NITRO COMPOUND HYDROGENATION REACTION PROCESS AND HYDROGENATION REACTION APPARATUS

Abstract

The present invention relates to a nitro compound hydrogenation reaction process and hydrogenation reaction apparatus, which can achieve the objects of the continuous reaction of the nitro compound and the long-period run of regeneration and activation. The nitro compound hydrogenation reaction process comprises a hydrogenation step, a regeneration step, an optional activation step and a recycling step. There exists at least one step of degassing the spent catalyst between the hydrogenation step and the regeneration step. According to circumstances, there exists at least one step of degassing the regenerated catalyst between the regeneration step and the activation step.

Claims

1. A nitro compound hydrogenation reaction process, comprising a hydrogenation step, a regeneration step, an optional activation step and a recycling step, which is characterized in that in the hydrogenation step, a nitro compound (especially nitrobenzene) as the reaction raw material is contacted with hydrogen gas and a hydrogenation catalyst in a reactor (referred to as hydrogenation reactor, preferably a fluidized bed reactor) to obtain a reaction product (for example an amino compound, especially aniline) and a spent catalyst, in the regeneration step, the spent catalyst is regenerated in a reactor (referred to as regeneration reactor, preferably a fluidized bed reactor) to obtain a regenerated catalyst, in the optional activation step, the regenerated catalyst is activated in a reactor (referred to as activation reactor, preferably a fluidized bed reactor) to obtain an activated catalyst, in the recycling step, the regenerated catalyst and/or the activated catalyst are recycled (preferably recycled with a lifting pipe) to the hydrogenation step, wherein there exists at least one step of degassing the spent catalyst (referred to as hydrogenation degassing step) between the hydrogenation step and the regeneration step, and (1) in the case that the activation step exists, there exists at least one step of degassing the regenerated catalyst (referred to as first regeneration degassing step) between the regeneration step and the activation step, optionally there exists at least one step of degassing the activated catalyst (referred to as activation degassing step) between the activation step and the recycling step, and optionally there exists at least one step of degassing the regenerated catalyst (referred to as second regeneration degassing step) between the regeneration step and the recycling step, or (2) in the case that the activation step is absent, there exists at least one step of degassing the regenerated catalyst (referred to as third regeneration degassing step) between the regeneration step and the recycling step.

2. The hydrogenation reaction process according to claim 1, wherein assuming that the average mass flowrate (the unit is kg/h) of the spent catalyst being transported from the hydrogenation step to the hydrogenation degassing step is A1, the average mass flowrate (the unit is kg/h) of the spent catalyst being transported from the hydrogenation degassing step to the regeneration step is B1, the average mass flowrate (the unit is kg/h) of the regenerated catalyst being transported from the regeneration step to the first regeneration degassing step is A2, the average mass flowrate (the unit is kg/h) of the regenerated catalyst being transported from the first regeneration degassing step to the activation step is B2, the average mass flowrate (the unit is kg/h) of the activated catalyst being transported from the activation step to the activation degassing step is A3, the average mass flowrate (the unit is kg/h) of the activated catalyst being transported from the activation degassing step to the recycling step is B3, the average mass flowrate (the unit is kg/h) of the regenerated catalyst being transported from the regeneration step to the second regeneration degassing step is A4, the average mass flowrate (the unit is kg/h) of the regenerated catalyst being transported from the second regeneration degassing step to the recycling step is B4, the average mass flowrate (the unit is kg/h) of the regenerated catalyst being transported from the regeneration step to the third regeneration degassing step is A5, the average mass flowrate (the unit is kg/h) of the regenerated catalyst being transported from the third regeneration degassing step to the recycling step is B5, the average mass flowrate (the unit is kg/h) of the regenerated catalyst or the activated catalyst being transported from the recycling step to the hydrogenation step is A6, then at least one (preferably all) of A1 to A6 and B1 to B5 are 5-100 kg/h (preferably 10-30 kg/h).

3. The hydrogenation reaction process according to claim 1, wherein assuming the particle volume fraction (the unit is %) in the transportation pipeline of the spent catalyst being transported from the hydrogenation step to the hydrogenation degassing step is C1, the particle volume fraction (the unit is %) in the transportation pipeline of the spent catalyst being transported from the hydrogenation degassing step to the regeneration step is D1, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst being transported from the regeneration step to the first regeneration degassing step is C2, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst being transported from the first regeneration degassing step to the activation step is D2, the particle volume fraction (the unit is %) in the transportation pipeline of the activated catalyst being transported from the activation step to the activation degassing step is C3, the particle volume fraction (the unit is %) in the transportation pipeline of the activated catalyst being transported from the activation degassing step to the recycling step is D3, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst being transported from the regeneration step to the second regeneration degassing step is C4, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst being transported from the second regeneration degassing step to the recycling step is D4, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst being transported from the regeneration step to the third regeneration degassing step is C5, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst being transported from the third regeneration degassing step to the recycling step is D5, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst or the activated catalyst being transported from the recycling step to the hydrogenation step is C6, then at least one (preferably all) of C1 to C6 and D1 to D5 are 0.1-15% (preferably 0.5-5%).

4. The hydrogenation reaction process according to claim 1, wherein the reaction conditions of the hydrogenation step comprise: the superficial gas velocity is 0.2-0.8 m/s (preferably 0.3-0.6 m/s), the molar ratio of hydrogen gas to the reaction raw material (for example nitrobenzene) is 6-21, the reaction temperature is 220-280° C., the reaction pressure is 0.05-1 MPa (gauge pressure), and/or, the reaction conditions of the regeneration step comprise: in the presence of oxygen-containing gas (for example air or oxygen gas), the superficial gas velocity is 0.1-0.6 m/s (preferably 0.2-0.4 m/s), the reaction temperature is 350-450° C., the reaction pressure is 0.05-1 MPa (gauge pressure), and/or, the reaction conditions of the activation step comprise: in the presence of hydrogen gas, the superficial gas velocity is 0.1-0.6 m/s, the reaction temperature is 200-250° C., the reaction pressure is 0.05-1 MPa (gauge pressure).

5. The hydrogenation reaction process according to claim 1, wherein the dimensionless particle diameter of the hydrogenation reactor is in the range of 1-60, and/or, the dimensionless particle diameter of the regeneration reactor is in the range of 1-40, and/or, the dimensionless particle diameter of the activation reactor is in the range of 1-30, wherein the dimensionless particle diameter is determined by the following equation: $\mathrm{Dimensionless}\mathrm{particle}\mathrm{diameter}=\mathrm{Average}\mathrm{particle}\mathrm{diameter}\times \sqrt[3]{\frac{\mathrm{Gas}\mathrm{density}\times \mathrm{Gas}-\mathrm{solid}\mathrm{density}\mathrm{difference}\times g}{\mathrm{Gas}\mathrm{kinetic}{\mathrm{viscosity}}^2}},$ Wherein, the average particle diameter is the volume average particle diameter (the unit is m) of solid particles in the reactor, the gas density is the density (the unit is kg/m.sup.3) of the gas in the reactor, the gas-solid density difference is the difference of the density (the unit is kg/m.sup.3) of solid particles minus the density (the unit is kg/m.sup.3) of the gas in the reactor, the gas kinetic viscosity is the kinetic viscosity (the unit is Pa.Math.s) of the gas in the reactor, and g is the absolute value of the gravity acceleration (9.8 m/s.sup.2).

6. The hydrogenation reaction process according to claim 1, which further comprises a step of transporting a supplement hydrogenation catalyst to at least one of the hydrogenation step, the regeneration step, the optional activation step and the recycling step, preferably comprises a step of transporting a supplement hydrogenation catalyst to the activation step (referred to as catalyst supplement step).

7. The hydrogenation reaction process according to claim 6, wherein in the catalyst supplement step, the ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor (the unit is kg) is 0-10 h.sup.−1 (preferably 0.00002-0.001 h.sup.−1).

8. The hydrogenation reaction process according to claim 6, wherein the hydrogenation reactor is a fluidized bed reactor, the fluidized bed reactor comprise a dense phase reaction zone (4), at least one dynamic pressure measuring point (preferably the response frequency is not less than 100 Hz) is mounted on the side wall of the dense phase reaction zone (4) to measure the instantaneous pressure fluctuation in the dense phase reaction zone (4), when the standard deviation of the instantaneous pressure fluctuation is greater than 600 Pa (preferably greater than 1500 Pa), the catalyst supplement step is initiated, and/or, the hydrogenation reactor is a fluidized bed reactor, the fluidized bed reactor comprises a dense phase reaction zone (4), when the catalyst particles having a particle diameter of less than 100 μm comprise greater than 3 wt % (preferably greater than 5 wt %) by mass percent of all catalyst particles in the dense phase reaction zone (4), the catalyst supplement step is initiated.

9. The hydrogenation reaction process according to claim 6, wherein the supplement hydrogenation catalyst is selected from at least one of a copper-based loaded catalyst, a nickel-based loaded catalyst and a noble metal-based loaded catalyst, having an average particle diameter of 5-150 μm (preferably 20-70 μm).

10. The hydrogenation reaction process according to claim 1, wherein the hydrogenation catalyst is selected from at least one of a copper-based loaded catalyst, a nickel-based loaded catalyst and a noble metal-based loaded catalyst, and/or, the hydrogenation catalyst has a bulk density of 300-1200 kg/m.sup.3, and/or, the hydrogenation catalyst has an average particle diameter of 30-800 μm (preferably 40-500 μm or 50-600 μm), and the catalyst particles having a particle diameter of less than 80 μm comprise not less than 2 wt % (preferably 5-15 wt %) by mass percent of all catalyst particles, and/or, the nitro compound is selected from at least one of the compounds represented by the following formula (1),
R—NO.sub.2  (1) In the structural formula (1), R is an optionally substituted C.sub.2-20 straight, branched or cyclic hydrocarbyl (preferably an optionally substituted C.sub.4-20 cyclic hydrocarbyl, especially an optionally substituted C.sub.6-20 aryl, more especially an optionally substituted phenyl).

11. A hydrogenation reaction apparatus of the nitro compound, comprising a hydrogenation reactor (preferably a fluidized bed reactor), a regeneration reactor (preferably a fluidized bed reactor), an activation reactor (preferably a fluidized bed reactor) and a recycling unit (for example a lifting pipe), the hydrogenation reactor is communicated with the regeneration reactor via at least one spent catalyst degasser through transportation pipelines, the regeneration reactor is communicated with the activation reactor via at least one regenerated catalyst degasser through transportation pipelines, the activation reactor is communicated with the recycling unit through transportation pipelines or communicated with the recycling unit via at least one activated catalyst degasser through transportation pipelines, the recycling unit is communicated with the hydrogenation reactor through transportation pipelines, wherein the solid particle inventory (the unit is kg) of the hydrogenation reactor: the solid particle inventory (the unit is kg) of the regeneration reactor: the solid particle inventory (the unit is kg) of the activation reactor=(10-200):(0.1-20):(0.1-20) (preferably (20-100):(0.5-8):(0.5-8)).

12. The hydrogenation reaction apparatus of claim 11, wherein the hydrogenation reactor has a height of 5-60 m (preferably 10-30 m), and a diameter of 0.5-12 m (preferably 1-8 m), and/or, the regeneration reactor has a height of 1-15 m (preferably 3-6 m), and a diameter of 0.1-3 m (preferably 0.3-1 m), and/or, the activation reactor has a height of 1-15 m (preferably 3-6 m), and a diameter of 0.1-3 m (preferably 0.3-1 m), and/or, the inner diameters of the transportation pipelines are, identical to or different from each other, each independently 30-400 mm (preferably 50-300 mm).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0041] FIG. 1 is a schematic flow diagram of the nitro compound hydrogenation reaction process and hydrogenation reaction apparatus of the present invention, in which a process and apparatus for producing aniline by the nitrobenzene hydrogenation is taken as an example.

[0042] In FIG. 1, 1: raw material of vaporized nitrobenzene and hydrogen gas; 2: gas distributor; 3: fluidized bed reactor; 4: dense-phase reaction zone; 7: dilute-phase zone; 8: crude product gas; 9: cyclone separator; 10: dipleg; 11: heat-exchanging pipe; 12: degassing tank for the spent catalyst; 13: regeneration reactor; 15: fluidization gas for regeneration; 16: degassing tank for the catalyst to be activated; 17: fluidization gas for activation; 19: activation reactor; 20: lifting gas; 21: lifting pipe; 22: supplement fine particle feed inlet; 23: supplement fresh catalyst feed inlet.

DETAILED DESCRIPTION

[0043] Reference will now be made in detail to the present embodiments of the present invention, but it should be understood that the scope of the invention is not limited by the embodiments, but is defined by the appended claims.

[0044] All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by those skilled in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

[0045] When the specification derives a material, a substance, a process, a step, a device, an element and the like with the expression such as “known to those skilled in the art”, “prior art”, or the analogous term, it is intended that the subject matter so derived encompasses those having been conventionally used in the art at the time of filing this application, but also includes those which may not be so commonly used at the present time, but will become known in the art as being suitable for a similar purpose.

[0046] In the context of the present specification, the term “substantially” means the allowance of the presence of a deviation acceptable to those skilled in the art or considered reasonable by those skilled in the art, for example, a deviation within ±10%, within ±5%, within ±1%, within ±0.5% or within ±0.10%.

[0047] In the context of the present specification, the expression “optionally substituted” refers to optionally substituted by one or more (for example 1-5, 1-4, 1-3, 1-2 or 1) substituent groups selected from halogen, hydroxy, mercapto, amino, aminocarbonyl, nitro, oxo, thio, cyano, C.sub.1-6 linear or branched (halo) alkane (oxy, thio, amino, carbonyl) group, C.sub.2-6 linear or branched (halo) alkene (oxy, thio, amino, carbonyl) group, C.sub.2-6 linear or branched (halo) alkyne (oxy, thio, amino, carbonyl) group, C.sub.3-20 cycloalkyl, C.sub.3-20 cycloalkane (oxy, thio, amino) group, C.sub.3-20 cycloalkyl C.sub.1-6 linear or branched (halo) alkane (oxy, thio, amino, carbonyl) group, C.sub.3-20 cycloalkyl C.sub.2-6 linear or branched (halo) alkene (oxy, thio, amino, carbonyl) group, C.sub.3-20 cycloalkyl C.sub.2-6 linear or branched (halo) alkyne (oxy, thio, amino, carbonyl) group, C.sub.3-20 cycloalkenyl, C.sub.3-20 cycloalkene (oxy, thio, amino) group, C.sub.3-20 cycloalkenyl C.sub.1-6 linear or branched (halo) alkane (oxy, thio, amino, carbonyl) group, C.sub.3-20 cycloalkenyl C.sub.2-6 linear or branched (halo) alkene (oxy, thio, amino, carbonyl) group, C.sub.3-20 cycloalkenyl C.sub.2-6 linear or branched (halo) alkyne (oxy, thio, amino, carbonyl) group, C.sub.6-20 aryl, C.sub.6-20 arene (oxy, thio, amino) group, C.sub.6-20 aryl C.sub.1-6 linear or branched (halo) alkane (oxy, thio, amino, carbonyl) group, C.sub.6-20 aryl C.sub.2-6 linear or branched (halo) alkene (oxy, thio, amino, carbonyl) group, C.sub.6-20 aryl C.sub.2-6 linear or branched (halo) alkyne (oxy, thio, amino, carbonyl) group, C.sub.4-20 heteroaryl, C.sub.4-20 heteroarene (oxy, thio, amino) group, C.sub.4-20 heteroaryl C.sub.1-6 linear or branched (halo) alkane (oxy, thio, amino, carbonyl) group, C.sub.4-20 heteroaryl C.sub.2-6 linear or branched (halo) alkene (oxy, thio, amino, carbonyl) group, C.sub.4-20 heteroaryl C.sub.2-6 linear or branched (halo) alkyne (oxy, thio, amino, carbonyl) group, C.sub.2-20 heterocyclyl, C.sub.2-20 heterocycle (oxy, thio, amino) group, C.sub.2-20 heterocyclyl C.sub.1-6 linear or branched (halo) alkane (oxy, thio, amino, carbonyl) group, C.sub.2-20 heterocyclyl C.sub.2-6 linear or branched (halo) alkene (oxy, thio, amino, carbonyl) group and C.sub.2-20 heterocyclyl C.sub.2-6 linear or branched (halo) alkyne (oxy, thio, amino, carbonyl) group. When a plurality of these substituent groups are present, two adjacent substituent groups (for example the molecular chain ends of two substituent groups) can be bonded to each other to form a divalent substituent group structure. For example, two adjacent C.sub.1-6 linear or branched alkyl groups can be bonded to each other to form a corresponding alkylene structure. Or, two adjacent C.sub.1-6 linear or branched alkyloxy groups for example can form a corresponding alkylenedioxy group structure, two adjacent C.sub.1-6 linear or branched alkylamino groups for example can form a corresponding alkylenediamino structure, two adjacent C.sub.1-5 linear or branched alkylthio groups for example can form a corresponding alkylenedithio structure, and so forth. As the preferred substituent group, for example, halogen, hydroxy, mercapto, amino, thio, oxo or C.sub.1-6 linear or branched (halo) alkane (oxy, thio, amino, carbonyl) group and others can be enumerated. Herein, the expression “(halo) alkane (oxy, thio, amino, carbonyl) group” means: alkyl, haloalkyl, alkyloxy, alkylthio, alkylamino, alkylcarbonyl, haloalkyloxy, haloalkylthio, haloalkylamino or haloalkylcarbonyl, the expression “(halo) alkene (oxy, thio, amino, carbonyl) group” means: alkenyl, haloalkenyl, alkenyloxy, alkenylthio, alkenylamino, alkenylcarbonyl, haloalkenyloxy, haloalkenylthio, haloalkenylamino or haloalkenylcarbonyl, the expression “(halo) alkyne (oxy, thio, amino, carbonyl) group” means: alkynyl, haloalkynyl, alkynyloxy, alkynylthio, alkynylamino, alkynylcarbonyl, haloalkynyloxy, haloalkynylthio, haloalkynylamino or haloalkynylcarbonyl, the expression “(oxy, thio, amino) group” means oxy, thio or amino. Here, the expression “halo” includes monohalo, dihalo, trihalo, or perhalo, and the like.

[0048] All percentages, parts, ratios, and the like referred to within this specification are by weight and pressures are gauge pressures unless explicitly indicated.

[0049] In the context of this specification, any two or more embodiments of the present invention may be combined in any combination, and the resulting technical solution is part of the original disclosure of this specification, and is within the scope of the present invention.

[0050] One embodiment according to the present invention relates to a nitro compound hydrogenation reaction process. The hydrogenation reaction process comprises a hydrogenation step, a regeneration step, an activation step and a recycling step. Herein, the activation step is an optional step.

[0051] According to one embodiment of the present invention, in the hydrogenation step, a nitro compound and hydrogen gas as the reaction raw material are contacted with a hydrogenation catalyst in the reactor to obtain a reaction product and a spent catalyst. Herein, as the reactor, a fluidized bed reactor is preferable, especially a reactor having a fluidized bed of catalyst particles.

[0052] According to one embodiment of the present invention, in the regeneration step, the spent catalyst is regenerated in a reactor (referred to as regeneration reactor) to obtain a regenerated catalyst. Herein, as the reactor, a fluidized bed reactor is preferable.

[0053] According to one embodiment of the present invention, in the activation step, the regenerated catalyst is activated in a reactor (referred to as activation reactor) to obtain an activated catalyst.

[0054] Herein, as the reactor, a fluidized bed reactor is preferable.

[0055] According to one embodiment of the present invention, in the recycling step, the regenerated catalyst and/or the activated catalyst are recycled to the hydrogenation step. Herein, the recycling is preferably performed in a lifting pipe.

[0056] According to one embodiment of the present invention, there exists at least one step of degassing the spent catalyst (referred to as hydrogenation degassing step) between the hydrogenation step and the regeneration step.

[0057] According to one embodiment of the present invention, in the case that the activation step exists, there exists at least one step of degassing the regenerated catalyst (referred to as first regeneration degassing step) between the regeneration step and the activation step, optionally there exists at least one step of degassing the activated catalyst (referred to as activation degassing step) between the activation step and the recycling step, and optionally there exists at least one step of degassing the regenerated catalyst (referred to as second regeneration degassing step) between the regeneration step and the recycling step.

[0058] According to one embodiment of the present invention, in the case that the activation step is absent, there exists at least one step of degassing the regenerated catalyst (referred to as third regeneration degassing step) between the regeneration step and the recycling step.

[0059] According to one embodiment of the present invention, assuming the average mass flowrate (the unit is kg/h) of the spent catalyst being transported from the hydrogenation step to the hydrogenation degassing step is A1, the average mass flowrate (the unit is kg/h) of the spent catalyst being transported from the hydrogenation degassing step to the regeneration step is B1, the average mass flowrate (the unit is kg/h) of the regenerated catalyst being transported from the regeneration step to the first regeneration degassing step is A2, the average mass flowrate (the unit is kg/h) of the regenerated catalyst being transported from the first regeneration degassing step to the activation step is B2, the average mass flowrate (the unit is kg/h) of the activated catalyst being transported from the activation step to the activation degassing step is A3, the average mass flowrate (the unit is kg/h) of the activated catalyst being transported from the activation degassing step to the recycling step is B3, the average mass flowrate (the unit is kg/h) of the regenerated catalyst being transported from the regeneration step to the second regeneration degassing step is A4, the average mass flowrate (the unit is kg/h) of the regenerated catalyst being transported from the second regeneration degassing step to the recycling step is B4, the average mass flowrate (the unit is kg/h) of the regenerated catalyst being transported from the regeneration step to the third regeneration degassing step is A5, the average mass flowrate (the unit is kg/h) of the regenerated catalyst being transported from the third regeneration degassing step to the recycling step is B5, the average mass flowrate (the unit is kg/h) of the regenerated catalyst or the activated catalyst being transported from the recycling step to the hydrogenation step is A6, then at least one (preferably all) of A1 to A6 and B1 to B5 is 5-100 kg/h, preferably 10-30 kg/h. Herein, the so-called average mass flowrate refers to the mass of the fluid (such as catalyst) passing through the cross section of the transportation pipeline per unit time. The average mass flowrate can be calculated by the equation

[00002]$G_s=M/\left(t.Math.\frac{2T}{4}{d}^2\right),$

where Gs is the average mass flowrate, a bypass is set at an arbitrary point of the pipeline, and a part of the catalyst particles is released during a period of time and collected, and the released amount of the catalyst particles is weighed and recorded as M (the unit is kg), the period time for releasing the catalyst particles is recorded as t (the unit is s), and the diameter of the pipeline at this point is recorded as d (the unit is m).

[0060] According to one embodiment of the present invention, assuming the particle volume fraction (the unit is %) in the transportation pipeline of the spent catalyst being transported from the hydrogenation step to the hydrogenation degassing step is C1, the particle volume fraction (the unit is %) in the transportation pipeline of the spent catalyst being transported from the hydrogenation degassing step to the regeneration step is D1, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst being transported from the regeneration step to the first regeneration degassing step is C2, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst being transported from the first regeneration degassing step to the activation step is D2, the particle volume fraction (the unit is %) in the transportation pipeline of the activated catalyst being transported from the activation step to the activation degassing step is C3, the particle volume fraction (the unit is %) in the transportation pipeline of the activated catalyst being transported from the activation degassing step to the recycling step is D3, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst being transported from the regeneration step to the second regeneration degassing step is C4, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst being transported from the second regeneration degassing step to the recycling step is D4, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst being transported from the regeneration step to the third regeneration degassing step is C5, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst being transported from the third regeneration degassing step to the recycling step is D5, the particle volume fraction (the unit is %) in the transportation pipeline of the regenerated catalyst or the activated catalyst being transported from the recycling step to the hydrogenation step is C6, then at least one (preferably all) of C1 to C6 and D1 to D5 is 0.1-15%, preferably 0.5-5%. Herein, the so-called particle volume fraction refers to the ratio of the volume of the particle phase to the total volume in the gas-solid two-phase mixture per unit volume. The particle volume fraction can be calculated by the equation

[00003]$\frac{\Delta P}{\Delta z}\approx \left[{\rho }_P\left(1-\mathrm{.Math.}\right)+\mathrm{\rho .Math.}\right]g,$

wherein ΔP is the difference (the unit is Pa) between the pressure (gauge pressure) at Δz/2 below the position and the pressure (gauge pressure) at Δz/2 above the position, Δz is the distance (the unit is m) between the point at Δz/2 below the position and the point at Δz/2 above the position, ρ.sub.P is the particle density (the unit is kg/m.sup.3) of the solid particles, ρ is the density (the unit is kg/m.sup.3) of the gas, 1-ε is the particle volume fraction, ε is the gas volume fraction, the sum of the particle volume fraction and the gas volume fraction is 1, g is the absolute value of the gravity acceleration (generally taking 9.8 m/s.sup.2).

[0061] According to one embodiment of the present invention, the superficial gas velocity of the hydrogenation step is generally 0.2-0.8 m/s, preferably 0.3-0.6 m/s, the molar ratio of hydrogen gas to the reaction raw material (for example nitrobenzene) is 6-21.

[0062] According to one embodiment of the present invention, the hydrogenation step has a reaction temperature (generally referring to the average reaction temperature in the dense phase reaction zone) of 220-280° C. and a reaction pressure (generally referring to the pressure in the dense phase reaction zone) of 0.05-1 MPa (gauge pressure). In addition, the temperature in the vicinity of the gas distributor 2 is generally controlled at 320° C. or less.

[0063] According to one embodiment of the present invention, the reaction conditions of the regeneration step comprise: in the presence of oxygen-containing gas (for example air or oxygen gas), the superficial gas velocity is 0.1-0.6 m/s, preferably 0.2-0.4 m/s.

[0064] According to one embodiment of the present invention, the regeneration step has a reaction temperature of 350-450° C. and a reaction pressure of 0.05-1 MPa (gauge pressure).

[0065] According to one embodiment of the present invention, the reaction conditions of the activation step comprise: in the presence of hydrogen gas, the superficial gas velocity is 0.1-0.6 m/s, the reaction temperature is 200-250° C., the reaction pressure is 0.05-1 MPa (gauge pressure).

[0066] According to one embodiment of the present invention, the hydrogenation reactor has a dimensionless particle diameter in the range of 1-60, and a dimensionless gas velocity in the range of 0.05-7.

[0067] According to one embodiment of the present invention, the regeneration reactor has a dimensionless particle diameter in the range of 1-40 and a dimensionless gas velocity in the range of 0.05-5.

[0068] According to one embodiment of the present invention, the activation reactor has a dimensionless particle diameter in the range of 1-30 and a dimensionless gas velocity in the range of 0.05-5.

[0069] According to one embodiment of the present invention, the dimensionless particle diameter of the hydrogenation reactor is in the range of 1-60, the dimensionless particle diameter of the regeneration reactor is in the range of 1-40, and the dimensionless particle diameter of the activation reactor is in the range of 1-30.

[0070] In the context of the present invention, the dimensionless particle diameter and the dimensionless gas velocity are respectively determined by the following two equations:

Dimensionless particle diameter=Average particle diameter×[(Gas density×Gas-solid density difference×g)/(Gas kinetic viscosity).sup.2].sup.1/3,

[00004]$\mathrm{Dimensionless}\mathrm{particle}\mathrm{diameter}=\mathrm{Average}\mathrm{particle}\mathrm{diameter}\times \sqrt[3]{\frac{\mathrm{Gas}\mathrm{density}\times \mathrm{Gas}-\mathrm{solid}\mathrm{density}\mathrm{difference}\times g}{\mathrm{Gas}\mathrm{kinetic}{\mathrm{viscosity}}^2}},\mathrm{Dimensionless}\mathrm{gas}\mathrm{velocity}=\mathrm{Superficial}\mathrm{gas}\mathrm{velocity}\times \sqrt[3]{\frac{\mathrm{Gas}{\mathrm{density}}^2}{\mathrm{Gas}-\mathrm{solid}\mathrm{density}\mathrm{difference}\times \mathrm{Gas}\mathrm{kinetic}\mathrm{viscosity}\times g}},$

[0071] In these equations, the average particle diameter is the volume average particle diameter (the unit is m) of solid particles in the reactor, the gas density is the density (the unit is kg/m.sup.3) of the gas in the reactor, the gas-solid density difference is the difference of the density (the unit is kg/m.sup.3) of solid particles minus the density (the unit is kg/m.sup.3) of the gas in the reactor, the gas kinetic viscosity is the kinetic viscosity (the unit is Pa.Math.s) of the gas in the reactor, the superficial gas velocity is the mean flow rate (the unit is m/s) of the gas passing through the reactor, and g is the absolute value of the gravity acceleration (9.8 m/s.sup.2). Herein, the volume-average particle diameter can be obtained by the analysis of the sampled solid catalyst particles with a particle-size analyzer.

[0072] According to one embodiment of the present invention, the hydrogenation reaction process further comprises a step of transporting a supplement hydrogenation catalyst to at least one of the hydrogenation step, the regeneration step, the optional activation step and the recycling step, and preferably comprises a step of transporting a supplement hydrogenation catalyst to the activation step (referred to as catalyst supplement step).

[0073] According to one embodiment of the present invention, in the catalyst supplement step, the ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor (the unit is kg) is 0-10 h.sup.−1 (preferably 0.00002-0.001 h.sup.−1). Herein, the hydrogenation catalyst inventory in the hydrogenation reactor can be calculated based on the bed pressure drop (the unit is Pa) and the reactor area (the unit is m.sup.2) in the hydrogenation reactor.

[0074] According to one embodiment of the present invention, the hydrogenation reactor is a fluidized bed reactor. The fluidized bed reactor comprise a dense phase reaction zone (4), at least one dynamic pressure measuring point is mounted on the side wall of the dense phase reaction zone (4) to measure the instantaneous pressure fluctuation in the dense phase reaction zone (4). When the standard deviation of the instantaneous pressure fluctuation is greater than 600 Pa (preferably greater than 1500 Pa), the catalyst supplement step is initiated, that is to say the supplement hydrogenation catalyst is transported to at least one of the hydrogenation step, the regeneration step, the optional activation step and the recycling step, especially the supplement hydrogenation catalyst is transported to the activation step. Herein, preferably, the response frequency of said at least one dynamic pressure measuring point is not less than 100 Hz. In addition, the instantaneous pressure P at any time is resolved into the sum of the average value p and the fluctuation value P′, that is, P.sub.i=P+P′, the standard deviation Sd at any measuring point is

[00005]$\mathrm{Sd}=\sqrt{\frac{1}{N}\underset{i=1}{\overset{N}{.Math.}}{\left(P_i-\stackrel{\_}{P}\right)}^2},$

and N is the number of the sampled data.

[0075] According to one embodiment of the present invention, the hydrogenation reactor is a fluidized bed reactor, the fluidized bed reactor comprise a dense phase reaction zone (4), when the catalyst particles having a particle diameter of less than 100 μm comprise greater than 3 wt % (preferably greater than 5 wt %) by mass percent of all catalyst particles in the dense phase reaction zone (4), the catalyst supplement step is initiated, that is to say the supplement hydrogenation catalyst is transported to at least one of the hydrogenation step, the regeneration step, the optional activation step and the recycling step, especially the supplement hydrogenation catalyst is transported to the activation step. Herein, the mass percent of the catalyst particles having a particle diameter of less than 100 μm relative to all catalyst particles is calculated by random sampling and then measurement by a particle size analyzer.

[0076] According to one embodiment of the present invention, as the supplement hydrogenation catalyst, any catalyst used in the art for the hydrogenation reaction of the nitro compound can be enumerated, and at least one selected from a copper-based loaded catalyst, a nickel-based loaded catalyst and a noble metal-based loaded catalyst, more especially a copper-based loaded catalyst can be particularly enumerated. Herein, for the copper-based loaded catalyst, copper is generally used as the main active component, and the support is generally alumina or silica.

[0077] According to one embodiment of the present invention, the average particle diameter of the supplement hydrogenation catalyst is generally 5-150 μm, preferably 20-70 μm. Herein, for example, the average particle diameter can be obtained by the analysis of the sampled solid catalyst particles with a particle-size analyzer.

[0078] According to one embodiment of the present invention, as the hydrogenation catalyst, any catalyst used in the art for the hydrogenation reaction of the nitro compound can be enumerated, and at least one selected from a copper-based loaded catalyst, a nickel-based loaded catalyst and a noble metal-based loaded catalyst, more especially a copper-based loaded catalyst can be particularly enumerated. Herein, for the copper-based loaded catalyst, copper is generally used as the main active component, and the support is generally alumina or silica.

[0079] According to one embodiment of the present invention, the average particle diameter of the hydrogenation catalyst is generally 30-800 μm, preferably 40-500 μm or 50-600 μm. Preferably, in the hydrogenation catalyst, the catalyst particles having a particle diameter of less than 80 μm comprises not less than 2 wt %, preferably 5-15 wt % by mass percent of all catalyst particles. For example, the average particle diameter can be obtained by the analysis of the sampled solid catalyst particles with a particle-size analyzer.

[0080] According to one embodiment of the present invention, the nitro compound is selected from at least one of the compounds represented by the following formula (1), preferably nitrobenzene.

R—NO.sub.2  (1)

[0081] According to the present invention, in the structural formula (1), R is an optionally substituted C.sub.2-20 straight, branched or cyclic hydrocarbyl, preferably an optionally substituted C.sub.4-20 cyclic hydrocarbyl, especially an optionally substituted C.sub.6-20 aryl, more especially an optionally substituted phenyl or phenyl.

[0082] According to one embodiment of the present invention, it also relates to a hydrogenation reaction apparatus of the nitro compound, comprising a hydrogenation reactor, a regeneration reactor, an activation reactor and a recycling unit. Herein, the hydrogenation reaction apparatus is particularly designed to implement the nitro compound hydrogenation reaction process of the present invention. In view of this, for the contents or items that are not detailed hereinafter, the contents or items described as before in the present description for the nitro compound hydrogenation reaction process can be directly applied, and no detail will be provided herein. In addition, the contents or items described hereinafter for the hydrogenation reaction apparatus of the nitro compound can also be applied to the nitro compound hydrogenation reaction process of the present invention.

[0083] According to one embodiment of the present invention, as the recycling unit, the lifting pipe can be particularly enumerated.

[0084] According to one embodiment of the present invention, the hydrogenation reactor is communicated with the regeneration reactor via at least one spent catalyst degasser through transportation pipelines, the regeneration reactor is communicated with the activation reactor via at least one regenerated catalyst degasser through transportation pipelines, the activation reactor is communicated with the recycling unit through transportation pipelines or communicated with the recycling unit via at least one activated catalyst degasser through transportation pipelines, the recycling unit is communicated with the hydrogenation reactor through transportation pipelines. According to one embodiment of the present invention, the solid particle inventory (the unit is kg) of the hydrogenation reactor: the solid particle inventory (the unit is kg) of the regeneration reactor: the solid particle inventory (the unit is kg) of the activation reactor=(10-200):(0.1-20):(0.1-20), preferably the solid particle inventory (the unit is kg) of the hydrogenation reactor: the solid particle inventory (the unit is kg) of the regeneration reactor:solid particle inventory (the unit is kg) of the activation reactor=(20-100):(0.5-8):(0.5-8). Herein, the solid particle inventory can be calculated based on the bed pressure drop (the unit is Pa) and the reactor area (the unit is m.sup.2) in the reactor. Specifically, for example, if the solid particle inventory in the hydrogenation reactor is 10-200 tons, the solid particle inventory in the regeneration reactor and the activation reactor corresponds to 0.1-20 tons, or if the solid particle inventory in the hydrogenation reactor is 20-100 tons, the solid particle inventory in the regeneration reactor and the activation reactor corresponds to 0.5-8 tons.

[0085] According to one embodiment of the present invention, the hydrogenation reactor has a height of generally 5-60 m, preferably 10-30 m and a diameter of generally 0.5-12 m, preferably 1-8 m.

[0086] According to one embodiment of the present invention, the regeneration reactor has a height of generally 1-15 m, preferably 3-6 m and a diameter of generally 0.1-3 m, preferably 0.3-1 m.

[0087] According to one embodiment of the present invention, the activation reactor has a height of generally 1-15 m, preferably 3-6 m, and a diameter of generally 0.1-3 m, preferably 0.3-1 m.

[0088] According to one embodiment of the present invention, the inner diameters of the aforementioned transportation pipelines are, identical to or different from each other, each independently 30-400 mm, preferably 50-300 mm.

[0089] According to one embodiment of the present invention, the operation conditions of the degassing steps or the degassers are not particularly limited, and those well known in the art can be directly applied. Specifically, for example, the operating temperature is generally 0-700° C., preferably 80-400° C.; the operating pressure is generally 0-3 MPaG, preferably 0.01-1 MPaG; the superficial velocity (absolute value) is generally 0.05-0.6 m/s, preferably 0.1-0.4 m/s; the degassing agent is generally gas or vapor or steam, especially at least one selected from nitrogen gas, water vapour, carbon dioxide, methane and argon gas, especially nitrogen gas.

[0090] According to one embodiment of the present invention, the degassers used in the degassing steps or the structural style of the degassers and the like are not particularly limited, those well known in the art can be directly applied. For example, degassing tanks having a chevron baffle or a disc-ring baffle can be specifically enumerated. These degassing tanks have a degassing efficiency of generally 80% or higher, preferably 90% or higher, more preferably 94% or higher.

[0091] With reference to FIG. 1, the nitro compound hydrogenation reaction process and the hydrogenation reaction apparatus will be specifically described. Specifically, the main equipments of the nitro compound hydrogenation reaction process and the hydrogenation reaction apparatus comprise: a fluidized bed reactor 3, a degassing tank for the spent catalyst 12, a regeneration reactor 13, a degassing tank for the catalyst to be activated 16, an activation reactor 19 and a lifting pipe 21, wherein in the fluidized bed reactor 3 are included a dense phase reaction zone 4 located in the lower section, a particle sputtering transition zone 5 located in the middle section and a dilute-phase zone 7 located in the upper section, the degassing tank for the spent catalyst 12 is communicated with the fluidized bed reactor 3 and the regeneration reactor 13 respectively, the degassing tank for the catalyst to be activated 16 is communicated with the regeneration reactor 13 and the activation reactor 19 respectively, the lifting pipe 21 is communicated with the activation reactor 19 and the fluidized bed reactor 3 respectively. In the activation reactor 19 are provided a supplement fine particle feed inlet 22 and a supplement fresh catalyst feed inlet 23. Herein, in the fluidized bed reactor 3 are provided a gas distributor 2, a heat-exchanging pipe 11 and a cyclone separator 9.

[0092] According to one embodiment of the present invention, in the nitro compound hydrogenation reaction process and the hydrogenation reaction apparatus, vaporized nitrobenzene and hydrogen gas as raw material are introduced into a gas chamber, then into the fluidized bed reactor 3 through the gas distributor 2 to push the catalyst in the reactor to be fluidized, then react in the dense phase reaction zone 4 to produce an aniline product, a part of the gas phase forms bubbles, the particle sputtering occurs at the top of the dense phase reaction zone 4 to form a particle sputtering transition zone 5, the particles enter the dilute-phase zone 7 to be separated with a cyclone separator 9 and return to the dense phase reaction zone 4, the crude product gas 8 flows out of the fluidized bed reactor 3 and is sent into the subsequent separation section. After the catalyst is partly coked in the reaction, the coked catalyst is degassed in the degassing tank for the spent catalyst 12, and introduced into the regeneration reactor 13, to which the oxygen is introduced, the catalyst is regenerated by carbon burning. The regenerated catalyst is then introduced into the degassing tank for the catalyst to be activated 16 and degassed, and then introduced into the activation reactor 19, mixed with the supplement fine particles in the supplement fine particle feed inlet 22 used to optimize the fluidization quality in the dense phase reaction zone 4, and the fresh catalysts in the supplement fresh catalyst feed inlet 23 for supplementing the loss in the fluidized bed reactor 3, hydrogen gas is introduced to perform the activation, and the activated catalyst is introduced into the lifting pipe 21, and lifted up to return to the fluidized bed reactor 3 to proceed with the catalysis.

EXAMPLES

[0093] The present invention will be described in further detail below by way of examples and comparative examples, but the present invention is not limited to the following examples.

Example 1

[0094] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle reserve (the unit is kg) of the hydrogenation reactor:the solid particle reserve (the unit is kg) of the regeneration reactor:the solid particle reserve (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0095] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0096] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0097] The expansion coefficient of the dense phase reaction zone (the expansion coefficient=the height of the dense phase reaction zone/the height of the static bed, the fluidization quality was generally represented by the expansion coefficient, in general, the larger the expansion coefficient was, the better the fluidization quality was) was 1.64, the maximum temperature difference at any part in the reaction zone was 7.1° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.7%, and the results were detailed in Table 1.

Example 2

[0098] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0099] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0100] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.001 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0101] The expansion coefficient of the dense phase reaction zone was 1.58, the maximum temperature difference at any part in the reaction zone was 8.2° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.51%, and the results were detailed in Table 1.

Example 3

[0102] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3.

[0103] The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0104] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0105] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00002 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0106] The expansion coefficient of the dense phase reaction zone was 1.61, the maximum temperature difference at any part in the reaction zone was 7.3° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.55%, and the results were detailed in Table 1.

Example 4

[0107] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0108] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0109] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 60, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0110] The expansion coefficient of the dense phase reaction zone was 1.56, the maximum temperature difference at any part in the reaction zone was 7.5° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.58%, and the results were detailed in Table 1.

Example 5

[0111] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0112] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0113] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 1, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0114] The expansion coefficient of the dense phase reaction zone was 1.55, the maximum temperature difference at any part in the reaction zone was 7.5° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.76%, and the results were detailed in Table 1.

Example 6

[0115] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3.

[0116] The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0117] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0118] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.05, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0119] The expansion coefficient of the dense phase reaction zone was 1.61, the maximum temperature difference at any part in the reaction zone was 7.3° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.72%, and the results were detailed in Table 2.

Example 7

[0120] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0121] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0122] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 7, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0123] The expansion coefficient of the dense phase reaction zone was 1.60, the maximum temperature difference at any part in the reaction zone was 7.3° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.72%, and the results were detailed in Table 2.

Example 8

[0124] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0125] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0126] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 1, the dimensionless gas velocity in the regenerator was 0.05, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0127] The expansion coefficient of the dense phase reaction zone was 1.59, the maximum temperature difference at any part in the reaction zone was 7.6° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.74%, and the results were detailed in Table 2.

Example 9

[0128] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0129] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0130] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 36, the dimensionless gas velocity in the regenerator was 5, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0131] The expansion coefficient of the dense phase reaction zone was 1.54, the maximum temperature difference at any part in the reaction zone was 8.0° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.8%, and the results were detailed in Table 2.

Example 10

[0132] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0133] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0134] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 1, the dimensionless gas velocity in the activator was 0.05, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0135] The expansion coefficient of the dense phase reaction zone was 1.59, the maximum temperature difference at any part in the reaction zone was 7.6° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.76%, and the results were detailed in Table 2.

Example 11

[0136] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0137] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0138] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 25, the dimensionless gas velocity in the activator was 5, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0139] The expansion coefficient of the dense phase reaction zone was 1.60, the maximum temperature difference at any part in the reaction zone was 7.4° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.75%, and the results were detailed in Table 3.

Example 12

[0140] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0141] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0142] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 700 Pa.

[0143] The expansion coefficient of the dense phase reaction zone was 1.62, the maximum temperature difference at any part in the reaction zone was 7.2° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.7%, and the results were detailed in Table 3.

Example 13

[0144] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0145] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0146] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 1500 Pa.

[0147] The expansion coefficient of the dense phase reaction zone was 1.52, the maximum temperature difference at any part in the reaction zone was 10.5° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.7%, and the results were detailed in Table 3.

Example 14

[0148] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0149] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 7 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.83%, C6 was 0.55%, D1-D5 were 1.06%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0150] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0151] The expansion coefficient of the dense phase reaction zone (the expansion coefficient=the height of the dense phase reaction zone/the height of the static bed, the fluidization quality was generally represented by the expansion coefficient, in general, the larger the expansion coefficient was, the better the fluidization quality was) was 1.62, the maximum temperature difference at any part in the reaction zone was 7.2° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.93%, and the results were detailed in Table 3.

Example 15

[0152] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0153] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 26 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 1.1%, C6 was 0.7%, D1-D5 were 1.5%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0154] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0155] The expansion coefficient of the dense phase reaction zone (the expansion coefficient=the height of the dense phase reaction zone/the height of the static bed, the fluidization quality was generally represented by the expansion coefficient, in general, the larger the expansion coefficient was, the better the fluidization quality was) was 1.67, the maximum temperature difference at any part in the reaction zone was 6.9° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.47%, and the results were detailed in Table 3.

Example 16

[0156] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=30:1:1.

[0157] The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0158] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0159] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0160] The expansion coefficient of the dense phase reaction zone (the expansion coefficient=the height of the dense phase reaction zone/the height of the static bed, the fluidization quality was generally represented by the expansion coefficient, in general, the larger the expansion coefficient was, the better the fluidization quality was) was 1.62, the maximum temperature difference at any part in the reaction zone was 7.2° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.7%, and the results were detailed in Table 4.

Example 17

[0161] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=2:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0162] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0163] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0164] The expansion coefficient of the dense phase reaction zone (the expansion coefficient=the height of the dense phase reaction zone/the height of the static bed, the fluidization quality was generally represented by the expansion coefficient, in general, the larger the expansion coefficient was, the better the fluidization quality was) was 1.64, the maximum temperature difference at any part in the reaction zone was 7.2° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.7%, and the results were detailed in Table 4.

Example 18

[0165] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=6:1:1.

[0166] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 13 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.9%, C6 was 0.6%, D1-D5 were 1.2%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0167] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the standard deviation value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles was 500 Pa.

[0168] The expansion coefficient of the dense phase reaction zone (the expansion coefficient=the height of the dense phase reaction zone/the height of the static bed, the fluidization quality was generally represented by the expansion coefficient, in general, the larger the expansion coefficient was, the better the fluidization quality was) was 1.66, the maximum temperature difference at any part in the reaction zone was 7.0° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.73%, and the results were detailed in Table 1.

Comparative Example 1

[0169] The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used. The apparatus for producing aniline by the hydrogenation of nitrobenzene as shown in FIG. 1 was used, the fluidized bed reactor had a diameter of 45 mm. The solid particle inventory (the unit is kg) of the hydrogenation reactor:the solid particle inventory (the unit is kg) of the regeneration reactor:the solid particle inventory (the unit is kg) of the activation reactor=40:3:3. The height (the unit is m) of the hydrogenation reactor:the height (the unit is m) of the regeneration reactor:the height (the unit is m) of the activation reactor=5:1:1. The diameter (the unit is m) of the hydrogenation reactor:the diameter (the unit is m) of the regeneration reactor:the diameter (the unit is m) of the activation reactor=4:1:1.

[0170] The average mass flowrates for the transportation in the pipelines (A1-A6 and B1-B5) were all 7 kg/h, and for the particle volume fractions for the pipelines (C1-C6 and D1-D5), C1-C5 were 0.83%, C6 was 0.55%, D1-D5 were 1.06%. The catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa. The reaction conditions in the regenerator were as follows: the superficial gas velocity was 0.3 m/s, the average regeneration temperature was 410° C.; the reaction conditions in the activator were as follows: the superficial gas velocity was 0.3 m/s, the average activation temperature was 220° C.

[0171] The ratio of the average mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor was 0.00005 kg/h, the dimensionless particle diameter in the fluidized bed reactor was 10, the dimensionless gas velocity in the fluidized bed reactor was 0.1, the dimensionless particle diameter in the regenerator was 8, the dimensionless gas velocity in the regenerator was 0.15, the particle diameter in the activator dimensionless was 8, the dimensionless gas velocity in the activator was 0.15, the supplement of the fine particle catalyst was controlled not according to the pressure pulsation in the reaction dense phase zone.

[0172] The expansion coefficient of the dense phase reaction zone was 1.46, the maximum temperature difference at any part in the reaction zone was 13.8° C., the carbon deposition content when the reaction time was 90 minutes under the high space velocity could be controlled at no greater than 0.7%, and the results were detailed in Table 4.

Comparative Example 2

[0173] The prior art fluidized bed reactor apparatus for producing aniline by the hydrogenation of nitrobenzene without a regenerator and an activator was used, and the supplement of the fine particle catalyst was controlled not according to the pressure pulsation in the reaction dense phase zone. The fluidized bed reactor had a diameter of 45 mm. The used catalyst was a metal loaded catalyst with copper as the main active component, the support was silica, the catalyst had an average particle diameter of 400 μm, and the content of particles lower than 100 μm was 5%. The reaction conditions in the fluidized bed reactor were as follows: the superficial gas velocity was 0.4 m/s, the molar ratio of hydrogen gas to nitrobenzene was 11, the average reaction temperature in the dense phase reaction zone was controlled at 240° C., the reaction pressure in the dense phase reaction zone was 0.1 MPa.

[0174] The expansion coefficient of the dense phase reaction zone was 1.38, the maximum temperature difference at any part in the reaction zone was 15.9° C., and the results were detailed in Table 4.

[0175] Obviously, the apparatus and the process of the present invention can solve the problems such as the poor fluidization quality of the coarse particles in the fluidized bed technology of the nitrobenzene hydrogenation to produce aniline, the uneven temperature distribution in the reaction zone were, the catalysts prone to coking and deactivation, the difficulty in the long-period run, the necessity for supplementing the catalyst and the like, and can be used in the industrial run for the nitrobenzene hydrogenation to produce aniline.

TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Average mass flowrate All 13 All 13 All 13 All 13 All 13 (A1-A6 and B1-B5), kg/h Particle volume C1-C5 were C1-C5 were C1-C5 were C1-C5 were C1-C5 were fractions for the 0.9%, C6 0.9%, C6 0.9%, C6 0.9%, C6 0.9%, C6 pipelines (C1-C6 and was 0.6%, was 0.6%, was 0.6%, was 0.6%, was 0.6%, D1-D5) D1-D5 D1-D5 D1-D5 D1-D5 D1-D5 were 1.2% were 1.2% were 1.2% were 1.2% were 1.2% Ratio of the average 0.00005 0.001 0.00002 0.00005 0.00005 mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor, h.sup.−1 Dimensionless particle 10 10 10 60 1 diameter in the fluidized bed reactor dimensionless gas 0.1 0.1 0.1 0.1 0.1 velocity in the fluidized bed reactor Dimensionless particle 8 8 8 8 8 diameter in the regenerator Dimensionless gas 0.15 0.15 0.15 0.15 0.15 velocity in the regenerator Dimensionless particle 8 8 8 8 8 diameter in the activator Dimensionless gas 0.15 0.15 0.15 0.15 0.15 velocity in the activator Standard deviation 500 500 500 500 500 value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles, Pa solid particle inventory 40:3:3  40:3:3  40:3:3  40:3:3  40:3:3  of hydrogenation reactor:solid particle inventory of regeneration reactor:solid particle inventory of activation reactor Height of the 5:1:1 5:1:1 5:1:1 5:1:1 5:1:1 hydrogenation reactor:height of the regeneration reactor:height of the activation reactor Diameter of the 4:1:1 4:1:1 4:1:1 4:1:1 4:1:1 hydrogenation reactor:diameter of the regeneration reactor:diameter of the activation reactor Expansion coefficient 1.64 1.58 1.61 1.56 1.55 of the dense phase reaction zone Maximum temperature 7.1 8.2 7.3 7.5 7.5 difference in the reaction zone, ° C. Carbon deposition could be could be could be could be could be content when the controlled controlled controlled controlled controlled reaction time was 90 at no at no at no at no at no minutes under the high greater than greater than greater than greater than greater than space velocity, % 0.7% 0.51% 0.55% 0.58% 0.76%

TABLE-US-00002 TABLE 2 Example 6 Example 7 Example 8 Example 9 Example 10 Average mass flowrate All 13 All 13 All 13 All 13 All 13 (A1-A6 and B1-B5), kg/h Particle volume C1-C5 were C1-C5 were C1-C5 were C1-C5 were C1-C5 were fractions for the 0.9%, C6 0.9%, C6 0.9%, C6 0.9%, C6 0.9%, C6 pipelines (C1-C6 and was 0.6%, was 0.6%, was 0.6%, was 0.6%, was 0.6%, D1-D5) D1-D5 D1-D5 D1-D5 D1-D5 D1-D5 were 1.2% were 1.2% were 1.2% were 1.2% were 1.2% Ratio of the average 0.00005 0.00005 0.00005 0.00005 0.00005 mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor, h.sup.−1 Dimensionless particle 10 10 10 10 10 diameter in the fluidized bed reactor dimensionless gas 0.05 7 0.1 0.1 0.1 velocity in the fluidized bed reactor Dimensionless particle 8 8 1 36 8 diameter in the regenerator Dimensionless gas 0.15 0.15 0.05 5 0.15 velocity in the regenerator Dimensionless particle 8 8 8 8 1 diameter in the activator Dimensionless gas 0.15 0.15 0.15 0.15 0.05 velocity in the activator Standard deviation 500 500 500 500 500 value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles, Pa solid particle inventory 40:3:3  40:3:3  40:3:3  40:3:3  40:3:3  of hydrogenation reactor:solid particle inventory of regeneration reactor:solid particle inventory of activation reactor Height of the 5:1:1 5:1:1 5:1:1 5:1:1 5:1:1 hydrogenation reactor:height of the regeneration reactor:height of the activation reactor Diameter of the 4:1:1 4:1:1 4:1:1 4:1:1 4:1:1 hydrogenation reactor:diameter of the regeneration reactor:diameter of the activation reactor Expansion coefficient 1.61 1.60 1.59 1.54 1.59 of the dense phase reaction zone Maximum temperature 7.3 7.3 7.6 8.0 7.6 difference in the reaction zone, ° C. Carbon deposition could be could be could be could be could be content when the controlled controlled controlled controlled controlled reaction time was 90 at no at no at no at no at no minutes under the high greater than greater than greater than greater than greater than space velocity, % 0.72% 0.72% 0.74% 0.8% 0.76%

TABLE-US-00003 TABLE 3 Example 11 Example 12 Example 13 Example 14 Example 15 Average mass flowrate All 13 All 13 All 13 All 7 All 26 (A1-A6 and B1-B5), kg/h Particle volume C1-C5 were C1-C5 were C1-C5 were C1-C5 were C1-C5 were fractions for the 0.9%, C6 0.9%, C6 0.9%, C6 0.83%, C6 1.1%, C6 pipelines (C1-C6 and was 0.6%, was 0.6%, was 0.6%, was 0.55%, was 0.7%, D1-D5) D1-D5 D1-D5 D1-D5 D1-D5 were D1-D5 were 1.2% were 1.2% were 1.2% 1.06% were 1.5% Ratio of the average 0.00005 0.00005 0.00005 0.00005 0.00005 mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor, h.sup.−1 Dimensionless particle 10 10 10 10 10 diameter in the fluidized bed reactor dimensionless gas 0.1 0.1 0.1 0.1 0.1 velocity in the fluidized bed reactor Dimensionless particle 8 8 8 8 8 diameter in the regenerator Dimensionless gas 0.15 0.15 0.15 0.15 0.15 velocity in the regenerator Dimensionless particle 25 8 8 8 8 diameter in the activator Dimensionless gas 5 0.15 0.15 0.15 0.15 velocity in the activator Standard deviation 500 700 1500 500 500 value of the pressure pulsation at any point of the bed layer of the dense phase reaction zone maintained by supplementing fine particles, Pa solid particle inventory 40:3:3  40:3:3  40:3:3  40:3:3  40:3:3  of hydrogenation reactor:solid particle inventory of regeneration reactor:solid particle inventory of activation reactor Height of the 5:1:1 5:1:1 5:1:1 5:1:1 5:1:1 hydrogenation reactor:height of the regeneration reactor:height of the activation reactor Diameter of the 4:1:1 4:1:1 4:1:1 4:1:1 4:1:1 hydrogenation reactor:diameter of the regeneration reactor:diameter of the activation reactor Expansion coefficient 1.60 1.62 1.52 1.62 1.67 of the dense phase reaction zone Maximum temperature 7.4 7.2 10.5 7.2 6.9 difference in the reaction zone, ° C. Carbon deposition could be could be could be could be could be content when the controlled controlled controlled controlled controlled reaction time was 90 at no at no at no at no greater at no minutes under the high greater than greater than greater than than 0.93% greater than space velocity, % 0.75% 0.7% 0.7% 0.47%

TABLE-US-00004 TABLE 4 Comparative Comparative Example 16 Example 17 Example 18 Example 1 Example 2 Average mass flowrate All 13 All 13 All 13 All 13 System (A1-A6 and B1-B5), without kg/h regenerator Particle volume C1-C5 were C1-C5 were C1-C5 were C1-C5 were and fractions for the 0.9%, C6 0.9%, C6 0.9%, C6 0.7%, C6 activator pipelines (C1-C6 and was 0.6%, was 0.6%, was 0.6%, was 0.3%, and without D1-D5) D1-D5 D1-D5 D1-D5 D1-D5 were the were 1.2% were 1.2% were 1.2% 1.2% supplement of the fresh catalyst and the fine particle catalyst Ratio of the average 0.00005 0.00005 0.00005 0.00005 mass flowrate of the supplement hydrogenation catalyst being transported to the hydrogenation catalyst inventory in the hydrogenation reactor, h.sup.−1 Dimensionless particle 10 10 10 10 diameter in the fluidized bed reactor dimensionless gas 0.1 0.1 0.1 0.1 velocity in the fluidized bed reactor Dimensionless particle 8 8 8 8 diameter in the regenerator Dimensionless gas 0.15 0.15 0.15 0.15 velocity in the regenerator Dimensionless particle 8 8 8 8 diameter in the activator Dimensionless gas 0.15 0.15 0.15 0.15 velocity in the activator Standard deviation 500 500 500 No control, value of the pressure without the pulsation at any point supplement of the bed layer of the of the fine dense phase reaction particle zone maintained by catalyst supplementing fine particles, Pa solid particle inventory 30:1:1  40:3:3  40:3:3  40:3:3  of hydrogenation reactor:solid particle inventory of regeneration reactor:solid particle inventoryof activation reactor Height of the 5:1:1 2:1:1 5:1:1 5:1:1 hydrogenation reactor:height of the regeneration reactor:height of the activation reactor Diameter of the 4:1:1 4:1:1 6:1:1 4:1:1 hydrogenation reactor:diameter of the regeneration reactor:diameter of the activation reactor Expansion coefficient 1.62 1.64 1.66 1.46 1.38 of the dense phase reaction zone Maximum temperature 7.2 7.2 7.0 13.8 15.9 difference in the reaction zone, ° C. Carbon deposition could be could be could be could be 4.1% content when the controlled controlled controlled controlled reaction time was 90 at no at no at no at no minutes under the high greater than greater than greater than greater than space velocity, % 0.7% 0.7% 0.73% 0.7%