CN1861253A - Catalyst for fluidized bed gaseous hydrogenation of o-nitrotoluene to produce o-methylaniline and process therefor - Google Patents
Catalyst for fluidized bed gaseous hydrogenation of o-nitrotoluene to produce o-methylaniline and process therefor Download PDFInfo
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- CN1861253A CN1861253A CN 200610016935 CN200610016935A CN1861253A CN 1861253 A CN1861253 A CN 1861253A CN 200610016935 CN200610016935 CN 200610016935 CN 200610016935 A CN200610016935 A CN 200610016935A CN 1861253 A CN1861253 A CN 1861253A
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Abstract
A catalyst for preparing o-methyl phenylamine from o-mitrotoluene by gas-phase hydrogenation in boiling bed is prepared from silica gel as carrier and the active component (Cu, Cu-Ni, Cu-Pd, or Cu-Ni-Pd) through immersing said silica gel in the nitrate solution containing said active component to obtain catalyst. It has high catalytic activity and selectivity, high strength and stability, and high output of 0-methyl phenylamine.
Description
Technical field
The present invention relates to a kind of fluidized bed gaseous hydrogenation of o-nitrotoluene to produce o methylaniline catalyst and technology, relate in particular to fluidized bed gaseous hydrogenation of o-nitrotoluene to produce o methylaniline Catalysts and its preparation method and method of hydrotreating.
Background technology
Ortho-methylnitrobenzene iron powder reducing method adopts batch production, under hydrochloric acid medium and about 100 ℃ ortho-methylnitrobenzene is reduced into o-toluidine.The o-toluidine yield is 95%～98%.
Ortho-methylnitrobenzene catalysis liquid-phase hydrogenatin method is to carry out under 150～250 ℃ and 0.15～1.0MPa, adopts noble metal catalyst, and the o-toluidine yield reaches 99%.Its operation is to carry out under 90～200 ℃ and 0.1～0.6MPa, adopts slurry bed reactor or fluidized-bed reactor, DuPont process using Pd-Pt/C catalyst.The liquid phase method technological advantage is that reaction temperature is low, side reaction is few, the catalysis load is high, equipment capacity is big.Weak point is that reactant must separate with solvent with catalyst, thereby equipment operation and maintenance costs height.
Summary of the invention
The objective of the invention is to overcome the existing problem that exists, provide a kind of active component content relatively low, and the catalyst strength height, active, that selectivity is good fluidized bed gaseous hydrogenation of o-nitrotoluene to produce o methylaniline catalyst and technology thereof.
The objective of the invention is to be achieved by following technical solution:
Fluidized bed gaseous hydrogenation of o-nitrotoluene to produce o methylaniline catalyst is characterized in that: it is by artificial synthetic 10～150 purposes, and pore volume is that the silica gel of 0.5～1.5ml/g is as carrier; With copper is active component; Or be active component with the copper and mickel; Or be active component, or be that active component constitutes with copper, nickel and palladium with copper and palladium; With the catalyst weight is benchmark, and described active component accounts for 10～30% of catalyst weight, and wherein nickel accounts for 0～3% of catalyst weight; Palladium accounts for 0～2%; Nickel adds palladium and accounts for 1.0～5.0%, and the weight ratio of nickel and palladium is 1.0: 0.5～3.0; All the other are carrier.
This catalyst is produced with following infusion process: forms by above-mentioned catalyst,
(1) with copper is active component
1. with the nitrate of active ingredient copper, be dissolved in the distilled water, the pH value of control solution is 5～7, is that 10～25% ammoniacal liquor adjusting pH value is 6～12 with weight percentage again, and the active component content of solution is 1～8%.
2. silica gel is added to pH value that 1. above-mentioned steps make and be in 6～12 the solution, at 50～100 ℃ of dippings 2～10 hours down, after filtration, after the washing, oven dry, after 2～10 hours, obtain described catalyst 200～500 ℃ of roastings.
(2) with the copper and mickel be active component
1. with the copper nitrate of active component, be dissolved in the distilled water, the pH value of control solution is 5～7, is that 10～25% ammoniacal liquor adjusting pH value is 6～12 with weight percentage again, the nitrate that adds the nickel of requirement again, the active component content of solution are 1%-10%.
2. silica gel is added to pH value that 1. above-mentioned steps make and be in 6～12 the solution, at 50～100 ℃ of dippings 2～10 hours down, after filtration, after the washing, oven dry, after 2～10 hours, obtain described catalyst 200～500 ℃ of roastings.
(3) be active component with copper and palladium
1. with the copper nitrate of active component, be dissolved in the distilled water, the pH value of control solution is 5～7, is that 10～25% ammoniacal liquor adjusting pH value is 6～12 with weight percentage again, the nitrate that adds the palladium of requirement again, the active component content of solution are 1%-10%.
2. silica gel is added to pH value that 1. above-mentioned steps make and be in 6～12 the solution, at 50～100 ℃ of dippings 2～10 hours down, after filtration, after the washing, oven dry, after 2～10 hours, obtain described catalyst 200～500 ℃ of roastings.
(3) be active component with copper, nickel and palladium
1. with the copper nitrate of active component, be dissolved in the distilled water, the pH value of control solution is 5～7, is that 10～25% ammoniacal liquor adjusting pH value is 6～12 with weight percentage again, add the nickel of requirement, the nitrate of palladium again, the active component content of solution is 1%-10%.
2. silica gel is added to pH value that 1. above-mentioned steps make and be in 6～12 the solution, at 50～100 ℃ of dippings 2～10 hours down, after filtration, after the washing, oven dry, after 2～10 hours, obtain described catalyst 200～500 ℃ of roastings.
The above-mentioned catalyst that makes is used for the method for fluidized bed gaseous hydrogenation of o-nitrotoluene to produce o methylaniline, it is characterized in that: catalyst is packed in the reactor, handled 4～16 hours in 200～300 ℃ of logical hydrogen reductions with the qualified back of nitrogen replacement, ortho-methylnitrobenzene gasification back is being faced under the state of hydrogen, 220～320 ℃ of temperature, pressure is to react under the normal pressure, ortho-methylnitrobenzene mass space velocity 0.1～0.5h
-1, hydrogen, ortho-methylnitrobenzene molar feed ratio are 10～20: 1.
Adopt the air oxidation roasting regeneration behind the above-mentioned catalysqt deactivation, airflow temperature is 300～500 ℃, 5～10 hours recovery times.
Carrier provided by the invention is surveyed it, and to survey its physical property as follows:
Physical property: pore volume 0.5～1.5ml/g
Specific area: 300～500m
2/ g
The catalyst that provides of the present invention can be widely used in all kinds of hydrogenation reactions, and especially being suitable for the ortho-methylnitrobenzene is that raw material is produced o-toluidine.Compare with existing technologies and to have following remarkable result.
1. the catalyst activity height can make ortho-methylnitrobenzene conversion ratio 〉=99.5%, thereby makes yield 〉=99% of o-toluidine; Catalyst selectivity 〉=99.64～99.77%.
2. have mechanical strength and good stable preferably, the mechanical wear rate of catalyst is less than 10%.
3. this catalyst preparation process is simple, and it is good to repeat performance, and raw material is easy to get, long service life, and the Preparation of Catalyst cost is low.
The specific embodiment
Now in conjunction with the embodiments the present invention is further described as follows:
Embodiment 1 (with copper is active component, Preparation of catalysts and evaluation)
1. blending process: by activity of such catalysts component in the technical solution of the present invention, take by weighing the nitrate of 100g copper, be dissolved in the 180ml water, quiet 24 hours, the pH value was 5-7; Adding mass percent concentration is the ammoniacal liquor 180ml of 10-25%, and the pH value is 6-12.
2. dipping process: take by weighing silica gel 100g and put in the solution that 1. above-mentioned steps configure, at 50 ℃ of dippings 8 hours down.
3. shaping of catalyst process: the solution that 2. step is obtained after filtration, washing, and in 120 ℃ down oven dry after 4 hours it in 450 ℃ of roastings 4 hours, is made catalyst prod, its main physical index sees Table 1.
4. evaluating catalyst: with ortho-methylnitrobenzene ebullated bed gas phase hydrogenation reaction device evaluate catalysts, taking by weighing catalyst 7.4g that 2. step make packs in the fluidized bed reactor, at first carrying out catalyst reduction handles: after using nitrogen replacement qualified, begin to feed hydrogen, begin simultaneously to heat up, when temperature rises to 220 ℃, reduced 8 hours.System is adjusted to the needed process conditions of ortho-methylnitrobenzene ebullated bed gas phase hydrogenation, 280 ℃ of control reaction temperatures, reaction pressure is a normal pressure, ortho-methylnitrobenzene mass space velocity 0.4h
-1, control hydrogen and ortho-methylnitrobenzene mol ratio are 10-20: 1.Raw material ortho-methylnitrobenzene, hydrogen behind vaporizer by above-mentioned reactor bottom charging, product gets the thick product of o-toluidine from reactor head through condensation, with the thick product content of polarograph analysis, calculate ortho-methylnitrobenzene conversion ratio, o-toluidine selectivity, o-toluidine yield, it sees Table 2, catalyst mechanical wear rate and one way life assessment see Table 4 (with ortho-methylnitrobenzene content 〉=0.5% in the thick product of o-toluidine, being considered as catalysqt deactivation).
Embodiment 2 (with copper is active component, Preparation of catalysts and evaluation)
1. blending process: by activity of such catalysts component in the technical solution of the present invention, take by weighing the nitrate of 110g copper, be dissolved in the 180ml water, static 24 hours, the pH value was 5-7; Adding mass percent concentration is the ammoniacal liquor 180ml of 10-25%, and the pH value is 6-12.
2. dipping process: take by weighing silica gel 100g and put in the solution that 1. above-mentioned steps configure, at 50 ℃ of dippings 8 hours down.
3. shaping of catalyst process: the solution that 2. step is obtained after filtration, washing, and in 120 ℃ down oven dry after 4 hours it in 450 ℃ of roastings 4 hours, is made catalyst prod, its main physical index sees Table 1.
4. evaluating catalyst: with ortho-methylnitrobenzene ebullated bed gas phase hydrogenation reaction device evaluate catalysts, taking by weighing catalyst 7.4g that 3. step make packs in the fluidized bed reactor, at first carrying out catalyst reduction handles: after using nitrogen replacement qualified, begin to feed hydrogen, begin simultaneously to heat up, when temperature rises to 220 ℃, reduced 8 hours.System is adjusted to the needed process conditions of ortho-methylnitrobenzene ebullated bed gas phase hydrogenation, 280 ℃ of control reaction temperatures, reaction pressure is a normal pressure, ortho-methylnitrobenzene mass space velocity 0.4h
-1, control hydrogen and ortho-methylnitrobenzene mol ratio are 10～20: 1.Raw material ortho-methylnitrobenzene, hydrogen behind vaporizer by above-mentioned reactor bottom charging, product gets the thick product of o-toluidine from reactor head through condensation, with the thick product content of polarograph analysis, calculate ortho-methylnitrobenzene conversion ratio, o-toluidine selectivity, o-toluidine yield, it sees Table 2, catalyst mechanical wear rate and one way life assessment see Table 4 (with ortho-methylnitrobenzene content 〉=0.5% in the thick product of o-toluidine, being considered as catalysqt deactivation).
Embodiment 3 (with the copper and mickel is active component, Preparation of catalysts and evaluation)
1. blending process: by activity of such catalysts component in the technical solution of the present invention, take by weighing the nitrate of 100g copper, be dissolved in the 180ml distilled water, static 24 hours, the pH value was 5～7; Adding mass percent concentration is the ammoniacal liquor 180ml of 10-25%, and the pH value is 6～12; The nitrate 11g that adds nickel.
2. dipping process: take by weighing silica gel 95g and put in the solution that 1. above-mentioned steps configure, at 50 ℃ of dippings 8 hours down.
3. shaping of catalyst process: the solution that 2. step is obtained after filtration, washing, and in 120 ℃ down oven dry after 4 hours it in 450 ℃ of roastings 4 hours, is made catalyst prod, its main physical index sees Table 1.
4. evaluating catalyst: with ortho-methylnitrobenzene ebullated bed gas phase hydrogenation reaction device evaluate catalysts, taking by weighing catalyst 7.4g that 3. step make packs in the fluidized bed reactor, at first carrying out catalyst reduction handles: after using nitrogen replacement qualified, begin to feed hydrogen, begin simultaneously to heat up, when temperature rises to 220 ℃, reduced 8 hours.System is adjusted to the needed process conditions of ortho-methylnitrobenzene ebullated bed gas phase hydrogenation, 280 ℃ of control reaction temperatures, reaction pressure is a normal pressure, ortho-methylnitrobenzene mass space velocity 0.4h
-1, control hydrogen and ortho-methylnitrobenzene mol ratio are 10～20: 1.Raw material ortho-methylnitrobenzene, hydrogen behind vaporizer by above-mentioned reactor bottom charging, product gets the thick product of o-toluidine from reactor head through condensation, with the thick product content of polarograph analysis, calculate ortho-methylnitrobenzene conversion ratio, o-toluidine selectivity, o-toluidine yield, it sees Table 2, catalyst mechanical wear rate and one way life assessment see Table 4 (with ortho-methylnitrobenzene content 〉=0.5% in the thick product of o-toluidine, being considered as catalysqt deactivation).
Embodiment 4 (with the copper and mickel is active component, Preparation of catalysts and evaluation)
1. blending process: by activity of such catalysts component in the technical solution of the present invention, take by weighing the nitrate of 100g copper, be dissolved in the 180ml distilled water, static 24 hours, the pH value was 5～7; Adding mass percent concentration is the ammoniacal liquor 180ml of 10-25%, and the pH value is 6～12; The nitrate 15g that adds nickel.
2. dipping process: take by weighing silica gel 95g and put in the solution that 1. above-mentioned steps configure, at 50 ℃ of dippings 8 hours down.
3. shaping of catalyst process: with step 2. obtain solution after filtration, washing, and in 120 ℃ down oven dry after 4 hours it in 450 ℃ of roastings 4 hours, is made catalyst prod, its main physical index sees Table 1.
4. evaluating catalyst: with ortho-methylnitrobenzene ebullated bed gas phase hydrogenation reaction device evaluate catalysts, taking by weighing catalyst 7.4g that 3. step make packs in the fluidized bed reactor, at first carrying out catalyst reduction handles: after using nitrogen replacement qualified, begin to feed hydrogen, begin simultaneously to heat up, when temperature rises to 220 ℃, reduced 8 hours.System is adjusted to the needed process conditions of ortho-methylnitrobenzene ebullated bed gas phase hydrogenation, 280 ℃ of control reaction temperatures, reaction pressure is a normal pressure, ortho-methylnitrobenzene mass space velocity 0.4h
-1, control hydrogen and ortho-methylnitrobenzene mol ratio are 10～20: 1.Raw material ortho-methylnitrobenzene, hydrogen behind vaporizer by above-mentioned reactor bottom charging, product gets the thick product of o-toluidine from reactor head through condensation, with the thick product content of polarograph analysis, calculate ortho-methylnitrobenzene conversion ratio, o-toluidine selectivity, o-toluidine yield, it sees Table 2, catalyst mechanical wear rate and one way life assessment see Table 4 (with ortho-methylnitrobenzene content 〉=0.5% in the thick product of o-toluidine, being considered as catalysqt deactivation).
Embodiment 5 (with copper, nickel and palladium is active component, Preparation of catalysts and evaluation)
1. blending process: by activity of such catalysts component in the technical solution of the present invention, take by weighing the nitrate of 100g copper, be dissolved in the 180ml water, static 24 hours, the pH value was 5-7; Adding mass percent concentration is the ammoniacal liquor 170ml of 10-25%, and the pH value is 6～12; The nitrate 11g that adds nickel, the nitrate 7g of adding palladium.
2. dipping process: take by weighing silica gel 95g and put in the solution that 1. above-mentioned steps configure, at 50 ℃ of dippings 8 hours down.
3. shaping of catalyst process: the solution that 2. step is obtained after filtration, washing, and in 120 ℃ down oven dry after 4 hours it in 450 ℃ of roastings 4 hours, is made catalyst prod, its main physical index sees Table 1.
4. evaluating catalyst: with ortho-methylnitrobenzene ebullated bed gas phase hydrogenation reaction device evaluate catalysts, taking by weighing catalyst 7.4g that 3. step make packs in the fluidized bed reactor, at first carrying out catalyst reduction handles: after using nitrogen replacement qualified, begin to feed hydrogen, begin simultaneously to heat up, when temperature rises to 220 ℃, reduced 8 hours.System is adjusted to the needed process conditions of ortho-methylnitrobenzene ebullated bed gas phase hydrogenation, 280 ℃ of control reaction temperatures, reaction pressure is a normal pressure, ortho-methylnitrobenzene mass space velocity 0.4h
-1, control hydrogen and ortho-methylnitrobenzene mol ratio are 10～20: 1.Raw material ortho-methylnitrobenzene, hydrogen behind vaporizer by above-mentioned reactor bottom charging, product gets the thick product of o-toluidine from reactor head through condensation, with the thick product content of polarograph analysis, calculate ortho-methylnitrobenzene conversion ratio, o-toluidine selectivity, o-toluidine yield, it sees Table 2, catalyst mechanical wear rate and one way life assessment see Table 4 (with ortho-methylnitrobenzene content 〉=0.5% in the thick product of o-toluidine, being considered as catalysqt deactivation).
Embodiment 6 (with copper, nickel and palladium is active component, Preparation of catalysts and evaluation)
1. blending process: by activity of such catalysts component in the technical solution of the present invention, take by weighing the nitrate of 100g copper, be dissolved in the 180ml water, static 24 hours, the pH value was 5～7; Adding mass percent concentration is the ammoniacal liquor 180ml of 10-25%, and the pH value is 6～12; The nitrate 11g that adds nickel, the nitrate 5g of adding palladium.
2. dipping process: take by weighing silica gel 95g and put in the solution that 1. above-mentioned steps configure, at 90 ℃ of dippings 8 hours down.
3. shaping of catalyst process: the solution that 2. step is obtained after filtration, washing, and in 120 ℃ down oven dry after 4 hours it in 450 ℃ of roastings 4 hours, is made catalyst prod, its main physical index sees Table 1.
4. evaluating catalyst: with ortho-methylnitrobenzene ebullated bed gas phase hydrogenation reaction device evaluate catalysts, taking by weighing catalyst 7.4g that 3. step make packs in the fluidized bed reactor, at first carrying out catalyst reduction handles: after using nitrogen replacement qualified, begin to feed hydrogen, begin simultaneously to heat up, when temperature rises to 220 ℃, reduced 8 hours.System is adjusted to the needed process conditions of ortho-methylnitrobenzene ebullated bed gas phase hydrogenation, 280 ℃ of control reaction temperatures, reaction pressure is a normal pressure, ortho-methylnitrobenzene mass space velocity 0.4h
-1, control hydrogen and ortho-methylnitrobenzene mol ratio are 10～20: 1.Raw material ortho-methylnitrobenzene, hydrogen behind vaporizer by above-mentioned reactor bottom charging, product gets the thick product of o-toluidine from reactor head through condensation, with the thick product content of polarograph analysis, calculate ortho-methylnitrobenzene conversion ratio, o-toluidine selectivity, o-toluidine yield, it sees Table 2, catalyst mechanical wear rate and one way life assessment see Table 4 (with ortho-methylnitrobenzene content 〉=0.5% in the thick product of o-toluidine, being considered as catalysqt deactivation).
Embodiment 7 (with copper and palladium is active component, Preparation of catalysts and evaluation)
1. blending process: by activity of such catalysts component in the technical solution of the present invention, take by weighing the nitrate of 100g copper, be dissolved in the 180ml water, static 24 hours, the pH value was 5-7; Adding mass percent concentration is the ammoniacal liquor 180ml of 20-24%, and the pH value is 6～12; The nitrate 7g that adds palladium.
2. dipping process: take by weighing silica gel 98g and put in the solution that 1. above-mentioned steps configure, at 90 ℃ of dippings 8 hours down.
3. shaping of catalyst process: the solution that 2. step is obtained after filtration, washing, and in 120 ℃ down oven dry after 4 hours it in 450 ℃ of roastings 4 hours, is made catalyst prod, its main physical index sees Table 1.
4. evaluating catalyst: with ortho-methylnitrobenzene ebullated bed gas phase hydrogenation reaction device evaluate catalysts, taking by weighing catalyst 7.4g that 3. step make packs in the fluidized bed reactor, at first carrying out catalyst reduction handles: after using nitrogen replacement qualified, begin to feed hydrogen, begin simultaneously to heat up, when temperature rises to 220 ℃, reduced 8 hours. system is adjusted to the needed process conditions of ortho-methylnitrobenzene ebullated bed gas phase hydrogenation, 255 ℃ of control reaction temperatures, reaction pressure is a normal pressure, ortho-methylnitrobenzene mass space velocity 0.4h
-1, control hydrogen and ortho-methylnitrobenzene mol ratio are 10-20: 1.Raw material ortho-methylnitrobenzene, hydrogen behind vaporizer by above-mentioned reactor bottom charging, product gets the thick product of o-toluidine from reactor head through condensation, with the thick product content of polarograph analysis, calculate ortho-methylnitrobenzene conversion ratio, o-toluidine selectivity, o-toluidine yield, it sees Table 2, catalyst mechanical wear rate and one way life assessment see Table 4 (with ortho-methylnitrobenzene content 〉=0.5% in the thick product of o-toluidine, being considered as catalysqt deactivation).
Embodiment 8 (with copper and palladium is active component, Preparation of catalysts and evaluation)
1. blending process: by activity of such catalysts component in the technical solution of the present invention, take by weighing the nitrate of 100g copper, be dissolved in the 180ml water, static 24 hours, the pH value was 5-7; Adding mass percent concentration is the ammoniacal liquor 180ml of 20-24%, and the pH value is 6～12; The nitrate 5g that adds palladium.
2. dipping process: take by weighing silica gel 98g and put in the solution that 1. above-mentioned steps configure, at 90 ℃ of dippings 8 hours down.
3. shaping of catalyst process: the solution that 2. step is obtained after filtration, washing, and in 120 ℃ down oven dry after 4 hours it in 450 ℃ of roastings 4 hours, is made catalyst prod, its main physical index sees Table 1.
4. evaluating catalyst: with ortho-methylnitrobenzene ebullated bed gas phase hydrogenation reaction device evaluate catalysts, taking by weighing catalyst 7.4g that 3. step make packs in the fluidized bed reactor, at first carrying out catalyst reduction handles: after using nitrogen replacement qualified, begin to feed hydrogen, begin simultaneously to heat up, when temperature rises to 220 ℃, reduced 8 hours. system is adjusted to the needed process conditions of ortho-methylnitrobenzene ebullated bed gas phase hydrogenation, 255 ℃ of control reaction temperatures, reaction pressure is a normal pressure, ortho-methylnitrobenzene mass space velocity 0.4h
-1, control hydrogen and ortho-methylnitrobenzene mol ratio are 10-20: 1.Raw material ortho-methylnitrobenzene, hydrogen behind vaporizer by above-mentioned reactor bottom charging, product gets the thick product of o-toluidine from reactor head through condensation, with the thick product content of polarograph analysis, calculate ortho-methylnitrobenzene conversion ratio, o-toluidine selectivity, o-toluidine yield, it sees Table 2, catalyst mechanical wear rate and one way life assessment see Table 4 (with ortho-methylnitrobenzene content 〉=0.5% in the thick product of o-toluidine, being considered as catalysqt deactivation).
Embodiment 9 (regeneration of catalyst)
To use 2000 hours o-methyl-benzene amine catalyst (catalyst that this fresh catalyst makes for embodiment 1) in fluidized bed reactor, adopt the oxidizing roasting method to regenerate, make regenerated catalyst. regeneration condition: earlier with the reactor cooling, with nitrogen purge qualified after, heat up, its programming rate is 10 ℃/h, be warming up to 180 ℃ after after the blowing air oxidation, carry out roasting again, stopped 8 hours at 450 ℃, reduce to 280 ℃ of reaction temperatures then, ortho-methylnitrobenzene mass space velocity 0.4h
-1, control hydrogen and ortho-methylnitrobenzene mol ratio are 10～20: 1.Raw material ortho-methylnitrobenzene, hydrogen behind vaporizer by above-mentioned reactor bottom charging, product gets the thick product of o-toluidine from reactor head through condensation, with the thick product content of polarograph analysis, calculate ortho-methylnitrobenzene conversion ratio, o-toluidine selectivity, o-toluidine yield, it the results are shown in Table 3.
Table 1 catalyst rerum natura of the present invention and content thereof
| The embodiment sequence number | Specific area m2/g | Pore volume ml/g | Catalytic component content % | |||
| Copper | Nickel | Palladium | Carrier % | |||
| 1 | 376 | 685 | 16.32 | 79.63 | ||
| 2 | 396 | 689 | 17.23 | 78.46 | ||
| 3 | 367 | 690 | 16.52 | 3.2 | 75.15 | |
| 4 | 384 | 692 | 16.30 | 3.8 | 74.74 | |
| 5 | 408 | 710 | 17.26 | 1.8 | 2.8 | 72.82 |
| 6 | 389 | 694 | 17.18 | 2.6 | 1.9 | 73.15 |
| 7 | 378 | 672 | 16.58 | 2.7 | 76.17 | |
| 8 | 385 | 694 | 16.67 | 2.2 | 76.63 | |
Table 2 catalyst system o-toluidine of the present invention evaluation result
| Example | Reaction pressure MPa | Reaction temperature ℃ | Ortho-methylnitrobenzene conversion ratio w% | O-toluidine selectivity w% | O-toluidine yield w% |
| 1 | Normal pressure | 280 | 99.986 | 99.67 | 99.66 |
| 2 | Normal pressure | 280 | 99.987 | 99.68 | 99.67 |
| 3 | Normal pressure | 280 | 99.985 | 99.69 | 99.68 |
| 4 | Normal pressure | 280 | 99.986 | 99.65 | 99.64 |
| 5 | Normal pressure | 280 | 99.990 | 99.77 | 99.76 |
| 6 | Normal pressure | 280 | 99.987 | 99.73 | 99.72 |
| 7 | Normal pressure | 255 | 99.978 | 99.64 | 99.62 |
| 8 | Normal pressure | 255 | 99.975 | 99.65 | 99.63 |
Above data are stable region mean value between the stage of reaction.
Table 3 regenerated catalyst evaluation result
| Catalyst | Reaction pressure MPa | Temperature ℃ | Ortho-methylnitrobenzene conversion ratio w% | O-toluidine selectivity w% | O-toluidine once through yield w% |
| Example 1 | Normal pressure | 280 | 99.986 | 99.67 | 99.66 |
| Example 9 (regeneration) | Normal pressure | 280 | 99.991 | 99.63 | 99.62 |
Table 4 catalyst abrasion rate and one way life assessment result
| Catalyst | Mechanical wear rate (%) | The catalyst reaction time (h) |
| Embodiment 1 | 7.9 | 690 |
| Embodiment 2 | 8.1 | 698 |
| Embodiment 3 | 8.3 | 715 |
| Embodiment 4 | 8.4 | 720 |
| Embodiment 5 | 7.6 | 700 |
| Embodiment 6 | 8.5 | 695 |
| Embodiment 7 | 9.1 | 710 |
| Embodiment 8 | 9.0 | 705 |
Claims (3)
- L, fluidized bed gaseous hydrogenation of o-nitrotoluene to produce o methylaniline are urged agent, it is characterized in that; It is that pore volume is 0.5～1.5ml/g by artificial 10～150 synthetic orders, and specific area is 300～500m 2The SiO of/g 2Being carrier, is active component with copper, or is active component with the copper and mickel or is active component with copper and palladium, or is that active component constitutes with copper, nickel and palladium; With the catalyst weight is benchmark, and described active component accounts for 10～30% of catalyst weight, and wherein nickel accounts for 0～3% of catalyst weight; Palladium accounts for 0～2%; Nickel adds palladium and accounts for 1.0～5.0%, and the weight ratio of nickel and palladium is 1.0: 0.5～3.0; All the other are carrier.This catalyst is produced with following infusion process: forms by above-mentioned catalyst,1. with the nitrate of active ingredient copper, be dissolved in the distilled water, the pH value of control solution is 5～7, be that to regulate the pH value be 6～12 for 10～25% ammoniacal liquor with weight percentage again, add other the above-mentioned active component nickel of requirement or palladium or nickel again and add the nitrate of palladium, the active component content of solution is 1～8%.2. silica gel is added to pH value that 1. above-mentioned steps make and be in 6～12 the solution, at 50～100 ℃ of dippings 2～10 hours down, after filtration, after the washing, oven dry, after 2～10 hours, obtain described catalyst 200～500 ℃ of roastings.
- 2, catalyst is used for the method for fluidized bed gaseous hydrogenation of o-nitrotoluene to produce o methylaniline according to claim 1, it is characterized in that: the above-mentioned catalyst that makes is packed in the fluidized bed reactor, with nitrogen replacement qualified after, logical hydrogen reduction place is after 4～16 hours under 200-300 ℃, react under 220～320 ℃ of normal pressures with hydrogen ortho-methylnitrobenzene gasification back, the ortho-methylnitrobenzene mass space velocity is 0.1～0.5h-1, and hydrogen and ortho-methylnitrobenzene molar feed ratio are 10～20: 1.
- 3, root is according to the described catalyst of claim 1, and it is characterized in that: behind this catalysqt deactivation, regenerate with the air oxidation method of roasting, its regeneration condition is that air themperature is 300～500 ℃, and the recovery time is 5～10 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200610016935 CN1861253A (en) | 2006-06-13 | 2006-06-13 | Catalyst for fluidized bed gaseous hydrogenation of o-nitrotoluene to produce o-methylaniline and process therefor |
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| CN 200610016935 CN1861253A (en) | 2006-06-13 | 2006-06-13 | Catalyst for fluidized bed gaseous hydrogenation of o-nitrotoluene to produce o-methylaniline and process therefor |
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| CN 200610016935 Pending CN1861253A (en) | 2006-06-13 | 2006-06-13 | Catalyst for fluidized bed gaseous hydrogenation of o-nitrotoluene to produce o-methylaniline and process therefor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008062906A1 (en) | 2008-12-23 | 2010-06-24 | Saltigo Gmbh | Process for the preparation of benzomorpholine derivatives by hydrogenation of o-nitrophenoxycarbonyl compounds |
| EP2206706A2 (en) | 2008-12-23 | 2010-07-14 | Saltigo GmbH | Method for producing acylamide compounds |
| EP2301660A1 (en) | 2009-09-25 | 2011-03-30 | LANXESS Deutschland GmbH | Method for hydrating halogenated nitroaromatics |
-
2006
- 2006-06-13 CN CN 200610016935 patent/CN1861253A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008062906A1 (en) | 2008-12-23 | 2010-06-24 | Saltigo Gmbh | Process for the preparation of benzomorpholine derivatives by hydrogenation of o-nitrophenoxycarbonyl compounds |
| EP2206706A2 (en) | 2008-12-23 | 2010-07-14 | Saltigo GmbH | Method for producing acylamide compounds |
| US8222408B2 (en) | 2008-12-23 | 2012-07-17 | Saltigo Gmbh | Process for preparing acyl amide compounds |
| US8252924B2 (en) | 2008-12-23 | 2012-08-28 | Saltigo Gmbh | Process for preparing benzomorpholine derivatives by hydrogenating o-nitrophenoxy carbonyl compounds |
| EP2301660A1 (en) | 2009-09-25 | 2011-03-30 | LANXESS Deutschland GmbH | Method for hydrating halogenated nitroaromatics |
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