CN113877232B - Treatment method and system for aniline-containing gas - Google Patents

Treatment method and system for aniline-containing gas Download PDF

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Publication number
CN113877232B
CN113877232B CN202010634241.7A CN202010634241A CN113877232B CN 113877232 B CN113877232 B CN 113877232B CN 202010634241 A CN202010634241 A CN 202010634241A CN 113877232 B CN113877232 B CN 113877232B
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aniline
quenching tower
gas
liquid
heat exchanger
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CN113877232A (en
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裴义霞
顾军民
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0027—Condensation of vapours; Recovering volatile solvents by condensation by direct contact between vapours or gases and the cooling medium
    • B01D5/003—Condensation of vapours; Recovering volatile solvents by condensation by direct contact between vapours or gases and the cooling medium within column(s)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
    • B01D47/06—Spray cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0033—Other features
    • B01D5/0039—Recuperation of heat, e.g. use of heat pump(s), compression
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • B01D53/185—Liquid distributors

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to the field of aniline preparation, and discloses a treatment method of aniline-containing gas, which comprises the following steps: (1) In the quenching tower, reversely contacting reaction balance mixed gas containing aniline with supplementary spray liquid to obtain a quenching tower bottom feed liquid and a quenching tower top gas phase; (2) The material liquid at the bottom of the quenching tower is divided into two parts, namely a produced material and a circulating material, and the circulating material returns to the quenching tower to be used as spray liquid for recycling; (3) Condensing the gas phase at the top of the quenching tower to obtain noncondensable gas and condensate; (4) And (3) carrying out oil-water separation on the condensate to obtain crude aniline and aniline-containing wastewater. The invention adopts the quenching tower with the supplementary spray liquid, thereby avoiding the equipment blockage, optimizing the energy utilization and realizing the purposes of long-period stable operation, energy conservation and consumption reduction of the device.

Description

Treatment method and system for aniline-containing gas
Technical Field
The invention relates to the field of aniline preparation, in particular to a method and a system for treating aniline-containing gas.
Background
Aniline is an organic chemical product with very wide application, and can be used as a rubber vulcanization accelerator, a dye, a medicine, an explosive raw material, a diphenylmethane polyurethane (MDI) raw material and the like.
Most of the existing aniline production devices adopt a nitrobenzene catalytic hydrogenation method, and the nitrobenzene catalytic hydrogenation method for preparing aniline is divided into a gas phase hydrogenation method and a liquid phase hydrogenation method. The gas phase hydrogenation method is divided into two processes of fixed bed gas phase catalytic hydrogenation and fluidized bed gas phase hydrogenation due to different reactor forms. At present, fluidized bed gas phase hydrogenation technology is adopted in domestic enterprises, the technology is gas-liquid two-phase reaction, reaction heat is carried out by vaporization of reaction products, the selectivity of aniline is more than 99%, the temperature of the reaction products at the outlet of the fluidized bed is 210-240 ℃, and the components mainly comprise aniline, water and hydrogen. After new hydrogen exchanges heat, the gas and the liquid are separated through two-step condensation. The method effectively avoids the situation of local overheating, reduces the occurrence of side reactions and prolongs the service life of the catalyst.
Because the strength of the copper-based catalyst for preparing aniline by nitrobenzene hydrogenation is not high, catalyst fine powder particles with the particle size of less than 10 microns can be formed after long-term abrasion in a fluidized bed. This fraction of the particles is difficult to fully capture by the cyclone in the fluidized bed, and therefore the reactants at the fluidized bed outlet contain many catalyst fines particles and are easily carried by the gas stream to the heat exchanger at the fluidized bed outlet. When the crude aniline is gradually cooled in the multistage heat exchanger, the catalyst particles are combined with tar in the reaction product, adhere to and accumulate in the tube array of the reaction gas heat exchanger, the scale layer on the inner wall of the tube array is gradually thickened along with the extension of the operation time, and the channels in the tube array are gradually reduced, so that the resistance of the pipeline is increased and the energy consumption is increased. When the scale layer reaches a certain thickness, the operating pressure of the reaction system is obviously increased, so that the operating condition of the fluidized bed reaction system is further deteriorated. When severe, the heat exchanger pipeline can be basically completely blocked after the device is operated for 4-5 months, and the device must be shut down for cleaning, thereby being time-consuming, polluting the environment and affecting normal production.
CN104098473A is prepared by adding a scrubber at the outlet of the reactor, allowing the reaction mixture gas phase material to enter from the middle lower part of the scrubber, forcibly spraying with crude aniline at 40-80deg.C, allowing the liquid phase material at the bottom outlet of the scrubber to have a temperature of 130-170deg.C, and removing solid particles from the liquid phase at the bottom of the scrubber by gravity sedimentation or cyclone separation to relieve the problem of blockage of the hydrogen heat exchanger, however, because the catalyst fine powder is below 10 μm, it is difficult to remove. CN105418437a discloses an energy-saving method for aniline device, which adopts the mixed gas phase material of crude aniline and high temperature reaction at 10-80 ℃ to exchange heat in a tower heat exchanger, so as to improve the operation period of the device to 8 months.
In summary, in the condensation process of the mixed gas phase material generated by the reaction in the prior art, the problem of blockage of a heat exchanger is not thoroughly solved, and the long-period stable operation of the aniline preparation process by nitrobenzene fluidized bed hydrogenation is further influenced.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, a heat exchanger is easy to block and a device cannot operate for a long time in the condensation process of aniline reaction balance mixed gas, and provides a treatment method and a treatment system of aniline-containing gas.
In order to achieve the above object, a first aspect of the present invention provides a method for treating an aniline-containing gas, comprising the steps of:
(1) In the quenching tower, reversely contacting reaction balance mixed gas containing aniline with supplementary spray liquid to obtain a quenching tower bottom feed liquid and a quenching tower top gas phase;
(2) The material liquid at the bottom of the quenching tower is divided into two parts, namely a produced material and a circulating material, and the circulating material returns to the quenching tower to be used as spray liquid for recycling;
(3) Condensing the gas phase at the top of the quenching tower to obtain noncondensable gas and condensate;
(4) And (3) carrying out oil-water separation on the condensate to obtain crude aniline and aniline-containing wastewater.
In a second aspect, the present invention provides a method for treating an aniline-containing gas, the method comprising the steps of:
(1) Feeding the reaction balance mixed gas containing aniline into a quenching tower from the bottom, and spraying the supplementary spraying liquid from the top of the quenching tower to obtain a material liquid at the bottom of the quenching tower and a gas phase at the top of the quenching tower;
(2) After the material liquid at the bottom of the quenching tower is led out by a circulating pump, part of the material liquid is taken as a produced material, and the rest part of the material liquid is taken as a circulating material and returned to the quenching tower to be taken as spraying liquid for recycling;
(3) The gas phase at the top of the quenching tower enters a condenser to be condensed, and noncondensable gas and condensate are obtained;
(4) And sending the condensate into an oil-water separator for oil-water separation to obtain crude aniline and aniline-containing wastewater.
Preferably, the supplementary spray liquid is used in an amount of 10 to 60 parts by weight, preferably 15 to 40 parts by weight, with respect to 100 parts by weight of the reaction balance mixture.
Preferably, at least part of the supplemental spray liquor of step (1) is provided by the aniline-containing wastewater of step (4).
Preferably, the method further comprises: the reaction balance mixed gas is sent to a hydrogen heat exchanger containing a solid particle injection system for heat exchange, and low-temperature reaction gas with solid particles, which is obtained at an outlet of the hydrogen heat exchanger, is sent to a quenching tower; the hydrogen heat exchanger with the solid particle injection system comprises a solid buffer tank and a hydrogen heat exchanger, and the bottom of the solid buffer tank is communicated with the top of the hydrogen heat exchanger.
Preferably, the method further comprises: when the pressure difference of the hydrogen heat exchanger exceeds a set value, solid particles are added into a solid buffer tank and are sprayed to the top of the hydrogen heat exchanger under the drive of carrier gas.
Preferably, the hydrogen heat exchanger is provided with a differential pressure sensor, and the carrier gas and solid buffer tank pipelines are provided with interlocking pneumatic valves; when the pressure difference of the hydrogen heat exchanger exceeds a set value, a signal is transmitted to the interlocking pneumatic valve through the pressure difference sensor, the valve is opened, solid particles are added into the solid buffer tank and are sprayed to the top of the hydrogen heat exchanger under the drive of carrier gas, and when the pressure difference of the hydrogen heat exchanger is lower than the set value, the valve of the interlocking pneumatic valve is closed in a linkage way. It is further preferable that the supplementary spray liquid is used in an amount of 10 to 30 parts by weight with respect to 100 parts by weight of the low-temperature reaction gas.
In a third aspect, the invention provides a process system for treating an aniline-containing gas, the system comprising:
a quench tower, a condenser and an oil-water separator; the tower top outlet of the quenching tower is communicated with the inlet of a condenser, and the liquid phase outlet of the condenser is communicated with the inlet of the oil-water separator;
the bottom and the top of the quenching tower are provided with circulating pipelines so that at least part of the material at the bottom of the quenching tower is circulated to the top of the quenching tower;
and the top of the quenching tower is also communicated with a supplementary spray pipeline so as to introduce supplementary spray liquid into the quenching tower.
Through the technical scheme, the quenching tower with the supplementary spray liquid is adopted, so that the energy utilization is optimized while equipment (comprising the hydrogen heat exchanger and/or the condenser) is prevented from being blocked, and the purposes of long-period stable operation, energy saving and consumption reduction of the device are realized.
Under the preferred condition, the method adopts the aniline-containing wastewater as the supplementary spray liquid, so that compared with the method adopting crude aniline, the method has the advantages that the consumption of the spray liquid is less, and the spray agent does not need to be supplemented from the outside of the device, thereby being more beneficial to saving the operation cost. The inventors of the present invention found that in this preferred case, the reaction equilibrium mixture undergoes a phase change with the aniline-containing wastewater in the quenching tower, a large amount of heat is absorbed during vaporization of the aniline-containing wastewater, and the reaction equilibrium mixture is condensed while the gas is washed with a liquid phase and catalyst particles are trapped.
Under the preferred condition, the invention adopts the hydrogen heat exchanger containing the solid particle injection system to exchange heat, on one hand, the heat of the reaction balance gas mixture can be effectively utilized, and on the other hand, the heat exchanger can be prevented from being blocked, thereby further ensuring the long-period stable operation of the device and improving the stability of the system.
Drawings
FIG. 1 is a flow diagram of a treatment system for aniline-containing gas in accordance with a preferred embodiment of the present invention;
FIG. 2 is a flow diagram of a treatment system for aniline-containing gas in accordance with a preferred embodiment of the present invention;
FIG. 3 is a flow chart of a treatment system for aniline-containing gas in accordance with a preferred embodiment of the present invention.
Description of the reference numerals
1. Solid-liquid separator 2, quench tower 3, and condenser
4. Oil-water separator 5, solid buffer tank 6 and hydrogen heat exchanger
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless specifically stated otherwise, the pressure refers to absolute pressure.
In the present invention, unless otherwise stated, the terms upper, middle and lower used in the azimuth terms may be three segments of the apparatus divided equally from top to bottom, or may be three segments which are not equally divided by using the internal components of the apparatus as a segment standard, so long as they can be distinguished by those skilled in the art.
The first aspect of the present invention provides a method for treating an aniline-containing gas, the method comprising the steps of:
(1) In the quenching tower, reversely contacting reaction balance mixed gas containing aniline with supplementary spray liquid to obtain a quenching tower bottom feed liquid and a quenching tower top gas phase;
(2) The material liquid at the bottom of the quenching tower is divided into two parts, namely a produced material and a circulating material, and the circulating material returns to the quenching tower to be used as spray liquid for recycling;
(3) Condensing the gas phase at the top of the quenching tower to obtain noncondensable gas and condensate;
(4) And (3) carrying out oil-water separation on the condensate to obtain crude aniline and aniline-containing wastewater.
In a second aspect, the present invention provides a method for treating an aniline-containing gas, the method comprising the steps of:
(1) Feeding the reaction balance mixed gas containing aniline into a quenching tower from the bottom, and spraying the supplementary spraying liquid from the top of the quenching tower to obtain a material liquid at the bottom of the quenching tower and a gas phase at the top of the quenching tower;
(2) After the material liquid at the bottom of the quenching tower is led out by a circulating pump, part of the material liquid is taken as a produced material, and the rest part of the material liquid is taken as a circulating material and returned to the quenching tower to be taken as spraying liquid for recycling;
(3) The gas phase at the top of the quenching tower enters a condenser to be condensed, and noncondensable gas and condensate are obtained;
(4) And sending the condensate into an oil-water separator for oil-water separation to obtain crude aniline and aniline-containing wastewater.
The size and the material of the quenching tower are not particularly limited, and can be selected by a person skilled in the art according to actual needs as long as the requirements of the throughput and the corrosion allowance of the materials in the quenching tower can be respectively met.
According to the invention, the source selection range of the reaction balance mixed gas is wide, and any mixed gas containing aniline can be treated by the method of the invention, and preferably, the reaction balance mixed gas is from nitrobenzene fluidized bed gas phase hydrogenation reaction.
The invention adopts the quenching tower with the supplementary spray liquid, has good condensation effect on the reaction balance mixed gas containing aniline, optimizes energy utilization while avoiding the blockage of equipment (comprising a hydrogen heat exchanger and/or a condenser), and realizes the purposes of long-period stable operation, energy conservation and consumption reduction of the device.
In the invention, the condition selection range of the nitrobenzene fluidized bed gas phase hydrogenation reaction is wider, and the condition selection can be the conventional selection in the field, and the invention is not repeated here. The equipment for the nitrobenzene fluidized bed gas phase hydrogenation reaction is not particularly limited, and can be a conventional choice in the field, and the invention is not repeated here.
According to the present invention, preferably, the reaction equilibrium mixture contains aniline, hydrogen and water. The present invention has a wide range of selection of the weight of aniline contained in the reaction balance mixture, preferably the aniline content is 40 to 80 wt%, preferably 55 to 75 wt%, based on the total amount of the reaction balance mixture.
According to the invention, the reaction equilibrium mixture preferably also contains catalyst particles in an amount of 100 to 10000ppm, preferably 1000 to 4000ppm.
The catalyst particles of the present invention are of a wide range of sizes, typically sizes that are difficult to fully capture by cyclone separators in a fluidized bed. Preferably, the catalyst particles have a size of from 2 to 20 μm. The catalyst is not particularly limited as long as it has a catalytic action in the fluidized bed gas phase hydrogenation of nitrobenzene. For example copper-based catalysts.
According to the invention, the reaction equilibrium mixture temperature is preferably 180-260 ℃, preferably 210-240 ℃.
According to a preferred embodiment of the invention, in step (1), the supplemental spray liquid is an aqueous solution containing aniline, the water content being 92-99.9 wt%, preferably 94-97 wt%. Under the preferable condition, the method is beneficial to reducing the running cost and realizes the purposes of energy conservation and consumption reduction.
According to the invention, the temperature of the supplemental spray liquid is preferably 10-60 ℃, preferably 20-50 ℃. In the preferred case, the condensation effect of the reaction balance mixture is better, which is beneficial to improving the system stability.
According to a preferred embodiment of the present invention, the supplementary spray liquid is used in an amount of 10 to 60 parts by weight, preferably 15 to 40 parts by weight, with respect to 100 parts by weight of the reaction balance mixture. Compared with the prior art, the method provided by the invention has the advantages that less supplementary spray liquid is used, and the running cost is saved.
According to a preferred embodiment of the invention, at least part of the supplemental spray liquor of step (1) is provided by the aniline-containing wastewater of step (4). In the preferred embodiment, no or a small amount of spray agent is required to be supplemented from outside the device, which is more beneficial to reducing the running cost of the device. More preferably, the supplemental spray liquid in step (1) is provided entirely by the aniline-containing wastewater in step (4). In the preferred embodiment, the spraying agent does not need to be supplemented from outside the device, and the running cost of the device is reduced.
The invention has wide selection range of the operation temperature of the quenching tower, preferably, the bottom temperature of the quenching tower is 70-115 ℃ and the top temperature of the quenching tower is 65-110 ℃. In the preferred case, the condensation effect of the reaction balance mixture is better, which is beneficial to improving the system stability.
Further preferably, the bottom temperature of the quenching tower is 75-110 ℃, and the top temperature is 69-100 ℃. In the preferred case, the condensation effect of the reaction balance mixture is better, which is beneficial to improving the system stability.
The invention has wider selection range of the internal structure of the quenching tower, for example, the quenching tower can be provided with at least a sprayer and a foam catcher, the selection range of the quantity of the sprayer and the foam catcher is wider, and of course, the more the quantity of the sprayer and the foam catcher is, the better the effect is, but the higher the cost is. Preferably, the quench tower comprises at least two layers of sprayers and at least one layer of mist eliminator, more preferably, the quench tower comprises 2-6 layers of sprayers and 2-4 layers of mist eliminator. In this preferred embodiment, it is more advantageous to enhance the condensing effect of the reaction equilibrium mixture and the trapping effect of the solid catalyst particles, thereby enhancing the stability of the apparatus.
In the present invention, the sprayer is not particularly limited, as long as the spraying effect of the spraying liquid can be achieved, and the sprayer can be selected conventionally in the art, and can be selected as required by a person skilled in the art according to actual needs. For example, the spray thrower comprises spray heads, the setting selection range of the spray heads is wider, and in order to further optimize the spray effect, the quenching tower comprises two layers of spray throwers, and the spray heads of the two layers of spray throwers are preferably densely arranged; alternatively, the quench tower comprises four layers of sprayers, and the spray heads of the four layers of sprayers are preferably staggered in 4 layers.
The foam trap is not particularly limited, and can be selected conventionally in the art, and can be selected as required by a person skilled in the art according to actual needs.
According to a preferred embodiment of the invention, in step (2), the withdrawn material comprises 3-25% by weight, preferably 5-20% by weight, of the recycled material. In this preferred case, it is advantageous to increase the condensation effect on the reaction equilibrium mixture, and thus to increase the stability of the system.
According to the invention, the aniline content in the quench tower bottom feed is preferably 90-99.9 wt.%, preferably 96-99.9 wt.%.
According to the present invention, preferably, the step (2) further includes solid-liquid separation of the extracted material to obtain a clear liquid. The solid-liquid separation allows the catalyst particles contained in the produced material to be removed. Preferably, the aniline content of the clear liquid is 90-99.9 wt%, preferably 96-99.9 wt%. The solid-liquid separation may be performed using a filter. The accuracy of the filter is selected to be wide as long as the catalyst particles can be separated, and preferably, a filter having a separation accuracy of 5 to 20 μm can be used.
According to the invention, the water content in the clear liquid is preferably 0.1 to 10% by weight, preferably 0.5 to 2% by weight. The clear liquid can be directly extracted or removed from the refining system.
According to the present invention, it is preferable that the liquefaction recovery rate of aniline in the reaction equilibrium mixture in step (1) in the quenching tower is not less than 50%, preferably not less than 60%, and more preferably 60% -90%. The liquefaction recovery rate refers to the weight of the aniline in the produced liquid of the tower kettle in unit time to be the weight percentage of the aniline in the reaction balance mixed gas.
According to the present invention, preferably, the quench tower overhead gas phase contains aniline, hydrogen and water.
In one embodiment, the quench tower overhead gas phase also contains nitrogen in an amount of 0 to 1 wt%.
According to a preferred embodiment of the invention, the aniline content in the gas phase at the top of the quench tower is not more than 40 wt.%, more preferably not more than 20 wt.%.
In the present invention, in the step (3), the setting mode of the condenser is selected in a wide range, specifically, for example, the condenser may be set to be one-stage condensation or two-stage condensation or multi-stage condensation. In the invention, the primary condensation refers to that the tower top gas phase of the quenching tower is introduced into one condenser, or two or more condensers connected in parallel are used for primary condensation. The two-stage condensation means that the gas phase at the top of the quenching tower is communicated with two condensers in series, the two condensers in series can be one group, two groups or multiple groups, and the meaning of the two-stage condensation is similar to that, and the two-stage condensation can be selected by a person skilled in the art according to the requirements.
And (3) obtaining noncondensable gas at the top of the condenser in the step (3), wherein the noncondensable gas can be used for a hydrogen recovery system.
According to the present invention, in the step (4), the apparatus for oil-water separation is not particularly limited, and may be selected conventionally in the art. In one embodiment, an oil-water separator is used. The oil-water separator is not particularly limited, and can be selected by a person skilled in the art according to actual needs.
The crude aniline obtained in the step (4) can be subjected to an aniline refining unit.
According to a preferred embodiment of the present invention, as shown in fig. 2, the treatment method for aniline-containing gas further includes: the reaction balance mixed gas is sent to a hydrogen heat exchanger containing a solid particle injection system for heat exchange, and low-temperature reaction gas with solid particles obtained at an outlet of the hydrogen heat exchanger is sent to a quenching tower;
the hydrogen heat exchanger with the solid particle injection system comprises a solid buffer tank and a hydrogen heat exchanger, and the bottom of the solid buffer tank is communicated with the top of the hydrogen heat exchanger. Under the preferred embodiment, the heat of the reaction balance gas mixture can be effectively utilized, the blockage of equipment can be avoided, and the stability of the device can be improved.
In the present invention, the operation mode of the solid particle injection system is not particularly limited, and the operation frequency may be adjusted according to a pressure difference or a temperature difference, or may be intermittently operated according to an interval time, and specifically, the interval time may be 1 to 150 hours, preferably 12 to 72 hours.
According to a preferred embodiment of the present invention, as shown in fig. 3, the method further comprises: when the pressure difference of the hydrogen heat exchanger exceeds a set value, solid particles are added into a solid buffer tank and are sprayed to the top of the hydrogen heat exchanger under the drive of carrier gas. Under the preferred embodiment, when the hydrogen heat exchanger is blocked (the pressure difference exceeds a set value), solid particles are sprayed to the top of the hydrogen heat exchanger under the drive of carrier gas, so that the blocking removal effect can be realized. The differential pressure setting value is not particularly limited in the present invention, and those skilled in the art can appropriately select it according to the specific conditions in the actual production process. In the present invention, preferably, the differential pressure set point is 1 to 30kPa, preferably 2 to 10kPa.
Preferably, the hydrogen heat exchanger is provided with a differential pressure sensor, and the carrier gas and solid buffer tank pipelines are provided with interlocking pneumatic valves; when the pressure difference of the hydrogen heat exchanger exceeds a set value, a signal is transmitted to the interlocking pneumatic valve through the pressure difference sensor, the valve is opened, solid particles are added into the solid buffer tank and are sprayed to the top of the hydrogen heat exchanger under the drive of carrier gas, and when the pressure difference of the hydrogen heat exchanger is lower than the set value, the valve of the interlocking pneumatic valve is closed in a linkage way. In this preferred embodiment, it is further advantageous to avoid equipment blockage and to increase the stability of the system.
The size and the kind of the solid particles are selected in a wide range, and preferably the solid particles are inert solid particles with the particle size of 0.1-5 mm. Preferably, the inert solid particles are selected from at least one of alumina, silica, zirconium silicate, iron wire spheres, silica gel and zirconia.
According to the present invention, preferably, the carrier gas is selected from at least one of nitrogen, helium, neon and hydrogen. In order to further reduce the operating costs, the carrier gas is preferably nitrogen and/or hydrogen.
According to the present invention, preferably, the temperature of the low-temperature reaction gas is 110 to 130 ℃.
According to a preferred embodiment of the invention, the supplemental spray liquid is an aqueous solution containing aniline, the water content being 92-99.9 wt.%, preferably 94-97 wt.%.
According to the invention, the temperature of the supplemental spray liquid is preferably 30-50 ℃.
According to a preferred embodiment of the present invention, the supplementary spray liquid is used in an amount of 10 to 30 parts by weight with respect to 100 parts by weight of the low temperature reaction gas. In this preferred embodiment, the supplemental spray is used in a lesser amount.
According to a preferred embodiment of the present invention, as shown in fig. 3, the supplementary spray liquid is divided into a supplementary spray liquid I and a supplementary spray liquid II having a weight ratio of 0.1 to 10, and the supplementary spray liquid I and the supplementary spray liquid II are sprayed on the top of the quenching tower and the middle of the quenching tower, respectively. Under the preferred embodiment, the condensation effect of the reaction balance mixed gas is improved, and the running cost of the device is reduced. Preferably, the total amount of the supplementary spray liquid is 5 to 25 parts by weight with respect to 100 parts by weight of the low temperature reaction gas. In this preferred case, the supplemental spray is used in a lesser amount.
In a third aspect, the invention provides a process system for treating an aniline-containing gas, the system comprising:
A quench tower, a condenser and an oil-water separator; the tower top outlet of the quenching tower is communicated with the inlet of a condenser, and the liquid phase outlet of the condenser is communicated with the inlet of the oil-water separator;
the bottom and the top of the quenching tower are provided with circulating pipelines so that at least part of the material at the bottom of the quenching tower is circulated to the top of the quenching tower;
and the top of the quenching tower is also communicated with a supplementary spray pipeline so as to introduce supplementary spray liquid into the quenching tower.
The condenser is not particularly limited in the present invention, and a person skilled in the art can select the condenser according to actual needs, and the specific selection is as described above and will not be repeated here. In the invention, the oil-water separator has a wide selection range, and can be selected as required by a person skilled in the art according to actual needs as long as the purpose of separating the oil phase from the water phase can be achieved.
According to the present invention, preferably, the quenching tower comprises at least two layers of sprayers and at least one layer of foam traps, more preferably, the quenching tower comprises 2-6 layers of sprayers and 2-4 layers of foam traps. The selection of the sprayer and the foam catcher is as described above and will not be described in detail here.
According to the invention, preferably, a circulating pump is further arranged on the circulating pipeline, and the circulating pump is used for leading out the tower bottom material of the quenching tower to obtain a produced material and a circulating material. The circulating pump has a wide selection range and can be a conventional selection in the field.
According to the present invention, preferably, the system further comprises a solid-liquid separator in communication with the circulation pump for solid-liquid separation of the produced material. The solid-liquid separator is not particularly limited as long as the purpose of solid-liquid separation of the produced material can be achieved, and specifically, the solid-liquid separator may be a filter having a separation accuracy of 1 to 20 μm. In the invention, the solid-liquid separation allows the catalyst particles contained in the produced material to be removed.
According to a preferred embodiment of the invention, the system further comprises a solid buffer tank and a hydrogen heat exchanger, wherein the outlet of the solid buffer tank is communicated with the top inlet of the hydrogen heat exchanger; the bottom outlet of the hydrogen heat exchanger is communicated with the inlet of the quenching tower; the solid buffer tank is provided with a carrier gas input line and a solid particle input line. In the preferred embodiment, the blockage of equipment is avoided, and the running stability of the device is improved.
In the present invention, the hydrogen heat exchanger is not particularly limited, and may be selected conventionally in the art. The solid buffer tank has a wide selection range, and can be selected by a person skilled in the art according to actual needs as long as the function of storing and buffering the solid particles can be realized.
According to the present invention, preferably, the hydrogen heat exchanger is provided with a differential pressure sensor, the carrier gas input line is provided with an interlocking pneumatic valve, and the differential pressure sensor controls the opening and closing of the interlocking pneumatic valve by a change in differential pressure.
In the present invention, the carrier gas is selected as described above, and the present invention will not be described herein. The differential pressure sensor is not particularly limited in the present invention, and may be selected conventionally in the art. In the present invention, the interlocking air-operated valve is not particularly limited, and one skilled in the art can select it as needed according to actual needs.
In a preferred embodiment, the treatment of the aniline-containing gas is performed according to the flow chart shown in fig. 1, in particular:
introducing reaction balance mixed gas (the temperature is 210-240 ℃ and the aniline content is 55-75 wt%) from the bottom of a quenching tower 2 (the tower bottom temperature is 75-110 ℃, the tower top temperature is 69-100 ℃, two layers of sprayers and one layer of foam traps) and supplementing spray liquid (the temperature is 20-60 ℃, the water content is 92-99.9 wt%), and the supplementing spray liquid is 15-40 wt% relative to 100 parts of the reaction balance mixed gas) from the tower top, leading out quench tower bottom feed liquid (the aniline content is 96-99.9 wt%) through a circulating pump, and obtaining a produced material and a circulating material (the produced material accounts for 3-25 wt%) and the circulating material returns to the tower top to be used as spray liquid; the extracted material passes through a solid-liquid separator 1, and after catalyst particles are separated, the obtained clear liquid is subjected to aniline refining unit. The gas phase (the aniline content of which is not more than 20 weight percent) at the top of the quench tower enters a condenser 3, a noncondensable gas and dehydrogenation gas recovery system at the top of the condenser 3, a condensate deoiling water separator 4, a crude aniline removing refining unit obtained from the lower layer, and part of aniline-containing wastewater obtained from the upper layer are recycled to be used as a supplementary spray liquid.
In a preferred embodiment, the treatment of the aniline-containing gas is performed according to the flow chart shown in fig. 2, in particular:
feeding the reaction balance mixed gas (the temperature is 210-240 ℃ and the aniline content is 55-75 wt%) into a hydrogen heat exchanger 6 containing a solid particle injection system for heat exchange; the low-temperature reaction gas (the temperature is 110-130 ℃) with solid particles, which is obtained at the outlet of the hydrogen heat exchanger 6, enters the quenching tower 2 (the temperature of the bottom of the tower is 75-110 ℃, the temperature of the top of the tower is 69-100 ℃, two layers of sprayers and one layer of foam-catching device are included), the supplementary spraying liquid (the temperature is 30-50 ℃, the water content is 92-99.9 weight percent), relative to 100 weight parts of the reaction balance mixed gas, the supplementary spraying liquid is 10-30 weight percent) is sprayed from the top of the tower, the liquid at the bottom of the quenching tower (the aniline content is 96-99.9 weight percent) enters the solid-liquid separator 1 through a circulating pump, after the catalyst particles are separated, the material is extracted into a aniline-removing refining unit, and the rest is taken as circulating material (the extracted material accounts for 3-25 weight percent of the circulating material) and returns to the top of the quenching tower 2 to be used as spraying liquid. Feeding the gas phase (wherein the aniline content is not more than 20 wt%) at the top of the quenching tower into a condenser 3, a noncondensable gas and dehydrogenation gas recovery system at the top of the condenser 3, and a condensate deoiling water separator 4, wherein the lower layer is provided with a crude aniline removing refining unit, and part of aniline-containing wastewater obtained from the upper layer is reused as a supplementary spray liquid;
The solid particle injection system is intermittently operated (for example, operated every 10-72 hours), when dredging the hydrogen heat exchanger 6, solid particles (with the particle size of 0.1-5 mm) are firstly added from the top of the solid buffer tank 5, and are injected to the top of the hydrogen heat exchanger 6 under the drive of carrier gas.
In a preferred embodiment, the treatment of the aniline-containing gas is performed according to the flow chart shown in fig. 3, in particular:
feeding the reaction equilibrium mixed gas (the temperature is 210-240 ℃ and the aniline content is 55-75 wt%) into a hydrogen heat exchanger 6 containing a solid particle injection system; the low-temperature reaction gas (with the temperature of 110-130 ℃) with solid particles, which is obtained at the outlet of the hydrogen heat exchanger 6, enters the quenching tower 2 from the bottom (with the temperature of 75-110 ℃ at the bottom and the temperature of 69-100 ℃ at the top of the tower; two layers of sprayers and one layer of foam-capturing device are included), the supplementary spraying liquid is divided into supplementary spraying liquid I and supplementary spraying liquid II (with the temperature of 30-50 ℃ and the water content of 92-99% by weight, and the total amount of the supplementary spraying liquid is 5-25 parts by weight relative to 100 parts by weight of the reaction balance mixed gas) which are respectively enters the quenching tower 2 from the top of the tower and the middle of the tower, the liquid at the bottom of the quenching tower (with the aniline content of 96-99.9% by weight) enters the solid-liquid separator 1 through a circulating pump, after the catalyst particles are separated, the obtained clear liquid part is taken as a collected material aniline removing refining unit, and the rest part is taken as circulating material (the collected material accounts for 3-25% by weight of circulating material) and returns to the top of the quenching tower 2 to make spraying liquid. The gas phase (the aniline content of which is not more than 20 weight percent) at the top of the quench tower enters a condenser 3, a noncondensable gas and dehydrogenation gas recovery system at the top of the condenser 3, a condensate deoiling water separator 4, a crude aniline removing refining unit obtained from the lower layer, and part of aniline-containing wastewater obtained from the upper layer are recycled to be used as a supplementary spray liquid.
The hydrogen heat exchanger 6 is provided with a differential pressure sensor, and the carrier gas pipeline and the pipeline of the solid buffer tank 5 are respectively provided with an interlocking pneumatic valve; when the pressure difference of the hydrogen heat exchanger 6 exceeds a set value (the set value is 1-30 kPa), a signal is transmitted to the pneumatic valve through the sensor, the valve is opened, solid particles (the particle size is 0.1-5 mm) are added into the solid buffer tank 5 from the top, the solid particles are sprayed to the top of the hydrogen heat exchanger 6 under the drive of carrier gas, and when the pressure difference is lower than the set value, the valve of the interlocking pneumatic valve is closed in a linkage way.
The present invention will be described in detail by examples.
In the following examples, alumina, silica and zirconium silicate are all commercially available;
liquefaction recovery rate of aniline= (weight of aniline in 1-tower top gas phase/weight of aniline in reaction equilibrium mixture) ×100%
Example 1
According to the flow chart shown in fig. 1, the method provided by the invention is used for treating the aniline-containing gas, and comprises the following specific steps:
feeding reaction balance mixed gas (the temperature is 220 ℃, the aniline content is 66 weight percent, the water content is 25.6 weight percent, the hydrogen content is 8.4 weight percent, and the catalyst particle content is 2600 ppm) directly from the bottom of the quenching tower 2, taking aniline-containing wastewater (the aniline content is 4%, the temperature is 20 ℃, and the consumption of the supplementary spraying liquid is 20 weight parts relative to 100 weight parts of the reaction balance mixed gas) as supplementary spraying liquid, and spraying from the top of the quenching tower;
The material liquid at the bottom of the quenching tower is led out by a circulating pump to obtain a produced material and a circulating material (the produced material accounts for 5 weight percent of the circulating material); the extracted material enters a solid-liquid separator 1 (filter) with the separation precision of 10 mu m, after catalyst particles are separated, clear liquid (the aniline content is 99.0 wt% and the water content is 1.0 wt%) is obtained and is subjected to an aniline refining unit, and the circulating material returns to a quenching tower 2 to be used as spray liquid.
After equilibrium is reached, the bottom temperature is 113 ℃, and the top temperature is 97 ℃; the gas phase (36.4 wt% of aniline content, 53.4 wt% of water content, 10 wt% of hydrogen content and 0.2 wt% of nitrogen content) at the top of the quenching tower enters a two-stage tandem condenser 3, a non-condensable gas and dehydrogenation gas recovery system at the top of the condenser 3, a condensate deoiling water separator 4 performs oil-water separation, and then the crude aniline is purified by a crude aniline purification unit obtained in the lower layer, the upper layer material is aniline-containing wastewater, part of the wastewater is recycled to be used as a supplementary spray liquid, and the rest is subjected to wastewater extraction treatment.
The results show that: the recovery rate of aniline in the quenching tower was about 50%. The device has no blocking phenomenon in the running process.
Comparative examples 1 to 1
Directly feeding a reaction balance mixed gas (the temperature is 220 ℃, the aniline content is 66 wt%, the water content is 25.6 wt%, the hydrogen content is 8.4 wt%, and the catalyst particle content is 2600 ppm) into a hydrogen heat exchanger, feeding low-temperature reaction gas (the temperature is 120 ℃) at the outlet of the hydrogen heat exchanger into a quenching tower from the bottom, spraying crude aniline with the aniline content of 96.5 wt% and the temperature of 20 ℃ from the top of the tower as a supplementary spraying liquid, wherein the consumption of the crude aniline is 20 parts by weight relative to 100 parts by weight of the reaction balance mixed gas;
After equilibrium is reached, the quench tower bottom temperature is 116℃and the top temperature is 113 ℃. The aniline content in the quench tower overhead gas phase was 63.4 wt.%, the water content was 27.7 wt.% and the hydrogen content was 8.9 wt.%.
The results show that: the liquefaction recovery rate of the aniline in the quenching tower of the reaction balance mixed gas is only 9%, and the effect of spraying and condensing and washing solid particles can not be achieved by adopting crude aniline as spraying liquid (the dosage is 20% of the weight of the reaction balance mixed gas).
Comparative examples 1 to 2
Directly feeding reaction balance mixed gas (the temperature is 220 ℃, the aniline content is 66 wt%, the water content is 25.6 wt%, the hydrogen content is 8.4 wt%, and the catalyst particle content is 2600 ppm) into a hydrogen heat exchanger, feeding low-temperature reaction gas (the temperature is 120 ℃) at the outlet of the hydrogen heat exchanger into the bottom of a quenching tower from the bottom, and feeding supplementary spray liquid (the aniline content is 96.5%, the temperature is 30 ℃ of crude aniline; the dosage of the supplementary spray liquid is 135 parts by weight relative to 100 parts by weight of the reaction balance mixed gas) from the top of the quenching tower;
the material liquid at the bottom of the quenching tower enters a solid-liquid separator (filter) with the separation precision of 10 mu m through a circulating pump, after catalyst particles are separated, clear liquid is extracted from a crude aniline material refining system (98.7% by weight of aniline and 1.3% by weight of water) according to the proportion of 20% by weight, and the rest 80% by weight of material returns to the top of the quenching tower to be used as spray material.
After equilibrium is reached, the bottom temperature of the quenching tower is 104 ℃, and the top temperature of the quenching tower is 96 ℃; the gas phase (the aniline content is 43 wt%, the water content is 43.9 wt%, and the hydrogen content is 13.1 wt%) at the top of the quenching tower enters a two-stage tandem condenser, and is condensed to a liquid phase material oil-water separator at 30 ℃, the separated lower layer is a crude aniline refining system, and the upper layer material is aniline-containing wastewater; and a non-condensable gas and dehydrogenation gas recovery system at the top of the condenser.
The results show that: after the device runs for 30 days, the pressure difference between the hydrogen heat exchanger and the condenser is obviously increased, which indicates that the blocking problem of catalyst particles occurs in the hydrogen heat exchanger and the condenser.
As can be seen from the comparison of the example 1 and the comparative example 1-1, the aniline-containing wastewater obtained by the oil-water separator is used as the supplementary spray liquid, so that the condensation of the reaction balance gas mixture can be achieved by using a small amount (the amount of the supplementary spray liquid is 20 parts by weight relative to 100 parts by weight of the reaction balance gas mixture), and the effects of washing the gas with a liquid phase and capturing catalyst particles are achieved; in comparative example 1-1, the same weight of crude aniline was used as the supplemental spray liquid, the liquefaction recovery rate of the reaction equilibrium mixed gas in the quenching tower was only 11%, and the effect of condensing the reaction equilibrium mixed gas and washing the reaction equilibrium mixed gas could not be achieved.
As is clear from a comparison of example 1 and comparative examples 1 to 2, although a larger amount of crude aniline (135 parts by weight of the supplemental spray liquid to 100 parts by weight of the reaction balance mixture) was used as the supplemental spray liquid, the liquefaction recovery rate of the reaction balance mixture in the quenching tower internal aniline was improved, but the inside of the tube array of the hydrogen heat exchanger was still clogged.
Example 2
According to the flow chart shown in fig. 1, the method provided by the invention is used for treating the aniline-containing gas, and comprises the following specific steps:
feeding reaction balance mixed gas (the temperature is 220 ℃, the aniline content is 66 weight percent, the water content is 25.6 weight percent, the hydrogen content is 8.4 weight percent, and the catalyst particle content is 2600 ppm) directly from the bottom of the quenching tower 2, taking aniline-containing wastewater (the aniline content is 4%, the temperature is 30 ℃, and the consumption of the supplementary spraying liquid is 30 weight parts relative to 100 weight parts of the reaction balance mixed gas) as supplementary spraying liquid, and spraying from the top of the quenching tower;
the material liquid at the bottom of the quenching tower is led out by a circulating pump to obtain a produced material and a circulating material (the produced material accounts for 10 weight percent of the circulating material); the extracted material enters a solid-liquid separator 1 (filter) with the separation precision of 10 mu m, the catalyst particles are separated, the obtained clear liquid (the aniline content is 97.3 weight percent and the water content is 2.7 weight percent) is subjected to an aniline refining unit, and the circulating material returns to a quenching tower 2 to be used as spray liquid.
After equilibrium is reached, the bottom temperature of the quenching tower is 93 ℃ and the top temperature of the quenching tower is 74 ℃; the gas phase (the aniline content is 14.8 wt%, the water content is 73.3 wt%, the hydrogen content is 11.7 wt%, and the nitrogen content is 0.2 wt%) at the top of the quench tower enters a two-stage series-connected condenser 3, a non-condensable gas and dehydrogenation gas recovery system at the top of the condenser 3, a condensate de-oiling water separator 4 performs oil-water separation, a crude aniline de-aniline refining unit is obtained at the lower layer after oil-water separation, the upper layer material is aniline-containing wastewater, part of the wastewater is recycled as a supplementary spray liquid, and the rest is subjected to wastewater extraction treatment.
The results show that: the recovery rate of aniline in the quenching tower was about 80%. The device has no blocking phenomenon in the running process.
As is clear from a comparison between example 2 and example 1, the amount of the supplemental shower liquid in example 2 was higher (the amount of the supplemental shower liquid was 30 parts by weight based on 100 parts by weight of the reaction balance mixed gas), and the liquefaction recovery rate of aniline in the quenching tower was higher for the reaction gas; the device runs stably.
Example 3
According to the flow chart shown in fig. 2, the method provided by the invention is used for treating the aniline-containing gas, and comprises the following specific steps:
The reaction balance mixed gas (the temperature is 220 ℃, the aniline content is 66 wt%, the water content is 25.6 wt%, the hydrogen content is 8.4 wt%, and the catalyst particle content is 2600 ppm) is firstly sent into a hydrogen heat exchanger 6 containing a solid particle injection system for heat exchange; the solid particles (alumina, particle size 2 mm) in the solid particle injection system were added from the top of the solid buffer tank 5 and injected to the top of the hydrogen heat exchanger 6 under the drive of carrier gas (nitrogen). The solid particle injection system was operated intermittently, running every 24 hours.
Feeding low-temperature reaction gas (the temperature is 115 ℃) with solid particles obtained at the outlet of the hydrogen heat exchanger 6 from the bottom of the quenching tower 2, taking aniline-containing wastewater (the aniline content is 4%, the temperature is 30 ℃ and the use amount of the supplementary spray liquid is 20 parts by weight relative to 100 parts by weight of the reaction balance mixed gas) as supplementary spray liquid, and spraying from the top of the tower;
introducing the material liquid at the bottom of the quenching tower into a solid-liquid separator 1 with the separation precision of 20 mu m after being led out by a circulating pump, and removing catalyst particles by solid-liquid separation to obtain clear liquid (the aniline content is 95.5 weight percent and the water content is 4.5 weight percent), wherein the clear liquid is divided into a extracted material and a circulating material (the extracted material accounts for 10 weight percent of the circulating material); the extracted material is sent to an aniline refining unit, and the circulating material returns to the quenching tower 2 to be used as spray liquid.
After equilibrium is reached, the bottom temperature of the quenching tower is 80 ℃ and the top temperature of the quenching tower is 73 ℃; the gas phase (the aniline content is 14.3 wt%, the water content is 71.2 wt%, the hydrogen content is 14.3 wt%, and the nitrogen content is 0.2 wt%) at the top of the quench tower enters a two-stage tandem condenser 3, and is condensed to a non-condensable gas dehydrogenation gas recovery system at the top of 30 ℃, a condensate de-oiling water separator 4 performs oil-water separation, and a crude aniline de-aniline refining unit is obtained at the lower layer, and aniline-containing wastewater is obtained at the upper layer, and is partially recycled to be used as a supplementary spray liquid.
The results show that: the recovery rate of aniline in the quenching tower was 85%. In the running process of the device, the pressure difference change of the hydrogen heat exchanger is not more than 10kPa, which indicates that the hydrogen heat exchanger has no blocking phenomenon.
Comparative examples 2 to 2
The same procedure as in comparative examples 1 to 2 was followed except that the separation accuracy of the solid-liquid separator was 20. Mu.m.
The results show that: after the device runs for 15 days, the pressure difference between the hydrogen heat exchanger and the condenser is obviously increased, which indicates that the blocking problem of catalyst particles occurs in the hydrogen heat exchanger and the condenser.
As can be seen from the comparison of the example 3 and the comparative example 1-1, the aniline-containing wastewater obtained by the oil-water separator is used as the supplementary spray liquid, so that the condensation of the reaction balance gas mixture can be achieved by using a small amount (the amount of the supplementary spray liquid is 20 parts by weight relative to 100 parts by weight of the reaction balance gas mixture), and the effects of washing the gas with a liquid phase and capturing catalyst particles are achieved; in comparative example 1-1, the same weight of crude aniline was used as the supplemental spray liquid, the liquefaction recovery rate of the reaction equilibrium mixed gas in the quenching tower was only 11%, and the effect of condensing the reaction equilibrium mixed gas and washing the reaction equilibrium mixed gas could not be achieved.
As is clear from a comparison of example 3 with comparative example 2-2, comparative example 2-2 can improve the liquefaction recovery rate of aniline in the quenching tower by using a larger amount of crude aniline (135 parts by weight of the supplemental spray liquid relative to 100 parts by weight of the reaction balance mixed gas) as the supplemental spray liquid, but without the solid particle injection system, the catalyst particles are difficult to be thoroughly removed by the solid-liquid separator, the inside of the tube array heat exchanger is still blocked, and the device cannot be stably operated for a long period of time.
As is clear from a comparison of example 3 with example 1, the separation accuracy of the solid-liquid separator of example 3 was increased to 20. Mu.m, but the apparatus was still stably operated for a long period of time due to the solid particle injection system.
Example 4
According to the flow chart shown in fig. 2, the method provided by the invention is used for treating the aniline-containing gas, and comprises the following specific steps:
the reaction equilibrium mixed gas (the temperature is 210 ℃, the aniline content is 66 wt%, the water content is 25.6 wt%, the hydrogen content is 8.4 wt%, and the catalyst particle content is 2600 ppm) is firstly sent into a hydrogen heat exchanger 6 containing a solid particle injection system for heat exchange; the solid particles (silica, particle size 2 mm) in the solid particle spraying system were added from the top of the solid buffer tank 5 and sprayed to the top of the hydrogen heat exchanger 6 under the drive of carrier gas (nitrogen). The solid particle injection system was operated intermittently, running every 30 hours.
Feeding low-temperature reaction gas (with the temperature of 120 ℃) with solid particles obtained at the outlet of the hydrogen heat exchanger 6 from the bottom of the quenching tower 2, taking aniline-containing wastewater (with the aniline content of 3.6% and the temperature of 35 ℃ and taking 10 parts by weight of supplementary spray liquid relative to 100 parts by weight of reaction balance mixed gas) as supplementary spray liquid, and spraying from the top of the tower;
introducing the material liquid at the bottom of the quenching tower into a solid-liquid separator 1 with the separation precision of 20 mu m after being led out by a circulating pump, and removing catalyst particles by solid-liquid separation to obtain clear liquid (the aniline content is 98.7 weight percent and the water content is 1.3 weight percent), wherein the clear liquid is divided into a extracted material and a circulating material (the extracted material accounts for 5.5 weight percent of the circulating material); the extracted material is sent to an aniline refining unit, and the circulating material returns to the quenching tower 2 to be used as spray liquid.
After equilibrium is reached, the bottom temperature of the quenching tower is 106.5 ℃ and the top temperature of the quenching tower is 96.4 ℃; the gas phase (the aniline content is 41.4 wt%, the water content is 47.1 wt%, the hydrogen content is 11.3 wt%, and the nitrogen content is 0.2 wt%) at the top of the quench tower enters a two-stage tandem condenser 3, and is condensed to a non-condensable gas dehydrogenation gas recovery system at the top of 35 ℃, a condensate de-oiling water separator 4 performs oil-water separation, and a crude aniline de-aniline refining unit is obtained at the lower layer, and aniline-containing wastewater is obtained at the upper layer, and part of the aniline-containing wastewater is recycled to be used as a supplementary spray liquid.
The results show that: the recovery rate of aniline in the quenching tower was 53%. In the running process of the device, the pressure difference change of the hydrogen heat exchanger is not more than 10kPa, which indicates that the hydrogen heat exchanger and the condenser have no blocking phenomenon, and the device runs stably.
Example 5
According to the flow chart shown in fig. 2, the method provided by the invention is used for treating the aniline-containing gas, and comprises the following specific steps:
the reaction balance mixed gas (the temperature is 220 ℃, the aniline content is 66 wt%, the water content is 25.6 wt%, the hydrogen content is 8.4 wt%, and the catalyst particle content is 2600 ppm) is firstly sent into a hydrogen heat exchanger 6 containing a solid particle injection system for heat exchange; the solid particles (zirconium silicate, particle size 1.5 mm) in the solid particle spraying system are added from the top of the solid buffer tank 5 and sprayed to the top of the hydrogen heat exchanger 6 under the drive of carrier gas (hydrogen). The solid particle injection system was operated intermittently, running every 24 hours.
Feeding low-temperature reaction gas (130 ℃) with solid particles obtained at the outlet of the hydrogen heat exchanger 6 from the bottom of the quenching tower 2, taking aniline-containing wastewater (the aniline content is 3.6%, the temperature is 40 ℃ and the consumption of the supplementary spraying liquid is about 25 parts by weight relative to 100 parts by weight of the reaction balance mixed gas) as the supplementary spraying liquid, and spraying from the top of the tower;
Introducing the material liquid at the bottom of the quenching tower into a solid-liquid separator 1 with the separation precision of 20 mu m after being led out by a circulating pump, and removing catalyst particles by solid-liquid separation to obtain clear liquid (the aniline content is 93.5 weight percent and the water content is 6.5 weight percent), wherein the clear liquid is divided into a extracted material and a circulating material (the extracted material accounts for 20.5 weight percent of the circulating material); the extracted material is sent to an aniline refining unit, and the circulating material returns to the quenching tower 2 to be used as spray liquid.
After equilibrium is reached, the bottom temperature of the quenching tower is 76 ℃ and the top temperature of the quenching tower is 69 ℃; the gas phase (the aniline content is 10.1 wt%, the water content is 75.5 wt%, and the hydrogen content is 14.4 wt%) at the top of the quench tower enters a condenser 3, a noncondensable gas and dehydrogenation gas recovery system at the top of the condenser 3, a condensate de-oiling water separator 4, and a crude aniline de-aniline refining unit is obtained at the lower layer after oil-water separation, and aniline-containing wastewater is obtained at the upper layer, and part of the wastewater is reused as a supplementary spray liquid.
The results show that: the recovery rate of aniline in the quenching tower was 90%. In the running process of the device, the pressure difference change of the hydrogen heat exchanger is not more than 10kPa, which indicates that the hydrogen heat exchanger and the condenser have no blocking phenomenon.
As is clear from comparison of example 5 with example 3, the amount of the supplemental shower liquid in example 5 is higher (the amount of the supplemental shower liquid is 25 parts by weight based on 100 parts by weight of the reaction balance mixture gas), and the liquefaction recovery rate of aniline in the quenching tower of the reaction gas is higher; the device runs stably.
Example 6
According to the flow chart shown in fig. 3, the method provided by the invention is used for treating the aniline-containing gas, and comprises the following specific steps:
the reaction balance mixed gas (the temperature is 220 ℃, the aniline content is 66 wt%, the water content is 25.6 wt%, the hydrogen content is 8.4 wt%, and the catalyst particle content is 2600 ppm) is firstly sent into a hydrogen heat exchanger 6 containing a solid particle injection system for heat exchange; the solid particles (alumina, particle size 2 mm) in the solid particle injection system were added from the top of the solid buffer tank 5 and injected to the top of the hydrogen heat exchanger 6 under the drive of carrier gas (nitrogen). The hydrogen heat exchanger 6 in the solid particle injection system is provided with a differential pressure sensor, and the carrier gas pipeline and the solid buffer tank 5 pipeline are provided with interlocking pneumatic valves; the differential pressure setting of the hydrogen heat exchanger 6 was 5kPa. When the pressure difference of the hydrogen heat exchanger 6 reaches a set value or reaches a set time, the solid particle injection system automatically operates.
The low-temperature reaction gas (temperature is 115 ℃) with solid particles obtained at the outlet of the hydrogen heat exchanger 6 is fed from the bottom of the quenching tower 2, aniline-containing wastewater (aniline content is 4%, temperature is 30 ℃ C.; the amount of the supplementary spray liquid is 20 parts by weight relative to 100 parts by weight of the reaction balance mixed gas) is taken as the supplementary spray liquid, and the weight ratio of the supplementary spray liquid to the supplementary spray liquid is 1:1, respectively spraying;
Introducing the material liquid at the bottom of the quenching tower into a solid-liquid separator 1 with the separation precision of 20 mu m after being led out by a circulating pump, and removing catalyst particles by solid-liquid separation to obtain clear liquid (the aniline content is 95.6 weight percent and the water content is 4.4 weight percent), wherein the clear liquid is divided into a extracted material and a circulating material (the extracted material accounts for 10 weight percent of the circulating material); the extracted material is sent to an aniline refining unit, and the circulating material returns to the quenching tower 2 to be used as spray liquid.
After equilibrium is reached, the bottom temperature of the quenching tower is 80 ℃ and the top temperature of the quenching tower is 73 ℃; the gas phase (with the aniline content of 14 weight percent, the water content of 71.6 weight percent, the hydrogen content of 14.2 weight percent and the nitrogen content of 0.2 weight percent) at the top of the quenching tower enters a two-stage tandem condenser 3, is condensed to a non-condensable gas dehydrogenation gas recovery system at the top of 30 ℃, is condensed to a condensate de-oiling water separator 4, is subjected to oil-water separation, and is subjected to crude aniline removal refining unit in the lower layer, and the upper layer is partially recycled to be used as a supplementary spray liquid.
The results show that: the recovery rate of aniline in the quenching tower was 88%. In the process of operating the device for 1 month, the pressure difference change of the hydrogen heat exchanger is not more than 5kPa, which indicates that the hydrogen heat exchanger and the condenser have no blocking phenomenon.
As can be seen from the comparison of the example 6 and the comparative example 1-1, the aniline-containing wastewater obtained by the oil-water separator is used as the supplementary spray liquid, so that the condensation of the reaction balance gas mixture can be achieved by using a small amount (the amount of the supplementary spray liquid is 20 parts by weight relative to 100 parts by weight of the reaction balance gas mixture), and the effects of washing the gas with a liquid phase and capturing catalyst particles are achieved; in comparative example 1-1, the same weight of crude aniline was used as the supplemental spray liquid, the liquefaction recovery rate of the reaction equilibrium mixed gas in the quenching tower was only 11%, and the effect of condensing the reaction equilibrium mixed gas and washing the reaction equilibrium mixed gas could not be achieved.
As is clear from a comparison of example 6 with comparative example 2-2, in comparative example 2-2, although a larger amount of crude aniline (135 parts by weight of the supplemental spray liquid to 100 parts by weight of the reaction balance mixture) was used as the supplemental spray liquid, the liquefaction recovery rate of aniline in the quenching tower could be improved, but without the solid particle injection system, the catalyst particles were difficult to be thoroughly removed by the solid-liquid separator, the inside of the tube array heat exchanger was still clogged, and the apparatus could not be stably operated for a long period of time.
As is clear from comparison of example 6 with example 3, the supplemental spray liquid in example 6 was sprayed from both the top and middle of the column, and in the case of the same amount as in example 3 (the supplemental spray liquid was used in an amount of 20 parts by weight relative to 100 parts by weight of the reaction equilibrium mixture), the liquefied recovery rate of the reaction gas in the quenching tower was higher, and the effect was remarkable; and the solid particle injection system automatically operates according to the pressure difference set value, so that the operation stability of the device is further improved, and the energy conservation and consumption reduction are facilitated.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (35)

1. A method of treating an aniline-containing gas, the method comprising the steps of:
(1) In the quenching tower, reversely contacting reaction balance mixed gas containing aniline with supplementary spray liquid to obtain a quenching tower bottom feed liquid and a quenching tower top gas phase, wherein the supplementary spray liquid is an aqueous solution containing aniline, the water content is 92-99.9 wt%, and the supplementary spray liquid is divided into supplementary spray liquid I and supplementary spray liquid II with the weight ratio of 0.1-10, and the supplementary spray liquid I and the supplementary spray liquid II are respectively sprayed at the quenching tower top and the quenching tower middle part;
(2) The material liquid at the bottom of the quenching tower is divided into two parts, namely a produced material and a circulating material, and the circulating material returns to the quenching tower to be used as spray liquid for recycling;
(3) Condensing the gas phase at the top of the quenching tower to obtain noncondensable gas and condensate;
(4) Oil-water separation is carried out on the condensate liquid to obtain crude aniline and aniline-containing wastewater;
wherein, the consumption of the supplementary spray liquid is 10-60 parts by weight relative to 100 parts by weight of the reaction balance mixed gas;
the method further comprises the steps of: the reaction balance mixed gas is sent to a hydrogen heat exchanger containing a solid particle injection system for heat exchange, and low-temperature reaction gas with solid particles obtained at an outlet of the hydrogen heat exchanger is sent to a quenching tower;
the hydrogen heat exchanger with the solid particle injection system comprises a solid buffer tank and a hydrogen heat exchanger, and the bottom of the solid buffer tank is communicated with the top of the hydrogen heat exchanger;
the hydrogen heat exchanger is provided with a differential pressure sensor, and the carrier gas and solid buffer tank pipelines are provided with interlocking pneumatic valves; when the pressure difference of the hydrogen heat exchanger exceeds a set value, a signal is transmitted to the interlocking pneumatic valve through the pressure difference sensor, the valve is opened, solid particles are added into the solid buffer tank and are sprayed to the top of the hydrogen heat exchanger under the drive of carrier gas, and when the pressure difference of the hydrogen heat exchanger is lower than the set value, the valve of the interlocking pneumatic valve is closed in a linkage way.
2. A method of treating an aniline-containing gas, the method comprising the steps of:
(1) The reaction balance mixed gas containing aniline enters a quenching tower from the bottom, and supplementary spray liquid is sprayed from the top of the quenching tower to obtain a quenching tower bottom feed liquid and a quenching tower top gas phase, wherein the supplementary spray liquid is an aqueous solution containing aniline, the water content is 92-99.9 wt%, and the supplementary spray liquid is divided into supplementary spray liquid I and supplementary spray liquid II with the weight ratio of 0.1-10, and the supplementary spray liquid I and the supplementary spray liquid II are sprayed at the top of the quenching tower and the middle part of the quenching tower respectively;
(2) After the material liquid at the bottom of the quenching tower is led out by a circulating pump, part of the material liquid is taken as a produced material, and the rest part of the material liquid is taken as a circulating material and returned to the quenching tower to be taken as a spray liquid for recycling;
(3) The gas phase at the top of the quenching tower enters a condenser to be condensed, and noncondensable gas and condensate are obtained;
(4) Feeding the condensate into an oil-water separator for oil-water separation to obtain crude aniline and aniline-containing wastewater;
wherein, the consumption of the supplementary spray liquid is 10-60 parts by weight relative to 100 parts by weight of the reaction balance mixed gas;
the method further comprises the steps of: the reaction balance mixed gas is sent to a hydrogen heat exchanger containing a solid particle injection system for heat exchange, and low-temperature reaction gas with solid particles obtained at an outlet of the hydrogen heat exchanger is sent to a quenching tower;
The hydrogen heat exchanger with the solid particle injection system comprises a solid buffer tank and a hydrogen heat exchanger, and the bottom of the solid buffer tank is communicated with the top of the hydrogen heat exchanger;
the hydrogen heat exchanger is provided with a differential pressure sensor, and the carrier gas and solid buffer tank pipelines are provided with interlocking pneumatic valves; when the pressure difference of the hydrogen heat exchanger exceeds a set value, a signal is transmitted to the interlocking pneumatic valve through the pressure difference sensor, the valve is opened, solid particles are added into the solid buffer tank and are sprayed to the top of the hydrogen heat exchanger under the drive of carrier gas, and when the pressure difference of the hydrogen heat exchanger is lower than the set value, the valve of the interlocking pneumatic valve is closed in a linkage way.
3. The process according to claim 1 or 2, wherein the reaction equilibrium mixture is derived from a nitrobenzene fluidized bed gas phase hydrogenation reaction;
the reaction balance mixed gas contains aniline, hydrogen and water, and the content of the aniline is 40-80 wt% based on the total amount of the reaction balance mixed gas.
4. A process according to claim 3, wherein,
the reaction balance mixed gas contains aniline, hydrogen and water, and the content of the aniline is 55-75 wt% based on the total amount of the reaction balance mixed gas.
5. A process according to claim 3, wherein,
the temperature of the reaction balance mixture is 180-260 ℃.
6. The process according to claim 5, wherein,
the temperature of the reaction balance mixture is 210-240 ℃.
7. The treatment method according to claim 1 or 2, wherein in the step (1), the supplemental shower is an aqueous solution containing aniline, and the water content is 94 to 97% by weight.
8. A process according to claim 1 or 2, wherein the temperature of the supplemental spray liquid is 10-60 ℃.
9. The process of claim 8, wherein the supplemental spray is at a temperature of 20-50 ℃.
10. A process according to claim 1 or 2, wherein,
the amount of the supplementary spray liquid is 15-40 parts by weight relative to 100 parts by weight of the reaction balance mixed gas.
11. A process according to claim 1 or 2, wherein,
at least part of the supplementary spray liquid in the step (1) is provided by the aniline-containing wastewater in the step (4).
12. The process according to claim 1 or 2, wherein the quench tower bottom temperature is 70-115 ℃ and the tower top temperature is 65-110 ℃.
13. The process according to claim 12, wherein,
The bottom temperature of the quenching tower is 75-110 ℃, and the top temperature of the quenching tower is 69-100 ℃.
14. A process according to claim 1 or 2, wherein,
the quench tower comprises at least two layers of sprayers and at least one layer of foam traps.
15. The process according to claim 14, wherein,
the quenching tower comprises 2-6 layers of sprayers and 2-4 layers of foam traps.
16. A process according to claim 1 or claim 2, wherein in step (2) the mined material is 3-25% by weight of the recycled material.
17. The process of claim 16, wherein in step (2) the mined material is 5-20% by weight of the recycled material.
18. A process according to claim 1 or 2, wherein,
the aniline content in the tower bottom feed liquid of the quenching tower is 90-99.9 wt%.
19. The process according to claim 18, wherein,
the aniline content in the tower bottom feed liquid of the quenching tower is 96-99.9 wt%.
20. The process according to claim 1 or 2, wherein the liquefaction recovery rate of aniline in the reaction-equilibrium mixture in step (1) in the quenching tower is not less than 50%.
21. The process according to claim 20, wherein the liquefaction recovery rate of aniline in the reaction equilibrium mixture in step (1) in the quenching tower is not less than 60%.
22. The process of claim 21, wherein the liquefaction recovery of aniline in the reaction equilibrium mixture of step (1) in the quench tower is 60% -90%.
23. The treatment method according to claim 1 or 2, wherein aniline, hydrogen and water are contained in the gas phase at the top of the quenching tower;
the aniline content in the gas phase at the top of the quenching tower is not more than 40 wt%.
24. The process of claim 23, wherein the aniline content in the quench tower overhead gas phase is no more than 20 wt%.
25. A process according to claim 1 or 2, wherein,
the solid particles are inert solid particles with the particle size of 0.1-5 mm.
26. A process according to claim 1 or 2, wherein,
the carrier gas is selected from at least one of nitrogen, helium, neon, and hydrogen.
27. A process according to claim 1 or 2, wherein,
the temperature of the low-temperature reaction gas is 110-130 ℃.
28. A process according to claim 1 or 2, wherein,
the temperature of the supplementary spray liquid is 30-50 ℃.
29. A process according to claim 1 or 2, wherein,
the amount of the supplementary spray liquid is 10-30 parts by weight relative to 100 parts by weight of the low-temperature reaction gas.
30. The process of claim 29, wherein,
the total amount of the supplementary spray liquid is 5 to 25 parts by weight with respect to 100 parts by weight of the low-temperature reaction gas.
31. A system for treating an aniline-containing gas, the system comprising:
a quench tower, a condenser and an oil-water separator; the tower top outlet of the quenching tower is communicated with the inlet of a condenser, and the liquid phase outlet of the condenser is communicated with the inlet of the oil-water separator;
the bottom and the top of the quenching tower are provided with circulating pipelines so that at least part of the material at the bottom of the quenching tower is circulated to the top of the quenching tower;
the top of the quenching tower is also communicated with a supplementary spray pipeline so as to introduce supplementary spray liquid into the quenching tower;
the system also comprises a solid buffer tank and a hydrogen heat exchanger, wherein an outlet of the solid buffer tank is communicated with an inlet at the top of the hydrogen heat exchanger; the bottom outlet of the hydrogen heat exchanger is communicated with the inlet of the quenching tower; the solid buffer tank is provided with a carrier gas input pipeline and a solid particle input pipeline;
the hydrogen heat exchanger is provided with a differential pressure sensor, the carrier gas input pipeline is provided with an interlocking pneumatic valve, and the differential pressure sensor controls the opening and closing of the interlocking pneumatic valve through the change of differential pressure.
32. The treatment system of claim 31, wherein the quench tower comprises at least two layers of sprayers and at least one layer of mist eliminator.
33. The treatment system of claim 32, wherein the quench tower comprises 2-6 layers of sprayers and 2-4 layers of mist traps.
34. The process system of any one of claims 31 to 33, wherein a circulation pump is further provided on the circulation line, the circulation pump being configured to draw off the quench tower bottoms to produce a produced stream and a recycled stream.
35. The processing system of claim 34, wherein,
the system also comprises a solid-liquid separator, wherein the solid-liquid separator is communicated with the circulating pump so as to carry out solid-liquid separation on the extracted materials.
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