Summary of the invention
The carbonylation that technical problem to be solved by this invention has provided a kind of alkanol and/or its reactive derivative prepares the method for carboxylic acid.Method reaction system of the present invention does not contain ionic iodide, and its catalytic reaction activity is still higher, has catalytic activity preferably under low ester and/or the low water content condition, and the catalyzer cost is lower and stable better.
The carbonylation of alkanol of the present invention and/or its reactive derivative prepares the method for carboxylic acid, it is in the liquid reaction medium that contains iridium catalyst, rhodium catalyst, metallic promoter agent, water, methyl acetate, methyl-iodide and acetate, with alkanol and/or its reactive derivative and carbon monoxide charging reaction, from the reaction product that obtains, reclaim carboxylic acid then, wherein, the content of described iridium catalyst is 500~4000ppm, and that preferable is 1000~2000ppm; The content of described rhodium catalyst is 50~400ppm, and that preferable is 100~300ppm; The molar ratio of described metallic promoter agent and iridium is 1~15, and preferable is 6~15, and better is 7~10.
Reaction system of the present invention adopts the coupling system of iridium catalyst and rhodium catalyst.Grope through a large amount of experiments, selected the proportioning of content range and the metallic promoter agent and the iridium of above-mentioned iridium rhodium especially, make the catalytic reaction activity and the speed of reaction be significantly improved, and the content of catalyst rhodium of the present invention rhodium content in the existing rhodium iridium catalyst coupling system significantly reduces, and greatly reduces cost; Simultaneously reaction system of the present invention also has catalytic activity preferably under low ester condition, for some use equipment such as methyl-iodide retrieving arrangement etc., can use the appliance arrangement of single rhodium catalyst system, and the saving resources costs cuts down the consumption of energy.
Wherein, described metallic promoter agent is the conventional metallic promoter agent of using in this area, one or more that preferable is in ruthenium, osmium and the rhenium, and better is ruthenium.The existence form of described metallic promoter agent is the salt of the metal catalyst of existing this area routine, generally can be any appropriate form and join the salt that dissolves or be converted into soluble form in the liquid reaction medium, that preferable is ruthenium chloride, ruthenium bromide, ruthenium metal, ruthenium oxide, ruthenium acetate, propionic acid ruthenium, butyric acid ruthenium, pentacarbonyl ruthenium, hydration osmium chloride, anhydrous chlorides of rase osmium, osmium metal, perosmic anhydride, ten dicarbapentaborane, three osmiums, Re
2(CO)
10, Re (CO)
5Cl, Re (CO)
5Br, Re (CO)
5I, ReCl
3XH
2O and ReCl
5YH
2Among the O one or more.
Wherein, the precursor of described iridium catalyst is the conventional iridium salt catalyst precursor that uses in this area, and that preferable is iridium acetate, iridium metals, iodate iridium, hydration iodate iridium, bromination iridium, hydration bromination iridium, iridium chloride, chloro-iridic acid, hydration iridium chloride, oxalic acid iridium, etheric acid iridium, iridium oxide, iridous oxide, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2, [Ir (CO)
2Br]
2, Ir
4(CO)
12, [Ir (CO)
2I
2]
-H
+, [Ir (CO)
2Br
2]
-H
+, [Ir (CO)
2I
4]
-H
+[Ir (CH
3) (CO)
2I
3]
-H
+In one or more, the better iridium catalyst precursor that preferably is dissolvable in water carbonylation reaction component such as water, alcohol and carboxylic acid is as in iridium acetate, oxalic acid iridium and the etheric acid iridium one or more.
Wherein, the precursor of described rhodium catalyst is the conventional rhodium salt catalyst precursor that uses in this area, the preferable rhodium salt catalyst precursor that is applicable to single rhodium catalyst system that is selected from, that better is rhodium chloride, three hydration rhodium chlorides, bromination rhodium, iodate rhodium, rhodium acetate, dicarbonyl rhodium acetylacetonate, [Rh (CO)
2Cl]
2[Rh (CO)
2I]
2In one or more.The content of catalyst rhodium of the present invention in rhodium iridium catalystic converter system obviously reduces, and makes catalystic converter system of the present invention under the prerequisite that has guaranteed good catalytic reaction activity, and the stability of catalyzer has better also further reduced the catalyzer cost simultaneously.
Wherein, the content of described water is this area conventional amount used, and preferable is 0.5~16%, and better is 0.5~14%, and best is 2~8%, and per-cent is mass percent.Applicable high water of catalystic converter system of the present invention or low aqueous systems, and in low aqueous systems, still have advantages of high catalytic activity, and lower water-content also makes, and the lock out operation difficulty and the cost of water and acetic acid product significantly reduces in the follow-up step.
Wherein, the content of described methyl acetate is this area conventional amount used, and preferable is 0.5~40%, and better is 0.5~5%, and per-cent is mass percent.Wherein, the content of preferred methyl acetate belongs to low ester content scope, and catalystic converter system of the present invention still has catalytic activity preferably under low ester condition, should hang down the operation easier that ester content also reduces the subsequent recovery methyl-iodide simultaneously.
Wherein, the content of described methyl-iodide is this area conventional amount used, and preferable is 5~30%, and better is 10~20%, and per-cent is mass percent.
Wherein, the content of described acetate is this area conventional amount used, is generally the amount of replenishing liquid reaction medium mass percent 100% among the present invention.
Among the present invention, described alkanol and/or its reactive derivative such as ether, ester, halogenide etc. are used for carbonylation reaction and produce carboxylic acid.Described alkanol preferable for carbonatoms is 1~5 alcohols, better is methyl alcohol.
The described content of above-mentioned each component is in the catalytic reaction process each components contents in the real reaction system among the present invention.
Among the present invention, the optimum condition of each above-mentioned technical characterictic can arbitrary combination, obtains preferred embodiment of the present invention.
The suitable device of method of the present invention is this area conventional equipment, generally can adopt typical reactive system, and the reactive system that the catalysis methanol carbonylation prepares acetate generally comprises liquid-phase carbonylation reactor, flash tank and separated from acetic acid tower.Autoclave when carbonylation reactor generally is the stirring that can automatically the reaction liquid capacity be maintained constant level can be introduced alkanol and/or its reactive derivative, water, continuously from the methyl-iodide and the methyl acetate of recycling catalyst solution at the bottom of the flash tank and recycle in this reactor.Carbon monoxide is carbonylate reactor and fully disperseing therein continuously also, and the top of reactor can emit steam state and dispel logistics simultaneously, with the accumulation of avoiding gaseous by-product and keep predetermined carbon monoxide pressure of tension under given total reactor pressure.The control method of the temperature and pressure of carbonylation reactor is with this area ordinary method among the present invention.Flash tank receives the liquid crude product from the carbonylation reactor discharging.Through the flash tank flash distillation, catalyst solution flows out as the bottom material and returns carbonylation reactor, and the top goes out the mixture that the condensation material package is drawn together crude product acetate and methyl-iodide, water and methyl acetate, and the gaseous feed at top is gaseous by-product methane, carbonic acid gas etc.The separated from acetic acid tower is accepted the condensation material of flashing tower, separating acetic acid and methyl-iodide and methyl acetate.Product acetate can carry out follow-up refining purification afterwards from the knockout tower bottom discharge; Methyl-iodide and methyl acetate are looped back in the carbonylation reactor by the discharging of knockout tower cat head.
Agents useful for same of the present invention and raw material are all commercially available to be got.
Positive progressive effect of the present invention is: the carbonylation that the invention provides a kind of alkanol and/or its reactive derivative prepares the method for carboxylic acid.Method reaction system of the present invention does not contain ionic iodide, and its catalytic reaction activity significantly improves, and has catalytic activity preferably under low ester and/or low water content condition, and the catalyzer cost is lower and stable better.
Embodiment
Mode below by embodiment further specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.
Rate of catalysis reaction when the content of embodiment 1 different iridium rhodiums and metallic promoter agent and iridium proportioning
In the zirconium material autoclave of a 200ml, add entry, acetate, methyl acetate, methyl-iodide, Trichlororhodium, iridous chloride and iodate ruthenium.Experiment numbers is that the weight percentage of each reactant feed of adding in 1~38 the reaction system mesohigh reactor is as follows: water 8%, methyl acetate 20%, methyl-iodide 14%, and all the other are acetate, the consumption of iridium, rhodium and ruthenium is as shown in table 1.After adding reaction solution 120 grams of above prescription in the autoclave, operate as follows:
(1) off-response still carries out leakage detection with nitrogen to reaction unit.After determining that reaction unit does not have leakage point,, with CO 0.5MPa is arrived in the reactive system pressurising then with slowly displacement twice of CO;
(2) start stirring, rotating speed is about 850 rev/mins, and setting temperature controlling system is 190 ℃, heating;
(3) along with the rising of temperature, the pressure of reactive system constantly increases, and when treating that temperature is raised to 190 ℃, opens the pressurising gas circuit of CO, and the reactive system pressurising to 2.8Mpa, is closed the valve of pressurising gas circuit afterwards; Open the CO constant voltage source of the gas gas circuit that the CO flow control is housed again, its pressure is 2.8Mpa; Beginning carbonylation reaction timing, keeping temperature of reaction is 190 ± 1 ℃, reaction pressure 2.8Mpa (gauge pressure), instantaneous delivery and the cumulative throughflow of CO under 1 second and computer record that reactive system links to each other;
When (4) the question response system does not absorb CO, " Quench " carried out in reaction handle termination reaction;
(5) treat that temperature reduces to room temperature,, open reactor, pour out reaction solution and weigh, sampling analysis with nitrogen replacement twice.
The content of methyl acetate is about 3wt% in the instantaneous delivery of CO when accessing the CO cumulative throughflow and be 5.2 liters from record, this moment reactive system, and water-content is about 4%, methyl-iodide content 14%, and the content of iridium, rhodium and ruthenium sees Table 1.Therefore, when methyl acetate content was 3wt% in reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represented speed of reaction, and the results are shown in Table 1.
Rate of catalysis reaction when the content of the different iridium rhodiums of table 1 and metallic promoter agent and iridium proportioning
Numbering |
Ir(ppm) |
Ru/Ir (mol ratio) |
Rh(ppm) |
STY(@3%MeOAC, mol/L.h) |
1 |
1000 |
1 |
300 |
16 |
2 |
1000 |
2 |
300 |
17 |
3 |
1000 |
4 |
300 |
19 |
4 |
1000 |
6 |
300 |
24 |
5 |
1000 |
7 |
300 |
28 |
6 |
1000 |
10 |
300 |
31 |
7 |
1000 |
12 |
300 |
31 |
8 |
1000 |
15 |
300 |
30 |
9 |
1500 |
1 |
300 |
17 |
10 |
1500 |
2.5 |
300 |
18 |
11 |
1500 |
3.5 |
300 |
21 |
12 |
1500 |
5 |
300 |
25 |
13 |
1500 |
6 |
300 |
29 |
14 |
1500 |
7 |
300 |
32 |
15 |
1500 |
8 |
300 |
32 |
16 |
1500 |
10 |
300 |
33 |
17 |
1500 |
12 |
300 |
33 |
18 |
1500 |
15 |
300 |
32 |
19 |
1800 |
2 |
200 |
20 |
20 |
1800 |
4 |
200 |
22 |
21 |
1800 |
6 |
200 |
25 |
22 |
1800 |
7 |
200 |
28 |
23 |
1800 |
10 |
200 |
28 |
24 |
2000 |
2 |
100 |
19 |
25 |
2000 |
4 |
100 |
20 |
26 |
2000 |
6 |
100 |
23 |
27 |
2000 |
7 |
100 |
27 |
28 |
2000 |
10 |
100 |
28 |
29 |
500 |
2 |
400 |
19 |
30 |
500 |
4 |
400 |
19 |
31 |
500 |
6 |
400 |
22 |
32 |
500 |
7 |
400 |
25 |
33 |
500 |
10 |
400 |
26 |
34 |
4000 |
2 |
50 |
20 |
35 |
4000 |
4 |
50 |
21 |
36 |
4000 |
6 |
50 |
24 |
37 |
4000 |
7 |
50 |
27 |
38 |
4000 |
10 |
50 |
27 |
Contrast 1 |
1500 |
7 |
500 |
20 (having precipitation to generate) |
Contrast 2 |
1500 |
7 |
40 |
9 |
By last table data as seen, catalystic converter system of the present invention, in the numerical range of the proportioning of the content range of iridium rhodium and metallic promoter agent and iridium, have higher catalytic reaction activity, and rate of catalysis reaction enlarges markedly along with the increase of metallic promoter agent and iridium proportioning.Compare with the catalystic converter system of contrast 2 with contrast 1, under iridium ruthenium content same case, experiment numbers of the present invention is that the speed of reaction of 14 catalystic converter system has significant leap (in this area if speed of reaction STY can improve 2 unit values and promptly belong to bigger raising).Simultaneously, the rhodium content in the significantly existing rhodium iridium catalyst coupling system of the content of the catalyst rhodium of using among the present invention is low, has reduced the catalyzer cost apparently.
The rate of catalysis reaction of embodiment 2 dissimilar metals promotor
Operation steps is with embodiment 1, wherein the weight percentage of each component of autoclave internal reaction system is as follows: experiment numbers is that the add-on of 39~48 each raw material of reaction system is: water 5%, methyl acetate 20%, methyl-iodide 14%, iridium 1500ppm, rhodium 200ppm, all the other are acetate, and per-cent is mass percent; The content of metallic promoter agent sees the following form; Reaction solution 120 grams that add above prescription in the autoclave.
The content of methyl acetate is about 3wt% in the instantaneous delivery of CO when accessing the CO cumulative throughflow and be 5.2 liters from record, this moment reactive system, and water-content is about 2%, methyl-iodide content 14%, and iridium 1500ppm, rhodium 200ppm, the content of metallic promoter agent sees the following form 2; When methyl acetate content was 3wt% in reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represented speed of reaction, and the results are shown in Table 2.
The catalytic activity of the iridium rhodium catalytic system of table 2 dissimilar metals promotor
Numbering |
Metallic promoter agent |
Metallic promoter agent/iridium (mol) |
STY (@3% methyl acetate, mol/L.h) |
39 |
Osmium |
2 |
17 |
40 |
Osmium |
4 |
17 |
41 |
Osmium |
5 |
20 |
42 |
Osmium |
7 |
23 |
43 |
Osmium |
10 |
23 |
44 |
Rhenium |
2 |
16 |
45 |
Rhenium |
4 |
17 |
46 |
Rhenium |
5 |
21 |
47 |
Rhenium |
7 |
24 |
48 |
Rhenium |
10 |
25 |
By last table data as seen, in the catalystic converter system of the present invention, although use metallic promoter agent not of the same race, reaction system still has catalytic reaction activity preferably, and wherein, rate of catalysis reaction is along with the increase of metallic promoter agent and iridium proportioning enlarges markedly.
Rate of catalysis reaction during the different methyl acetate content of embodiment 3
Operation steps is with embodiment 1, wherein the weight percentage of each component of autoclave internal reaction system is as follows: experiment numbers is that the add-on of each raw material of reaction system of 49 is: water 5%, methyl acetate 20%, methyl-iodide 14%, iridium 1800ppm, rhodium 200ppm, osmium/iridium mol ratio are 7, all the other are acetate, and per-cent is mass percent; Reaction solution 120 grams that add above prescription in the autoclave.
Access from record when the content of methyl acetate is about the following table data in the reactive system, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represents speed of reaction; This moment reaction system in methyl-iodide content 14%, iridium 1800ppm, rhodium 200ppm, osmium/iridium mol ratio are 7, the results are shown in Table 3.
Rate of catalysis reaction during the different methyl acetate content of table 3
By last table data as seen, catalyst system of the present invention is applicable to high ester or low ester system, although rate of catalysis reaction is along with the increase of methyl acetate concentration increases gradually, still have advantages of high catalytic activity but catalyst body of the present invention ties up in the low ester system, under the low ester condition lock out operation difficulty and the cost of methyl-iodide in the follow-up step are significantly reduced.
The rate of catalysis reaction of embodiment 4 different water-contents
Operation steps is with embodiment 1, wherein the weight percentage of each component of autoclave internal reaction system is as follows: experiment numbers is that the add-on of each raw material of reaction system of 50~55 is: methyl acetate 20%, methyl-iodide 14%, iridium 1500ppm, rhodium 200ppm, rhenium/iridium mol ratio is 7, all the other are acetate, per-cent is mass percent, and water-content sees the following form; Reaction solution 120 grams that add above prescription in the autoclave.
Access that the content of methyl acetate is about at 5% o'clock in the reactive system from record, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represents speed of reaction; This moment reaction system in methyl-iodide content 14%, iridium 1800ppm, rhodium 200ppm, osmium/iridium mol ratio are 7, the results are shown in Table 4.
The rate of catalysis reaction of the different water-contents of table 4
Numbering |
The concentration wt% of water |
STY (@5% methyl acetate, mol/L.h) |
50 |
0.5 |
18 |
51 |
2 |
21 |
52 |
3 |
22 |
53 |
8 |
25 |
54 |
10 |
24 |
55 |
14 |
22 |
By last table data as seen, catalyst system of the present invention is applicable to high water or low aqueous systems, and catalyst body of the present invention ties up in the low aqueous systems still has advantages of high catalytic activity, also makes that the lock out operation difficulty and the cost of water and acetic acid product significantly reduces in the follow-up step simultaneously.
The rate of catalysis reaction of embodiment 5 different methyl-iodide content
Operation steps is with embodiment 1, wherein the weight percentage of each component of autoclave internal reaction system is as follows: experiment numbers is that the add-on of each raw material of reaction system of 56~60 is: water 8%, methyl acetate 20%, iridium 1500ppm, rhodium 200ppm, ruthenium/iridium mol ratio is 5, and all the other are acetate; Reaction solution 120 grams that add above prescription in the autoclave.
Access that the content of methyl acetate is about at 5% o'clock in the reactive system from record, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represents speed of reaction; Water 4%, iridium 1500ppm, rhodium 200ppm in this moment reaction system, ruthenium/iridium mol ratio is 5, the results are shown in Table 5.
The rate of catalysis reaction of the different methyl-iodide content of table 5
Numbering |
The concentration wt% of methyl-iodide |
STY (@5% methyl acetate, mol/L.h) |
56 |
5 |
15 |
57 |
10 |
16 |
58 |
15 |
22 |
59 |
20 |
24 |
60 |
30 |
26 |
By last table data as seen, the conventional content range that is suitable for all has rate of catalysis reaction preferably to methyl-iodide in this area in the catalyst system of the present invention, but rate of catalysis reaction increases gradually along with the increase of concentrationofmethyiodide iodide.
Metallic promoter agent and iridium mol ratio are to the influence of speed of reaction under the single iridium system of comparative example
Operation steps is with embodiment 1, and wherein the add-on of each raw material of autoclave internal reaction system is that weight percentage is as follows: water 5%, methyl acetate 20%, methyl-iodide 14%, and all the other are acetate, the consumption of iridium and ruthenium is as shown in table 6; Reaction solution 120 grams that add above prescription in the autoclave.
Access that the content of methyl acetate is about at 3% o'clock in the reactive system from record, the STY that calculates with the instantaneous absorbed dose of the CO that is measured represents speed of reaction; Water 2%, methyl-iodide 14% in this moment reaction system, the results are shown in Table 6.
Table 6 metallic promoter agent and iridium mol ratio are to the influence of speed of reaction
Numbering |
Ir(ppm) |
Ru/Ir(mol) |
Rh(ppm) |
STY(@3%MeOAC,mol/L.h) |
1 |
1200 |
2.5 |
- |
4.69 |
2 |
1200 |
3.5 |
- |
4.70 |
3 |
1200 |
5 |
- |
5.90 |
4 |
1200 |
6 |
- |
5.99 |
5 |
1200 |
7 |
- |
5.99 |
With metallic promoter agent in the table 6 and iridium mol ratio rate of catalysis reaction is mapped, visible accompanying drawing 1, under single iridium system, under similarity condition, along with the increase of metallic promoter agent and iridium mol ratio, and the rate of catalysis reaction intensity of variation is less.
Simultaneously, investigated in the catalystic converter system of iridium rhodium of the present invention coupling, different metal promotor and iridium mol ratio are to the influence of rate of catalysis reaction, adopt the experimental data of experiment numbers 2~10 among the embodiment 1, rate of catalysis reaction is mapped, visible accompanying drawing 1 with metallic promoter agent and iridium mol ratio, under the iridium rhodium coupling system, under similarity condition, along with the increase of metallic promoter agent and iridium mol ratio, rate of catalysis reaction significantly increases.