CN107055742B - Desalination method and system for supercritical water oxidation of organic wastewater - Google Patents
Desalination method and system for supercritical water oxidation of organic wastewater Download PDFInfo
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Abstract
The invention belongs to the field of organic wastewater treatment, relates to a method for solving the problem of salt deposition and blockage of a reactor in a supercritical water oxidation process by utilizing a liquid-liquid layered extraction method, provides a technology and a process for solving the salt deposition and blockage at the bottom of the reactor, a technology and a process for recycling salt, and a technology and a process for removing deposited salt on the side wall of the reactor, organically couples the two processes together, and discloses a technology and a process for solving the salt deposition problem in the supercritical water oxidation process. The process integrates resource utilization and energy recovery, and effectively solves the problem of reactor salt deposition and blockage in the supercritical water oxidation process.
Description
Technical Field
The invention belongs to the field of organic wastewater, and particularly relates to a method and a treatment system for salt deposition generated by organic wastewater based on supercritical water oxidation treatment.
Technical Field
Supercritical Water (SCW) is Water having a particular state of properties at a temperature and pressure above its critical point (T374 ℃, P22 MPa). The supercritical water has high diffusivity and low viscosity, can be mutually dissolved with organic matters and oxygen according to any proportion, realizes reaction under homogeneous phase condition in the supercritical water oxidation process, and greatly reduces resistance of mass transfer and heat transfer, thereby realizing complete oxidation of the organic matters in extremely short time.
The supercritical water oxidation technology is applied to the field of wastewater treatment, has a very wide prospect, but still faces two industrialization problems at present, one is salt deposition and blockage, and the other is equipment corrosion. Aiming at the problem of salt deposition blockage, because of the extremely low dielectric constant of supercritical water, salts are extremely low in solubility in the supercritical water, are easy to precipitate and deposit on the bottom and the side wall of a reactor, and the salts deposited on the reactor can block equipment and pipelines on the one hand, and on the other hand can seriously influence the heat transfer of the equipment, so that the heat transfer efficiency is reduced, and even the normal use of the equipment is influenced. In order to solve the problem of salt deposition blockage, extensive research is carried out at home and abroad, and different technical solutions are proposed, including reactor design, mechanical brushes, high flow rate, additives, extreme pressure operation and the like, although the effects of slowing down the deposition blockage to a certain extent are achieved, the problem is not fundamentally solved, and a good effect is achieved. Taking a vapor wall reactor as an example, although the problem of salt deposition in the reactor can be greatly alleviated, some problems such as poor mechanical properties of the porous tube, local salt deposition in the reactor and the like still exist and need to be solved.
Effectively solves the problem of salt deposition and blockage in the reactor and becomes a key ring in the industrial application of supercritical water oxidation.
Disclosure of Invention
In order to solve the technical problem that salt is easy to precipitate and block a reactor in the supercritical water oxidation treatment method of organic wastewater, particularly high-salinity organic wastewater, the invention provides a desalting method for supercritical water oxidation of organic wastewater, which aims to effectively treat the precipitated salt deposited on the supercritical water reactor.
The invention also aims to provide a desalination system for supercritical water oxidation of organic wastewater, aiming at realizing efficient removal of salt through the system.
A desalting method for supercritical water oxidation of organic wastewater comprises the steps of adding ionic liquid into a reactor for supercritical water oxidation of organic wastewater, and enriching salt in a supercritical water oxidation treatment process into an ionic liquid phase.
The ionic liquid is originally adopted by the inventor for dissolving the salt in the supercritical water oxidation process, so that the salt in the reactor is enriched in the ionic liquid; and then the ionic liquid enriched with salt is transferred out of the reactor to realize the removal of the salt.
Under the supercritical state of water, ionic liquid has larger difference with the material properties in the supercritical water oxidation process, is not dissolved with the materials in the supercritical water oxidation process, has larger density than the materials in the supercritical water oxidation process, and realizes the layering of two-phase liquid and liquid. In addition, the ionic liquid also has the characteristics of strong salt dissolving capacity and no oxidation by an oxidant. Salt substances insoluble in the supercritical water oxidation system enter the lower ionic liquid phase under the action of gravity to realize redissolution, so that the deposition and blockage of salt precipitated in the supercritical water oxidation process at the bottom of the reactor are effectively avoided.
In the invention, the ionic liquid is preferably added before supercritical water oxidation treatment, so that salt in the reaction process is synchronously enriched into the ionic liquid in the supercritical water oxidation reaction process, and the ionic liquid enriched with salt is timely transferred out, thereby achieving online and synchronous removal of salt precipitate in the supercritical water oxidation process of the organic wastewater.
The ionic liquid of the invention can be the ionic liquid which is well known in the prior art; for example, imidazole-based ionic liquids.
Preferably, the ionic liquid is [ emim]BF4、[C4min]FeBr4、[Bmim]Br、[Bmim]BF6、[Bmim]FeCl4At least one of (1).
The preferred ionic liquid has low vapor pressure, wide liquid path and strong dissolving capacity. And in a supercritical water state, the composite material has larger property difference with supercritical water. Is insoluble in supercritical water, has higher density than supercritical water, and has good solubility to salt substances. The preferred ionic liquids of the present invention are effective in removing salt deposits from supercritical water oxidation reaction systems and reactors.
The organic wastewater is preferably high-salt organic wastewater.
The invention also discloses a desalting system for supercritical water oxidation of organic wastewater, which comprises a reactor for supercritical water oxidation, a liquid-solid separator, a heat exchanger and a mixer;
the mixer is provided with a wastewater inlet, an oxygen inlet and a feed liquid outlet, and the feed liquid outlet is connected with the material inlet of the reactor;
the reactor is also provided with a reaction liquid outlet, an ionic liquid inlet and an ionic liquid outlet; wherein, the ionic liquid outlet is connected with the feed liquid inlet of the liquid-solid separator;
the liquid-solid separator is also provided with a salt outlet and an ionic liquid recycling outlet; an ionic liquid recycling outlet is connected with an inlet of a shell pass of the heat exchanger, and a shell pass outlet of the heat exchanger is connected with an ionic liquid inlet of the reactor;
the tube side inlet of the heat exchanger is connected with the reaction liquid outlet of the reactor.
In the system, the ionic liquid rich in salt and positioned at the lower part of the reactor is transferred into a liquid-solid separator, so that the salt in a solution system is separated out; the separated mother liquor (ionic liquid) is recycled to the reactor after heat exchange by the heat exchanger. The system can effectively prevent salt substances dissolved in the ionic liquid at the lower layer from being saturated and separated out in the long-period operation process of the reactor; the online, synchronous and continuous removal of salt in the supercritical water oxidation treatment process is realized; in addition, the ionic liquid can be recycled.
In the system, an ionic liquid phase at the lower layer of the reactor is transferred into a liquid-solid separator, a half pipe is wound on the outer wall of the liquid-solid separator, cooling water is introduced into the half pipe for cooling and crystallizing the ionic liquid phase substances, the separated salt is subjected to solid-liquid separation after standing, the deposited salt is output from the lower part of the liquid-solid separator and enters the drying and recycling process of downstream salt, and the ionic liquid at the upper layer is subjected to heat exchange with the reaction liquid flowing out of the upper layer in the reactor and then returns to the reactor, so that the aim of circularly desalting the ionic liquid phase at the lower layer is fulfilled.
The high salt wastewater incoming path is connected to the wastewater inlet of the mixer through check valve V1 and valve V2. The method specifically comprises the following steps: the high-salt wastewater incoming path is connected with the input end of a check valve V1, the output end of a check valve V1 is connected with the input end of a valve V2, and the output end of a valve V2 is connected with the wastewater inlet of the mixer.
The oxygen inlet is connected to the oxygen inlet of the mixer through check valve V3 and valve V4. The method specifically comprises the following steps: the oxygen inlet is connected to the input of a check valve V3, the output of a check valve V3 is connected to the input of a valve V4, and the output of a valve V4 is connected to the oxygen inlet of the mixer.
Preferably, the connection line between the mixer outlet and the material inlet of the reactor is inserted into the reactor chamber, and the insertion end of the connection line is close to the liquid level in the reactor.
The connecting pipeline for connecting the reactor and the mixer extends into the reactor to a certain height, and the liquid-liquid two phases are contained in the reactor, so that the disturbance to the liquid-liquid two phases is reduced as much as possible; the height of the pipe line extending into the reactor cannot be too low, so that the inlet pipe line is prevented from being immersed in the reaction liquid due to the liquid level being raised during the process of removing the deposited salt on the side wall of the reactor.
A pressure reducing valve V6 and a check valve V5 are sequentially arranged on a pipeline connecting an ionic liquid outlet of the reactor and a feed liquid inlet of the liquid-solid separator; the ionic liquid outlet of the reactor is connected with the input end of a pressure reducing valve V6, the output end of the pressure reducing valve V6 is connected with the input end of a check valve V5, and the output end of the check valve V5 is connected with the feed liquid inlet of the liquid-solid separator.
Preferably, a pipeline connecting an ionic liquid outlet of the reactor and a feed liquid inlet of the liquid-solid separator is inserted into the cavity of the liquid-solid separator, and an insertion end of the connecting pipeline is close to the liquid level in the liquid-solid separator. The connecting pipeline is at a certain height from the liquid level of the liquid-solid separator, so that disturbance to the liquid is avoided, and the solid-liquid separation efficiency is not influenced.
The liquid-solid separator is provided with a cooling device, for example, the liquid-solid separator is provided with a jacket, a cooling medium circulates in the jacket, or a half pipe is wound on the outer side wall of the liquid-solid separator, and cooling water is introduced into the half pipe to effectively cool substances in the device.
The bottom of the liquid-solid separator adopts a conical form, so that deposited salt substances can be conveniently and intensively output quickly through an outlet pipeline
Preferably, the temperature of the solution in the liquid-solid separator is controlled to be 100-180 ℃.
Preferably, an ionic liquid storage tank is further arranged in parallel on a connecting pipeline between the ionic liquid recycling outlet of the liquid-solid separator and the shell pass inlet of the heat exchanger.
And an ionic liquid recycling outlet of the liquid-solid separator is respectively connected with a shell pass inlet of the heat exchanger and an inlet of the ionic liquid storage tank. The outlet of the ionic liquid storage tank is also connected with the shell side inlet of the heat exchanger. The ionic liquid storage tank is connected with a pipeline connected with the liquid-solid separator and the heat exchanger in parallel, and part of pipeline lines of the ionic liquid storage tank are communicated in the process of removing the deposited salt on the side wall of the reactor; in the process of removing salt deposition blockage at the bottom of the reactor, part of pipeline lines of the ionic liquid storage tank are closed, and the fast switching of two process pipelines is realized.
The parallel ionic liquid storage tanks are specifically connected in the following mode: an ionic liquid recycling outlet of the liquid-solid separator is connected with an input end of a valve V10, and an output end of the valve V10 is connected with a shell-side inlet of the heat exchanger. A branch connected with an inlet of the ionic liquid storage tank is also arranged between an ionic liquid recycling outlet of the liquid-solid separator and an input end connecting pipeline of the valve V10; a valve V11 is provided in this branch. The outlet of the ionic liquid storage tank is connected with a pipeline connecting the output end of the valve 10 with the inlet of the heat exchanger through a valve V12.
The temperature of the ionic liquid at the shell pass outlet of the heat exchanger is 350-380 ℃.
Preferably, the side wall of the reactor is provided with a liquid level meter for monitoring the height of an interface position of the ionic liquid and the supercritical water liquid.
Preferably, a control regulating valve for regulating and controlling the flow of the backflow ionic liquid is arranged on a connecting pipeline between a shell side outlet of the heat exchanger and an ionic liquid inlet of the reactor; the control regulating valve is controlled by a control signal of the liquid level meter.
And a connecting pipeline between the shell side outlet of the heat exchanger and the ionic liquid inlet of the reactor is sequentially and serially provided with a valve V13, a booster pump P1, a valve V14, a check valve V16, a control regulating valve V17 and a valve V18. And the shell side outlet of the heat exchanger is connected with the input end of a valve V13, and the output end of the valve V18 is connected with the ionic liquid inlet of the reactor.
Preferably, two reaction liquid outlets of the reactor are arranged, and comprise an upper outlet positioned at the upper part and a lower outlet positioned at the lower part; the upper outlet and the lower outlet are respectively or jointly connected with a tube pass inlet of the heat exchanger.
The reactor is provided with two parallel upper layer reaction liquid outlet pipelines, and the lower layer reaction liquid outlet pipeline is opened and the upper layer reaction liquid outlet pipeline is closed in the process of removing the salt deposition blockage at the lower layer of the reactor. In the process of removing the salt deposit on the side wall of the reactor, since the upper reaction liquid level is raised, the upper reaction liquid outlet line is opened and the lower reaction liquid outlet line is closed.
Preferably, the upper outlet of the reactor is connected with the input end of a valve V19, the lower outlet is connected with the input end of a valve V20, the output end of V19 and the output end of the valve V20 are combined or respectively connected with the input end of a pressure reducing valve V21, and the output end of V21 is connected with the tube-side inlet of the heat exchanger; and the tube pass outlet of the heat exchanger is connected with an energy recycling system.
Closing the valve V10, opening the valves V11 and V12, pumping the ionic liquid in the ionic liquid storage tank D1 into the lower ionic liquid phase of the reactor R1 through the pump P1, controlling the opening degree of the control valve V17 through a DCS system, and effectively controlling the height of a liquid-liquid two-phase interface in the reactor through the opening degree of the control valve V17, so that the liquid level of the lower ionic liquid phase rises to a position which is not higher than the upper liquid level, and the part of the side wall of the oxidation reaction phase deposited with the salt is immersed in the lower ionic liquid phase with the raised liquid level. After the salt is completely dissolved into the lower ionic liquid phase, the opening degree of the control valve V17 is reduced, and the opening degree of the valve V11 is increased, so that the liquid level height of the lower ionic liquid phase is effectively reduced, the upper and lower layer heights of the liquid and the interface position are restored as before, and the technological process of removing the salt on the side wall of the reactor is realized.
The system integrates a reaction unit, a desalting unit, a storage unit, a heat exchange unit and a control unit:
the reaction unit adopts a kettle type reactor, and a certain amount of ionic liquid is added into the reactor in advance before reaction to realize liquid-liquid layering, so that the problem of salt deposition and blockage of the lower layer is effectively solved;
the desalting unit adopts a liquid-solid separator, adopts cooling water for cooling, and realizes the cooling separation of salt at low temperature and low pressure, thereby recovering salt substances on line and recycling ionic liquid;
the storage unit is provided with an ionic liquid storage tank and is used for storing a certain amount of ionic liquid, and the ionic liquid is used for increasing the liquid level height of a lower layer of ionic liquid phase in the reactor so as to remove deposited salt on the side wall of the reactor;
the heat exchange unit adopts a shell-and-tube heat exchanger, the shell side is introduced with ionic liquid in which salts are separated out in the online desalting process, and the tube side is introduced with upper layer reaction liquid flowing out of the reactor, so that the heat is recycled;
the control unit adopts a DCS control system, takes the height of the liquid-liquid layered interface position in the reactor as an input signal, logically adjusts the opening size of the control valve, and realizes the stable operation of the online desalting process and the reactor side wall deposited salt removing process
Has the advantages that:
(1) the invention originally adopts the ionic liquid to remove the salt precipitate in the supercritical water oxidation of the organic wastewater, and the preferred ionic liquid has the following characteristics in the supercritical state of water: is not soluble in supercritical water; the density is higher than that of supercritical water; the solubility of the salt in the solvent is high;
(2) a two-phase layering method is provided, and salt deposited and blocked at the bottom of a reactor in the supercritical water oxidation process is effectively removed;
(3) a method for removing deposited salt on the side wall of a supercritical water oxidation reactor by a piston is provided;
(4) a combined new process for removing salt deposition blockage, salt recovery and energy integration utilization is provided;
(5) according to the invention, the salt generated in the supercritical water oxidation reaction process is transferred out of the reactor on line and continuously, and the wastewater treatment effect is improved.
Drawings
The invention is described in further detail below with reference to the figures and the detailed description.
FIG. 1 is a process flow diagram of a desalination system for supercritical water oxidation of organic wastewater.
In the figure: r1 is a reactor for supercritical water oxidation; m1 is a mixer; s1 is a liquid-solid separator; d1 is an ionic liquid storage tank; e1 is a heat exchanger; p1 is an additional pump; v1, V3, V5, V16 are check valves; v6 and V21 are pressure reducing valves; v17 is a control regulating valve; other valves are stop valves (the invention is also referred to as valves for short).
Detailed Description
As shown in FIG. 1, the desalination system for supercritical water oxidation of organic wastewater comprises a reactor R1 for supercritical water oxidation, a liquid-solid separator S1, a heat exchanger E1 and a mixer M1;
the mixer M1 is provided with a wastewater inlet, an oxygen inlet and a feed liquid outlet, and the feed liquid outlet is connected with the material inlet of the reactor R1;
the reactor R1 is also provided with a reaction liquid outlet, an ionic liquid inlet and an ionic liquid outlet; wherein the ionic liquid outlet is connected with the feed liquid inlet of the liquid-solid separator S1;
the liquid-solid separator S1 is also provided with a salt outlet and an ionic liquid recycling outlet; an ionic liquid recycling outlet is connected with an inlet of a shell side of the heat exchanger E1, and a shell side outlet of the heat exchanger E1 is connected with an ionic liquid inlet of the reactor R1;
the tube side inlet of the heat exchanger E1 was connected to the reaction liquid outlet of the reactor R1.
The high-salt wastewater incoming path is connected with the wastewater inlet of the mixer M1 through a check valve V1 and a valve V2. Wherein, the high salt waste water incoming path is connected with the input end of a check valve V1, the output end of a check valve V1 is connected with the input end of a valve V2, and the output end of a valve V2 is connected with the waste water inlet of a mixer M1.
The oxygen inlet is connected to the oxygen inlet of mixer M1 through check valve V3 and valve V4. The oxygen inlet is connected with the input end of a check valve V3, the output end of a check valve V3 is connected with the input end of a valve V4, and the output end of a valve V4 is connected with the oxygen inlet of a mixer M1.
The connecting line between the outlet of the mixer M1 and the material inlet of the reactor R1 was inserted into the chamber of the reactor R1, and the inserted end of the connecting line was close to the liquid level in the reactor R1.
A pressure reducing valve V6 and a check valve V5 are sequentially arranged on a pipeline connecting an ionic liquid outlet of the reactor R1 and a feed liquid inlet of the liquid-solid separator S1; wherein, the ionic liquid outlet of the reactor R1 is connected with the input end of a pressure reducing valve V6, the output end of the pressure reducing valve V6 is connected with the input end of a check valve V5, and the output end of the check valve V5 is connected with the feed liquid inlet of a liquid-solid separator S1.
The ionic liquid outlet of the reactor R1 and the feed liquid inlet of the liquid-solid separator S1 are connected by a pipeline inserted into the cavity of the liquid-solid separator S1, and the insertion end of the connecting pipeline is close to the liquid level in the liquid-solid separator S1. The connecting pipeline has a certain height from the liquid level of S1 of the liquid-solid separator, thereby avoiding disturbing the liquid and influencing the solid-liquid separation efficiency
The liquid-solid separator S1 is provided with a cooling device, for example, the liquid-solid separator S1 is provided with a jacket in which a cooling medium circulates, or the outer side wall of the liquid-solid separator S1 is wound in a half pipe mode, and cooling water is introduced into the half pipe to effectively cool the substances in the device.
The bottom of the liquid-solid separator S1 adopts a conical form, so that deposited salt substances can be conveniently and intensively output quickly through an outlet pipeline
An ionic liquid storage tank D1 is also arranged in parallel on a connecting pipeline between the ionic liquid recycling outlet of the liquid-solid separator S1 and the shell pass inlet of the heat exchanger E1. Wherein, an ionic liquid recycling outlet of the liquid-solid separator S1 is connected with an input end of a valve V10, and an output end of the valve V10 is connected with a shell-side inlet of a heat exchanger E1. A branch connected with an inlet of an ionic liquid storage tank D1 is also arranged between an ionic liquid recycling outlet of the liquid-solid separator S1 and an input end connecting pipeline of the valve V10; a valve V11 is provided in this branch. The outlet of the ionic liquid storage tank D1 is connected with a pipeline connecting the output end of the valve 10 and the inlet of the heat exchanger E1 through a valve V12.
And a connecting pipeline between the shell-side outlet of the heat exchanger E1 and the ionic liquid inlet of the reactor R1 is sequentially and serially provided with a valve V13, a booster pump P1, a valve V14, a check valve V16, a control regulating valve V17 and a valve V18. And the shell side outlet of the heat exchanger E1 is connected with the input end of a valve V13, and the output end of the valve V18 is connected with the ionic liquid inlet of the reactor R1.
Two reaction liquid outlets of the reactor R1 are arranged, and comprise an upper outlet positioned at the upper part and a lower outlet positioned at the lower part; the upper outlet and the lower outlet are respectively or jointly connected with a tube pass inlet of a heat exchanger E1. The upper outlet of the reactor R1 is connected with the input end of a valve V19, the lower outlet is connected with the input end of a valve V20, the output end of the valve V19 and the output end of the valve V20 are combined or respectively connected with the input end of a pressure reducing valve V21, and the output end of the valve V21 is connected with the tube-side inlet of a heat exchanger E1; and a tube pass outlet of the heat exchanger E1 is connected to an energy recycling system.
And a liquid level meter for monitoring ionic liquid and supercritical water liquid level is arranged on the inner wall of the reactor R1.
The ionic liquid is pumped into the bottom of the reactor R1 by a booster pump P1, the ionic liquid with certain salt content dissolved therein is transferred to a liquid-solid separator S1 through an ionic liquid outlet along with the injection of the ionic liquid, the salt is separated out by cooling, the upper-layer desalted ionic liquid directly exchanges heat through a heat exchanger E1 or flows through an ionic liquid storage tank D1 and then flows through a heat exchanger E1, and the ionic liquid after heat exchange circulates to the reactor R1.
The specific desalting method of the system comprises the following steps:
after the high-salinity wastewater and the oxidant (oxygen) are heated and pressurized, the high-salinity wastewater and the oxidant (oxygen) are fully mixed in the inlet mixer M1 and then enter the reactor to carry out a supercritical water oxidation process, so that the high-salinity organic wastewater is quickly oxidized. Before supercritical water oxidation reaction of the reactor R1, an ionic liquid with a certain liquid level height is added in advance in the reactor, wherein the ionic liquid refers to ionic liquid [ emim ] BF4 (the same applies below). Under the supercritical state of water, because ionic liquid has great polarity, and is great with supercritical water oxidation in-process material nature difference, does not dissolve with supercritical water oxidation in-process material, and the density is great than supercritical water oxidation in-process material, realizes two-phase liquid layering, and the lower floor is ionic liquid phase, and the upper strata is oxidation reaction phase.
The salt separated out from the oxidation reaction phase is settled and enters the lower ionic liquid phase under the action of gravity to realize redissolution. In order to avoid the salt substances dissolved in the lower ionic liquid phase from being precipitated due to saturation, the lower ionic liquid phase is decompressed by a decompression valve V6 and then enters a liquid-solid separator S1, the outer wall of the liquid-solid separator is wound by a half pipe, cooling water (inlet: CWS; outlet: CWR) is introduced into the half pipe for cooling crystallization of salt in the ionic liquid phase (for example, the temperature of feed liquid in the liquid-solid separator S1 is controlled to be 100-180 ℃), the precipitated salt is subjected to solid-liquid separation after standing, the precipitated salt enters a drying and recovery process of downstream salt after passing through a valve V9, the ionic liquid in the upper layer passes through a heat exchanger E1 (for example, the temperature of the recycled ionic liquid is raised to be 350-380 ℃), heat exchange with the reaction liquid flowing out of the middle-upper layer of the reactor R1 is realized, pressurization is realized through a pump P1, and finally the ionic liquid in the lower layer returns to the reactor R1 through a valve V18, so that the purpose of cyclic desalting of the ionic.
The process effectively solves the problem of salt deposition and blockage at the bottom of a reactor in the supercritical water oxidation process, and in order to further solve the problem of salt deposition on the side wall of the reactor, the process adopts the following steps that a valve V10 is closed, valves V11 and V12 are opened, ionic liquid in an ionic liquid storage tank D1 is pumped into a lower ionic liquid phase of a reactor R1 through a pump P1, the opening degree of a control valve V17 is controlled through a DCS system, the height of a liquid-liquid two-phase interface in the reactor is effectively controlled through the opening degree of a control valve V17, the liquid level height of the lower ionic liquid phase is raised to a position higher than the previous upper liquid level height, the position of salt deposition on the side wall of the previous oxidation reaction phase is completely immersed in the lower ionic liquid phase with the raised liquid level, and the salt deposition on the side wall is dissolved in the lower ionic liquid phase again because the ionic liquid has good dissolving effect on the salt in the supercritical state of water, thereby effectively solving the problem of salt deposition on the side wall of the reactor. After the salt is completely dissolved into the lower ionic liquid phase, the opening degree of the control valve V17 is reduced, and the opening degree of the valve V11 is increased, so that the liquid level height of the lower ionic liquid phase is effectively reduced, the upper and lower layer heights of the liquid and the interface position are restored as before, and the technological process of removing the salt on the side wall of the reactor is realized.
The whole process realizes the effective solution of the salt deposition problem in the whole reactor in the supercritical water oxidation process. The invention can transfer salt deposition in the reactor R1 efficiently, continuously and online.
Claims (8)
1. A desalination method for supercritical water oxidation of organic wastewater is characterized in that ionic liquid is added into a reactor for supercritical water oxidation of organic wastewater, and salt is enriched into an ionic liquid phase;
the ionic liquid is [ emim]BF4、[C4min]FeBr4、[Bmim]Br、[Bmim]BF6、[Bmim]FeCl4At least one of (1).
2. The desalination method for supercritical water oxidation of organic wastewater as claimed in claim 1, wherein the ionic liquid is added before supercritical water oxidation.
3. A desalination system for supercritical water oxidation of organic wastewater is characterized by comprising a reactor for supercritical water oxidation, a liquid-solid separator, a heat exchanger and a mixer;
the mixer is provided with a wastewater inlet, an oxygen inlet and a feed liquid outlet, and the feed liquid outlet is connected with the material inlet of the reactor;
the reactor is also provided with a reaction liquid outlet, an ionic liquid inlet and an ionic liquid outlet; wherein, the ionic liquid outlet is connected with the feed liquid inlet of the liquid-solid separator;
the liquid-solid separator is also provided with a salt outlet and an ionic liquid recycling outlet; an ionic liquid recycling outlet is connected with an inlet of a shell pass of the heat exchanger, and a shell pass outlet of the heat exchanger is connected with an ionic liquid inlet of the reactor; an ionic liquid recycling outlet of the liquid-solid separator and a connecting pipeline of a shell pass inlet of the heat exchanger are also provided with an ionic liquid storage tank in parallel;
the tube side inlet of the heat exchanger is connected with the reaction liquid outlet of the reactor.
4. The system for desalting organic wastewater for supercritical water oxidation according to claim 3, wherein the reactor has two reaction solution outlets, including an upper outlet at an upper portion and a lower outlet at a lower portion; the upper outlet and the lower outlet are respectively or jointly connected with a tube pass inlet of the heat exchanger.
5. The system of claim 3, wherein the reactor is equipped with a level gauge on its sidewall for monitoring the level of the interface between the ionic liquid and supercritical water.
6. The system for desalting of organic wastewater by supercritical water oxidation according to claim 5, wherein a control regulating valve for regulating and controlling the flow of the refluxing ionic liquid is arranged on a connecting pipeline between the shell-side outlet of the heat exchanger and the ionic liquid inlet of the reactor; the control regulating valve is controlled by a control signal of the liquid level meter.
7. The desalination system for supercritical water oxidation of organic wastewater as claimed in claim 3, wherein the connecting pipeline of the mixer outlet and the material inlet of the reactor is inserted into the reactor chamber, and the insertion end of the connecting pipeline is close to the liquid level in the reactor;
a pipeline connecting an ionic liquid outlet of the reactor and a feed liquid inlet of the liquid-solid separator is inserted into a cavity of the liquid-solid separator, and an insertion end of the connecting pipeline is close to the liquid level in the liquid-solid separator.
8. An application method of the organic wastewater supercritical water oxidation desalination system as defined in any one of claims 3 to 7, characterized in that the temperature of the liquid in the liquid-solid separator is 100 to 180 ℃; the temperature of the ionic liquid at the shell pass outlet of the heat exchanger is 350-380 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544419A (en) * | 2008-03-27 | 2009-09-30 | 楼龙春 | Method and device for oxidizing and treating sewage or sludge containing organic substances by supercritical water |
| CN102642947A (en) * | 2012-04-23 | 2012-08-22 | 西安交通大学 | Supercritical water oxidization treatment system for high-salinity organic waste water |
| CN105617936A (en) * | 2016-03-10 | 2016-06-01 | 西安交通大学 | Two-pass tube-type supercritical water reaction device |
| CN105705612A (en) * | 2013-11-19 | 2016-06-22 | 环球油品公司 | Process for removing a contaminant from coal tar |
| CN105722954A (en) * | 2013-11-19 | 2016-06-29 | 环球油品公司 | Process for removing mercury from coal tar product |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974317A (en) * | 2012-12-29 | 2013-03-20 | 中南大学 | Treatment method for arsenic non-ferrous heavy metal containing wastewater |
| EP2964402A4 (en) * | 2013-03-05 | 2016-11-30 | Hyrax Energy Inc | Biomass processing using ionic liquids |
| US20150136696A1 (en) * | 2013-11-19 | 2015-05-21 | Uop Llc | Process for removing aromatics from water used in processing coal tar |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544419A (en) * | 2008-03-27 | 2009-09-30 | 楼龙春 | Method and device for oxidizing and treating sewage or sludge containing organic substances by supercritical water |
| CN102642947A (en) * | 2012-04-23 | 2012-08-22 | 西安交通大学 | Supercritical water oxidization treatment system for high-salinity organic waste water |
| CN105705612A (en) * | 2013-11-19 | 2016-06-22 | 环球油品公司 | Process for removing a contaminant from coal tar |
| CN105722954A (en) * | 2013-11-19 | 2016-06-29 | 环球油品公司 | Process for removing mercury from coal tar product |
| CN105617936A (en) * | 2016-03-10 | 2016-06-01 | 西安交通大学 | Two-pass tube-type supercritical water reaction device |
Non-Patent Citations (2)
| Title |
|---|
| 《Salt deposition problems in supercritical water oxidation》;Donghai Xu等;《Chemical Engineering Journal》;20150521;1010-1022 * |
| Improvement of recovery performance in the solvent extraction of Cu(II)using [bmim][Tf2N] and a β-diketone as extractant and its stripping with supercritical carbon dioxide;Rossana Sepúlveda等;《The Journal of Supercritical Fluids》;20170504;26-31 * |
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