about 28-30atm, then reactant liquor is shifted out the acetic acid 10 of moisture, methyl acetate, iodomethane and some other impurity by flash distillation, the about 50wt% of acetic acid content, and remove the part heat, rely on the forced circulation cooling system of reactor to remove remaining reaction heat simultaneously.Here it is reaction system (1) is consistent in the patent 2003101082903 of the embodiment of this system and applicant's application, is not described in detail at this.
The acetic acid 10 that contains a large amount of impurity enters lightness-removing column 2 and carries out the rectifying first time, carries dense acetic acid 12 from 2 times tower extraction of lightness-removing column, and acetate concentration is about 90wt%, and all the other are water, methyl acetate, iodomethane and some trace impurities.Keep sub-fraction to carry 16 times reaction systems 1 of dense acetic acid liquid in lightness-removing column 2 bottoms.Contain the light component gaseous stream 17 of low boilers in lightness-removing column 2 top extraction, contain water, methyl acetate, iodomethane, acetic acid and some impurity in the logistics 17.The temperature that logistics 17 condensation and being cooled in condenser 39 needs, condensator outlet logistics 11 contains the gas-liquid two-phase, gas phase is isolated in logistics 11 earlier in decanter 8, be separated into two liquid phases then, it is two-layer up and down that liquid phase relies on the difference of density to be separated into, 13 times reactant liquor systems 1 of high density logistics, and low-density logistics 13 is divided into two-way, one logistics 14 is as the backflow of tower, 44 times reaction systems 1 of another burst logistics.
Introduce two bursts of logistics in decanter 8 simultaneously: one is a water 42, and another strand is the high density logistics 21 from decanter 9.These two bursts of logistics add according to control mode separately.
In decanter 9, introduce water 43 simultaneously.
In implementation process, all examples of implementation write down the input of raw material and the extraction of product and accessory substance in the set time, as the examination to the catalyst ability.Simultaneously, be that the yield that benchmark calculates is weighed catalyst conversion ratio and optionally examination with raw material CO and methyl alcohol.
Embodiment 1:
Reactant liquor consists of in the catalyst system: acetic acid 70.5wt%, methyl acetate 1wt%, iodomethane 12wt%, water 14wt%, Fe0.0025wt%, Ni0.0024wt%, Cr0.0050wt%, Mo0.0100wt%, I
-2.5wt%, Rh0.04wt%.
Experimentize according to embodiment, and temperature are about 40 ℃ in the maintenance decanter 8 that keeping decanter 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 100kg/h, and keeping logistics 42 flows is 100kg/h.Experiment is to catalyst composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25127kg, spent acid 300.2kg.What table 1 write down is logistics capacity and the process conditions of embodiment 1.
Table 1
| Title | Numerical value | Unit |
| Logistics (41) flow | 100 | kg/h |
| Logistics (42) flow | 100 | kg/h |
| Logistics (43) flow | 0 | kg/h |
| Logistics (15) density | 1835 | kg/m 3 |
| The temperature of decanter (8) | 34 | ℃ |
| The temperature of decanter (9) | / | ℃ |
| The input amount of methyl alcohol | 71.0 | kg(100％) |
| The input amount of CO | 68.62 | kg(100％) |
| Product (25) amount of obtaining | 127 | kg |
| Spent acid (30) amount of obtaining | 0.20 | kg |
| Calculate yield with CO | 0.86 | ％ |
| Calculate yield with methyl alcohol | 0.95 | ％ |
Embodiment 2:
Reactant liquor consists of in the catalyst system: acetic acid 59.8wt%, methyl acetate 1.94wt%, iodomethane 10.37wt%, water 7.17wt%, K
+0.5000wt%, Li
+0.3700wt%, Fe 0.1357wt%, Ni 0.0798wt%, Cr 0.0916wt%, I
-10.83wt%, Rh 0.0650wt%.
Experimentize according to embodiment, and temperature are about 36 ℃ in the maintenance decanter 8 that keeping decanter 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 100kg/h, and keeping logistics 42 flows is 75kg/h.Experiment is to catalyst composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25179.5kg, spent acid 300.23kg.What table 2 write down is logistics capacity and the process conditions of embodiment 2.
Table 2
| Title | Numerical value | Unit |
| Logistics (41) flow | 100 | kg/h |
| Logistics (42) flow | 75 | kg/h |
| Logistics (43) |
25 | kg/h |
| Logistics (15) density | 1810 | kg/m 3 |
| The temperature of decanter (8) | 38.9 | ℃ |
| The temperature of decanter (9) | 42.7 | ℃ |
| The input amount of methyl alcohol | 98.8 | kg(100％) |
| The input amount of CO | 93.7 | kg(100％) |
| Product (25) amount of obtaining | 179.5 | kg |
| Spent acid (30) amount of obtaining | 0.23 | kg |
| Calculate yield with CO | 0.89 | |
| Calculate yield with methyl alcohol | 0.97 |
Embodiment 3:
Reactant liquor consists of in the catalyst system: acetic acid 64.9wt%, methyl acetate 3.0wt%, iodomethane 14.0wt%, water 8.4wt%, propionic acid 0.0341wt%, K
+0.4000wt%, Li
+0.3600wt%, Fe 0.1551wt%, Ni 0.1027wt%, Cr 0.1085wt%, Mo 0.0708wt%, I
-9.5wt%, Rh 0.0740wt%.
Experimentize according to embodiment, and temperature are about 32 ℃ in the maintenance decanter 8 that keeping decanter 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 90kg/h, and keeping logistics 42 flows is 50kg/h.Experiment is to catalyst composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25225.8kg, spent acid 300.25kg.What table 3 write down is logistics capacity and the process conditions of embodiment 3.
Table 3
| Title | Numerical value | Unit |
| Logistics (41) flow | 90 | kg/h |
| Logistics (42) flow | 50 | kg/h |
| Logistics (43) |
40 | kg/h |
| Logistics (15) density | 1822 | kg/m 3 |
| The temperature of decanter (8) | 32.2 | ℃ |
| The temperature of decanter (9) | 42.7 | ℃ |
| The input amount of methyl alcohol | 123 | kg(100％) |
| The input amount of CO | 113.6 | kg(100％) |
| Product (25) amount of obtaining | 225.8 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.93 | ％ |
| Calculate yield with methyl alcohol | 0.98 | ％ |
Embodiment 4:
Reactant liquor consists of in the catalyst system: acetic acid 64.4wt%, methyl acetate 2.50wt%, iodomethane 13.0wt%, water 7.8wt%, K
+0.4000wt%, Li
+0.3600wt%, Fe0.1503wt%, Ni 0.1083wt%, Cr0.1019wt%, Mo 0.0687wt%, I
-10.0wt%, Rh 0.0780wt%.
Experimentize according to embodiment, and temperature are about 28 ℃ in the maintenance decanter 8 that keeping decanter 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 110kg/h, and keeping logistics 42 flows is 40kg/h.Experiment is to catalyst composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25231.3kg, spent acid 300.25kg.What table 4 write down is logistics capacity and the process conditions of embodiment 4.
Table 4
| Title | Numerical value | Unit |
| Logistics (41) flow | 110 | kg/h |
| Logistics (42) |
40 | kg/h |
| Logistics (43) flow | 70 | kg/h |
| Logistics (15) density | 1831 | kg/m 3 |
| The temperature of decanter (8) | 28.7 | ℃ |
| The temperature of decanter (9) | 35 | ℃ |
| The input amount of methyl alcohol | 125.5 | kg(100％) |
| The input amount of CO | 117.5 | kg(100％) |
| Product (25) amount of obtaining | 231.3 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.92 | ％ |
| Calculate yield with methyl alcohol | 0.98 | ％ |
Embodiment 5:
Reactant liquor consists of in the catalyst system: acetic acid 66.0wt%, methyl acetate 2.9wt%, iodomethane 13.9wt%, water 6.8wt%, propionic acid 0.0481wt%, K
+0.3800wt%, Li
+0.3600wt%, Fe 0.1627wt%, Ni 0.0798wt%, Cr 0.1231wt%, Mo 0.0737wt%, I
-10.1wt%, Rh 0.0800wt%.
Experimentize according to embodiment, and temperature are about 25 ℃ in the maintenance decanter 8 that keeping decanter 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 100kg/h, and keeping logistics 42 flows is 25kg/h.Experiment is to catalyst composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 251kg, spent acid 30 0.25kg.What table 5 write down is logistics capacity and the process conditions of embodiment 5.
Table 5
| Title | Numerical value | Unit |
| Logistics (41) flow | 100 | kg/h |
| Logistics (42) flow | 25 | kg/h |
| Logistics (43) flow | 75 | kg/h |
| Logistics (15) density | 1837 | kg/m 3 |
| The temperature of decanter (8) | 25 | ℃ |
| The temperature of decanter (9) | 40 | ℃ |
| The input amount of methyl alcohol | 135.0 | kg(100％) |
| The input amount of CO | 126.8 | kg(100％) |
| Product (25) amount of obtaining | 251.0 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.92 | ％ |
| Calculate yield with methyl alcohol | 0.99 | ％ |
Embodiment 6:
Reactant liquor consists of in the catalyst system: acetic acid 59.0wt%, methyl acetate 2.1wt%, iodomethane 14.7wt%, water 5.5wt%, K
+0.2600wt%, Li
+0.4500wt%, Fe0.1545wt%, Ni 0.0755wt%, Cr0.0176wt%, Mo 0.0169wt%, I
-12.2wt%, Rh 0.100wt%.
Experimentize according to embodiment, and temperature are about 23 ℃ in the maintenance decanter 8 that keeping decanter 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 100kg/h, and keeping logistics 42 flows is 0kg/h.Experiment is to catalyst composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25255kg, spent acid 300.35kg.What table 6 write down is logistics capacity and the process conditions of embodiment 6.
Table 6
| Title | Numerical value | Unit |
| Logistics (41) flow | 100 | kg/h |
| Logistics (42) flow | 0 | kg/h |
| Logistics (43) flow | 100 | kg/h |
| Logistics (15) density | 1840 | kg/m 3 |
| The temperature of decanter (8) | 23.3 | ℃ |
| The temperature of decanter (9) | 40 | ℃ |
| The input amount of methyl alcohol | 138.0 | kg(100％) |
| The input amount of CO | 129.0 | kg(100％) |
| Product (25) amount of obtaining | 255 | kg |
| Spent acid (30) amount of obtaining | 0.35 | kg |
| Calculate yield with CO | 0.92 | ％ |
| Calculate yield with methyl alcohol | 0.99 | ％ |
Embodiment 7:
Reactant liquor consists of in the catalyst system: acetic acid 60.7wt%, methyl acetate 2.3wt%, iodomethane 15.2wt%, water 5.0wt%, K
+0.2500wt%, Li
+0.4100wt%, Fe 0.1537wt%, Ni 0.0684wt%, Cr0.023wt%, Mo 0.0217wt%, I
-11.6wt%, Rh0.0780wt%.
Experimentize according to embodiment, and temperature are about 23 ℃ in the maintenance decanter 8 that keeping decanter 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 120kg/h, and keeping logistics 42 flows is 90kg/h.Experiment is to catalyst composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 263kg, spent acid 30 0.25kg.What table 7 write down is logistics capacity and the process conditions of embodiment 7.
Table 7
| Title | Numerical value | Unit |
| Logistics (41) flow | 120 | kg/h |
| Logistics (42) flow | 90 | kg/h |
| Logistics (43) flow | 30 | kg/h |
| Logistics (15) density | 1830 | kg/m 3 |
| The temperature of decanter (8) | 30 | ℃ |
| The temperature of decanter (9) | 40 | ℃ |
| The input amount of methyl alcohol | 143.0 | kg(100％) |
| The input amount of CO | 134.0 | kg(100％) |
| Product (25) amount of obtaining | 263 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.92 | ％ |
| Calculate yield with methyl alcohol | 0.98 | ％ |
Embodiment 8:
Reactant liquor consists of in the catalyst system: acetic acid 58.7wt%, methyl acetate 2.70wt%, iodomethane 16.4wt%, water 4.4wt%, propionic acid 1.0774wt%, K
+0.2100wt%, Li
+0.5000wt%, Fe 0.1537wt%, Ni 0.0684wt%, Cr 0.0230wt%, Mo 0.0217wt%, I
-12.2wt%, Rh 0.0900wt%.
Experimentize according to embodiment, and temperature are about 30 ℃ in the maintenance decanter 8 that keeping decanter 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 75kg/h, and keeping logistics 42 flows is 60kg/h.Experiment is to catalyst composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 255kg, spent acid 30 0.35kg.What table 8 write down is logistics capacity and the process conditions of embodiment 8.
Table 8
| Title | Numerical value | Unit |
| Logistics (41) flow | 75 | kg/h |
| Logistics (42) flow | 60 | kg/h |
| Logistics (43) flow | 15 | kg/h |
| Logistics (15) density | 1831 | kg/m 3 |
| The temperature of decanter (8) | 30 | ℃ |
| The temperature of decanter (9) | 40 | ℃ |
| The input amount of methyl alcohol | 143.5 | kg(100％) |
| The input amount of CO | 134.0 | kg(100％) |
| Product (25) amount of obtaining | 263 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.92 | ％ |
| Calculate yield with methyl alcohol | 0.98 | ％ |
Embodiment 9:
Reactant liquor consists of in the catalyst system: acetic acid 58.7wt%, methyl acetate 3.80wt%, iodomethane 18.8wt%, water 7.0wt%, K
+0.1700wt%, Li
+0.5500wt%, Fe 0.0537wt%, Ni 0.0284wt%, I
-10.1wt%, Rh 0.0640wt%.
Experimentize according to embodiment, and temperature are about 30 ℃ in the maintenance decanter 8 that keeping decanter 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 75kg/h, and keeping logistics 42 flows is 60kg/h.Experiment is to catalyst composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 251kg, spent acid 30 0.25kg.What table 9 write down is logistics capacity and the process conditions of embodiment 9.
Table 9
| Title | Numerical value | Unit |
| Logistics (41) flow | 75 | kg/h |
| Logistics (42) flow | 60 | kg/h |
| Logistics (43) flow | 15 | kg/h |
| Logistics (15) density | 1851 | kg/m 3 |
| The temperature of decanter (8) | 30 | ℃ |
| The temperature of decanter (9) | 40 | ℃ |
| The input amount of methyl alcohol | 135.2 | kg(100％) |
| The input amount of CO | 126.7 | kg(100％) |
| Product (25) amount of obtaining | 251.0 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.99 | ％ |
| Calculate yield with methyl alcohol | 0.92 | ％ |
Embodiment 10:
Reactant liquor consists of in the catalyst system: acetic acid 59.7wt%, methyl acetate 3.8wt%, iodomethane 21.2wt%, water 7.3wt%, K
+0.1600wt%, Li
+0.4300wt%, Fe 0.0637wt%, Ni 0.0284wt%I
-8.9wt%, Rh 0.055wt%.
Experimentize according to embodiment, and temperature are about 30 ℃ in the maintenance decanter 8 that keeping decanter 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 65kg/h, and keeping logistics 42 flows is 65kg/h.Experiment is to catalyst composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of logistics (25), the composition of logistics 30 detect.And obtain product 25 225kg, spent acid 30 0.25kg.What table 10 write down is logistics capacity and the process conditions of embodiment 10.
Table 10
| Title | Numerical value | Unit |
| Logistics (41) flow | 75 | kg/h |
| Logistics (42) flow | 60 | kg/h |
| Logistics (43) flow | 15 | kg/h |
| Logistics (15) density | 1881 | kg/m 3 |
| The temperature of decanter (8) | 30 | ℃ |
| The temperature of decanter (9) | 40 | ℃ |
| The input amount of methyl alcohol | 124 | kg(100％) |
| The input amount of CO | 113 | kg(100％) |
| Product (25) amount of obtaining | 225 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.97 | ％ |
| Calculate yield with methyl alcohol | 0.93 | ％ |
Embodiment 11:
Reactant liquor consists of in the catalyst system: acetic acid 63.4wt%, methyl acetate 2.7wt%, iodomethane 14.2wt%, water 5.6wt%, K
+0.1700wt%, Li
+0.6300wt%, Fe 0.1537wt%, Ni 0.0684wt%, Cr 0.0230wt%, Mo 0.0217wt%, I
-13.8wt%, Rh 0.085wt%.
Experimentize according to embodiment, and temperature are about 30 ℃ in the maintenance decanter 8 that keeping decanter 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 70kg/h, and keeping logistics 42 flows is 50kg/h.Experiment is to catalyst composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 260kg, spent acid 30 0.25kg.What table 11 write down is logistics capacity and the process conditions of embodiment 11.
Table 11
| Title | Numerical value | Unit |
| Logistics (41) flow | 70 | kg/h |
| Logistics (42) flow | 50 | kg/h |
| Logistics (43) flow | 20 | kg/h |
| Logistics (15) density | 1811 | kg/m 3 |
| The temperature of decanter (8) | 30 | ℃ |
| The temperature of decanter (9) | 40 | ℃ |
| The input amount of methyl alcohol | 140.1 | kg(100％) |
| The input amount of CO | 134.1 | kg(100％) |
| Product (25) amount of obtaining | 260 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.99 | ％ |
| Calculate yield with methyl alcohol | 0.90 | ％ |
More than show and described basic principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (10)
1, a kind of catalyst system and catalyzing of acetic acid synthesized by low pressure methanol carbonylation, adopting the halide of rhodium is catalyst, methyl acetate, iodomethane are co-catalyst, inorganic salt compounded of iodine is a stabilizing agent, wherein this catalyst system liquid reaction medium specifically comprises: mass concentration is in rhodium metal 0.03-0.12wt% rhodium catalyst, 0.3-1.0wt% alkali metal ion, 3-15wt% iodide ion, the 2-4wt% methyl acetate, iodomethane＞15wt% to 18wt%, 0.1-0.5wt%VIIIB family and group vib metallic element, water 4.4-7.0wt%, remainder is an acetic acid.
2, catalyst system and catalyzing according to claim 1, wherein said inorganic salt compounded of iodine are the mixture of a kind of alkali metal salt compounded of iodine or two kinds of alkali metal salt compounded of iodine.
3, catalyst system and catalyzing according to claim 1, wherein said inorganic salt compounded of iodine are lithium iodide, KI or their mixture.
4, catalyst system and catalyzing according to claim 1, wherein said VIIIB family element are a kind of in iron, nickel, iridium, ruthenium, the osmium, and described group vib element is a kind of in chromium, molybdenum, the tungsten.
5, catalyst system and catalyzing according to claim 1, wherein said VIIIB family element is iron or nickel, described group vib element is chromium or molybdenum.
6, catalyst system and catalyzing as claimed in claim 1, wherein said alkali metal ion are potassium ion and/or lithium ion.
7, catalyst system and catalyzing as claimed in claim 1, wherein said rhodium catalyst mass concentration is 0.06-0.09wt%.
8, catalyst system and catalyzing as claimed in claim 1, wherein said alkali metal ion mass concentration is 0.4wt%-0.6wt%.
9, catalyst system and catalyzing as claimed in claim 1, wherein said iodide ion mass concentration is 7-12wt%.
10, catalyst system and catalyzing as claimed in claim 1, wherein said VIIIB family and group vib metallic element mass concentration are 0.3-0.45wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100277787A CN100450621C (en) | 2006-06-19 | 2006-06-19 | Catalyst system used in low pressure methanol carbonyl synthesizing acetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100277787A CN100450621C (en) | 2006-06-19 | 2006-06-19 | Catalyst system used in low pressure methanol carbonyl synthesizing acetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1868596A CN1868596A (en) | 2006-11-29 |
| CN100450621C true CN100450621C (en) | 2009-01-14 |
Family
ID=37442457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100277787A Active CN100450621C (en) | 2006-06-19 | 2006-06-19 | Catalyst system used in low pressure methanol carbonyl synthesizing acetic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100450621C (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6211405B1 (en) * | 1998-10-23 | 2001-04-03 | Celanese International Corporation | Addition of iridium to the rhodium/inorganic iodide catalyst system |
-
2006
- 2006-06-19 CN CNB2006100277787A patent/CN100450621C/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6211405B1 (en) * | 1998-10-23 | 2001-04-03 | Celanese International Corporation | Addition of iridium to the rhodium/inorganic iodide catalyst system |
Non-Patent Citations (2)
| Title |
|---|
| 甲醇羰基化制乙酸. 王玉和，贺德华，徐柏庆.化学进展，第15卷第3期. 2003 |
| 甲醇羰基化制乙酸. 王玉和，贺德华，徐柏庆.化学进展，第15卷第3期. 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1868596A (en) | 2006-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101244984B (en) | Method for the production of 1,4-butanediol | |
| US20100019192A1 (en) | Method of producing lower alcohols from glycerol | |
| US8252961B2 (en) | Method of producing lower alcohols from glycerol | |
| CN101544539A (en) | Method for producing polymer grade ethylene glycol and co-producing methyl glycolate | |
| CN104926657B (en) | The method of oxalate gas phase hydrogenation synthesizing alcohol acid esters | |
| CN111689845B (en) | Process for producing succinic acid by maleic anhydride aqueous phase hydrogenation | |
| CN107141213A (en) | A kind of method of acetic acid synthesis from methanol carbonylation | |
| CN102060767B (en) | Method for producing caprolactam by methylbenzene | |
| UA54592C2 (en) | A process for producing acetic acid | |
| CN109748791B (en) | Energy-saving method for producing dimethyl adipate | |
| EP2240429B1 (en) | Method of producing lower alcohols from glycerol | |
| CN104557454B (en) | A kind of method of acetic acid Hydrogenation for high-quality ethanol | |
| CN105418372B (en) | A kind of method of acetic acid hydrogenation production ethanol | |
| CN100450621C (en) | Catalyst system used in low pressure methanol carbonyl synthesizing acetic acid | |
| US20110124926A1 (en) | Process for preparing diols by hydrogenating a carboxylic acid-comprising mixture by means of cobalt-comprising catalysts | |
| CN100427449C (en) | Purification method for acetic acid synthesized by low pressure methanol carbonylation | |
| CN105198704A (en) | Method for low-energy consumption acetic acid hydrogenation production of ethanol | |
| CN115282913A (en) | Reaction system and method for preparing methyl propionate | |
| CN105481649B (en) | A kind of method that acetic acid hydrogenation prepares ethanol | |
| CN110878006B (en) | Method and device for separating ethanol and ethyl acetate | |
| CN102001938A (en) | Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid | |
| CN105566057B (en) | A kind of method of acetic acid hydrogenation production ethanol | |
| CN100450988C (en) | Low pressure device for synthesizing acetic acid by methanol carbonylation | |
| CN105566060B (en) | The method of acetic acid preparation of ethanol through hydrogenation | |
| CN107011118A (en) | The technique that a kind of methanol prepares and refines ethanol |
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 | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI HUAYI ENERGY + CHEMICAL INDUSTRY CO., LTD Free format text: FORMER OWNER: WUJING CHEMICAL CO., LTD., SHANGHAI Effective date: 20150120 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20150120 Address after: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd Address before: 200241 No. 4600 Wu Long Road, Shanghai Patentee before: Wujing Chemical Co., Ltd., Shanghai |