CN112916054A - Method and device for regenerating ion exchange resin by gas-liquid mixing - Google Patents
Method and device for regenerating ion exchange resin by gas-liquid mixing Download PDFInfo
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- CN112916054A CN112916054A CN202110053460.0A CN202110053460A CN112916054A CN 112916054 A CN112916054 A CN 112916054A CN 202110053460 A CN202110053460 A CN 202110053460A CN 112916054 A CN112916054 A CN 112916054A
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- 239000007788 liquid Substances 0.000 title claims abstract description 241
- 238000000034 method Methods 0.000 title claims abstract description 61
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003456 ion exchange resin Substances 0.000 title claims abstract description 38
- 229920003303 ion-exchange polymer Polymers 0.000 title claims abstract description 38
- 238000002156 mixing Methods 0.000 title claims abstract description 37
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 28
- 238000011069 regeneration method Methods 0.000 claims abstract description 148
- 230000008929 regeneration Effects 0.000 claims abstract description 144
- 239000003480 eluent Substances 0.000 claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 41
- 230000003213 activating effect Effects 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims description 208
- 229920005989 resin Polymers 0.000 claims description 208
- 238000001179 sorption measurement Methods 0.000 claims description 107
- 229920006395 saturated elastomer Polymers 0.000 claims description 106
- 238000005273 aeration Methods 0.000 claims description 82
- 230000002378 acidificating effect Effects 0.000 claims description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 44
- 238000003860 storage Methods 0.000 claims description 44
- 230000004913 activation Effects 0.000 claims description 32
- 239000003729 cation exchange resin Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 abstract description 76
- 239000003513 alkali Substances 0.000 abstract description 52
- 238000005406 washing Methods 0.000 abstract description 52
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 239000002585 base Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 55
- 238000001994 activation Methods 0.000 description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 27
- 229910052759 nickel Inorganic materials 0.000 description 27
- 229910052802 copper Inorganic materials 0.000 description 25
- 239000010949 copper Substances 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 24
- 230000008569 process Effects 0.000 description 21
- 238000010828 elution Methods 0.000 description 15
- 239000002351 wastewater Substances 0.000 description 15
- 239000008399 tap water Substances 0.000 description 14
- 235000020679 tap water Nutrition 0.000 description 14
- 238000004064 recycling Methods 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000005086 pumping Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 238000003795 desorption Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
- B01J49/53—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for cationic exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a method and a device for regenerating ion exchange resin by gas-liquid mixing, wherein the method comprises the following steps: using acid liquor for regeneration; the water is used for regeneration by water washing acid liquor; washing with water after acid; activating with alkali solution and washing with water after alkali. The method has the advantages of short time consumption, high regeneration efficiency, low acid and base consumption and the like, the ion exchange resin can be completely regenerated within 2-3h, and the concentration of the obtained high-concentration heavy metal eluent is not less than 60g/L, so that the method can be directly used for the subsequent heavy metal resource treatment, and the aim of obtaining the high-concentration eluent by using the least regeneration reagent is fulfilled.
Description
Technical Field
The invention relates to the technical field of electroplating wastewater treatment, in particular to a method and a device for regenerating ion exchange resin by gas-liquid mixing.
Background
A large amount of heavy metal wastewater is generated in the production processes of mining and metallurgy, mechanical manufacturing, chemical industry, electronics, instruments and other industries. The most widely applied heavy metal wastewater treatment process is an alkali precipitation method, but the method has high treatment cost, large sludge production amount and difficult recycling of metal resources.
The ion exchange resin has good chemical stability and ion selectivity, has larger exchange adsorption capacity to heavy metal ions in the wastewater, and the effluent water quality of the heavy metal-containing wastewater treated by the ion exchange resin is good, so that the dual recycling of water and heavy metals can be realized, and the ion exchange resin is more and more concerned in the field of heavy metal wastewater treatment. However, in the prior art, the regeneration of the ion exchange resin needs a large amount of acid and alkali, the regeneration and activation process is slow, the time required by the regeneration and activation is long, and the concentration of metal ions in the obtained regenerated liquid is generally less than 30g/L, so that the subsequent resource treatment is not facilitated. The regenerated liquid is returned to the tank or is subjected to electrodeposition, the concentration of metal ions is not less than 60g/L, and the eluent with lower concentration needs to be concentrated again.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a method and an apparatus for regenerating ion exchange resin by mixing gas and liquid, which greatly reduce the reagent amount and time consumed by the regeneration of ion exchange resin, and obtain high-concentration heavy metal eluent.
In one aspect of the invention, a method for regenerating an ion exchange resin by mixing gas and liquid is provided. According to an embodiment of the invention, the method comprises:
(1) introducing the first acidic regeneration liquid into an adsorption saturated resin column, and aerating at the bottom of the adsorption saturated resin column to obtain a first eluent, wherein the heavy metal concentration of the first eluent is not lower than 60 g/L;
(2) introducing a second acidic regeneration liquid into the adsorption saturated resin column, aerating at the bottom of the adsorption saturated resin column to obtain a second eluent, and returning the second eluent serving as the first acidic regeneration liquid to the step (1);
(3) introducing water into the adsorption saturated resin column, aerating at the bottom of the adsorption saturated resin column to obtain a third eluent, and returning the third eluent serving as a second acidic regeneration liquid to the step (2);
(4) introducing an alkaline activating solution into the adsorption saturated resin column, and aerating at the bottom of the adsorption saturated resin column to obtain a fourth eluent;
(5) and (3) introducing water into the adsorption saturated resin column, aerating at the bottom of the adsorption saturated resin column to obtain a fifth eluent, completing regeneration until the pH of the fifth eluent is less than 9, and returning the fifth eluent as an alkaline activating solution to the step (4).
According to the method for regenerating the ion exchange resin by gas-liquid mixing in the embodiment of the invention, 1) the first acidic regeneration liquid is quickly and fully contacted with the resin in a mode of aerating at the bottom of the adsorption saturated resin column (namely, in a gas-liquid mixing mode), so that the high-concentration heavy metal eluent with the concentration of not less than 60g/L is obtained, and further recycling is facilitated; 2) the method is characterized in that the alkali activating solution is fully contacted and activated with the resin by an aeration mode (namely a gas-liquid mixing mode) at the bottom of the resin column, so that the alkali activating speed is remarkably increased, the alkali activating time is shortened, and the using amount of the alkali activating solution is reduced; 3) after acid washing, alkali washing and water washing, the hardening of the resin is removed and the resin is fluidized by bottom aeration, and the gas and the liquid are fully mixed with the resin; 4) recycling of acid washing and liquid removing is realized by returning the second eluent as the first acidic regeneration liquid to the step (1) and returning the third eluent as the second acidic regeneration liquid to the step (2), so that the sum of the volumes of fresh concentrated acid (namely 36.5% of concentrated hydrochloric acid or 98% of concentrated sulfuric acid) and tap water added in the whole acid regeneration process is equal to the volume of the generated high-concentration heavy metal regeneration liquid (namely the first eluent), and no additional wastewater is generated; recycling of the alkaline eluent is realized by returning the fifth eluent as the alkaline activating solution to the step (4); except for first elution, the mechanically applied acid solution used in the step (1) is the low-concentration heavy metal regeneration liquid obtained by the last cyclic elution, and the mechanically applied water washing acid solution used in the step (2) is the acid solution obtained by the last cyclic washing. The volume of fresh acid (namely 36.5 percent of concentrated hydrochloric acid or 98 percent of concentrated sulfuric acid) actually consumed by the invention is about 0.5-1.0BV (BV, bed layer volume), the volume of 4-6 percent of NaOH (w/w) consumed by the invention is about 2.0-2.5BV, while the volume of fresh acid consumed by the prior art is 1.5-3.0BV and the volume of 4-6 percent of NaOH (w/w) consumed by the prior art is 3.0-3.5BV under the same condition, so that compared with the prior art, the amount of acid and alkali consumed by the invention is greatly reduced; according to the invention, the elution rate of 95-99% can be achieved within 1h in the acid washing regeneration process, the complete desorption and transformation process can be completed within 2-3h, and the ion exchange resin can be regenerated efficiently and rapidly, while the time consumed in the complete desorption and transformation process is more than 10h when the same elution rate is achieved under the same conditions by adopting the prior art, so that the regeneration time is greatly shortened compared with the prior art; the concentration of the heavy metal eluent obtained by the method is not lower than 60g/L, the heavy metal eluent can be directly used for electrodeposition to obtain metal simple substance nickel or returned to a tank, further concentration is not needed, the economic benefit is remarkable, and the concentration of the heavy metal eluent obtained under the same condition by adopting the prior art is less than 30g/L, so that the heavy metal eluent is not beneficial to subsequent recycling treatment. In conclusion, the method disclosed by the invention is short in time consumption, high in regeneration efficiency and small in acid and alkali consumption, the ion exchange resin can be completely regenerated within 2-3h, the obtained regenerated liquid with the heavy metal concentration of not less than 60g/L and the pH value of more than 2 can be directly used for subsequent heavy metal resource treatment, and the purpose of obtaining the high-concentration regenerated liquid with the least regeneration reagent is realized. The invention solves the technical problems that the regeneration of the ion exchange resin in the prior art needs a large amount of acid and alkali, the regeneration and activation process is slow, the time required by the regeneration and activation is long, the concentration of metal ions in the obtained regenerated liquid is generally less than 30g/L, and the subsequent resource treatment is not facilitated.
In addition, the method for regenerating the ion exchange resin by gas-liquid mixing according to the above embodiment of the invention may further have the following additional technical features:
in some embodiments of the invention, in step (1), aeration is performed on the bottom of the adsorption saturated resin column for 5-10 min.
In some embodiments of the invention, in step (2), aeration is performed on the bottom of the adsorption saturated resin column for 5-10 min.
In some embodiments of the invention, in step (3), aeration is performed on the bottom of the adsorption saturated resin column for 5-10 min.
In some embodiments of the invention, in step (4), aeration is performed on the bottom of the adsorption saturated resin column for 5-10 min.
In some embodiments of the invention, in step (5), aeration is performed on the bottom of the adsorption saturated resin column for 5-10 min.
In some embodiments of the present invention, in step (1), the pressure range of aeration at the bottom of the adsorption saturated resin column is 0.1-0.3 MPa.
In some embodiments of the present invention, in step (2), the pressure range of aeration at the bottom of the adsorption saturated resin column is 0.1-0.3 MPa.
In some embodiments of the present invention, in step (3), the pressure range of aeration at the bottom of the adsorption saturated resin column is 0.1-0.3 MPa.
In some embodiments of the present invention, in the step (4), the pressure range of aeration at the bottom of the adsorption saturated resin column is 0.1-0.3 MPa.
In some embodiments of the present invention, in the step (5), the pressure range of aeration at the bottom of the adsorption saturated resin column is 0.1-0.3 MPa.
In some embodiments of the invention, in step (2), the heavy metal concentration of the second eluent is not less than 10 g/L.
In some embodiments of the invention, in step (3), the pH of the third eluent is not greater than 4.
In some embodiments of the invention, in step (4), the pH of the fourth eluent is not greater than 11.
In some embodiments of the invention, in step (1), the first acidic regeneration liquid is selected from a solution of HCl having a mass fraction of 4-12% and H having a mass fraction of 5-10%2SO4At least one of (1).
In some embodiments of the invention, in step (2), the second acidic regeneration liquid is selected from a solution of HCl with a mass fraction of 4-12% and H with a mass fraction of 5-10%2SO4At least one of (1).
In some embodiments of the invention, in the step (4), the alkaline activating solution is a NaOH solution with a mass fraction of 4-6%.
In some embodiments of the invention, in the step (4), the alkaline activating solution is passed into the adsorption saturated resin column in a counter-current manner.
In some embodiments of the invention, in step (5), water is passed into the column of adsorption saturated resin in a counter-current manner.
In some embodiments of the invention, the ion exchange resin is a cation exchange resin.
In another aspect of the present invention, the present invention provides an apparatus for implementing the method for regenerating ion exchange resin by mixing gas and liquid as described in the above embodiments. According to an embodiment of the invention, the apparatus comprises:
the adsorption saturated resin column comprises a liquid inlet, a liquid inlet and outlet, a gas inlet and a gas outlet, wherein the liquid inlet and the gas outlet are arranged at the top of the adsorption saturated resin column, and the liquid inlet and the gas outlet are arranged at the bottom of the adsorption saturated resin column;
the first acidic regenerated liquid storage tank is respectively connected with the liquid inlet and the liquid outlet;
a first eluent storage tank connected to the liquid inlet and outlet;
the second acidic regeneration liquid storage tank is respectively connected with the liquid inlet and the liquid outlet;
the alkaline activation liquid storage tank is respectively connected with the liquid inlet and the liquid outlet;
the water supply unit is respectively connected with the liquid inlet and the liquid outlet;
an aeration unit connected to the gas inlet.
According to the device for regenerating the ion exchange resin by gas-liquid mixing, disclosed by the embodiment of the invention, the process of regenerating the ion exchange resin by gas-liquid mixing is implemented by adopting the device disclosed by the embodiment, the time consumption is short, the regeneration efficiency is high, the acid and alkali consumption is small, the ion exchange resin can be completely regenerated within 2-3h, the regenerated liquid with the heavy metal concentration not less than 60g/L and the pH value greater than 2 is obtained, the regenerated liquid can be directly used for the subsequent heavy metal resource treatment, and the purpose of obtaining the high-concentration regenerated liquid by using the minimum regeneration reagent is realized. In addition, the system can be stably and accurately controlled by the PLC automatic control operation.
In addition, the device for regenerating ion exchange resin by gas-liquid mixing according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the adsorption saturated resin column further comprises: the first water distributor is arranged at the top of the adsorption saturated resin column and is arranged below the liquid inlet and the gas outlet; the adsorption saturated resin column further comprises: and the second water distributor is arranged at the bottom of the adsorption saturated resin column and is arranged above the liquid inlet, the liquid outlet and the gas inlet.
In some embodiments of the present invention, a pH meter is disposed in the first acidic regeneration liquid storage tank.
In some embodiments of the present invention, a pH meter is disposed in the second acidic regeneration liquid storage tank.
In some embodiments of the invention, a pH meter is disposed in the alkaline activating solution storage tank.
In addition, it should be noted that all the features and advantages described in the present invention for the method for regenerating ion exchange resin by gas-liquid mixing are also applicable to the device for regenerating ion exchange resin by gas-liquid mixing, and are not described in detail herein.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a flow chart of a method for regenerating an ion exchange resin by gas-liquid mixing according to an embodiment of the invention.
Fig. 2 is a structural view of an apparatus for regenerating an ion exchange resin by gas-liquid mixing according to an embodiment of the present invention.
FIG. 3 is a graph showing the relationship between the volume of the nickel-containing regeneration liquid and the concentration of nickel in example 1.
FIG. 4 is a graph of the volume of nickel-containing regenerant liquid versus the concentration of nickel in comparative example 1.
FIG. 5 is a graph showing the relationship between the volume of the copper-containing regeneration liquid and the copper concentration in example 2.
Fig. 6 is a graph of the volume of the copper-containing regeneration liquid in comparative example 2 as a function of the copper concentration.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "axial", "radial", "circumferential", and the like, indicate orientations and positional relationships based on the orientations and positional relationships shown in the drawings, and are used merely for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the device or element so referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore, should not be construed as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In one aspect of the present invention, the present invention provides a method for regenerating ion exchange resin by mixing gas and liquid, referring to fig. 1, the method comprises the following steps:
s100: regenerating by using acid liquor
In the step, a first acidic regeneration liquid is introduced into an adsorption saturated resin column, the liquid is stopped to be fed after the first acidic regeneration liquid enters a resin tank and passes through a resin bed layer, the liquid feeding amount is about 0.5BV, the resin is fully contacted with acid liquid through bottom aeration, the first acidic regeneration liquid is kept stand for resin sedimentation, a first eluent is obtained, and the heavy metal concentration of the first eluent is not lower than 60 g/L. And (5) repeatedly feeding the regeneration liquid for aeration until the concentration of the discharged liquid is less than 60g/L, and then entering the step S200. The resin layer is fluidized by a mode of aerating at the bottom of the adsorption saturated resin column (namely a gas-liquid mixing mode), so that the first acidic regeneration liquid is quickly and fully contacted with the resin, and the high-concentration heavy metal eluent with the concentration of not less than 60g/L is obtained, and further recycling is facilitated.
According to a specific embodiment of the invention, aeration is carried out on the bottom of the adsorption saturated resin column for 5-10min, and the inventor finds that the aeration time is limited in the range, so that the first acidic regeneration liquid can be rapidly and sufficiently contacted with the resin, and the high-concentration heavy metal eluent with the concentration of not less than 60g/L can be obtained, and further recycling is facilitated; if the aeration time is less than 5min, the mixing of the resin is not uniform, and the resin column interior knots are difficult to eliminate, and if the aeration time is more than 10min, the resin is abraded, and the service life is shortened.
According to still another embodiment of the present invention, the pressure range of aeration at the bottom of the column of the adsorption saturated resin is 0.1 to 0.3MPa, and the inventors have found that by limiting the aeration pressure to the above range, the resin and the regeneration liquid can be sufficiently fluidized, mixed and contacted, if the aeration pressure is less than 0.1MPa, the resin cannot be sufficiently mixed in the tank, elution is insufficient, and if the aeration pressure is more than 0.3MPa, the resin is vigorously mixed, and the pressure in the resin tank is excessively high.
In yet another embodiment according to the present invention, the first acidic regeneration liquid is selected from the group consisting of a solution of HCl with a mass fraction of 4-12% and H with a mass fraction of 5-10%2SO4Thereby, it can be ensured that the resin is sufficiently eluted and the utilization rate of the acid is high.
S200: regenerated by using water washing acid liquor
In the step, a second acidic regeneration liquid is introduced into the adsorption saturated resin column, the second acidic regeneration liquid enters the resin tank downstream and stops feeding liquid after passing through the resin bed layer, aeration is carried out at the bottom of the adsorption saturated resin column to obtain a second eluent, the second eluent is used as the first acidic regeneration liquid and returns to the step S100, and the heavy metal concentration of the second eluent is not lower than 10 g/L. And repeating the aeration of the regenerated liquid until the concentration of the effluent liquid is less than 10g/, and then entering the step S300. The second acidic regeneration liquid is quickly and fully contacted with the resin in an aeration mode (namely a gas-liquid mixing mode) at the bottom of the adsorption saturated resin column, so that the acid liquid regeneration speed is remarkably accelerated.
According to a specific embodiment of the invention, aeration is carried out on the bottom of the adsorption saturated resin column for 5-10min, and the inventor finds that the aeration time is limited in the range, so that the second acidic regeneration liquid can be quickly and sufficiently contacted with the resin, and the acid liquid regeneration speed is accelerated; if the aeration time is less than 5min, the mixing of the resin is not uniform, and the resin column interior knots are difficult to eliminate, and if the aeration time is more than 10min, the resin is abraded, and the service life is shortened.
According to still another embodiment of the present invention, the pressure range of aeration at the bottom of the column of the adsorption saturated resin is 0.1 to 0.3MPa, and the inventors have found that by limiting the aeration pressure to the above range, the resin and the regeneration liquid can be sufficiently fluidized, mixed and contacted, if the aeration pressure is less than 0.1MPa, the resin cannot be sufficiently mixed in the tank, elution is insufficient, and if the aeration pressure is more than 0.3MPa, the resin is vigorously mixed, and the pressure in the resin tank is excessively high.
In yet another embodiment according to the present invention, the second acidic regeneration liquid is selected from a solution of HCl with a mass fraction of 4-12% and H with a mass fraction of 5-10%2SO4Thereby, it can be ensured that the resin is sufficiently eluted and the utilization rate of the acid is high.
S300: acid post-wash with water
In this step, water (for example, tap water) is introduced into the adsorption saturated resin column, aeration is performed on the bottom of the adsorption saturated resin column to obtain a third eluent, and the third eluent is returned to step S200 as a second acidic regeneration liquid, wherein the pH of the third eluent is not more than 4. And (4) repeatedly feeding tap water for aeration until the pH value of the effluent is greater than 4, and then entering the step S400. The aeration mode (namely the gas-liquid mixing mode) at the bottom of the adsorption saturated resin column enables water to be quickly and fully contacted with the resin for washing, and the washing speed after acid is remarkably increased. Recycling of the acid-washing and stripping solution is realized by returning the second eluent as the first acidic regeneration solution to step S100 and the third eluent as the second acidic regeneration solution to step S200, so that the sum of the volumes of fresh concentrated acid (i.e. 36.5% concentrated hydrochloric acid or 98% concentrated sulfuric acid) and tap water added in the whole acid regeneration process is equal to the volume of the generated high-concentration heavy metal regeneration solution (i.e. the first eluent), and no additional wastewater is generated.
According to a specific embodiment of the invention, aeration is carried out on the bottom of the adsorption saturated resin column for 5-10min, and the inventor finds that the aeration time is limited in the range, so that water can be quickly and sufficiently contacted with the resin, and the washing speed after acid is accelerated; if the aeration time is less than 5min, the resin is not uniformly mixed, multiple times of water washing are needed, the water consumption is increased, and if the aeration time is more than 10min, the resin is abraded, and the service life is shortened.
According to still another embodiment of the present invention, the pressure range of aeration at the bottom of the column of the adsorption saturated resin is 0.1 to 0.3MPa, and the inventors have found that by limiting the aeration pressure to the above range, the resin and water can be sufficiently fluidized, mixed and contacted, if the aeration pressure is less than 0.1MPa, the resin cannot be sufficiently mixed in the tank, and if the aeration pressure is more than 0.3MPa, the mixing is vigorous, and the pressure in the resin tank is excessively high.
S400: activation with lye
In the step, introducing an alkaline activating solution into the adsorption saturated resin column, and aerating at the bottom of the adsorption saturated resin column to obtain a fourth eluent, wherein the pH value of the fourth eluent is not more than 11. And (5) repeatedly adding alkali liquor and uniformly mixing until the pH value of the effluent is more than 11, and then entering the step S500. The method is characterized in that the method of aeration (namely a gas-liquid mixing method) at the bottom of the adsorption saturated resin column makes the alkaline activating solution and the resin fully contact and activate, so that the alkali activation speed is remarkably increased, the alkali activation time is shortened, and the dosage of the alkaline activating solution is reduced.
According to a specific embodiment of the invention, aeration is carried out on the bottom of the adsorption saturated resin column for 5-10min, and the inventor finds that the aeration time is limited in the range, so that the alkaline activation liquid can be quickly and fully contacted with the resin, the alkaline activation speed is increased, the alkaline activation time is shortened, and the dosage of the alkaline activation liquid is reduced; if the aeration time is less than 5min, the resin is not uniformly mixed, multiple times of alkali is needed, the alkali consumption is increased, and if the aeration time is more than 10min, the resin is abraded, and the service life is shortened.
According to still another embodiment of the present invention, the pressure range of aeration at the bottom of the column of the adsorption saturated resin is 0.1 to 0.3MPa, and the inventors have found that by limiting the aeration pressure to the above range, the resin and the activating solution can be sufficiently fluidized, mixed and contacted, and if the aeration pressure is less than 0.1MPa, the resin cannot be sufficiently mixed in the tank, the resin cannot be sufficiently transformed, the adsorption amount in the next cycle is reduced, and if the aeration pressure is more than 0.3MPa, the resin can be vigorously mixed, and the pressure in the resin tank is excessively high.
According to another embodiment of the invention, the alkaline activating solution is a NaOH solution with a mass fraction of 4-6%, thereby ensuring that the resin is fully activated and the utilization rate of the alkali is high.
In accordance with yet another embodiment of the present invention, the alkaline activating solution is introduced into the adsorption saturated resin column in a counter-current manner, thereby preventing the tank from being damaged due to the expansion of the resin transition volume.
S500: alkaline post-wash with water
In this step, water (e.g. tap water) is introduced into the adsorption saturated resin column, and aeration is performed on the bottom of the adsorption saturated resin column to obtain a fifth eluent, and the fifth eluent is returned to step S400 as an alkaline activating solution until the pH of the fifth eluent is less than 9. The aeration mode (namely the gas-liquid mixing mode) at the bottom of the adsorption saturated resin column makes water and resin fully contact and wash, and the washing speed after alkali is remarkably accelerated. And returning the fifth eluent as the alkaline activation solution to the step S400, so that the alkaline elution solution is recycled, and the alkaline activation solution is saved. In the step, the using amount of water is 3-3.5 BV.
According to a specific embodiment of the invention, aeration is carried out on the bottom of the adsorption saturated resin column for 5-10min, and the inventor finds that the aeration time is limited in the range, so that water and resin can be quickly and sufficiently contacted for washing, and the washing speed after alkali is accelerated; if the aeration time is less than 5min, the mixing of the resin is not uniform, hardening in the resin column is difficult to eliminate or the consumption of the reagent is increased, and if the aeration time is more than 10min, the resin is abraded, and the service life is shortened.
According to still another embodiment of the present invention, the pressure range of aeration at the bottom of the column of the adsorption saturated resin is 0.1 to 0.3MPa, and the inventors have found that by limiting the aeration pressure to the above range, the resin can be sufficiently fluidized, mixed and contacted with the regeneration liquid or the activation liquid, if the aeration pressure is less than 0.1MPa, the resin cannot be sufficiently mixed in the tank, and the aeration advantage is hardly exhibited, and if the aeration pressure is more than 0.3MPa, the mixing is vigorous and the pressure in the resin tank is excessively high.
In accordance with yet another embodiment of the present invention, water is passed into the column of adsorbent saturated resin in a counter-current manner, thereby avoiding tank damage due to resin transition volume expansion.
According to another embodiment of the invention, the ion exchange resin is cation exchange resin, and the regeneration method is suitable for regeneration of the cation exchange resin, so that the regeneration efficiency is improved, and the regeneration liquid containing high-concentration heavy metals is obtained. The object of resin adsorption treatment comprises electroplating wastewater containing copper, nickel, lead, zinc, silver and the like.
The principle of the embodiment of the invention is as follows: the cation exchange resin regeneration reaction utilized by the invention is as follows:
regeneration: 2R-M +2H+→2R-H+M2+；
And (3) activation: R-H + NaOH → R-Na + H2O；
Wherein R is the effective functional group of the resin, M is heavy metal, and the activated resin can be put into the next adsorption cycle.
According to the method for regenerating the ion exchange resin by gas-liquid mixing in the embodiment of the invention, 1) the first acidic regeneration liquid is quickly and fully contacted with the resin in a mode of aerating at the bottom of the adsorption saturated resin column (namely, in a gas-liquid mixing mode), so that the high-concentration heavy metal eluent with the concentration of not less than 60g/L is obtained, and further recycling is facilitated; 2) the method is characterized in that an aeration mode (namely a gas-liquid mixing mode) is carried out at the bottom of the adsorption saturated resin column, so that the alkaline activating solution and the resin are fully contacted and activated, the alkaline activating speed is remarkably increased, the alkaline activating time is shortened, and the using amount of the alkaline activating solution is reduced; 3) after acid washing, alkali washing and water washing, the hardening of the resin is removed and the resin is fluidized by bottom aeration, and the gas and the liquid are fully mixed with the resin; 4) recycling of acid washing and liquid removing is realized by returning the second eluent as the first acidic regeneration liquid to the step (1) and returning the third eluent as the second acidic regeneration liquid to the step (2), so that the sum of the volumes of fresh concentrated acid (namely 36.5% of concentrated hydrochloric acid or 98% of concentrated sulfuric acid) and tap water added in the whole acid regeneration process is equal to the volume of the generated high-concentration heavy metal regeneration liquid (namely the first eluent), and no additional wastewater is generated; recycling of the alkaline eluent is realized by returning the fifth eluent as the alkaline activating solution to the step (4); except for primary elution, the mechanically applied acid solution used in the step (1) is the low-concentration heavy metal regeneration liquid obtained by the last cyclic elution, and the mechanically applied water washing acid solution used in the step (2) is the acid solution obtained by the last cyclic washing; the alkali liquor activation step is characterized in that except for the preparation of tap water and NaOH for primary activation, alkali activation liquid is used as the water washing liquid after the last circulation of alkali and the preparation of liquid alkali or pure NaOH. The volume of fresh acid (namely 36.5 percent of concentrated hydrochloric acid or 98 percent of concentrated sulfuric acid) actually consumed by the invention is 0.5-1.0BV (BV, bed layer volume), the volume of 4-6 percent of NaOH (w/w) consumed by the invention is 2.0-2.5BV, while the volume of fresh acid consumed by the prior art is 1.5-3.0BV and the volume of 4-6 percent of NaOH (w/w) consumed by the prior art is 3.0-3.5BV under the same condition, so that compared with the prior art, the amount of acid and alkali consumed by the invention is greatly reduced; according to the invention, the elution rate of 95-99% can be achieved within 1h in the acid washing regeneration process, the complete desorption and transformation process can be completed within 2-3h, and the ion exchange resin can be regenerated efficiently and rapidly, while the time consumed in the complete desorption and transformation process is more than 10h when the same elution rate is achieved under the same conditions by adopting the prior art, so that the regeneration time is greatly shortened compared with the prior art; the concentration of the heavy metal eluent obtained by the method is not lower than 60g/L, the heavy metal eluent can be directly used for electrodeposition to obtain metal simple substance nickel or returned to a tank, further concentration is not needed, the economic benefit is remarkable, and the concentration of the heavy metal eluent obtained under the same condition by adopting the prior art is less than 30g/L, so that the heavy metal eluent is not beneficial to subsequent recycling treatment. In conclusion, the method disclosed by the invention is short in time consumption, high in regeneration efficiency and small in acid and alkali consumption, the ion exchange resin can be completely regenerated within 2-3h, the obtained regenerated liquid with the heavy metal concentration of not less than 60g/L and the pH value of more than 2 can be directly used for subsequent heavy metal resource treatment, and the purpose of obtaining the high-concentration regenerated liquid with the least regeneration reagent is realized. The invention solves the technical problems that the regeneration of the ion exchange resin in the prior art needs a large amount of acid and alkali, the regeneration and activation process is slow, the time required by the regeneration and activation is long, the concentration of metal ions in the obtained regenerated liquid is generally less than 30g/L, and the subsequent resource treatment is not facilitated.
In another aspect of the present invention, the present invention provides an apparatus for implementing the method for regenerating ion exchange resin by gas-liquid mixing described in the above embodiment, referring to fig. 2, the apparatus includes an adsorption saturated resin column 10, a first acidic regeneration liquid storage tank 20, a first eluent storage tank 30, a second acidic regeneration liquid storage tank 40, an alkaline activation liquid storage tank 50, a water supply unit 60, and an aeration unit 70. The following further describes the apparatus for regenerating ion exchange resin by gas-liquid mixing according to an embodiment of the present invention.
According to an embodiment of the present invention, referring to fig. 2, an adsorption saturated resin column 10, the adsorption saturated resin column 10 includes a liquid inlet 11, a liquid inlet and outlet 12, a gas inlet 13, and a gas outlet 14, the liquid inlet 11 and the gas outlet 14 are both disposed at the top of the adsorption saturated resin column 10, and the liquid inlet and outlet 12 and the gas inlet 13 are both disposed at the bottom of the adsorption saturated resin column 10.
According to an embodiment of the present invention, referring to fig. 2, a first acidic regeneration liquid storage tank 20, where the first acidic regeneration liquid storage tank 20 is connected to the liquid inlet 11 and the liquid outlet 12, respectively, the first acidic regeneration liquid storage tank 20 can be used as a storage tank for the first acidic regeneration liquid in step S100 and can also be used as a storage tank for the second eluent in step S200, the first acidic regeneration liquid in step S100 enters the adsorption saturated resin column 10 through the liquid inlet 11, and the second eluent in step S200 flows into the first acidic regeneration liquid storage tank 20 through the liquid outlet 12.
According to an embodiment of the present invention, a pH meter (not shown in the figures) is disposed in the first acidic regeneration liquid storage tank 20, so as to measure the pH of the liquid in the first acidic regeneration liquid storage tank 20.
According to the embodiment of the invention, referring to fig. 2, the first eluent storage tank 30 is connected with the liquid inlet/outlet 12, the heavy metal concentration of the first eluent in the first eluent storage tank 30 is not lower than 60g/L, and the first eluent can be directly used for electrodeposition to obtain metal elementary nickel or returned to the tank without further concentration, so that the method has remarkable economic benefit.
According to an embodiment of the present invention, referring to fig. 2, a second acidic regeneration liquid storage tank 40, wherein the second acidic regeneration liquid storage tank 40 is connected to the liquid inlet 11 and the liquid outlet 12, respectively, the second acidic regeneration liquid storage tank 40 can be used as a storage tank for the second acidic regeneration liquid of step S200 and a storage tank for the third eluent of step S300, the second acidic regeneration liquid of step S200 enters the adsorption saturated resin column 10 through the liquid inlet 11, and the third eluent of step S300 flows into the second acidic regeneration liquid storage tank 40 through the liquid outlet 12.
According to a further embodiment of the present invention, a pH meter (not shown in the figure) is provided in the second acidic regeneration liquid storage tank 40, so as to measure the pH of the liquid in the second acidic regeneration liquid storage tank 40.
According to an embodiment of the present invention, referring to fig. 2, an alkaline activation solution storage tank 50 is provided, the alkaline activation solution storage tank 50 is connected to the liquid inlet 11 and the liquid outlet 12, the alkaline activation solution storage tank 50 can be used as a storage tank for the alkaline activation solution of step S400 and also can be used as a storage tank for the fifth eluent of step S500, the alkaline activation solution of step S400 enters the adsorption saturated resin column 10 through the liquid outlet 12 (i.e. enters in a counter-current manner), and the fifth eluent of step S500 flows into the alkaline activation solution storage tank 50 through the liquid outlet 12.
According to a further embodiment of the present invention, a pH meter (not shown in the drawings) is provided in the alkaline activation solution storage tank 50, thereby measuring the pH of the liquid in the alkaline activation solution storage tank 50.
According to an embodiment of the present invention, referring to fig. 2, the water supply unit 60 is connected to the liquid inlet 11 and the liquid outlet 12, respectively, when the water supply unit 60 supplies water in step S300, the water supply unit 60 is connected to the liquid inlet 11 (i.e., downstream), and when the water supply unit 60 supplies water in step S500, the water supply unit 60 is connected to the liquid outlet 12 (i.e., upstream).
According to an embodiment of the present invention, referring to fig. 2, an aeration unit 70, wherein the aeration unit 70 is connected to the gas inlet 13 to provide aeration for steps S100-S500, and when the gas inlet 13 is opened, the gas outlet 14 is simultaneously opened to avoid the increase of the pressure in the column when compressed air is introduced.
Further, according to an embodiment of the present invention, referring to fig. 2, the adsorption saturated resin column 10 further includes a first water distributor 15, where the first water distributor 15 is disposed at the top of the adsorption saturated resin column 10 and below the liquid inlet and the gas outlet; the adsorption saturated resin column 10 further comprises a second water distributor 16, and the second water distributor 16 is arranged at the bottom of the adsorption saturated resin column 10 and above the liquid inlet, the liquid outlet and the gas inlet, so that resin loss and bias flow are avoided, gas uniformly enters the column body during bottom aeration, and water flow dead angles are reduced.
It should be noted that the liquid inlet/outlet 12 and the gas inlet 13 are both connected to a second water distributor 16.
Further, according to an embodiment of the present invention, referring to fig. 2, the fourth eluent of step S400 is introduced into a waste liquid treatment system (not shown in the figure) as a waste liquid according to an embodiment of the present invention.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
The embodiment provides a regeneration method of saturated resin after certain nickel-containing wastewater is treated. The nickel ion concentration of the actual nickel-containing wastewater is 750mg/L, the pH value is 6.5, the resin volume (BV) of the cation exchange resin tank is 600L, and when the nickel concentration of the adsorbed effluent reaches 80% of that of the raw water, the regeneration is carried out.
The specific regeneration steps are as follows:
(1) eluting and regenerating by using a low nickel acid solution: pumping the regeneration liquid containing 8% sulfuric acid in the low nickel barrel into a saturated adsorption tank from top, stopping feeding the liquid after the regeneration liquid passes through a resin bed layer, introducing gas to aerate and mix the resin for 5 minutes, and controlling the pressure of an air compressor to be 0.3 MPa. The above operation was repeated twice. The discharged liquid enters a nickelic acid liquid tank.
(2) Eluting and regenerating by using water-washing acid liquor: the concentration is 10% H2SO4Pumping the post-acid washing liquid into a resin tank from top, stopping feeding the liquid after the post-acid washing liquid submerges in a resin bed layer, introducing gas to carry out aeration treatment on the resin for 5 minutes, and controlling the pressure of an air compressor to be 0.3 MPa. And (4) discharging liquid into a low nickel acid liquid barrel, repeating twice, and discharging liquid into a low nickel acid liquid tank.
(3) Washing the excessive acid: and (3) pumping tap water into the resin tank, wherein the specific operation and parameter setting are the same as those in the step (1), and the effluent in the resin tank enters a washing acid liquid barrel.
(4) Activating resin by alkali liquor: and (3) reversely flowing 4% NaOH solution to activate the resin, stopping feeding the liquid after submerging the resin bed layer, discharging the liquid after aerating for 10 minutes, repeating for 4 times, and feeding the discharged liquid into a nickel alkali barrel.
(5) Washing with water after alkali: and (3) reversely flowing 0.5BV of tap water for aeration, and discharging the liquid into a nickel alkali barrel under the pressure of 0.3MPa of an air compressor, repeating the same steps for four times, and finishing regeneration to wait for the next adsorption.
The regeneration implementation effect is as follows:
the concentration of the obtained high-concentration nickel regeneration liquid is 67g/L, the concentration change of nickel in the regeneration process effluent is shown in figure 3, and the regeneration rate of the resin reaches 98% within 40 min. The regeneration process consumes 0.6BV of 98% concentrated sulfuric acid and 4% NaHOH 2.0 BV.
Comparative example 1
The conventional regeneration method for the saturated resin after certain nickel-containing wastewater is treated is provided by the comparative example. The nickel ion concentration of the actual nickel-containing wastewater is 521mg/L, the pH value is 6, the resin volume (BV) of the cation exchange resin tank is 600L, and when the nickel concentration of the adsorbed effluent reaches 90% of that of the raw water, regeneration is carried out.
The specific regeneration steps are as follows:
(1) acid liquor is applied for elution and regeneration: and (3) passing the regeneration liquid containing 8% sulfuric acid in the low-nickel barrel through the resin layer at the flow rate of 1BV/h, carrying out downstream elution, removing the high-concentration part for subsequent electrolysis to recover nickel, supplementing concentrated hydrochloric acid to the residual low-concentration part, and eluting the nickel-saturated resin column again to improve the nickel content of the eluent.
(2) Washing with water after acid: after the completion of the acid washing, the resin was washed with about 1.5BV of tap water at a flow rate of 1BV/h to remove free acid.
(3) Alkali liquor transformation: 4 percent NaOH flows in a reverse flow way, the flow rate is 1BV/h, and the alkali is continuously added for about 1h after the effluent shows alkalinity. The resin volume expands when alkali is added.
(4) Washing with water after alkali: the flow rate is 1BV/h, the resin is washed with tap water until the pH is less than 9, and the next cycle of adsorption is carried out.
The regeneration implementation effect is as follows:
the concentration of the obtained high-concentration nickel regeneration liquid is 29.9g/L, the concentration change of nickel in the regeneration process effluent is shown in figure 4, and the regeneration rate of the resin reaches 95% after 5.5 h. The regeneration process consumes 98% concentrated sulfuric acid 2BV, the activating solution consumption in the activation process is 3BV, and the water consumption for washing after alkali is 5 BV.
As can be seen from the comparison between the example 1 and the comparative example 1, the gas and the liquid are fully mixed by adding aeration in the processes of acid solution regeneration, water acid washing, alkali liquid activation and alkali water washing, so that the consumption of acid and alkali is greatly reduced, and the regeneration time is greatly shortened.
Example 2
The embodiment provides a method for regenerating saturated resin after treating certain copper-containing wastewater. The actual copper ion concentration in the copper-containing wastewater was 472mg/L, pH 3.5, and the resin volume (BV) in the cation exchange resin tank was 600L, and when the copper concentration of the adsorbed effluent reached 80% of the raw water, regeneration was performed.
The specific regeneration steps are as follows:
(1) eluting and regenerating by using low-copper acid solution: pumping the regenerated liquid containing 6% hydrochloric acid in a low copper barrel into a saturated adsorption tank from top, stopping feeding the liquid after the regenerated liquid submerges a resin bed layer, introducing gas to aerate and mix the resin for 10 minutes, and controlling the pressure of an air compressor to be 0.1 MPa. The above operation was repeated twice.
(2) Eluting and regenerating by using water-washing acid liquor: pumping the acid water washing liquid with the concentration of 12% HCl into a resin tank from the top, stopping feeding the liquid after the acid water washing liquid submerges in a resin bed layer, introducing gas to carry out aeration treatment on the resin for 8 minutes, and controlling the pressure of an air compressor to be 0.1 MPa. And (4) discharging liquid into a low copper acid liquid barrel, repeating twice, and discharging liquid into a low copper acid liquid tank.
(3) Washing the excessive acid: and (3) pumping tap water into the resin tank, wherein the specific operation and parameter setting are the same as those in the step (1), and the effluent in the resin tank enters a washing acid liquid barrel.
(4) Activating resin by alkali liquor: and (3) carrying out resin activation by counter-current flow of 6% NaOH solution, stopping feeding liquid after submerging a resin bed layer, carrying out aeration for 10 minutes, then discharging liquid, repeating for 4 times, and feeding the discharged liquid into a copper alkali barrel.
(5) Washing with water after alkali: aerating 0.5BV of running water in reverse flow, aerating with 0.1MPa of air compressor, discharging the liquid into copper alkali barrel, repeating the same steps for four times, and completing regeneration to wait for next adsorption.
The regeneration implementation effect is as follows: the concentration of the obtained high-concentration copper desorption liquid is 62g/L, and after the acid is added into the water washing liquid and the clear water, the concentration of copper in the effluent liquid is gradually reduced, and the final concentration is less than 10 g/L. The change of the copper concentration in the effluent liquid in the regeneration process is shown in figure 5, and the regeneration rate of the resin reaches 99 percent within 50 min. The regeneration process consumed 36.5% concentrated hydrochloric acid 0.5BV and 4% NaOH2.5BV.
Comparative example 2
The conventional regeneration method for the saturated resin after the copper-containing wastewater is treated is provided by the comparative example. The actual copper-containing wastewater had a copper ion concentration of 375mg/L, a pH of 3.3, and a resin volume (BV) of the cation exchange resin tank of 600L, and when the copper concentration of the adsorbed effluent reached 95% of the raw water, regeneration was performed.
The specific regeneration steps are as follows:
(1) acid liquor is applied for elution and regeneration: and (3) passing the regeneration liquid containing 4% hydrochloric acid in the low copper barrel through the resin layer at the flow rate of 1BV/h, carrying out downstream elution, removing the high-concentration part for subsequent electrolysis to recover copper, supplementing concentrated hydrochloric acid to the residual low-concentration part, and eluting the copper-saturated resin column again to improve the copper content of the eluent.
(2) Washing with water after acid: after the completion of the acid washing, the resin was washed with about 1.5BV of tap water at a flow rate of 1BV/h to remove free acid.
(3) Alkali liquor transformation: 4 percent NaOH flows in a reverse flow way, the flow rate is 1BV/h, and the alkali is continuously added for about 1h after the effluent shows alkalinity.
(4) Washing with water after alkali: the flow rate is 1BV/h, the resin is washed with tap water until the pH is less than 9, and the next cycle of adsorption is carried out.
The regeneration implementation effect is as follows:
the concentration of the obtained high-concentration copper regeneration liquid is 27.6g/L, the concentration change of copper in the regeneration process effluent is shown in figure 6, and the regeneration rate of the resin reaches 92% after 5.5 h. The regeneration process consumes 36% concentrated hydrochloric acid 1.5BV, the consumption of the activating solution is 2BV, and the water consumption for washing after the alkali is 5 BV.
As can be seen from the comparison between the example 2 and the comparative example 2, the gas and the liquid are fully mixed by adding aeration in the processes of acid solution regeneration, water acid washing, alkali liquid activation and alkali water washing, so that the consumption of acid and alkali is greatly reduced, and the regeneration time is greatly shortened.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for regenerating ion exchange resin by gas-liquid mixing is characterized by comprising the following steps:
(1) introducing the first acidic regeneration liquid into an adsorption saturated resin column, and aerating at the bottom of the adsorption saturated resin column to obtain a first eluent, wherein the heavy metal concentration of the first eluent is not lower than 60 g/L;
(2) introducing a second acidic regeneration liquid into the adsorption saturated resin column, aerating at the bottom of the adsorption saturated resin column to obtain a second eluent, and returning the second eluent serving as the first acidic regeneration liquid to the step (1);
(3) introducing water into the adsorption saturated resin column, aerating at the bottom of the adsorption saturated resin column to obtain a third eluent, and returning the third eluent serving as a second acidic regeneration liquid to the step (2);
(4) introducing an alkaline activating solution into the adsorption saturated resin column, and aerating at the bottom of the adsorption saturated resin column to obtain a fourth eluent;
(5) and (3) introducing water into the adsorption saturated resin column, aerating at the bottom of the adsorption saturated resin column to obtain a fifth eluent, completing regeneration until the pH of the fifth eluent is less than 9, and returning the fifth eluent as an alkaline activating solution to the step (4).
2. The method according to claim 1, wherein in the step (1), aeration is carried out for 5-10min at the bottom of the adsorption saturated resin column;
optionally, in the step (2), aerating at the bottom of the adsorption saturated resin column for 5-10 min;
optionally, in the step (3), aerating at the bottom of the adsorption saturated resin column for 5-10 min;
optionally, in the step (4), aerating at the bottom of the adsorption saturated resin column for 5-10 min;
optionally, in the step (5), aerating at the bottom of the adsorption saturated resin column for 5-10 min.
3. The method according to claim 1, wherein in step (1), the pressure of aeration at the bottom of the adsorption saturated resin column is in the range of 0.1 to 0.3 MPa;
optionally, in the step (2), aerating at the bottom of the adsorption saturated resin column at the pressure ranging from 0.1 to 0.3 MPa;
optionally, in the step (3), aerating at the bottom of the adsorption saturated resin column at the pressure ranging from 0.1 to 0.3 MPa;
optionally, in the step (4), aerating at the bottom of the adsorption saturated resin column at the pressure ranging from 0.1 to 0.3 MPa;
optionally, in the step (5), the pressure range of aeration at the bottom of the adsorption saturated resin column is 0.1-0.3 MPa.
4. The method according to claim 1, wherein in step (2), the heavy metal concentration of the second eluent is not lower than 10 g/L;
optionally, in step (3), the pH of the third eluent is not greater than 4;
optionally, in step (4), the pH of the fourth eluent is not greater than 11.
5. The method according to claim 1, wherein in step (1), the first acidic regeneration liquid is selected from a group consisting of a HCl solution with a mass fraction of 4-12% and H with a mass fraction of 5-10%2SO4At least one of (a);
optionally, in the step (2), the second acidic regeneration liquid is selected from a HCl solution with the mass fraction of 4-12% and H with the mass fraction of 5-10%2SO4At least one of (a);
optionally, in the step (4), the alkaline activating solution is a 4-6% NaOH solution by mass fraction.
6. The method according to claim 1, wherein in the step (4), the alkaline activating solution is passed into the adsorption saturated resin column in a counter-current manner;
optionally, in step (5), water is passed into the column of adsorption saturated resin in a counter-current manner.
7. The method according to any one of claims 1 to 6, wherein the ion exchange resin is a cation exchange resin.
8. An apparatus for carrying out the method for regenerating an ion exchange resin by mixing gas and liquid according to any one of claims 1 to 7, comprising:
the adsorption saturated resin column comprises a liquid inlet, a liquid inlet and outlet, a gas inlet and a gas outlet, wherein the liquid inlet and the gas outlet are arranged at the top of the adsorption saturated resin column, and the liquid inlet and the gas outlet are arranged at the bottom of the adsorption saturated resin column;
the first acidic regenerated liquid storage tank is respectively connected with the liquid inlet and the liquid outlet;
a first eluent storage tank connected to the liquid inlet and outlet;
the second acidic regeneration liquid storage tank is respectively connected with the liquid inlet and the liquid outlet;
the alkaline activation liquid storage tank is respectively connected with the liquid inlet and the liquid outlet;
the water supply unit is respectively connected with the liquid inlet and the liquid outlet;
an aeration unit connected to the gas inlet.
9. The apparatus of claim 8, wherein the column of adsorption saturated resin further comprises:
the first water distributor is arranged at the top of the adsorption saturated resin column and is arranged below the liquid inlet and the gas outlet;
and the second water distributor is arranged at the bottom of the adsorption saturated resin column and is arranged above the liquid inlet, the liquid outlet and the gas inlet.
10. The apparatus of claim 8, wherein a pH meter is disposed in the first acidic regeneration liquid storage tank;
optionally, a pH meter is arranged in the second acidic regeneration liquid storage tank;
optionally, a pH meter is arranged in the alkaline activation solution storage tank.
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| CN202110053460.0A Pending CN112916054A (en) | 2021-01-15 | 2021-01-15 | Method and device for regenerating ion exchange resin by gas-liquid mixing |
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| CN113461098A (en) * | 2021-06-30 | 2021-10-01 | 钱中明 | Regeneration equipment and process for adsorbing heavy metal in water by using complexing resin |
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