CN115888586A - Device and method for continuously and synchronously hydrolyzing and acylating reaction liquid in grading manner - Google Patents
Device and method for continuously and synchronously hydrolyzing and acylating reaction liquid in grading manner Download PDFInfo
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Abstract
The invention provides a device and a method for continuously and synchronously hydrolyzing acylation reaction liquid in a grading manner, wherein the acylation reaction liquid and a water phase are firstly mixed in a low-temperature cooler and then subjected to primary hydrolysis through a primary micro-channel reactor, a primary hydrolysate is subjected to liquid separation by using a separation tank, an oil phase is subjected to secondary hydrolysis through a secondary micro-channel reactor, a secondary hydrolysate is subjected to liquid separation by using the separation tank, and a secondary oil phase is further subjected to emulsion water separation by using a coalescence separator. The method adopts a graded hydrolysis mode to treat the acylation reaction liquid, aluminum resources can be recovered after primary hydrolysis, and the standard of wastewater discharge can be met through Fenton coupling electrocatalytic oxidation technology after secondary hydrolysis; the liquid separating tank in the device adopts a one-opening one-standby mode to realize stable and continuous synchronous hydrolysis of the acylation reaction liquid; the device of the invention reduces the content of emulsified water in the nitrobenzene oil phase by arranging the liquid separation tank and the coalescence separator.
Description
Technical Field
The invention relates to the technical field of hydrolysis treatment of acylation reaction liquid, in particular to a device and a method for continuously and synchronously hydrolyzing acylation reaction liquid in a grading manner.
Background
2, 6-naphthalene dicarboxylic acid is a key monomer for synthesizing high-performance poly naphthalene ester, polyurethane and liquid crystal polyester resin, 2, 6-naphthalene dicarboxylic acid and ethylene glycol react to prepare polyethylene naphthalate (PEN) which has excellent physical and chemical properties compared with polyethylene terephthalate (PET) widely used at present, and PEN has wide application prospects in the fields of fibers, films, packaging containers, electronic components and the like.
2-methyl-6-acyl naphthalene is an important raw material for preparing 2, 6-naphthalene dicarboxylic acid, 2-methyl naphthalene is wide in source, cheap and easily available (coal tar, ethylene tar and the like are rich in a considerable amount of 2-methyl naphthalene), and 2-methyl-6-acyl naphthalene can be prepared by performing acylation reaction on 2-methyl naphthalene, hydrolyzing and purifying. After the acylation reaction is finished, the reaction is hydrolyzed and quenched, and then the 2-methyl-6-propionyl naphthalene with high purity is obtained by purification methods such as reduced pressure distillation, rectification, recrystallization and the like.
When hydrolysis quenching is carried out, a large amount of water washing agent is needed to acidify the oil phase, strong-acid aluminum-containing wastewater can be generated, the acidylated wastewater has high toxicity, strong acid (pH is less than 1.0) and high COD (8000-15000) and is difficult to treat, meanwhile, a large amount of aluminum resources are contained in the acidylated wastewater, the wastewater is directly treated, discharged, wastes resources and pollutes the environment, but when the water amount of direct hydrolysis is large, the concentration of aluminum ions is diluted, excessive moisture needs to be evaporated when the aluminum resources are recovered, and energy waste can be caused; only adopt stationary method separation nitrobenzene and water, if equipment structure is too simple, when meetting the emulsification degree of nitrobenzene and water higher, the separation effect is not good, for follow-up distillation technology processing increased the difficulty, on the other hand, the nitrobenzene separator separation effect is not good also makes the aquatic of separating out smugglied secretly have nitrobenzene, when this part of water enters into nitrobenzene waste water stripping tower again and handles, can the efficiency of greatly reduced tower, increase the use amount of steam, the energy consumption and the running cost of nitrobenzene waste water treatment have been increased.
In the prior art, there are documents disclosing batch or semi-continuous hydrolysis schemes which are not synchronized with the acylation and hydrolysis reactions. After the acylation reaction liquid is obtained, a certain time interval is provided before the hydrolysis reaction, the acylation reaction liquid cannot be hydrolyzed in time, the acylation reaction liquid is easy to generate the hydrolysis reaction with water in the air when being placed, and HCl gas overflows to pollute the air. Further, when the acylation reaction liquid is brought into contact with water, a large amount of heat is released, and cooling is required. Some documents disclose a method for continuously and synchronously hydrolyzing acylation reaction liquid, and the hydrolyzed liquid can directly enter a liquid separator for synchronous liquid separation. But the scheme does not adopt the step hydrolysis, the oil-water ratio is relatively large, the concentration of aluminum ions in the water phase is low, the subsequent recovery of aluminum resources is inconvenient, the integral water consumption is high, and the content of emulsified water in the obtained oil phase is high.
Disclosure of Invention
The invention aims to provide a device and a method for continuously and synchronously hydrolyzing acylation reaction liquid in a grading way, which can realize stable and continuous synchronous hydrolysis of the acylation reaction liquid by using a spare storage tank, facilitate the recovery of aluminum resources by adopting a grading hydrolysis method and meet the discharge standard of waste water.
The embodiment of the application provides a device for continuously and synchronously grading hydrolysis and acylation reaction liquid, which comprises a raw material oil tank, a first water storage tank, a second water storage tank, a low-temperature cold bath device, a first-stage microchannel reactor, a second-stage microchannel reactor, a first-stage liquid separation tank, a second-stage liquid separation tank, a first-stage water tank, a first-stage oil tank, a second-stage water tank, a second-stage oil tank and a coalescence separator, wherein an outlet of the raw material oil tank and an outlet of the first water storage tank are jointly connected to an inlet of the low-temperature cold bath device through a pipeline, an outlet of the low-temperature cold bath device is connected to an inlet of the first-stage microchannel reactor, hydrolysis outlets of the first-stage microchannel reactor are connected to inlets of a plurality of first-stage liquid separation tanks in parallel, each first-stage liquid separation tank is provided with a water outlet, a water outlet of each first-stage liquid separation tank is connected to an inlet of the first-stage water tank, and an oil outlet of each first-stage liquid separation tank is connected to an inlet of the first-stage oil tank;
the outlet of the first-stage oil tank and the outlet of the second water storage tank are connected to the inlet of the second-stage micro-channel reactor through pipelines, the hydrolysis outlet of the second-stage micro-channel reactor is connected with the inlets of a plurality of second-stage liquid separation tanks in parallel, each second-stage liquid separation tank is provided with a water outlet and an oil outlet, the water outlets of the second-stage liquid separation tanks are connected with the inlet of the second-stage water tank, the oil outlets of the second-stage liquid separation tanks are connected with the inlet of the second-stage oil tank, the outlet of the second-stage oil tank is connected with the inlet of the coalescence separator, and the coalescence separator is provided with a water phase outlet and an oil phase outlet.
In some embodiments, the first-stage liquid separation tank is provided with two first-stage liquid separation tanks and two second-stage liquid separation tanks, a pipeline of a hydrolysis outlet of the first-stage microchannel reactor is connected with an inlet of the first-stage liquid separation tank and an inlet of the second-stage liquid separation tank through a three-way valve, the bottom end of the first-stage liquid separation tank and the bottom end of the second-stage liquid separation tank are both connected with three-way valves, one branch of the three-way valve of the first-stage liquid separation tank is connected with an inlet of the first-stage water tank, the other branch of the three-way valve of the first-stage liquid separation tank is connected with an inlet of the first-stage oil tank, one branch of the three-way valve of the second-stage liquid separation tank is connected with an inlet of the first-stage water tank, and the other branch of the three-way valve of the second-stage liquid separation tank is connected with an inlet of the first-stage oil tank.
In some embodiments, the two second-stage liquid separation tanks are respectively a third liquid separation tank and a fourth liquid separation tank, a pipeline of a hydrolysis outlet of the second-stage microchannel reactor is connected with an inlet of the third liquid separation tank and an inlet of the fourth liquid separation tank through a three-way valve, the bottom end of the third liquid separation tank and the bottom end of the fourth liquid separation tank are both connected with three-way valves, one branch of the three-way valve of the third liquid separation tank is connected with an inlet of the second-stage water tank, the other branch of the three-way valve of the third liquid separation tank is connected with an inlet of the second-stage oil tank, one branch of the three-way valve of the fourth liquid separation tank is connected with an inlet of the second-stage water tank, and the other branch of the three-way valve of the fourth liquid separation tank is connected with an inlet of the second-stage oil tank.
In some embodiments, the first liquid separation tank, the second liquid separation tank, the third liquid separation tank and the fourth liquid separation tank are all connected with an air pump for pumping off waste gas, and an outlet of the air pump is connected with the lye tank.
In another aspect of the present application, a method for continuously and synchronously hydrolyzing and acylating a reaction solution in stages is provided, in which the apparatus for continuously and synchronously hydrolyzing and acylating a reaction solution in stages comprises the following steps:
s1, starting a first water storage tank and a raw material oil tank storing an acylation reaction liquid, wherein the flow rates of a water phase and an oil phase are in a proportion of 1:1, mixing in a low-temperature cold bath device, then entering a first-stage microchannel reactor, ultrasonically oscillating for a period of time, and enabling mixed liquid to flow out of a hydrolysis outlet of the first-stage microchannel reactor and then enter a first liquid separation tank;
s2, when the first liquid separating tank reaches a set liquid level, a hydrolysis outlet is switched to a second liquid separating tank by using a three-way valve, mixed liquid in the first liquid separating tank is heated and stirred at the same time, after oil and water in the first liquid separating tank are stood for layering, a three-way valve at the bottom end of the first liquid separating tank is opened, oil phase at the lower layer in the first liquid separating tank is collected into a first-stage oil tank, a pipeline of the three-way valve at the bottom end of the first liquid separating tank is switched after the oil phase is collected, residual water in the first liquid separating tank is collected into a first-stage water tank, the three-way valve of the first liquid separating tank is closed after the water phase is collected, and the first liquid separating tank is reserved;
s3, when the second liquid separating tank reaches a set liquid level, a hydrolysis outlet is switched to the first liquid separating tank by using a three-way valve, mixed liquid in the second liquid separating tank is heated and stirred at the same time, after oil and water in the second liquid separating tank are stood for layering, a three-way valve at the bottom end of the second liquid separating tank is opened, oil phase at the lower layer in the second liquid separating tank is collected into a first-stage oil tank, a pipeline of the three-way valve at the bottom end of the second liquid separating tank is switched after the oil phase is collected, residual water in the second liquid separating tank is collected into a first-stage water tank, the three-way valve of the second liquid separating tank is closed after the water phase is collected, the second liquid separating tank is reserved, and the steps S2 and S3 are repeated for a plurality of times until the whole raw oil tank is emptied;
s4, when the first-stage oil tank reaches the set liquid level, the first-stage oil tank and the second water storage tank are started, and the flow rates of the water phase and the oil phase are as follows: 1, mixing the mixture in a secondary microchannel reactor, ultrasonically oscillating the mixture for a period of time, and allowing the mixed liquid to flow out of a hydrolysis outlet of the secondary microchannel reactor and then enter a third liquid separation tank;
s5, when the third liquid separating tank reaches a set liquid level, a hydrolysis outlet is switched to a fourth liquid separating tank by using a three-way valve, mixed liquid in the third liquid separating tank is heated and stirred at the same time, after oil and water in the third liquid separating tank are stood for layering, a three-way valve at the bottom end of the third liquid separating tank is opened, oil phase at the lower layer in the third liquid separating tank is collected into a second-stage oil tank, a pipeline of the three-way valve at the bottom end of the third liquid separating tank is switched after the oil phase is collected, residual water in the third liquid separating tank is collected into a second-stage water tank, the three-way valve of the third liquid separating tank is closed after the water phase is collected, and the third liquid separating tank is reserved;
s6, when the fourth liquid separating tank reaches a set liquid level, a hydrolysis outlet is switched to the third liquid separating tank by using a three-way valve, mixed liquid in the fourth liquid separating tank is heated and stirred at the same time, after oil and water in the fourth liquid separating tank are stood for layering, a three-way valve at the bottom end of the fourth liquid separating tank is opened, oil phase at the lower layer in the fourth liquid separating tank is collected into a second-stage oil tank, a pipeline of the three-way valve at the bottom end of the fourth liquid separating tank is switched after the oil phase is collected, residual water in the fourth liquid separating tank is collected into a second-stage water tank, the three-way valve of the fourth liquid separating tank is closed after the water phase is collected, the fourth liquid separating tank is reserved, and the steps S5 and S6 are repeated for a plurality of times until all the inside of the first-stage oil tank is emptied;
and S7, introducing the oil phase into a coalescence separator by the secondary oil tank to further remove emulsified water.
The method has the characteristics of continuity, high efficiency and stability, and the primary hydrolyzed water is rich in aluminum ions and chloride ions, so that the recovery of aluminum resources is facilitated; the difficulty of secondary hydrolysis water treatment is small, the standard discharge of wastewater can be met through a Fenton coupling electro-catalysis process, and the emulsified water content in an oil phase is reduced through liquid-liquid separator treatment and rear-end coalescence-separation device separation.
In some embodiments, the water in the primary water tank is subjected to steam stripping of organic matters, decolorized by activated carbon, and polymerized by an alkalizer to obtain liquid PAC.
In some embodiments, the water in the secondary water tank, the stripped water in the primary water tank and the water separated by the coalescence separator are mixed and then filtered, and then the Fenton oxidation and the electrocatalytic oxidation are carried out to treat organic matters, so that the COD is reduced to be below 500.
In some embodiments, the temperature within the primary and secondary microchannel reactors is from 30 to 35 ℃.
In some embodiments, the heating temperature in the first liquid separation tank, the second liquid separation tank, the third liquid separation tank and the fourth liquid separation tank is 60 ℃, the stirring speed is 200r/min, and the stirring time is 30min.
In some embodiments, the temperature of the low temperature cold bath is 0 ℃.
The beneficial effects of the invention are as follows:
(1) The method adopts a graded hydrolysis mode to treat the acylation reaction liquid, aluminum resources can be recovered after primary hydrolysis, and the standard of wastewater discharge can be met through Fenton coupling electrocatalytic oxidation technology after secondary hydrolysis;
(2) The liquid separating tank in the device adopts a one-opening one-standby mode, so that the stable and continuous synchronous hydrolysis of the acylation reaction liquid is realized;
(3) The device of the invention reduces the content of emulsified water in the nitrobenzene oil phase by arranging the liquid separation tank and the coalescence separator.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent from and readily appreciated by reference to the following description of the embodiments taken in conjunction with the accompanying drawings,
wherein:
FIG. 1 is a schematic view showing the structure of an apparatus for continuously and simultaneously hydrolyzing an acylation reaction liquid in stages in an embodiment of the present application;
reference numerals:
1-raw oil tank; 2-a first water storage tank; 3-a first-stage microchannel reactor; 4-a liquid separating tank; 5-second liquid separating tank; 6-first-level water tank; 7-first-stage oil tank; 8-a second water storage tank; 9-a secondary microchannel reactor; 10-third liquid separation tank; no. 11-four liquid separation tank; 12-a secondary oil tank; 13-a secondary water tank; 14-coalescer separator.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The apparatus and method for continuous simultaneous staged hydrolysis and acylation reaction liquid according to the embodiment of the present invention will be described with reference to the accompanying drawings.
As shown in fig. 1, an embodiment of the present application provides a device for continuously and synchronously hydrolyzing and acylating a reaction solution in stages, which includes a raw oil tank 1, a first water storage tank 2, a second water storage tank 8, a low-temperature cold bath (not identified in the figure), a first-stage microchannel reactor 3, a second-stage microchannel reactor 9, a first-stage liquid separating tank, a second-stage liquid separating tank, a first-stage water tank 6, a first-stage oil tank 7, a second-stage water tank 13, a second-stage oil tank 12 and a coalescer 14, wherein an outlet of the raw oil tank 1 and an outlet of the first water storage tank 2 are commonly connected to an inlet of the low-temperature cold bath through a pipeline, an outlet of the low-temperature cold bath is connected to an inlet of the first-stage microchannel reactor 3, a hydrolysis outlet of the first-stage microchannel reactor 3 is connected to inlets of the plurality of first-stage liquid separating tanks in parallel, the first-stage liquid separating tank is provided with a water outlet and an oil outlet, a water outlet of the first-stage liquid separating tank is connected to an inlet of the first-stage water tank 6, and an oil outlet of the first-stage liquid separating tank is connected to an inlet of the first-stage oil tank 7;
an outlet of the first-stage oil tank 7 and an outlet of the second water storage tank 8 are connected to an inlet of the second-stage micro-channel reactor 9 through pipelines, a hydrolysis outlet of the second-stage micro-channel reactor 9 is connected with inlets of a plurality of second-stage liquid separation tanks in parallel, each second-stage liquid separation tank is provided with a water outlet and an oil outlet, a water outlet of each second-stage liquid separation tank is connected with an inlet of the second-stage water tank 13, an oil outlet of each second-stage liquid separation tank is connected with an inlet of the second-stage oil tank 12, an outlet of the second-stage oil tank 12 is connected with an inlet of the coalescence separator 14, and the coalescence separator 14 is provided with a water phase outlet and an oil phase outlet.
In some specific embodiments, the number of the first-stage liquid separation tanks is two, namely a first-stage liquid separation tank 4 and a second-stage liquid separation tank 5, the pipeline of the hydrolysis outlet of the first-stage microchannel reactor 3 is connected with the inlet of the first-stage liquid separation tank 4 and the inlet of the second-stage liquid separation tank 5 through a three-way valve, the bottom end of the first-stage liquid separation tank 4 and the bottom end of the second-stage liquid separation tank 5 are both connected with the three-way valve, one branch of the three-way valve of the first-stage liquid separation tank 4 is connected with the inlet of the first-stage water tank 6, the other branch of the three-way valve of the first-stage liquid separation tank 4 is connected with the inlet of the first-stage oil tank 7, one branch of the three-way valve of the second-stage liquid separation tank 5 is connected with the inlet of the first-stage oil tank 6, and the other branch of the three-way valve of the second-stage liquid separation tank 5 is connected with the inlet of the first-stage oil tank 7.
In some specific embodiments, two secondary liquid separation tanks are provided, which are a third liquid separation tank 10 and a fourth liquid separation tank 11, the pipeline of the hydrolysis outlet of the secondary microchannel reactor 9 is connected with the inlet of the third liquid separation tank 10 and the inlet of the fourth liquid separation tank 11 through a three-way valve, the bottom end of the third liquid separation tank 10 and the bottom end of the fourth liquid separation tank 11 are both connected with a three-way valve, one branch of the three-way valve of the third liquid separation tank 10 is connected with the inlet of the secondary water tank 13, the other branch of the three-way valve of the third liquid separation tank 10 is connected with the inlet of the secondary oil tank 12, one branch of the three-way valve of the fourth liquid separation tank 11 is connected with the inlet of the secondary water tank 13, and the other branch of the three-way valve of the fourth liquid separation tank 11 is connected with the inlet of the secondary oil tank 12.
In some specific embodiments, the first liquid separating tank 4, the second liquid separating tank 5, the third liquid separating tank 10 and the fourth liquid separating tank 11 are all connected with a micro-air pump for pumping away acidic waste gas in time during hydrolysis, and an outlet of the air pump is connected with an alkaline solution tank for collecting acidic gas to avoid equipment corrosion.
The first liquid separating tank 4, the second liquid separating tank 5, the third liquid separating tank 10 and the fourth liquid separating tank 11 are storage tanks and also play a role in liquid-liquid separation.
In some specific embodiments, the first liquid separation tank 4, the second liquid separation tank 5, the third liquid separation tank 10 and the fourth liquid separation tank 11 are all equipped with a stirring device, a heating device and an air suction port, and the air suction port is connected with an acid gas suction pump.
In some specific embodiments, the pipelines at the outlets of the raw oil tank 1, the primary oil tank 7, and the secondary oil tank 12 are all connected with oil injection pumps for providing power for transporting oil phase, and the pipelines at the outlets of the first water storage tank 2 and the second water storage tank 8 are all connected with water injection pumps for providing power for transporting water phase.
In some specific embodiments, the length of the stirring paddles of the stirring devices in the first liquid separation tank 4, the second liquid separation tank 5, the third liquid separation tank 10 and the fourth liquid separation tank 11 is longer, and the stirring paddles are similar to a scraper structure, so that the sedimentation of the floating oil on the surface is accelerated, and the water-oil separation effect is better. The four liquid separation tanks are pretreated by heating and stirring to accelerate separation and sedimentation.
In some specific embodiments, the outlet pipes of the first separating tank 4, the second separating tank 5, the third separating tank 10 and the fourth separating tank 11 are all connected with a delivery pump for providing power for liquid delivery. Besides the delivery pump, the liquid separation is realized mainly by the gravity liquid level difference in the liquid separation tank, and the equipment has less faults.
The embodiment of another aspect of the present application provides a method for continuously and synchronously hydrolyzing acylation reaction liquid in stages, which utilizes the above apparatus for continuously and synchronously hydrolyzing acylation reaction liquid in stages, and comprises the following steps:
s1, deionized water (namely a water phase) for hydrolyzing an acylation reaction liquid is stored in the first water storage tank 2, the acylation reaction liquid to be hydrolyzed is stored in the raw material oil tank 1, and the acylation reaction liquid is an oil phase. Starting a water injection pump of the first water storage tank 2, starting the oil injection pump of the raw oil tank 1 when the deionized water flows out from the outlet of the first-level microchannel reactor 3, and controlling the flow velocity to enable the flow of the water phase and the oil phase to be 1:1, mixing an oil phase and a water phase in a low-temperature cold bath device, and then feeding the mixture into a first-stage micro-channel reactor 3, wherein the temperature of the low-temperature cold bath device is 0 ℃, the temperature of the micro-channel reactor is controlled to be 30-35 ℃, ultrasonic oscillation is carried out simultaneously, turbid light brown liquid flows out from a hydrolysis outlet of the first-stage micro-channel reactor 3 after a period of time, and then enters a first liquid separation tank 4, and a micro-suction pump is started;
and S2, when the first liquid separation tank 4 reaches a set liquid level, switching the hydrolysis outlet to a second liquid separation tank 5 by using a three-way valve, and simultaneously heating and stirring the mixed liquid in the first liquid separation tank 4 for 30min at a stirring speed of 200r/min at a heating temperature of 60 ℃. After standing and layering the oil water in the first separating tank 4, opening a three-way valve at the bottom end of the first separating tank 4, firstly collecting the oil phase positioned at the lower layer in the first separating tank 4 into a first-stage oil tank 7, switching a pipeline of the three-way valve at the bottom end of the first separating tank 4 after the oil phase is collected, collecting the residual water phase in the first separating tank 4 into a first-stage water tank 6, closing the three-way valve of the first separating tank 4 after the water phase is collected, and reserving the first separating tank 4;
and S3, the function of the second liquid separating tank 5 is consistent with that of the first liquid separating tank 4, and the two liquid separating tanks are opened and prepared for ensuring that the first-stage hydrolysis is continuously carried out. When the second liquid separation tank 5 reaches a set liquid level, a hydrolysis outlet is switched to the first liquid separation tank 4 by using a three-way valve, the mixed liquid in the second liquid separation tank 5 is heated and stirred for 30min at the same time, the stirring speed is 200r/min, the heating temperature is 60 ℃, after the oil water in the second liquid separation tank 5 is kept standing and layered, the three-way valve at the bottom end of the second liquid separation tank 5 is opened, the oil phase at the lower layer in the second liquid separation tank 5 is collected into the first-stage oil tank 7, the pipeline of the three-way valve at the bottom end of the second liquid separation tank 5 is switched after the oil phase is collected, the residual water phase in the second liquid separation tank 5 is collected into the first-stage water tank 6, the three-way valve of the second liquid separation tank 5 is closed after the water phase is collected, the second liquid separation tank 5 is reserved, and the steps S2 and S3 are repeated for a plurality of times until the whole raw material oil tank 1 is emptied;
s4, when the primary oil tank 7 reaches a set liquid level, starting a water injection pump of the second water storage tank 8, when deionized water flows out of an outlet of the secondary microchannel reactor 9, starting an oil injection pump of the primary oil tank 7, and controlling the flow rate to enable the flow rates of the water phase and the oil phase to be 2:1, mixing the water phase and the oil phase in a secondary microchannel reactor 9, controlling the mixing temperature to be 30-35 ℃, simultaneously starting ultrasonic oscillation, after a period of time, enabling turbid light brown liquid to flow out from a hydrolysis outlet of the secondary microchannel reactor 9, entering a third separating tank 10, and starting a micro-suction pump;
s5, when the third liquid separation tank 10 reaches a set liquid level, a hydrolysis outlet is switched to the fourth liquid separation tank 11 through a three-way valve, mixed liquid in the third liquid separation tank 10 is heated and stirred for 30min at the stirring speed of 200r/min at the heating temperature of 60 ℃, after oil water in the third liquid separation tank 10 is kept standing and layered, the three-way valve at the bottom end of the third liquid separation tank 10 is opened, oil phase at the lower layer in the third liquid separation tank 10 is collected into the second-stage oil tank 12, a pipeline of the three-way valve at the bottom end of the third liquid separation tank 10 is switched after the oil phase is collected, residual water phase in the third liquid separation tank 10 is collected into the second-stage water tank 13, the three-way valve of the third liquid separation tank 10 is closed after the water phase is collected, and the third liquid separation tank 10 is reserved;
s6, the third liquid separating tank 10 and the fourth liquid separating tank 11 are consistent in function, and the two liquid separating tanks are opened for one time and are ready for continuous secondary hydrolysis. When the fourth liquid separating tank 11 reaches a set liquid level, a hydrolysis outlet is switched to the third liquid separating tank 10 by using a three-way valve, mixed liquid in the fourth liquid separating tank 11 is heated and stirred for 30min at the same time, the stirring speed is 200r/min, the heating temperature is 60 ℃, after oil water in the fourth liquid separating tank 11 is kept standing and layered, the three-way valve at the bottom end of the fourth liquid separating tank 11 is opened, oil phase at the lower layer in the fourth liquid separating tank 11 is collected into the second-stage water tank 12, a pipeline of the three-way valve at the bottom end of the fourth liquid separating tank 11 is switched after the oil phase is collected, residual water phase in the fourth liquid separating tank 11 is collected into the second-stage water tank 13, the three-way valve of the fourth liquid separating tank 11 is closed after the water phase is collected, the fourth liquid separating tank 11 is reserved, and the steps S5 and S6 are repeated for a plurality of times until all the inside the first-stage oil tank 7 is emptied;
and S7, the secondary oil tank 12 leads the oil phase into a coalescence separator 14 to further remove the emulsified water. The emulsion water in nitrobenzene is further separated by a coalescer 14 for subsequent distillation.
In some embodiments, the water in the primary water tank 6 is subjected to steam stripping of organic substances, decolorized with activated carbon, and polymerized with an alkalizing agent to obtain liquid PAC (polyaluminum chloride).
In some embodiments, the water in the secondary water tank 13, the stripped water in the primary water tank 6, and the water separated by the coalescer 14 are mixed and then filtered, and then subjected to fenton oxidation and electrocatalytic oxidation to treat organic matters, so as to reduce the COD to below 500, thereby reaching the discharge standard of a park pipe network.
The method adopts synchronous hydrolysis reaction, avoids long-term storage of acylation reaction liquid, and reduces the overflow and pollution of HCl gas.
According to the method, the acylation reaction is quenched in a graded hydrolysis mode, the concentration of aluminum ions in the wastewater after primary hydrolysis is high, organic matters are treated through steam stripping, aluminum resources are recovered, the method can be used for preparing liquid PAC, and the difficulty in treating secondary water is reduced. Meanwhile, the whole water consumption is less than that of direct hydrolysis, and the used liquid separation storage tank adopts a liquid-liquid separator and is provided with stirring and heating functions and an air extraction opening, so that the oil and water can be quickly separated. In addition, the second-stage oil phase is treated by the coalescence separator 14, so that emulsified water carried in nitrobenzene can be further removed, and the subsequent distillation of the oil phase is facilitated.
The present application is further illustrated by the following specific examples.
Example 1
A method for continuously and synchronously hydrolyzing acylation reaction liquid in stages is disclosed, as shown in figure 1, an apparatus for continuously and synchronously hydrolyzing acylation reaction liquid in stages comprises the following steps:
s1, deionized water (namely a water phase) for hydrolyzing an acylation reaction liquid is stored in the first water storage tank 2, the acylation reaction liquid to be hydrolyzed is stored in the raw material oil tank 1, and the acylation reaction liquid is an oil phase. The water injection pump of the first water storage tank 2 is started, when the deionized water flows out from the outlet of the first-level micro-channel reactor 3, the oil injection pump of the raw oil tank 1 is started, the flow rate is controlled, and the flow of the water phase and the oil phase is controlled according to the ratio of 1:1, mixing an oil phase and a water phase in a low-temperature cold bath device, then entering a first-stage micro-channel reactor 3, wherein the temperature of the low-temperature cold bath device is 0 ℃, the temperature of the micro-channel reactor is controlled to be 35 ℃, simultaneously performing ultrasonic oscillation, after a period of time, enabling turbid light brown liquid to flow out from a hydrolysis outlet of the first-stage micro-channel reactor 3, entering a first liquid separating tank 4, and starting a micro-suction pump;
s2, when the first liquid separation tank 4 reaches a set liquid level, switching the hydrolysis outlet to a second liquid separation tank 5 by using a three-way valve, simultaneously heating and stirring the mixed liquid in the first liquid separation tank 4 for 30min, and then standing for 50min, wherein the stirring speed is 200r/min, and the heating temperature is 60 ℃. Standing and then standing and layering the oil and water in the first separating tank 4, opening a three-way valve at the bottom end of the first separating tank 4, firstly collecting the oil phase positioned at the lower layer in the first separating tank 4 into a first-stage oil tank 7, switching a pipeline of the three-way valve at the bottom end of the first separating tank 4 after the oil phase is collected, collecting the residual water phase in the first separating tank 4 into a first-stage water tank 6, closing the three-way valve of the first separating tank 4 after the water phase is collected, and reserving the first separating tank 4;
and S3, the function of the second liquid separating tank 5 is consistent with that of the first liquid separating tank 4, and the two liquid separating tanks are opened and prepared for ensuring that the first-stage hydrolysis is continuously carried out. When the second liquid separation tank 5 reaches a set liquid level, a hydrolysis outlet is switched to the first liquid separation tank 4 by using a three-way valve, mixed liquid in the second liquid separation tank 5 is heated and stirred for 30min and then is kept stand for 50min, wherein the stirring speed is 200r/min, the heating temperature is 60 ℃, oil and water in the second liquid separation tank 5 are kept stand for layering after the standing, a three-way valve at the bottom end of the second liquid separation tank 5 is opened, the oil phase at the lower layer in the second liquid separation tank 5 is collected into a first-stage oil tank 7, a pipeline of the three-way valve at the bottom end of the second liquid separation tank 5 is switched after the oil phase is collected, the residual water phase in the second liquid separation tank 5 is collected into a first-stage water tank 6, the three-way valve of the second liquid separation tank 5 is closed after the water phase is collected, the second liquid separation tank 5 is reserved, and the steps S2 and S3 are repeated for a plurality of times until all the raw material oil tank 1 is emptied;
s4, when the primary oil tank 7 reaches a set liquid level, starting a water injection pump of the second water storage tank 8, when deionized water flows out of an outlet of the secondary microchannel reactor 9, starting an oil injection pump of the primary oil tank 7, and controlling the flow rate to enable the flow rates of the water phase and the oil phase to be 2:1, mixing the water phase and the oil phase in a secondary microchannel reactor 9, controlling the mixing temperature to be 35 ℃, simultaneously starting ultrasonic oscillation, after a period of time, enabling turbid light brown liquid to flow out from a hydrolysis outlet of the secondary microchannel reactor 9, entering a third separating tank 10, and starting a micro air pump;
s5, when the third liquid separation tank 10 reaches a set liquid level, switching a hydrolysis outlet to a fourth liquid separation tank 11 by using a three-way valve, simultaneously heating and stirring the mixed liquid in the third liquid separation tank 10 for 30min, then standing for 30min, wherein the stirring speed is 200r/min, the heating temperature is 60 ℃, standing, then standing for layering oil and water in the third liquid separation tank 10, opening a three-way valve at the bottom end of the third liquid separation tank 10, firstly collecting the oil phase positioned at the lower layer in the third liquid separation tank 10 into a second-stage oil tank 12, switching a pipeline of the three-way valve at the bottom end of the third liquid separation tank 10 after the oil phase is collected, collecting the residual water phase in the third liquid separation tank 10 into a second-stage water tank 13, closing the three-way valve of the third liquid separation tank 10 after the water phase is collected, and reserving the third liquid separation tank 10;
s6, the third liquid separating tank 10 and the fourth liquid separating tank 11 are consistent in function, and the two liquid separating tanks are opened for one time and are ready for continuous secondary hydrolysis. When the fourth separating tank 11 reaches a set liquid level, a hydrolysis outlet is switched to the third separating tank 10 by using a three-way valve, mixed liquid in the fourth separating tank 11 is heated and stirred for 30min and then is kept stand for 30min, wherein the stirring speed is 200r/min, the heating temperature is 60 ℃, oil and water in the fourth separating tank 11 are kept stand for layering after the standing, a three-way valve at the bottom end of the fourth separating tank 11 is opened, the oil phase at the lower layer in the fourth separating tank 11 is collected into the second-stage oil tank 12, a pipeline of the three-way valve at the bottom end of the fourth separating tank 11 is switched after the oil phase is collected, residual water phase in the fourth separating tank 11 is collected into the second-stage water tank 13, the three-way valve of the fourth separating tank 11 is closed after the water phase is collected, the fourth separating tank 11 is reserved, and the steps S5 and S6 are repeated for a plurality of times until all the first-stage oil tank 7 is emptied;
and S7, introducing the oil phase into a coalescence separator 14 by a secondary oil tank 12 to further remove emulsified water to obtain a final oil phase, wherein the water content of the final oil phase is 2500ppm, the concentration of aluminum ions in the primary water is 14%, and the pH value of the oil phase is 6-7.
Comparative example 1
The difference from example 1 is that: the oil phase was further separated without passing through the rear coalescer 14 to obtain a final oil phase with a water content of 2%, a primary wastewater aluminum ion concentration of 14%, and an oil phase pH of 5-6.
Comparative example 2
The difference from example 1 is that: only one hydrolysis was used, the flow rates of the aqueous and oil phases were as follows 3:1, and the oil phase is treated by a liquid-liquid separator and then is not subjected to further oil phase separation by a coalescence separator 14, so that the final water content of the oil phase is 4%, the concentration of aluminum ions in the wastewater is 5%, and the pH of the oil phase is 4-5.
Conclusion analysis: the difference between comparative example 1 and example 1 is that the oil phase is not further separated by the backend coalescer 14, resulting in an increase in the water content of the final oil phase, which on the one hand leads to an increase in the subsequent distillation load, and on the other hand contains water, which may entrain aluminium ions, and acidic species in the water corrode the backend equipment.
The difference between comparative example 2 and example 1 is that only one hydrolysis is used and the oil phase is not further separated by the back-end coalescer 14, resulting in an increase in the water content of the final oil phase, which on the one hand leads to an increase in the subsequent distillation load, and on the other hand contains water, which may entrain aluminium ions, and acidic species in the water corrode the back-end equipment. And the concentration of the aluminum ions in the separated water phase is low, so that the subsequent recovery of aluminum resources is inconvenient.
Although the final oil phase of example 1 contained a trace amount of water, it was within the normal range, and the subsequent distillation load was not increased, and the acidic substances in the water did not corrode the rear-end equipment.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise.
In the present invention, unless otherwise explicitly stated or limited, the terms "mounted," "connected," "fixed," and the like are to be construed broadly, e.g., as being permanently connected, detachably connected, or integral; may be mechanically coupled, may be electrically coupled or may be in communication with each other; they may be directly connected or indirectly connected through intervening media, or they may be interconnected within two elements or in a relationship where two elements interact with each other unless otherwise specifically limited. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A device for continuously and synchronously grading hydrolysis and acylation reaction liquid is characterized by comprising a raw material oil tank, a first water storage tank, a second water storage tank, a low-temperature cold bath device, a primary microchannel reactor, a secondary microchannel reactor, a primary grade liquid separation tank, a secondary grade liquid separation tank, a primary water tank, a primary oil tank, a secondary water tank, a secondary oil tank and a coalescence separator, wherein an outlet of the raw material oil tank and an outlet of the first water storage tank are jointly connected to an inlet of the low-temperature cold bath device through a pipeline;
the outlet of the first-stage oil tank and the outlet of the second water storage tank are connected to the inlet of the second-stage micro-channel reactor through pipelines, the hydrolysis outlet of the second-stage micro-channel reactor is connected with the inlets of a plurality of second-stage liquid separation tanks in parallel, each second-stage liquid separation tank is provided with a water outlet and an oil outlet, the water outlets of the second-stage liquid separation tanks are connected with the inlet of the second-stage water tank, the oil outlets of the second-stage liquid separation tanks are connected with the inlet of the second-stage oil tank, the outlet of the second-stage oil tank is connected with the inlet of the coalescence separator, and the coalescence separator is provided with a water phase outlet and an oil phase outlet.
2. The device for continuously and synchronously hydrolyzing and acylating the reaction liquid in a grading manner according to claim 1, wherein the first-stage liquid separating tank is provided with two first-stage liquid separating tanks and two second-stage liquid separating tanks, the pipeline of the hydrolysis outlet of the first-stage microchannel reactor is connected with the inlet of the first-stage liquid separating tank and the inlet of the second-stage liquid separating tank through three-way valves, the bottom end of the first-stage liquid separating tank and the bottom end of the second-stage liquid separating tank are both connected with three-way valves, one branch of the three-way valve of the first-stage liquid separating tank is connected with the inlet of the first-stage water tank, the other branch of the three-way valve of the first-stage liquid separating tank is connected with the inlet of the first-stage oil tank, one branch of the three-way valve of the second-stage liquid separating tank is connected with the inlet of the first-stage water tank, and the other branch of the three-way valve of the second-stage liquid separating tank is connected with the inlet of the first-stage oil tank.
3. The device for continuously and synchronously hydrolyzing and acylating the reaction liquid in a graded manner according to claim 2, wherein the two grade separation tanks are respectively a third grade separation tank and a fourth grade separation tank, a pipeline of a hydrolysis outlet of the second-grade microchannel reactor is connected with an inlet of the third grade separation tank and an inlet of the fourth grade separation tank through a three-way valve, the bottom end of the third grade separation tank and the bottom end of the fourth grade separation tank are both connected with a three-way valve, one branch of the three-way valve of the third grade separation tank is connected with an inlet of the second-grade water tank, the other branch of the three-way valve of the third grade separation tank is connected with an inlet of the second-grade oil tank, one branch of the three-way valve of the fourth grade separation tank is connected with an inlet of the second-grade water tank, and the other branch of the three-way valve of the fourth grade separation tank is connected with an inlet of the second-grade oil tank.
4. The apparatus for continuous and synchronous fractional hydrolysis-acylation reaction solution according to claim 3, wherein the first liquid separation tank, the second liquid separation tank, the third liquid separation tank and the fourth liquid separation tank are connected with a suction pump for pumping off waste gas, and an outlet of the suction pump is connected with an alkali liquor tank.
5. A method for continuously and synchronously hydrolyzing an acylation reaction liquid in stages, which is characterized in that the device for continuously and synchronously hydrolyzing the acylation reaction liquid in stages as claimed in any one of claims 1 to 4 is used, and comprises the following steps:
s1, starting a first water storage tank and a raw material oil tank storing an acylation reaction liquid, wherein the flow rates of a water phase and an oil phase are in a proportion of 1:1, mixing in a low-temperature cold bath device, then entering a first-stage microchannel reactor, ultrasonically oscillating for a period of time, and enabling mixed liquid to flow out of a hydrolysis outlet of the first-stage microchannel reactor and then enter a first liquid separation tank;
s2, when the first liquid separating tank reaches a set liquid level, a hydrolysis outlet is switched to a second liquid separating tank by using a three-way valve, mixed liquid in the first liquid separating tank is heated and stirred at the same time, after oil and water in the first liquid separating tank are stood for layering, a three-way valve at the bottom end of the first liquid separating tank is opened, oil phase at the lower layer in the first liquid separating tank is collected into a first-stage oil tank, a pipeline of the three-way valve at the bottom end of the first liquid separating tank is switched after the oil phase is collected, residual water in the first liquid separating tank is collected into a first-stage water tank, the three-way valve of the first liquid separating tank is closed after the water phase is collected, and the first liquid separating tank is reserved;
s3, when the second liquid separating tank reaches a set liquid level, a hydrolysis outlet is switched to the first liquid separating tank by using a three-way valve, mixed liquid in the second liquid separating tank is heated and stirred at the same time, after oil and water in the second liquid separating tank are stood for layering, a three-way valve at the bottom end of the second liquid separating tank is opened, oil phase at the lower layer in the second liquid separating tank is collected into a first-stage oil tank, a pipeline of the three-way valve at the bottom end of the second liquid separating tank is switched after the oil phase is collected, residual water in the second liquid separating tank is collected into a first-stage water tank, the three-way valve of the second liquid separating tank is closed after the water phase is collected, the second liquid separating tank is reserved, and the steps S2 and S3 are repeated for a plurality of times until the whole raw oil tank is emptied;
s4, when the first-stage oil tank reaches the set liquid level, the first-stage oil tank and the second water storage tank are started, and the flow rates of the water phase and the oil phase are as follows: 1, mixing the mixture in a secondary microchannel reactor, ultrasonically oscillating the mixture for a period of time, and allowing the mixed liquid to flow out of a hydrolysis outlet of the secondary microchannel reactor and then enter a third liquid separation tank;
s5, when the third liquid separating tank reaches a set liquid level, a hydrolysis outlet is switched to a fourth liquid separating tank by using a three-way valve, mixed liquid in the third liquid separating tank is heated and stirred at the same time, after oil and water in the third liquid separating tank are stood for layering, a three-way valve at the bottom end of the third liquid separating tank is opened, oil phase at the lower layer in the third liquid separating tank is collected into a second-stage oil tank, a pipeline of the three-way valve at the bottom end of the third liquid separating tank is switched after the oil phase is collected, residual water in the third liquid separating tank is collected into a second-stage water tank, the three-way valve of the third liquid separating tank is closed after the water phase is collected, and the third liquid separating tank is reserved;
s6, when the fourth liquid separating tank reaches a set liquid level, a hydrolysis outlet is switched to the third liquid separating tank by using a three-way valve, mixed liquid in the fourth liquid separating tank is heated and stirred at the same time, after oil and water in the fourth liquid separating tank are stood for layering, a three-way valve at the bottom end of the fourth liquid separating tank is opened, oil phase at the lower layer in the fourth liquid separating tank is collected into a second-stage oil tank, a pipeline of the three-way valve at the bottom end of the fourth liquid separating tank is switched after the oil phase is collected, residual water in the fourth liquid separating tank is collected into a second-stage water tank, the three-way valve of the fourth liquid separating tank is closed after the water phase is collected, the fourth liquid separating tank is reserved, and the steps S5 and S6 are repeated for a plurality of times until all the inside of the first-stage oil tank is emptied;
and S7, introducing the oil phase into a coalescence separator by the secondary oil tank to further remove emulsified water.
6. The method for continuous and synchronous fractional hydrolysis-acylation reaction liquid according to claim 5, wherein the water in the primary water tank is subjected to steam stripping of organic substances by using steam, decolorized by using activated carbon, and polymerized by using an alkalizer to obtain liquid PAC.
7. The method of claim 5, wherein the water in the secondary tank, the water stripped from the primary tank, and the water separated by the coalescer are mixed and filtered, and then subjected to Fenton oxidation and electrocatalytic oxidation to treat the organic substances, thereby reducing the COD to 500 or less.
8. The method for continuous and synchronous hydrolysis-acylation reaction liquid according to claim 5, wherein the temperature in the first-stage microchannel reactor and the second-stage microchannel reactor is 30-35 ℃.
9. The method for continuous and synchronous hydrolysis and acylation reaction liquid in stages as claimed in claim 5, wherein the heating temperature in the first liquid separation tank, the second liquid separation tank, the third liquid separation tank and the fourth liquid separation tank is 60 ℃, the stirring speed is 200r/min, and the stirring time is 30min.
10. The method for continuous and simultaneous hydrolysis and fractional acylation reaction liquid according to claim 5, wherein the temperature of the low-temperature cold bath is 0 ℃.
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| CN115594357A (en) * | 2022-11-08 | 2023-01-13 | 煤炭科学技术研究院有限公司（Cn） | Acylation wastewater grading treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115594357A (en) * | 2022-11-08 | 2023-01-13 | 煤炭科学技术研究院有限公司（Cn） | Acylation wastewater grading treatment method |
| CN115594357B (en) * | 2022-11-08 | 2024-04-19 | 煤炭科学技术研究院有限公司 | Fractional treatment method for acylated wastewater |
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