CN213771442U - Electrodialysis and bipolar membrane electrodialysis coupled degraded amine liquid purification and recovery device - Google Patents
Electrodialysis and bipolar membrane electrodialysis coupled degraded amine liquid purification and recovery device Download PDFInfo
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- CN213771442U CN213771442U CN202021682612.0U CN202021682612U CN213771442U CN 213771442 U CN213771442 U CN 213771442U CN 202021682612 U CN202021682612 U CN 202021682612U CN 213771442 U CN213771442 U CN 213771442U
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Abstract
The utility model discloses a degradation amine liquid purification recovery unit of electrodialysis and bipolar membrane electrodialysis coupling, including electrodialysis membrane stack, bipolar membrane electrodialysis membrane stack, high frequency DC switching power supply, water pump, storage tank, filter and heat exchanger, the storage tank connects gradually behind water pump, filter and the heat exchanger with the electrodialysis membrane stack is connected, electrodialysis membrane stack, high frequency DC switching power supply, water pump, storage tank, filter and heat exchanger constitute electrodialysis processing unit, bipolar membrane electrodialysis membrane stack, high frequency DC switching power supply, water pump, storage tank, filter and heat exchanger constitute Bipolar Membrane Electrodialysis (BMED) processing unit, electrodialysis processing unit and Bipolar Membrane Electrodialysis (BMED) processing unit are connected, high frequency DC switching power supply does electrodialysis membrane stack and bipolar membrane electrodialysis membrane stack power supply.
Description
Technical Field
The utility model relates to a purify recovery unit technical field, especially relate to a deterioration amine liquid of electrodialysis and bipolar membrane electrodialysis coupling purifies recovery unit.
Background
The alcohol amine method desulfurization is widely applied to the purification of sulfur-containing gases such as refinery gas, natural gas and the like. The alcohol amine solution is degraded to a certain degree in the recycling process, and the degraded acid product reacts with the alcohol amine to generate a series of salts which are difficult to be resolved from a regeneration tower through temperature change, so the salts are called as Heat Stable Salts (HSS). At present, the most commonly used alcohol amine desulfurizing agent is N-Methyldiethanolamine (MDEA), and the formed thermal stable salt has the molecular formula of MDEA. HX, wherein X is acid radical ions (such as oxalate, acetate, sulfate, chloride and the like). Because the alcohol amine solution has almost no metal ions, the essence of HSS removal is to remove inorganic acid and organic acid which are difficult to volatilize. HSS 'restrains' alcohol amine molecules, so that the property degradation of the alcohol amine desulfurizer, such as reduction of effective concentration and reduction of absorption capacity, can also cause increase of viscosity of alcohol amine solution and increase of energy consumption for transportation, and in addition, the increase of the concentration of heat stable salt can also cause foaming and tower washing of alcohol amine desulfurization and difficult elimination, thereby causing adverse effects on equipment, pipelines and subsequent sections.
Currently, there are several ways to release the HSS "tethering" effect:
1. adding liquid alkali to the degraded amine liquid:
through the reaction of NaOH and heat stable salt (NaOH + MDEA. HX = MDEA + NaX + H2O), the effect of releasing the alcohol amine molecule MDEA is achieved, but in the process, Na + is introduced into the amine liquid, the content of inorganic salt in the amine liquid is increased, and even if liquid alkali is added, the content of Na + is accumulated continuously, and finally, crystallized salt NaX is separated out to block pipelines and tower plates.
2. Anion resin exchange method:
and introducing the degraded amine liquid into an anion exchange resin column, and replacing acid radical ions X-by OH-in the anion resin to achieve the effect of releasing alcohol amine molecules MDEA. After the replacement is finished, the amine liquid remained in the resin column needs to be flushed back to the system by using desalted water so as to reduce the loss of the amine liquid, and water and Na + are inevitably brought into the system in the process, so that the amine liquid concentration of the system is diluted and the Na + content is increased; in addition, after the anion resin exchange capacity is saturated, 3-4% NaOH solution needs to be used for regeneration, and a large amount of desalted water needs to be consumed for resin column washing, so that a large amount of alkaline wastewater is finally generated.
3. An electrodialysis method:
the electrodialysis technology is a process for separating charged ions from aqueous solution and other charged components by utilizing the permselectivity of a charged ion membrane, and is a membrane separation process taking potential difference as driving force. The electrodialyzer consists of a cathode plate, an anode plate, an anion exchange membrane, a cation exchange membrane and a clapboard. The anion exchange membrane, the cation exchange membrane and the partition plates are alternately arranged between the cathode plate and the anode plate according to a certain sequence to form a desalting chamber and a concentrating chamber. Under the action of DC electric field, the positive ions introduced into the desalting compartment of the electrodialyzer pass through the positive membrane and move to the negative plate, and the negative ions pass through the negative membrane and move to the positive plate and are finally converged in the concentrating chamber, so that the effects of desalting and concentrating the solution are achieved.
The degraded amine liquid is introduced into a desalting chamber of an electrodialyzer, desalted water is introduced into a concentrating chamber, then a certain direct current voltage is applied to a negative plate and a positive plate to form a direct current electric field, and at the moment, cations and anions enter the concentrating chamber through a positive membrane and a negative membrane respectively to achieve the aim of desalting. Because the cation membrane has no selectivity to cation type, the alcohol amine molecules MDEA & H + which are bound by heat stable salt can pass through the cation membrane to enter the concentration chamber of the electrodialyzer to be discharged as waste water, which can cause the loss of part of amine liquid on one hand and the increase of COD value of the waste water on the other hand, thereby increasing the difficulty of waste water treatment.
Disclosure of Invention
The utility model aims at providing a degradation amine liquid purification recovery unit of electrodialysis and bipolar membrane electrodialysis coupling for solving above-mentioned problem.
The utility model discloses a following technical scheme realizes above-mentioned purpose:
the utility model provides a degradation amine liquid purification recovery unit of electrodialysis and bipolar membrane electrodialysis coupling, includes electrodialysis membrane stack, bipolar membrane electrodialysis membrane stack, high frequency DC switching power supply, water pump, storage tank, filter and heat exchanger, the storage tank connects gradually behind water pump, filter and the heat exchanger with the electrodialysis membrane stack is connected, electrodialysis membrane stack, high frequency DC switching power supply, water pump, storage tank, filter and heat exchanger constitute electrodialysis processing unit, bipolar membrane electrodialysis membrane stack, high frequency DC switching power supply, water pump, storage tank, filter and heat exchanger constitute Bipolar Membrane Electrodialysis (BMED) processing unit, electrodialysis processing unit and Bipolar Membrane Electrodialysis (BMED) processing unit are connected, high frequency DC switching power supply does electrodialysis membrane stack and bipolar membrane electrodialysis membrane stack power supply.
The utility model discloses preferred, the water pump includes amine liquid circulating pump, dense water circulating pump, utmost point water circulating pump, arranges dense pump, arranges amine pump, alkali lye circulating pump, acidizing fluid circulating pump, alkali lye pump, arranges sour pump, the storage tank includes amine liquid jar, dense water jar, utmost point water jar, alkali lye jar and acidizing fluid jar, the filter includes amine liquid filter, dense water filter, utmost point water filter, alkali lye filter and acidizing fluid filter; the heat exchanger includes amine liquid heat exchanger, dense water heat exchanger, utmost point water heat exchanger, alkali lye heat exchanger and acidizing fluid heat exchanger, dense water irritate connect gradually behind dense water circulating pump, dense water filter and the dense water heat exchanger with the electrodialysis membrane pile is connected, the amine fluid reservoir connect gradually behind amine liquid circulating pump, amine liquid filter and the amine liquid heat exchanger with the electrodialysis membrane pile is connected, the utmost point water reservoir connect gradually behind utmost point water circulating pump, utmost point water filter and the utmost point water heat exchanger with the electrodialysis membrane pile is connected, the acidizing fluid reservoir connect gradually, be connected with bipolar membrane electrodialysis membrane pile behind acidizing fluid filter and the acidizing fluid heat exchanger, the alkali fluid reservoir connects gradually, is connected with the electrodialysis membrane pile behind alkali lye filter and the alkali lye heat exchanger, electrodialysis membrane pile and bipolar membrane electrodialysis membrane pile all include negative plate and anode plate, contain the multiunit between negative plate and the anode plate by negative membrane, Desalination chamber and the concentrated chamber that positive membrane and baffle constitute between negative plate, anode plate and the adjacent positive membrane constitute cathode chamber and anode chamber respectively, the electrodialysis membrane stack in proper order by anode chamber, concentrated chamber, desalination chamber and cathode chamber connect gradually the setting, contain the alkali room and the acid room that the multiunit comprises bipolar membrane, negative membrane and baffle between negative plate, the anode plate, constitute cathode chamber and anode chamber between negative plate, the anode plate and the adjacent bipolar membrane respectively, bipolar membrane electrodialysis membrane stack is connected in proper order by anode chamber, acid room alkali room, acid room, alkali room and cathode chamber and is constituted, high frequency direct current switching power supply is just, the negative pole output links to each other with anode plate, cathode plate terminal respectively.
The utility model discloses it is preferred, amine liquid tank top import links to each other with degradation amine liquid pipeline, and its one side bottom export links to each other with the import of amine liquid circulating pump, and the export of opposite side bottom links to each other with the import of amine discharging pump, and amine liquid filter and amine liquid heat exchanger are distributing in proper order on the pipeline between the export of amine liquid circulating pump and the import of electrodialysis membrane stack light chamber, and electrodialysis membrane stack light chamber export links to each other with amine liquid tank top return water mouth and bipolar membrane electrodialysis processing unit acidizing fluid tank top import pipeline respectively, and the export of amine discharging pump links to each other with purification amine liquid pipeline. The top inlet of the concentrated water tank is connected with a demineralized water pipeline, the bottom outlet of one side of the concentrated water tank is connected with the inlet of a concentrated water circulating pump, and the bottom outlet of the other side of the concentrated water tank is connected with the inlet of a concentrated water discharging pump; a concentrated water filter and a concentrated water heat exchanger are sequentially distributed on a pipeline between an outlet of the concentrated water circulating pump and an inlet of the electrodialysis membrane stack concentration chamber, and an outlet of the electrodialysis membrane stack concentration chamber is respectively connected with a water return port at the top of a concentrated water tank and an inlet pipeline at the top of an acid liquor tank of the bipolar membrane electrodialysis treatment unit; the concentration discharge pump is connected with an inlet at the top of an alkali liquor tank of the bipolar membrane electrodialysis treatment unit, an inlet at the top of the polar water tank is connected with a demineralized water pipeline, and an outlet at the bottom of the polar water tank is connected with an inlet of a polar water circulating pump; an electrode water filter and an electrode water heat exchanger are sequentially distributed on a pipeline from an outlet of the electrode water circulating pump to the cathode chamber of the electrodialysis membrane stack and the inlet of the anode chamber, and the cathode chamber of the electrodialysis membrane stack and the outlet pipeline of the anode chamber are synthesized into one path to be connected with a water return port at the top of the electrode water tank.
An outlet at the bottom of one side of the alkali liquor tank is connected with an inlet of an alkali liquor circulating pump, and an outlet at the bottom of the other side of the alkali liquor tank is connected with an inlet of an alkali discharge pump; an alkali liquor heat exchanger of an alkali liquor filter is sequentially distributed on a pipeline between an outlet of the alkali liquor circulating pump and an inlet of the bipolar membrane electrodialysis membrane stack alkali chamber, and an outlet of the bipolar membrane electrodialysis membrane stack alkali chamber is connected with a water return port at the top of the alkali liquor tank; the outlet of the alkali discharge pump is connected with a pipeline of the degraded amine liquid inlet amine liquid tank.
An outlet at the bottom of one side of the acid liquor tank is connected with an inlet of the acid liquor circulating pump, and an outlet at the bottom of the other side of the acid liquor tank is connected with an inlet of the acid discharge pump; an acid liquor filter and an acid liquor heat exchanger are sequentially distributed on a pipeline between an outlet of the acid liquor circulating pump and an inlet of the bipolar membrane electrodialysis membrane stacking acid chamber, and an outlet of the bipolar membrane electrodialysis membrane stacking acid chamber is respectively connected with a water return port at the top of the acid liquor tank; the outlet of the acid discharge pump is respectively connected with the electrodialysis membrane stack concentration chamber and the inlet pipeline of the dilute chamber of the electrodialysis treatment unit.
The bottom outlet of the polar water tank is connected with the inlet of the polar water circulating pump, the outlet of the polar water circulating pump is connected to a pipeline between the cathode chamber of the bipolar membrane electrodialysis membrane stack and the inlet of the anode chamber, the polar water filter and the polar water heat exchanger are sequentially distributed on the pipeline, and the cathode chamber of the bipolar membrane electrodialysis membrane stack and the outlet pipeline of the anode chamber are synthesized to be connected with the water return port at the top of the polar water tank.
The utility model discloses it is preferred, the dense water that the electrodialysis membrane stack produced carries the lye tank in bipolar membrane electrodialysis processing unit through arranging the concentration pump, the alkali lye that bipolar membrane electrodialysis membrane stack produced carries the amine liquid jar in the electrodialysis processing unit through arranging the alkali pump.
The utility model discloses preferred, bipolar membrane electrodialysis processing unit sour liquid jar is as the washing jar of electrodialysis processing unit, and produced acidizing fluid is as the pickling medicament of electrodialysis processing unit membrane stack, carries to the dense room and the light room of electrodialysis membrane stack respectively through arranging the sour pump output.
The utility model discloses preferred, dense room pickling agent import is located on the pipeline between dense water circulation export and the import of dense water filter, and weak room pickling agent import is located on the pipeline between the export of amine liquid circulating pump and the import of amine liquid filter.
The utility model discloses preferred, the operation mode of unit includes batch type operation and continuous type operation.
The utility model discloses preferred, the electrodialysis membrane stack is two compartments homogeneous phase membrane stacks, and the size is one kind of 200X 400mm, 400X 800mm, 550X 1100mm, 400X 1600mm, and the negative and positive membrane group number is 50~300 pairs.
The utility model discloses preferred, the row's dense pump is controlled by dense salt content, starts when dense salt content > 10%, closes when being < 8%.
The utility model discloses preferred, bipolar membrane said electrodialysis membrane stack be two compartments homogeneous phase membrane bipolar membrane stacks, and the size is one kind of 200 x 400mm, 400 x 800mm, 550 x 1100mm, 400 x 1600mm, and negative and positive membrane group number is 50~300 right.
The beneficial effects of the utility model reside in that:
the utility model discloses electrodialysis technique destabilization salt process need not to add NaOH, do not introduce inorganic salt Na +, and do not need the regeneration, the demineralized water consumption is few, the waste water output is few, bipolar membrane electrodialysis technique can high-efficiently retrieve the MDEA molecule in the electrodialysis waste water, reduce the amine liquid loss, the by-product acid HX that bipolar membrane electrodialysis technique produced, can be used as the pickling medicament of electrodialysis membrane heap, reduce pickling medicament cost, in addition can also neutralize the alkaline waste water that the electrodialysis membrane heap washed out, reduce the waste water follow-up processing degree of difficulty.
Drawings
Fig. 1 is a schematic structural diagram of a deteriorated amine liquid purification and recovery device with electrodialysis coupled with bipolar membrane electrodialysis according to the present invention;
FIG. 2 is a schematic diagram of the electrodialysis technique for removing heat stable salt;
FIG. 3 is a schematic diagram of the recovery of MDEA by the bipolar membrane electrodialysis technology of the present invention.
Detailed Description
The present invention will be further explained with reference to the accompanying drawings:
as shown in fig. 1, 2 and 3: the utility model provides a degradation amine liquid purification recovery unit of electrodialysis and bipolar membrane electrodialysis coupling, includes electrodialysis membrane stack 40, bipolar membrane electrodialysis membrane stack 70, high frequency direct current switching power supply, water pump, storage tank, filter and heat exchanger, the storage tank connects gradually behind water pump, filter and the heat exchanger with electrodialysis membrane stack 40 is connected, electrodialysis membrane stack 40, high frequency direct current switching power supply, water pump, storage tank, filter and heat exchanger constitute the electrodialysis processing unit, bipolar membrane electrodialysis membrane stack 70, high frequency direct current switching power supply, water pump, storage tank, filter and heat exchanger constitute Bipolar Membrane Electrodialysis (BMED) processing unit, the electrodialysis processing unit is connected with Bipolar Membrane Electrodialysis (BMED) processing unit, high frequency direct current switching power supply does electrodialysis membrane stack 40 and bipolar membrane electrodialysis membrane stack 70 power supply.
As shown in fig. 1, 2 and 3, the water pump includes an amine liquid circulating pump 21, a concentrated water circulating pump 11, an extreme water circulating pump 31, a concentration discharge pump 14, an amine discharge pump 24, an alkali liquid circulating pump 61, an acid liquid circulating pump 51, an alkali discharge pump 64 and an acid discharge pump 54, the storage tanks include an amine liquid tank 20, a concentrated water tank 10, an extreme water tank 30, an alkali liquid tank 60 and an acid liquid tank 50, and the filters include an amine liquid filter 22, a concentrated water filter 12, an extreme water filter 32, an alkali liquid filter 62 and an acid liquid filter 52; the heat exchanger comprises an amine liquid heat exchanger 23, a concentrated water heat exchanger 13, a polar water heat exchanger 33, an alkali liquor heat exchanger 63 and an acid liquor heat exchanger 53, the concentrated water tank 10 is connected with the electrodialysis membrane stack 40 after being sequentially connected with a concentrated water circulating pump 11, a concentrated water filter 12 and the concentrated water heat exchanger 13, the amine liquid tank 20 is connected with the electrodialysis membrane stack 40 after being sequentially connected with the amine liquid circulating pump 21, the amine liquid filter 22 and the amine liquid heat exchanger 23, the polar water tank 30 is connected with the electrodialysis membrane stack 40 after being sequentially connected with a polar water circulating pump 31, a polar water filter 32 and a polar water heat exchanger 33, the acid liquid tank 50 is connected with the bipolar membrane electrodialysis membrane stack 70 after being sequentially connected with a liquid tank 51, an acid liquor filter 52 and an acid liquor heat exchanger 53, the alkali liquor tank 60 is connected with the bipolar membrane electrodialysis membrane stack 70 after being sequentially connected with a liquid alkali liquor filter 62 and the alkali liquor heat exchanger 63, and the electrodialysis membrane stack 40 and the bipolar membrane electrodialysis membrane stack 70 both comprise 45 and an anode plate 41, the membrane bioreactor comprises a cathode plate 45, an anode plate 41, a cathode plate 45, an anode plate 42, a separator 43, a plurality of desalting chambers 48 and concentrating chambers 47, wherein the desalting chambers 48 and the concentrating chambers 47 are formed by the cathode plate 44, the anode plate 42 and the adjacent anode membrane 42 respectively, the electrodialysis membrane stack 40 is formed by sequentially connecting the anode chamber 46, the concentrating chamber 47, the desalting chamber 48 and the cathode chamber 49, the cathode plate 45 and the anode plate 41 are formed by a plurality of alkaline chambers 73 and acid chambers 72, wherein the alkaline chambers 73 and the acid chambers 72 are formed by the bipolar membranes 71, the cathode plate 44 and the separator 43, the cathode chamber 49 and the anode chamber 46 are formed by the cathode plate 45, the anode plate 41 and the adjacent bipolar membranes 71 respectively, the bipolar membrane electrodialysis membrane stack 70 is formed by sequentially connecting the anode chamber 46, the acid chamber 72, the alkaline chamber 73 and the cathode chamber 49, and the high-frequency direct current switching power supply positive, negative, positive, negative and positive and negative, The negative output end is respectively connected with the binding posts of the anode plate 41 and the cathode plate 45.
As shown in fig. 1, the top inlet of the amine liquid tank 20 is connected with a deteriorated amine liquid 2 pipeline, one side of the bottom outlet is connected with the inlet of an amine liquid circulating pump 21, and the other side of the bottom outlet is connected with the inlet of an amine discharging pump 24; an amine liquid filter 22 and an amine liquid heat exchanger 23 are sequentially distributed on a pipeline between the outlet of the amine liquid circulating pump 21 and the inlet of the dilute chamber 48 of the electrodialysis membrane stack 40, the outlet of the dilute chamber 48 of the electrodialysis membrane stack 40 is respectively connected with a water return port at the top of the amine liquid tank 20 and an inlet pipeline at the top of the acid liquid tank 50 of the bipolar membrane electrodialysis treatment unit, and the outlet of the amine discharging pump 24 is connected with a purified amine liquid 5 pipeline. The top inlet of the concentrated water tank 10 is connected with the pipeline of the desalted water 1, the bottom outlet of one side of the concentrated water tank is connected with the inlet of a concentrated water circulating pump 11, and the bottom outlet of the other side of the concentrated water tank is connected with the inlet of a concentrated water discharging pump 14; a concentrated water filter 12 and a concentrated water heat exchanger 13 are sequentially distributed on a pipeline between the outlet of the concentrated water circulating pump 11 and the inlet of the concentrated chamber 47 of the electrodialysis membrane stack 40, and the outlet of the concentrated chamber 47 of the electrodialysis membrane stack 40 is respectively connected with a water return port at the top of the concentrated water tank 10 and an inlet pipeline at the top of the acid liquid tank 50 of the bipolar membrane electrodialysis treatment unit; the concentration discharge pump 14 is connected with the top inlet of an alkaline liquor tank 60 of the bipolar membrane electrodialysis treatment unit, the top inlet of a polar water tank 30 is connected with a pipeline of the desalted water 1, and the bottom outlet of the polar water tank is connected with the inlet of a polar water circulating pump 31; an electrode water filter 32 and an electrode water heat exchanger 33 are sequentially distributed on a pipeline between the outlet of the electrode water circulating pump and the inlets of the cathode chamber 49 and the anode chamber 46 of the electrodialysis membrane stack 40, and the outlet pipelines of the cathode chamber 49 and the anode chamber 46 of the electrodialysis membrane stack 40 are combined into a path to be connected with a water return port at the top of the electrode water tank 30.
The outlet at the bottom of one side of the alkali liquor tank 60 is connected with the inlet of an alkali liquor circulating pump 61, and the outlet at the bottom of the other side of the alkali liquor tank is connected with the inlet of an alkali liquor discharging pump 64; an alkali liquor filter 62 and an alkali liquor heat exchanger 63 are sequentially distributed on a pipeline between the outlet of the alkali liquor circulating pump 61 and the inlet of the alkali chamber 73 of the bipolar membrane electrodialysis membrane stack 70, and the outlet of the alkali chamber 73 of the bipolar membrane electrodialysis membrane stack 70 is connected with a water return port at the top of the alkali liquor tank 60; the outlet of the alkali discharging pump 64 is connected with a pipeline of the degraded amine liquid 2 into the amine liquid tank 20.
The outlet at the bottom of one side of the acid liquid tank 50 is connected with the inlet of an acid liquid circulating pump 51, and the outlet at the bottom of the other side of the acid liquid tank is connected with the inlet of an acid discharging pump 54; an acid filter 52 and an acid exchanger 53 are sequentially distributed on a pipeline between the outlet of the acid circulation pump 51 and the inlet of the acid chamber 72 of the bipolar membrane electrodialysis membrane stack 70, and the outlet of the acid chamber 72 of the bipolar membrane electrodialysis membrane stack 70 is respectively connected with a water return port at the top of the acid tank 50; the outlet of the acid discharge pump 54 is respectively connected with the inlet pipelines of the electrodialysis membrane stack 40 concentration chamber 47 and the dilute chamber 48 of the electrodialysis treatment unit.
An outlet at the bottom of the polar water tank 30 is connected with an inlet of a polar water circulating pump 31, a polar water filter 32 and a polar water heat exchanger 33 are sequentially distributed on a pipeline from the outlet of the polar water circulating pump 31 to an inlet of a cathode chamber 49 and an inlet of an anode chamber 46 of the bipolar membrane electrodialysis membrane stack 70, and the cathode chamber 49 and the outlet of the anode chamber 46 of the bipolar membrane electrodialysis membrane stack 70 are synthesized into one pipeline which is connected with a water return port at the top of the polar water tank 30.
As shown in fig. 1, fig. 2 and fig. 3, the concentrated water produced by the electrodialysis membrane stack 40 is delivered to an alkali liquor tank 60 in the bipolar membrane electrodialysis treatment unit through a concentration discharge pump 14, the alkali liquor produced by the bipolar membrane electrodialysis membrane stack 70 is delivered to an amine liquor tank 20 in the electrodialysis treatment unit through an alkali discharge pump 64, the acid liquor tank 50 of the bipolar membrane electrodialysis treatment unit is used as a cleaning tank of the electrodialysis treatment unit, the produced acid liquor is used as an acid cleaning agent of the electrodialysis treatment unit membrane stack 40 and is delivered to a thick chamber 47 and a thin chamber 48 of the electrodialysis membrane stack 40 through an acid discharge pump 54, respectively, the acid cleaning agent inlet of the thick chamber 47 is positioned on a pipeline between the outlet of a concentrated water circulating pump 11 and the inlet of a concentrated water filter 12, the acid cleaning agent inlet of the thin chamber 48 is positioned on a pipeline between the outlet of an amine liquor circulating pump 21 and the inlet of the amine liquor filter 22, the operation modes of the unit comprise batch operation and continuous operation, the electrodialysis membrane stack 40 is a two-compartment homogeneous membrane stack, the size of the electrodialysis membrane stack is 200 mm multiplied by 400mm, 400mm multiplied by 800mm, 550 mm multiplied by 1100mm or 400mm multiplied by 1600mm, the number of the negative and positive membrane groups is 50-300 pairs, the concentration discharge pump 14 is controlled by the content of concentrated water and salt, the bipolar membrane stack 70 is a two-compartment homogeneous membrane bipolar membrane stack, the size of the bipolar membrane stack is 200 mm multiplied by 400mm, 400mm multiplied by 800mm, 550 mm multiplied by 1100mm or 400mm multiplied by 1600mm, and the number of the negative and positive membrane groups is 50-300 pairs, wherein the content of the concentrated water and salt is started when the content of the concentrated water and salt is more than 10% and is closed when the content of the concentrated water and salt is less than 8%.
Example (b):
as shown in fig. 1, when the electrodialysis treatment unit is operated continuously, the deteriorated amine liquid 2 is continuously injected into the amine liquid tank 20, and the amine discharging pump 24 is continuously started to convey the purified amine liquid 3 back to the desulfurization system.
When the electrodialysis treatment unit operates intermittently and the content of heat stable salt in the amine liquid is below 1%, the amine discharging pump 24 is started to convey the purified amine liquid 3 back to the desulfurization system, and the amine liquid tank 20 is replenished with fresh degraded amine liquid 2 for continuous treatment.
As shown in fig. 1, when the electrodialysis treatment unit is operated, the amine liquid tank 20 is initially filled with degraded amine liquid 2, the concentrated water tank 10 and the polar water tank 30 are both filled with desalted water 1, and then analytically pure NaCl is added into the polar water tank 30 to prepare a sodium chloride solution with a mass concentration of 1-5%; simultaneously starting an amine liquid circulating pump 21, a concentrated water circulating pump 11 and an electrode water circulating pump 31, enabling degraded amine liquid 2 to enter a dilute chamber 48 of the electrodialysis membrane stack 40, enabling desalted water 1 to enter a concentrated chamber 47 of the electrodialysis membrane stack, and enabling 1-5% of sodium chloride solution to respectively enter a cathode chamber 49 and an anode chamber 46 of the electrodialysis membrane stack 40; regulating the flow of the amine liquid and the concentrated water to 2-10 m3/h, regulating the flow of the cathode water and the anode water to 1-3 m3/h, and then turning on a high-frequency direct-current switching power supply to regulate the voltage value to 50-300V.
As shown in fig. 2, under the action of the dc electric field, the cations MDEA · H + and the anions X "of the thermal stable salts in the dilute chamber pass through the positive membrane 42 and the negative membrane 44 respectively to enter the dense chamber 47, recombine into the thermal stable salts MDEA · HX in the dense chamber 47 and return to the dense water tank 10 along with the desalted water; along with the migration of the heat stable salt ions, the degraded amine liquid is gradually purified, and the salt content of the concentrated water gradually rises; when the content of the thermal stable salt in the concentrated water is more than 10 percent, the concentrated water discharging pump 14 is started to convey the concentrated water to the alkali liquor tank 60 of the bipolar membrane electrodialysis treatment unit, and the concentrated water tank 10 is supplemented with the desalted water 1.
As shown in fig. 1, when the bipolar membrane electrodialysis treatment unit is operated, the alkali solution tank 60 is initially filled with concentrated water generated by the electrodialysis treatment unit, the acid solution tank 50 and the polar water tank 30 are both filled with desalted water 1, and then analytically pure NaCl is added to the polar water tank 30 to prepare a sodium chloride solution with a mass concentration of 1-5%; simultaneously starting an alkali liquor circulating pump 61, an acid liquor circulating pump 51 and a polar water circulating pump 31, enabling 10% of electrodialysis concentrated water to enter a bipolar membrane electrodialysis membrane 70 alkali piling chamber 73, enabling desalted water to enter a bipolar membrane electrodialysis membrane acid piling chamber 72, and enabling 1-5% of sodium chloride solution to respectively enter a bipolar membrane electrodialysis membrane pile cathode chamber 49 and an anode chamber 46; adjusting the flow rates of the alkali liquor and the acid liquor to 2-10 m3/h, adjusting the flow rates of the cathode water and the anode water to 1-3 m3/h, and then turning on a high-frequency direct-current switching power supply to adjust the voltage value to 50-300V.
As shown in fig. 3, under the action of the dc electric field, the heat stable salt anions X "in the alkali chamber 73 penetrate through the negative membrane 44 and enter the acid chamber, and combine with H + generated by water dissociation of the bipolar membrane 71 to generate acid HX; the cation MDEA & H & lt + & gt of the thermal stable salt left in the alkali chamber 73 is combined with OH & lt- & gt generated by water dissociation of the bipolar membrane 71 to generate an MDEA molecule which is free from the constraint of the thermal stable salt; as X-migrates, MDEA molecules are gradually released, and the acid solution concentration gradually rises. When the content of the thermal stable salt in the alkali chamber 73 is less than 1%, the alkali discharging pump 64 is started to convey the alkali liquor to the amine liquor tank 20 of the electrodialysis treatment unit, when the electrodialysis treatment unit is subjected to chemical cleaning, the acid discharging pump 54 is started to convey the acid liquor to the thick chamber 47 and the thin chamber 48 of the electrodialysis membrane stack 40 respectively, then the acid liquor returns to the acid liquor tank 50 from the outlets of the thick chamber 47 and the thin chamber 48, the cyclic cleaning is carried out for 0.5-1.0 h, then the acid liquor is discharged through a waste water 4 pipeline, and finally the salt removing water is introduced for washing.
To sum up, the utility model discloses electrodialysis technique destabilization salt process need not to add NaOH, do not introduce inorganic salt Na +, and do not need the regeneration, the demineralized water consumption is few, waste water production volume is few, bipolar membrane electrodialysis technique can high-efficient recovery the MDEA molecule in the electrodialysis waste water, reduce amine liquid loss, the sour HX of accessory substance that bipolar membrane electrodialysis technique produced, can be used as the pickling medicament of electrodialysis membrane stack, reduce pickling medicament expense, in addition can also neutralize the alkaline waste water that the electrodialysis membrane stack washed out, reduce the waste water subsequent processing degree of difficulty.
The present invention can be implemented by various modifications without departing from the spirit and spirit of the present invention, and the above description is only a preferred and feasible embodiment of the present invention, and is not intended to limit the scope of the present invention, and all the equivalent structural changes made by using the contents of the present invention and the accompanying drawings are included in the scope of the present invention.
Claims (10)
1. The utility model provides a degradation amine liquid purification recovery unit of electrodialysis and bipolar membrane electrodialysis coupling, its characterized in that, including electrodialysis membrane stack, bipolar membrane electrodialysis membrane stack, high frequency DC switching power supply, water pump, storage tank, filter and heat exchanger, the storage tank connect gradually behind water pump, filter and the heat exchanger with the electrodialysis membrane stack is connected, electrodialysis membrane stack, high frequency DC switching power supply, water pump, storage tank, filter and heat exchanger constitute electrodialysis processing unit, bipolar membrane electrodialysis membrane stack, high frequency DC switching power supply, water pump, storage tank, filter and heat exchanger constitute Bipolar Membrane Electrodialysis (BMED) processing unit, electrodialysis processing unit and Bipolar Membrane Electrodialysis (BMED) processing unit are connected, high frequency DC switching power supply is electrodialysis membrane stack and bipolar membrane electrodialysis membrane stack power supply.
2. An electrodialysis and bipolar membrane electrodialysis coupled deteriorated amine liquid purification and recovery device according to claim 1, wherein said water pump comprises an amine liquid circulating pump, a concentrated water circulating pump, a polar water circulating pump, a concentration discharge pump, an amine discharge pump, an alkali liquor circulating pump, an acid liquor circulating pump, an alkali discharge pump, and an acid discharge pump, said storage tanks comprise an amine liquid tank, a concentrated water tank, a polar water tank, an alkali liquid tank, and an acid liquor tank, and said filters comprise an amine liquid filter, a concentrated water filter, a polar water filter, an alkali liquor filter, and an acid liquor filter; the heat exchanger includes amine liquid heat exchanger, dense water heat exchanger, utmost point water heat exchanger, alkali lye heat exchanger and acidizing fluid heat exchanger, dense water irritate connect gradually behind dense water circulating pump, dense water filter and the dense water heat exchanger with the electrodialysis membrane pile is connected, the amine fluid reservoir connect gradually behind amine liquid circulating pump, amine liquid filter and the amine liquid heat exchanger with the electrodialysis membrane pile is connected, the utmost point water reservoir connect gradually behind utmost point water circulating pump, utmost point water filter and the utmost point water heat exchanger with the electrodialysis membrane pile is connected, the acidizing fluid reservoir connect gradually, be connected with bipolar membrane electrodialysis membrane pile behind acidizing fluid filter and the acidizing fluid heat exchanger, the alkali fluid reservoir connects gradually, is connected with the electrodialysis membrane pile behind alkali lye filter and the alkali lye heat exchanger, electrodialysis membrane pile and bipolar membrane electrodialysis membrane pile all include negative plate and anode plate, contain the multiunit between negative plate and the anode plate by negative membrane, Desalination chamber and the concentrated chamber that positive membrane and baffle constitute between negative plate, anode plate and the adjacent positive membrane constitute cathode chamber and anode chamber respectively, the electrodialysis membrane stack in proper order by anode chamber, concentrated chamber, desalination chamber and cathode chamber connect gradually the setting, contain the alkali room and the acid room that the multiunit comprises bipolar membrane, negative membrane and baffle between negative plate, the anode plate, constitute cathode chamber and anode chamber between negative plate, the anode plate and the adjacent bipolar membrane respectively, bipolar membrane electrodialysis membrane stack is connected in proper order by anode chamber, acid room alkali room, acid room, alkali room and cathode chamber and is constituted, high frequency direct current switching power supply is just, the negative pole output links to each other with anode plate, cathode plate terminal respectively.
3. The electrodialysis and bipolar membrane electrodialysis coupled deteriorated amine liquid purification and recovery device according to claim 2,
the top inlet of the amine liquid tank is connected with a degraded amine liquid pipeline, the bottom outlet of one side of the amine liquid tank is connected with the inlet of an amine liquid circulating pump, the bottom outlet of the other side of the amine liquid circulating pump is connected with the inlet of an amine liquid discharging pump, an amine liquid filter and an amine liquid heat exchanger are sequentially distributed on a pipeline between the outlet of the amine liquid circulating pump and the inlet of a dilute chamber of an electrodialysis membrane stack, the outlet of the dilute chamber of the electrodialysis membrane stack is respectively connected with a top water return port of the amine liquid tank and a top inlet pipeline of an acid liquid tank of a bipolar membrane electrodialysis treatment unit, the outlet of the amine liquid discharging pump is connected with a purified amine liquid pipeline, the top inlet of a concentrated water tank is connected with a desalted water pipeline, the bottom outlet of one side of the concentrated water tank is connected with the inlet of a concentrated water circulating pump, and the bottom outlet of the other side of the concentrated water tank is connected with the inlet of a concentrated water discharging pump; a concentrated water filter and a concentrated water heat exchanger are sequentially distributed on a pipeline between an outlet of the concentrated water circulating pump and an inlet of the electrodialysis membrane stack concentration chamber, and an outlet of the electrodialysis membrane stack concentration chamber is respectively connected with a water return port at the top of a concentrated water tank and an inlet pipeline at the top of an acid liquor tank of the bipolar membrane electrodialysis treatment unit; the concentration discharge pump is connected with an inlet at the top of an alkali liquor tank of the bipolar membrane electrodialysis treatment unit, an inlet at the top of the polar water tank is connected with a demineralized water pipeline, and an outlet at the bottom of the polar water tank is connected with an inlet of a polar water circulating pump; an electrode water filter and an electrode water heat exchanger are sequentially distributed on a pipeline from an outlet of the electrode water circulating pump to an inlet of a cathode chamber and an anode chamber of the electrodialysis membrane stack, and the cathode chamber and the anode chamber outlet pipeline of the electrodialysis membrane stack are combined into a pipeline which is connected with a water return port at the top of the electrode water tank;
an outlet at the bottom of one side of the alkali liquor tank is connected with an inlet of an alkali liquor circulating pump, and an outlet at the bottom of the other side of the alkali liquor tank is connected with an inlet of an alkali discharge pump; an alkali liquor heat exchanger of an alkali liquor filter is sequentially distributed on a pipeline between an outlet of the alkali liquor circulating pump and an inlet of the bipolar membrane electrodialysis membrane stack alkali chamber, and an outlet of the bipolar membrane electrodialysis membrane stack alkali chamber is connected with a water return port at the top of the alkali liquor tank; the outlet of the alkali discharge pump is connected with a pipeline of the degraded amine liquid inlet amine liquid tank;
an outlet at the bottom of one side of the acid liquor tank is connected with an inlet of the acid liquor circulating pump, and an outlet at the bottom of the other side of the acid liquor tank is connected with an inlet of the acid discharge pump; an acid liquor filter and an acid liquor heat exchanger are sequentially distributed on a pipeline between an outlet of the acid liquor circulating pump and an inlet of the bipolar membrane electrodialysis membrane stacking acid chamber, and an outlet of the bipolar membrane electrodialysis membrane stacking acid chamber is respectively connected with a water return port at the top of the acid liquor tank; the outlet of the acid discharge pump is respectively connected with the electrodialysis membrane stack concentration chamber and the inlet pipeline of the dilute chamber of the electrodialysis treatment unit;
the bottom outlet of the polar water tank is connected with the inlet of the polar water circulating pump, the outlet of the polar water circulating pump is connected to a pipeline between the cathode chamber of the bipolar membrane electrodialysis membrane stack and the inlet of the anode chamber, the polar water filter and the polar water heat exchanger are sequentially distributed on the pipeline, and the cathode chamber of the bipolar membrane electrodialysis membrane stack and the outlet pipeline of the anode chamber are synthesized to be connected with the water return port at the top of the polar water tank.
4. The electrodialysis and bipolar membrane electrodialysis coupled deteriorated amine liquid purification and recovery device of claim 3, wherein concentrated water produced by the electrodialysis membrane stack is delivered to the lye tank in the bipolar membrane electrodialysis treatment unit through the concentration discharge pump, and lye produced by the bipolar membrane electrodialysis membrane stack is delivered to the amine liquid tank in the electrodialysis treatment unit through the lye discharge pump.
5. An electrodialysis and bipolar membrane electrodialysis coupled deteriorated amine liquid purification and recovery device as claimed in claim 4, wherein the acid liquid tank of the bipolar membrane electrodialysis treatment unit is used as a cleaning tank of the electrodialysis treatment unit, and the generated acid liquid is used as acid cleaning agent of the membrane stack of the electrodialysis treatment unit and is respectively delivered to the thick room and the thin room of the electrodialysis membrane stack through an acid discharge pump.
6. The electrodialysis and bipolar membrane electrodialysis coupled deteriorated amine liquid purification and recovery device according to claim 5, wherein the concentrated cell pickling agent inlet is located on a line between a concentrated water circulation outlet and a concentrated water filter inlet, and the weak cell pickling agent inlet is located on a line between an amine liquid circulation outlet and an amine liquid filter inlet.
7. The electrodialysis and bipolar membrane electrodialysis coupled deteriorated amine liquid purification and recovery device of claim 6, wherein the unit is operated in a manner comprising batch operation and continuous operation.
8. The electrodialysis and bipolar membrane electrodialysis coupled deteriorated amine liquid purification and recovery device of claim 7, wherein the electrodialysis membrane stack is a two-compartment homogeneous membrane stack with one of the sizes of 200 x 400mm, 400 x 800mm, 550 x 1100mm and 400 x 1600mm, and the number of the negative and positive membrane groups is 50-300 pairs.
9. The electrodialysis and bipolar membrane electrodialysis coupled deteriorated amine liquid purification and recovery device of claim 8, wherein said concentration discharge pump is controlled by concentrated water salt content, and is started when the concentrated water salt content is greater than 10% and is closed when the concentrated water salt content is less than 8%.
10. The electrodialysis and bipolar membrane electrodialysis coupled deteriorated amine liquid purification and recovery device of claim 9, wherein the bipolar membrane electrodialysis membrane stack is a two-compartment homogeneous membrane bipolar membrane stack with one of the dimensions of 200 x 400mm, 400 x 800mm, 550 x 1100mm and 400 x 1600mm, and the number of the cathode and anode membrane groups is 50-300 pairs.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114210206A (en) * | 2021-12-15 | 2022-03-22 | 浙江大学 | Recovery of organic amine CO2Two-stage electrodialysis system and method for barren liquor waste liquid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114210206A (en) * | 2021-12-15 | 2022-03-22 | 浙江大学 | Recovery of organic amine CO2Two-stage electrodialysis system and method for barren liquor waste liquid |
| CN114210206B (en) * | 2021-12-15 | 2022-09-20 | 浙江大学 | Recovery of organic amine CO 2 Two-stage electrodialysis system and method for barren liquor waste liquid |
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