CN111701397B - Process for removing sulfate ions and chloride ions in organic amine desulfurization solution and reducing loss of organic amine solution - Google Patents

Process for removing sulfate ions and chloride ions in organic amine desulfurization solution and reducing loss of organic amine solution Download PDF

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CN111701397B
CN111701397B CN202010635211.8A CN202010635211A CN111701397B CN 111701397 B CN111701397 B CN 111701397B CN 202010635211 A CN202010635211 A CN 202010635211A CN 111701397 B CN111701397 B CN 111701397B
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organic amine
solution
ions
sulfate ions
desulfurization
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CN111701397A (en
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张小龙
邱正秋
王建山
刘鹏举
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
Chengdu Advanced Metal Materials Industry Technology Research Institute Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
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    • B01D2258/0283—Flue gases

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Abstract

The invention discloses a process for removing sulfate ions and chloride ions in an organic amine desulfurization solution and reducing the loss of the organic amine solution, belonging to the technical field of organic amine liquid purification. The invention aims to overcome the defects thatThe process for removing impurity ions in organic amine desulfurization solution and reducing solution loss comprises the following steps: SO is absorbed and separated by organic amine desulfurization solution through amphoteric resin exchange column4 2‑Organic amine cation and separation of Cl‑Ions then containing Cl‑Removing Cl by adsorbing the ion and a small amount of organic amine cation solution through an anion resin exchange column‑And the purified liquid is mixed and then returns to the desulfurizing tower. The invention can be used for solving the problems of poisoning, desulfurizer loss, poor desulfurization effect and the like of the organic amine process desulfurizer, so as to ensure the stable and efficient operation of a desulfurization system and greatly reduce the operation cost of the process.

Description

Process for removing sulfate ions and chloride ions in organic amine desulfurization solution and reducing loss of organic amine solution
Technical Field
The invention belongs to the technical field of organic amine liquid, and particularly relates to a process for removing sulfate ions and chloride ions in an organic amine desulfurization solution and reducing the loss of the organic amine solution.
Background
Organic amine technology is adopted for desulfurization of No. 3 steel sintering flue gas, the pH value of the desulfurization barren solution is controlled to be 5.0-6.0 in the operation process of a desulfurization system, and SO is absorbed2The pH value of the post-pregnant solution is controlled to be 4.0-5.0, and Cl in the solution is generated due to the cyclic absorption-desorption of the desulfurizer-And SO4 2-There is severe enrichment when Cl is present-The concentration reaches a certain degree, so that the corrosion of components in the system is serious, the outer wall of the desulfurizing tower is corroded and leaked, and the operation of the desulfurizing system is seriously influenced; and SO4 2-The increase can cause the desulfurization solution to become invalid, produces the crystallization and then blocks up the system at analytic process when the content is high, and these impurity ions have not only seriously influenced the sulphur absorption effect of desulfurizer, have reduced desulfurization efficiency, have increased the risk of the unstable operation of system moreover, and the energy consumption rises sharply, and the cost is increased.
Currently, the ion exchange resin desalination method in CN101966424A is adopted on site, which comprises the following steps: (1) contacting an organic amine absorbent comprising sulfate ions and chloride ions with NaOH to obtain a first mixtureMixing the liquid; (2) cooling the first mixed liquid to below 12 ℃ to form a crystalline solid in the first mixed liquid, and then separating the crystalline solid to obtain a second mixed liquid; (3) the second mixed liquid is contacted with an anion exchange resin. However, this method is only for Cl-、SO4 2-Ions are removed to a certain extent, the problems of low Cl removal effect and large loss of a desulfurization solution still exist, the discharge of waste alkaline wastewater generated by regenerating and using alkali liquor is difficult to treat, and meanwhile, the service life of the resin is short.
CN105540935A discloses a method for removing fluoride ions and sulfate ions in an organic amine solution, calcium carbonate is added into the solution to react with acid radical ions to generate precipitates, the precipitates are filtered and then enter an ion exchange column to further remove impurities, but the impurity ions, namely sodium ions, in the organic amine solution are increased, the loss of the organic amine solution is large, and the recycling of the amine solution is not facilitated.
Therefore, an efficient, long-term removal of Cl was investigated-And SO4 2-The ionic process and the method thereof, and a device which does not discharge waste water, stabilizes the operation of a desulfurization system and saves investment are urgent.
Disclosure of Invention
The invention aims to solve the problems of insufficient removal rate of impurity ions in a desulfurization solution, large loss of the desulfurization solution, high impurity removal cost, difficult discharge of wastewater and the like in the conventional organic amine desulfurization process for sintering flue gas.
The invention provides a process for removing sulfate ions and chloride ions in an organic amine desulfurization solution and reducing the loss of the organic amine solution, which comprises the following steps:
A. the organic amine absorbent containing sulfate ions and chloride ions enters an amphoteric resin exchange column after being adsorbed and filtered by an activated carbon adsorption tank to adsorb organic amine cations and sulfate ions;
B. washing and regenerating the amphoteric resin adsorbing the organic amine cations and the sulfate ions to obtain a first purifying solution containing the sulfate ions and the organic amine cations;
C. and (3) allowing the solution containing chloride ions obtained after adsorption by the amphoteric resin to enter an anion resin exchange column, and adsorbing the chloride ions to obtain a second purified liquid.
In the above step B, the first purified liquid is treated as follows:
when the concentration of sulfate ions is less than 40g/L, directly returning to a desulfurization system;
when the concentration of sulfate ions is 40-60 g/L and the concentration of sodium ions is less than or equal to 5g/L, directly returning to the desulfurization system;
when the concentration of sulfate ions is 40-60 g/L and the concentration of sodium ions is more than 5g/L, returning to a desulfurization system after freezing and crystallizing;
when the concentration of the sulfate ions is more than 60g/L, the sulfate ions return to the desulfurization system after being frozen and crystallized.
Wherein, in the process, the operation of freezing and crystallizing is as follows: through a freezing crystallization system, adjusting the pH value of the solution to 9.5-10.0 by adopting 20-30 wt% of NaOH, and rapidly crystallizing Na at the temperature of 4-7 DEG C2SO4And (3) a solid.
And C, directly returning the obtained second purified liquid to the desulfurization system.
In the step A, the concentration of sulfate ions in the organic amine absorbent containing sulfate ions and chloride ions is 30-120 g/L, and the concentration of chloride ions is 0.5-2.8 g/L.
In the step A, after the solution is treated by an activated carbon adsorption tank, the temperature of the obtained solution is 55-60 ℃, and the pH value is 4.6-5.2.
Wherein, in the step A, the amphoteric resin is adsorbed by adopting an upper inlet and lower outlet mode, and the liquid inlet amount is 10-30 m3The time is 38-42 min.
In the step A, the amphoteric resin is strong in alkali and weak in acid, and the particle size is 0.1-0.3 mm.
In the step B, when the amphoteric resin is washed and regenerated, an upper inlet and lower outlet mode is adopted, and the washing flow is 20-30 m3The time is 18-22 min.
In the step C, the anion resin is macroporous weak base resin.
Wherein, in the step C, when the anion resin is absorbed, an upper inlet and lower outlet mode is adopted, and the liquid inlet amount is 20-24 m3The time is 28-32 min.
Wherein, in the step C, the method further comprises the following steps: the anion resin for adsorbing chloride ions is sequentially subjected to washing 1, washing 2, regeneration, washing 3, washing 4 and evacuation treatment, and the method comprises the following steps:
the washing 1 adopts an up-in and down-out mode, and the flow is controlled to be 4-5 m3；
The washing 2 adopts a mode of downward feeding and upward discharging, and the flow is controlled to be 4-5 m3；
The regeneration adopts a mode of feeding in and discharging out of 3-5% NaOH solution with the flow of 12-15 m3H, the time is 8-10 min;
the washing 3 adopts an upward-in and downward-out mode of industrial water, and the flow is controlled to be 2-3 m3；
The washing 4 adopts an upward-in and downward-out mode of industrial water, and the flow is controlled to be 4-5 m3。
The invention has the beneficial effects that:
the invention firstly contacts the surface of amphoteric resin with external concentrated salt (sulfate ion, organic amine cation) solution, sulfate ion and most of organic amine cation are adsorbed by the surface to form inner salt, low-salt chloride ion and a small amount of desulfurizer are separated, and the adsorbed sulfate ion and organic amine cation are regenerated by water washing to obtain the product containing high-concentration SO4 2-And organic amine cation solution, removing SO by freezing4 2-When the temperature is below the system control index, the gas can directly return to the desulfurization system; then the solution containing chloride ions and a small amount of desulfurizer is subjected to anion exchange to remove Cl-Removing Cl-The purified liquid can be directly returned to the desulfurization system. In the invention, after the amphoteric resin is separated, the desulfurizer in the solution containing chloride ions is reduced (the concentration of organic amine cations is reduced to below 10 percent from about 40 percent before separation), and the organic amine desulfurizer is prevented from entering an anion resin bed from the source, thereby reducing the loss.
The invention can effectively solve the problems of chemical loss and thermal stability removal of the desulfurizer, ensures the cleanness of the desulfurizer in a desulfurization system, and ensures the cleanness of the desulfurizerThe desulfurization effect is ensured, the regeneration energy consumption is reduced, and the desulfurization operation cost is greatly saved; meanwhile, the waste liquid generated in the steps of washing, regeneration and the like can be effectively recycled, secondary pollution is avoided, and water for sintering and purchased CaCl are reduced2And (3) solution.
Drawings
FIG. 1 is a process flow diagram of the present invention for removing sulfate ions and chloride ions from an organic amine desulfurization solution and reducing the loss of the organic amine solution.
Detailed Description
Due to SO4 2-Ions with Cl-Ions have competition effect in the process of anion resin adsorption, and SO is generated when CN101966424A is directly adsorbed by anion resin4 2-Ion adsorption capacity greater than Cl-Ions, SO adsorbing SO4 2-More ions and Cl-The ion removal rate is low; in addition, the anionic resin adsorbs SO by internal structural cross-linking4 2-After ionization, the organic amine ions will react with SO4 2-The ions are combined and adsorbed (the radius of the chloride ions is small, the combination is very little), organic amine ions adsorbed on the surface can be only recovered by adopting water washing, and after the internal adsorption, the organic amine ions can not be recovered by adopting water washing, so that NaOH regeneration is needed, the desulfurization solution is lost along with the regenerated solution, and the risk of introducing sodium ions exists.
Based on the problems, the invention develops a process for removing sulfate ions and chloride ions in an organic amine desulfurization solution and reducing the loss of the organic amine solution, which comprises the following steps:
A. the organic amine absorbent containing sulfate ions and chloride ions enters an amphoteric resin exchange column after being adsorbed and filtered by an activated carbon adsorption tank to adsorb organic amine cations and sulfate ions;
B. washing and regenerating the amphoteric resin adsorbing the organic amine cations and the sulfate ions to obtain a first purifying solution containing the sulfate ions and the organic amine cations;
C. and (3) allowing the solution containing chloride ions obtained after adsorption by the amphoteric resin to enter an anion resin exchange column, and adsorbing the chloride ions to obtain a second purified liquid.
In the invention, the organic amine absorbent containing sulfate ions and chloride ions is used for removing acid components (such as sulfur dioxide, sulfur trioxide, hydrogen chloride and nitrogen oxide) in the mixed gas, purifying the mixed gas to obtain a rich solution (the temperature of the rich solution is generally 48-52 ℃), exchanging heat of the rich solution through a lean solution heat exchanger, then entering a regeneration tower, and regenerating SO at 102-110 DEG C2And changing the solution into barren solution, and then exchanging heat (namely, absorbing and desorbing acid components) through a barren and rich solution heat exchanger to obtain mixed liquid, wherein the sulfate ion concentration of the mixed liquid is 30-120 g/L, and the chloride ion concentration of the mixed liquid is 0.5-2.8 g/L. The organic amine absorbent for removing the acidic components in the mixed gas can be various conventional organic amine absorbents, and can be flue gas desulfurization agent disclosed in CN101721884A, for example.
In the invention, the method for removing sulfate ions and chloride ions in the organic amine absorbent is particularly suitable for treating the organic amine absorbent to purify sintering flue gas in a sintering process and obtaining the organic amine absorbent containing solid suspended matters, sulfate ions and chloride ions after desorption. In this case, the organic amine absorbent containing sulfate ions and chloride ions can also contain suspended solids, so that the invention is matched with an activated carbon adsorption tank (which is a commonly used filter tank, and the activated carbon is generally cylindrical with the diameter of 3-5 mm and the height of 10 mm), and has the effects of removing large suspended solids including solid particles and the like; and secondly, as pretreatment before resin adsorption, the solution is filtered and adsorbed by an activated carbon adsorption tank, so that the filtering precision reaches below 0.45 micrometer, and then the solution enters subsequent precision filtration. The solid suspension is usually calcium sulfate, sulfur, calcium fluoride, aluminum calcium sulfate, TiO2PbO, calcium sulfite, dust and the like; the active carbon adsorption tank is mainly used for removing suspended matters, and the concentrations of organic amine cations, sulfate ions and chloride ions are basically unchanged.
In the step A, after the treatment of the activated carbon adsorption tank, the temperature of the obtained solution is 55-60 ℃, the pH value is 4.6-5.2, and the solution is beneficial to adsorption of SO by amphoteric resin4 2-And an organic amine cation, and a cationic group,is more favorable for separating Cl-Ions.
In the step A of the invention, amphoteric resin is adopted, so that sulfate ions and most of organic amine cations are adsorbed on the surface of the adsorption resin, and can be directly regenerated by water washing, thereby not only effectively separating chloride ions and reducing the chance of the organic amine desulfurizer entering the anion resin, but also avoiding the problem of loss of the organic amine cations (desulfurizer components).
The organic amine solution (barren solution) after passing through the activated carbon adsorption tank is discharged with a liquid of 10-30 m3The solution enters the amphoteric resin separation column, and the rest of the solution returns to the desulfurization system, so that the normal operation of the desulfurization system can not be influenced under the flow control; the steps of amphoteric resin adsorption-water washing regeneration are used for recovering a large amount of organic amine desulfurizer and SO4 2-Reduction with Cl-The content of the carried-out desulfurizer is 10-30 m in liquid inlet amount during adsorption3The reaction time is 38-42 min, and the regeneration flow of water washing is 20-30 m3The time is 18-22 min, namely, the operation is carried out for about 60min in one period; the washing regeneration adopts soft water to run from top to bottom so as to keep the stability of the resin bed; the regeneration liquid (i.e., the first purified liquid) is treated as follows:
when the concentration of sulfate ions is less than 40g/L, directly returning to a desulfurization system;
when the concentration of sulfate ions is 40-60 g/L and the concentration of sodium ions is less than or equal to 5g/L, directly returning to the desulfurization system;
when the concentration of sulfate ions is 40-60 g/L and the concentration of sodium ions is more than 5g/L, returning to a desulfurization system after freezing and crystallizing;
when the concentration of the sulfate ions is more than 60g/L, the sulfate ions return to the desulfurization system after being frozen and crystallized.
Wherein, the operation of freezing and crystallizing comprises the following steps: through a freezing crystallization system, adjusting the pH value of the solution to 9.5-10.0 by adopting 20-30 wt% of NaOH, and rapidly crystallizing Na at the temperature of 4-7 DEG C2SO4And (3) a solid.
The amphoteric resin adopted by the invention is strong in alkali and weak in acid, and the particle size is 0.1-0.3 mm. SO in solution during adsorption4 2-Adsorption on the resin (SO) simultaneously with the organic amine cation4 2-Ion-preferred Cl-Adsorption), i.e. when C is presentl-The separation rate of ions and other ions reaches the maximum, the discharge valve is opened after the general system operates for about 5-10 min, the valve is closed when the general system operates for 38-42 min, and the discharged solution enters an intermediate tank containing high-concentration Cl-And low concentrations of organic amine cations and SO4 2-For the next step to ensure the removal of Cl-The loss of the organic amine component is reduced to less than 1.0 kg/cycle.
In step C of the present invention, the anion resin is treated with macroporous weak base resin (such as D296, D301T, etc.) containing Cl-And a low-concentration desulfurizer solution, which comprises the following treatment steps:
adsorption-washing 1-washing 2-regeneration-washing 3-washing 4-evacuation: the adsorption is carried out by feeding in and discharging out from the top, and the liquid inlet amount is 20-24 m3H, the time is 28-32 min; the water washing step 1 is that the water enters from the top and goes out from the bottom, and the soft water quantity is controlled to be 4-5 m3The discharged waste liquid can be used for regenerating amphoteric resin, so that the loss of a desulfurizing agent is reduced to be below 0.5 kg/period, and the stable and efficient desulfurizing effect is ensured; the washing step 2 is that the water enters from the bottom and goes out from the top, and the soft water amount is controlled to be 4-5 m3The discharged water is stored in a circulating tank to be used as water for the next water washing 1; the regeneration is that the water enters from the bottom and goes out from the top, a 3-5% NaOH solution is adopted, and the flow rate is 12-15 m3Discharging waste alkali liquor for neutralizing the acid wastewater for 8-10 min; the washing step 3 is that the water enters from the top and goes out from the bottom, and the industrial water amount is controlled to be 2-3 m3The discharged wastewater is used for preparing CaCl2Spraying the solution on the sinter; the washing step 4 is that the water enters from the top and goes out from the bottom, and the industrial water amount is controlled to be 4-5 m3The wastewater is used as dilution water of a 3-5% NaOH solution; finally emptying to ensure Na+Not entering the system; the control time is about 75min after 1 cycle of operation.
In the step C, the second purified liquid obtained by the adsorption of the anion resin can be directly returned to the desulfurization system.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the following examples and comparative examples, the organic amine absorbent containing sulfate ions and chloride ions is according to CN101721884AThe flue gas desulfurizing agent (i.e. organic amine absorbent) and the flue gas desulfurizing method disclosed in the publication adopt the flue gas desulfurizing agent with the sulfur dioxide concentration of 3000-3The sulfur trioxide concentration is 100-500mg/Nm3The chlorine concentration is 100-250mg/Nm3The sintering flue gas of the sintering machine is purified and desorbed (SO)2Regeneration) and the desorbed solution is circularly used for purifying and desorbing the sintering flue gas for 10 times.
In the following examples and comparative examples, the amphoteric resin (i.e., the delayed resin) was TP resin of Zhejiang light industry Co., Ltd. having a total exchange capacity of 4.5mmol/ml or more; the anion exchange resin is preferably D301R macroporous weakly basic styrene system available from Tianjin Nankai Hechengzhi resin Co., Ltd, and has a total exchange capacity of 4.8 mmol/g.
In the following examples and comparative examples, the concentration of sulfate ions was as BaSO4Measured by gravimetric method, the concentration of chloride ions is AgNO3Measured by titration.
Example 1
A. When the process is in initial operation, SO is absorbed by the desulfurization solution2Enters a heat exchanger and regenerates SO at the temperature of between 102 and 110 DEG C2After heat exchange, an organic amine solution containing sulfate ions and chloride ions is obtained and flows into an activated carbon adsorption tank, wherein the sulfate ions in the solution are 37g/L, the chloride ions are 0.7g/L, the content of a desulfurizing agent is 32g/L, the temperature is 55-60 ℃, and the pH value is 4.8-5.2;
B. take about 12.5m3Pumping the solution into amphoteric resin exchange column, and adsorbing organic amine cation (desulfurizer component) and SO by top-in-bottom-out mode4 2-After running for 5-10 min, opening an exhaust valve to enable organic amine cations and SO4 2-With Cl-Separation, i.e. containing a high concentration of Cl-Discharging the solution, closing the valve after running for 40min, and carrying out water washing regeneration on the amphoteric resin at the regeneration flow of 21m3After a time of 20min, the sulphate-containing solution obtained (about 9.5 m)3) 42g/L of sulfate radical, 0.06g/L of chloride ion and 36g/L of desulfurizer content, and directly returning to the desulfurization system;
C. chloride ion-containing solution (about 10 m)3) 6.3g/L of sulfate radical, 0.8g/L of chloride ion and 5.8g/L of desulfurizer, pumping into an intermediate tank, pumping into an anion resin exchange column by a pump, treating for 30min by adopting an up-in-down discharging mode, and removing chloride ions to obtain a solution (about 10 m)3) 0.02g/L of medium chloride ion, 1.2g/L of sulfate radical and 5.7g/L of desulfurizer content; directly returning to a desulfurization system;
after adsorption, the anion resin is washed by water 1, water 2, regeneration, water 3, water 4 and emptied: washing with water 1 to remove the surface desulfurizer, wherein the washing solution is used for the regenerated water of the amphoteric resin; washing 2 is used for washing away residual desulfurizer, and the washing liquid is used for water for washing 1; regeneration adopts a mode of downward feeding and upward discharging, and the flow rate of NaOH solution is 3-5 percent and is 12-15 m3The time is 8min, so that the resin can be fully soaked and regenerated; after regeneration, washing with water 3 to remove Na+And residual Cl-(ii) a Washing with Water 4 to remove the residual Na+And finally emptying the washing liquid as water for preparing 3-5% NaOH.
The whole system can directly return to the system when running with the chloride ion removal rate of 91.4%, the organic amine loss of 0.25% and the sulfate radical concentration being low.
Example 2
A. When the process is in normal operation, the desulfurization solution absorbs SO2Entering a heat exchanger, and regenerating SO at 110 DEG C2After heat exchange, the organic amine solution flows into an activated carbon adsorption tank to obtain an organic amine solution containing sulfate ions and chloride ions, and then flows into the activated carbon adsorption tank, wherein the sulfate ions in the solution are 84g/L, the chloride ions in the solution are 2.4g/L, the content of a desulfurizing agent is 61g/L, the temperature is 55 ℃, and the pH value is 5.2;
B. take about 20m3Pumping the solution into amphoteric resin exchange column, and adsorbing organic amine cation (desulfurizer component) and SO by top-in-bottom-out mode4 2-After running for 5-10 min, opening an exhaust valve to enable organic amine cations and SO4 2-With Cl-Separation, i.e. containing a high concentration of Cl-Discharging the solution, operating for 40min, closing the valve for water washing regeneration, wherein the regeneration flow is 24m3After a time of 20min, the sulphate-containing solution obtained (about 13 m)3) 96g/L of sulfate radical, 0.2g/L of chloride ion and 82g/L of desulfurizer content, freezing and crystallizing,2g/L of sulfate radical, 0.19g/L of chloride ion and 82g/L of desulfurizer in the solution are returned to the desulfurization system;
C. chloride ion-containing solution (about 15 m)3) 28.2g/L of sulfate radical, 3.02g/L of chloride ions and 10.2g/L of desulfurizer, entering an intermediate tank, pumping into an anion resin exchange column through a pump, adopting an upper inlet and lower outlet mode, and treating capacity of 20-30 m3H, time 30min, after removal of chloride ions, the resulting solution (about 15 m)3) 0.3g/L of medium chloride ion, 9.6g/L of sulfate radical and 8.6g/L of desulfurizer content;
after adsorption, the anion resin is washed by water 1, water 2, regeneration, water 3, water 4 and emptied: washing with water 1 to remove the surface desulfurizer, wherein the washing solution is used for the regenerated water of the amphoteric resin; washing 2 is used for washing away residual desulfurizer, and the washing liquid is used for water for washing 1; regeneration adopts a mode of downward feeding and upward discharging, and the flow rate of NaOH solution is 3-5 percent and is 12-15 m3The time is 8min, so that the resin can be fully soaked and regenerated; after regeneration, washing with water 3 to remove Na+And residual Cl-(ii) a Washing with Water 4 to remove the residual Na+And finally emptying the washing liquid as water for preparing 3-5% NaOH.
The removal rate of chloride ions, sulfate radicals and organic amine of the whole system is 85.3%, 90.2% and 0.7%.
Comparative example 1
The existing organic amine desulfurization solution desalination process adopts ion exchange resin for dechlorination and freeze crystallization for desulfate radical removal, ion exchange resin D301R for dechlorination ion is adopted, and the amount of treated solution is 15m3The content of the desulfurizer is 753kg, the concentration of chloride ions is 2.1g/L, the concentration of sulfate radicals is 72g/L, the concentration of the absorbed chloride ions is 0.8g/L, the removal rate is 61.9 percent, the removal rate of the sulfate radicals is about 30 percent (80 percent of sulfate radicals are removed by freezing crystallization, and the total removal rate is 86 percent), the loss amount of the desulfurizer is 36 kg/period, namely the loss rate is 4.8 percent, the desulfurization effect is influenced, and then fresh desulfurizer needs to be supplemented to stabilize the concentration of the desulfurizer.

Claims (10)

1. The process for removing sulfate ions and chloride ions in the organic amine desulfurization solution and reducing the loss of the organic amine solution is characterized by comprising the following steps of: the method comprises the following steps:
A. the organic amine absorbent containing sulfate ions and chloride ions enters an amphoteric resin exchange column after being adsorbed and filtered by an activated carbon adsorption tank to adsorb organic amine cations and sulfate ions;
B. washing and regenerating the amphoteric resin adsorbing the organic amine cations and the sulfate ions to obtain a first purifying solution containing the sulfate ions and the organic amine cations;
C. and (3) allowing the solution containing chloride ions obtained after adsorption by the amphoteric resin to enter an anion resin exchange column, and adsorbing the chloride ions to obtain a second purified liquid.
2. The process of claim 1 for removing sulfate ions and chloride ions from an organic amine desulfurization solution and reducing loss of the organic amine solution, wherein: in step B, the obtained first purified liquid is treated as follows:
when the concentration of sulfate ions is less than 40g/L, directly returning to a desulfurization system;
when the concentration of sulfate ions is 40-60 g/L and the concentration of sodium ions is less than or equal to 5g/L, directly returning to the desulfurization system;
when the concentration of sulfate ions is 40-60 g/L and the concentration of sodium ions is more than 5g/L, returning to a desulfurization system after freezing and crystallizing;
when the concentration of the sulfate ions is more than 60g/L, the sulfate ions return to the desulfurization system after being frozen and crystallized.
3. The process for removing sulfate ions and chloride ions from an organic amine desulfurization solution and reducing the loss of the organic amine solution as set forth in claim 2, wherein: the operation of freezing and crystallizing is as follows: through a freezing crystallization system, adjusting the pH value of the solution to 9.5-10.0 by adopting 20-30 wt% of NaOH, and rapidly crystallizing Na at the temperature of 4-7 DEG C2SO4And (3) a solid.
4. The process of claim 1 for removing sulfate ions and chloride ions from an organic amine desulfurization solution and reducing loss of the organic amine solution, wherein: and C, directly returning the obtained second purified liquid to a desulfurization system.
5. The process of claim 1 for removing sulfate ions and chloride ions from an organic amine desulfurization solution and reducing loss of the organic amine solution, wherein: in the step A, at least one of the following items is satisfied:
in the organic amine absorbent containing sulfate ions and chloride ions, the concentration of the sulfate ions is 30-120 g/L, and the concentration of the chloride ions is 0.5-2.8 g/L;
after the treatment of the activated carbon adsorption tank, the temperature of the obtained solution is 55-60 ℃, and the pH value is 4.6-5.2.
6. The process of claim 1 for removing sulfate ions and chloride ions from an organic amine desulfurization solution and reducing loss of the organic amine solution, wherein: in the step A, when the amphoteric resin is adsorbed, an upper inlet and lower outlet mode is adopted, and the liquid inlet amount is 10-30 m3The time is 38-42 min.
7. The process of claim 1 for removing sulfate ions and chloride ions from an organic amine desulfurization solution and reducing loss of the organic amine solution, wherein: in the step A, the amphoteric resin is strong in alkali and weak in acid, and the particle size is 0.1-0.3 mm.
8. The process of claim 1 for removing sulfate ions and chloride ions from an organic amine desulfurization solution and reducing loss of the organic amine solution, wherein: in the step B, when the amphoteric resin is washed and regenerated by water, an upper inlet and lower outlet mode is adopted, and the washing flow is 20-30 m3The time is 18-22 min.
9. The process of claim 1 for removing sulfate ions and chloride ions from an organic amine desulfurization solution and reducing loss of the organic amine solution, wherein: in the step C, at least one of the following items is satisfied:
the anion resin is macroporous weak base resin;
when the anion resin is absorbed, an upper inlet and a lower outlet mode are adopted, and the liquid inlet quantity is20～24m3The time is 28-32 min.
10. The process of claim 1 for removing sulfate ions and chloride ions from an organic amine desulfurization solution and reducing loss of the organic amine solution, wherein: in the step C, the method also comprises the following steps: the anion resin for adsorbing chloride ions is sequentially subjected to washing 1, washing 2, regeneration, washing 3, washing 4 and evacuation treatment, and the method comprises the following steps:
the washing 1 adopts an upper inlet and lower outlet mode, and the water quantity is controlled to be 4-5 m3；
The washing 2 adopts a mode of downward feeding and upward discharging, and the water quantity is controlled to be 4-5 m3；
The regeneration adopts a mode of feeding in and discharging out of 3-5% NaOH solution with the flow of 12-15 m3H, the time is 8-10 min;
the washing 3 adopts an upward-in and downward-out mode of industrial water, and the water quantity is controlled to be 2-3 m3；
The washing 4 adopts an upward-in and downward-out mode of industrial water, and the water quantity is controlled to be 4-5 m3。
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Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076618A (en) * 1976-07-09 1978-02-28 Photocircuits Division Of Kollmorgen Corporation Treatment of liquids containing complexed heavy metals and complexing agents
AU579647B2 (en) * 1985-02-21 1988-12-01 Asahi Kasei Kogyo Kabushiki Kaisha Process for adsorption treatment of dissolved fluorine
US4952386A (en) * 1988-05-20 1990-08-28 Athens Corporation Method and apparatus for purifying hydrogen fluoride
WO2012012027A1 (en) * 2010-07-20 2012-01-26 Powerspan Corp. Absorption media for scrubbing co2 from a gas stream and methods using the same
CN101966424B (en) * 2010-09-09 2013-08-14 攀钢集团钢铁钒钛股份有限公司 Method for removing sulfate ions and chloride ions in organic amine absorbent
CN203564814U (en) * 2013-01-29 2014-04-30 天津大港油田滨港集团博弘石油化工有限公司 Liquid acrylamide refining device
CN103663798B (en) * 2013-12-30 2015-04-22 南京大学 Gradual treatment and recovery method for secondary treatment effluent of printing and dyeing wastewater
CN106178591B (en) * 2015-05-08 2019-03-15 北京思践通科技发展有限公司 A method of purification organic amine
US11453636B2 (en) * 2017-06-22 2022-09-27 Archer Daniels Midland Company Process for separation and purification of a dicarboxylic acid containing mixture
CN107827977A (en) * 2017-11-15 2018-03-23 广东天普生化医药股份有限公司 A kind of method based on ion-exchange resin purification UTI
CN107930399A (en) * 2017-11-21 2018-04-20 攀钢集团攀枝花钢铁研究院有限公司 The removal methods of foreign ion in a kind of organic amine desulfuration solution
CN110721553A (en) * 2018-07-16 2020-01-24 北京思践通科技发展有限公司 System and method for removing heat stable salt in organic amine liquid
CN210044941U (en) * 2019-04-17 2020-02-11 浙江沧创环境科技有限公司 Novel tower amine liquid purifies device
CN110975612A (en) * 2019-11-20 2020-04-10 金堆城钼业股份有限公司 Method for removing sodium ions in organic amine liquid with low amine loss
CN111203026A (en) * 2020-01-19 2020-05-29 成都能净科技有限公司 Purification and recovery method suitable for amine liquid

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