CN114150328B - Online adjustable acid liquor recovery method - Google Patents
Online adjustable acid liquor recovery method Download PDFInfo
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- CN114150328B CN114150328B CN202111262859.6A CN202111262859A CN114150328B CN 114150328 B CN114150328 B CN 114150328B CN 202111262859 A CN202111262859 A CN 202111262859A CN 114150328 B CN114150328 B CN 114150328B
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- acid
- resin bed
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- resin
- metal salt
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention provides an on-line adjustable acid liquor recovery method, which comprises an adsorption step and a desorption step, wherein the adsorption step comprises the steps that acid liquor in an acid tank is pumped into a resin bed from bottom to top, free acid is adsorbed by resin, waste water containing metal salt flows out from an outlet pipeline at the top end of the resin bed, an acid concentration detector and a metal salt concentration detector at the outlet pipeline at the top end of the resin bed detect the concentration of the solution in the outlet pipeline at the top end, and whether the solution flows into a water tank or a waste water collecting tank is judged according to the detection result, or the acid pumping to the resin bed is stopped; the desorption step comprises pumping water in a water tank into a resin bed from top of the resin bed from top to bottom, desorbing and eluting the adsorbed free acid, and flowing out from an outlet pipeline at the bottom end of the resin bed, wherein an acid concentration detector and a metal salt concentration detector at the outlet pipeline at the bottom end of the resin bed detect the concentration of the solution in the outlet pipeline at the bottom end, and judging whether the solution flows into an acid tank or a regenerated acid collecting tank or stops pumping water to the resin bed according to the detection result.
Description
Technical Field
The invention relates to the technical field of steel rolling waste acid liquid regeneration, in particular to an online adjustable acid liquid recovery method.
Background
In the surface treatment process of steel materials, a chemical pickling method is generally adopted to remove surface iron scales so as to improve the surface quality of products, and one or more of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid and other acid solutions are generally adopted for combined pickling. The waste acid liquid generated after the acid washing by the method has strong corrosiveness. If the waste acid is not treated, serious pollution is caused to the environment, and meanwhile, due to the large discharge of the waste acid, great resource waste is caused, so that the pickling cost is increased.
The current recovery treatment technology for the pickling waste liquid comprises a spray roasting method, a resin adsorption method, a diffusion dialysis method and the like, wherein the resin adsorption method has a good application prospect because other chemical media and energy media are not required to be additionally consumed. However, the resin adsorption method adopted at present usually adopts a fixed volume of waste acid liquid for adsorption and a fixed volume of industrial water for desorption, however, the concentration of recovered acid is diluted because the concentration of waste acid liquid from different sources is different, and the recovery efficiency of acid liquid is not high easily due to the adoption of a fixed volume mode.
Therefore, it is necessary to design an on-line adjustable acid recovery method to overcome the above problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an on-line adjustable acid liquor recovery method, aims to determine the absorption acid consumption and desorption water consumption by detecting the acid concentration and the metal salt concentration of a solution in real time, improves the acid recovery efficiency, and simultaneously reduces the industrial water consumption and the wastewater production.
The invention is realized in the following way:
the invention provides an on-line adjustable acid liquor recovery method, which comprises an adsorption step and a desorption step, wherein the adsorption step comprises the steps that acid liquor in an acid tank is pumped into a resin bed from bottom to top, free acid is adsorbed by resin, waste water containing metal salt flows out from an outlet pipeline at the top end of the resin bed, a first acid concentration detector and a first metal salt concentration detector of the outlet pipeline at the top end of the resin bed detect the concentration of the solution in the outlet pipeline at the top end simultaneously, and whether the solution flows into a water tank or a waste water collecting tank is judged again according to the detection result, or the resin is adsorbed and saturated, and acid pumping to the resin bed is stopped; the desorption step comprises the steps that water in a water tank is pumped into a resin bed from the top of the resin bed from top to bottom, adsorbed free acid is desorbed and eluted, and flows out of an outlet pipeline at the bottom end of the resin bed, in the process, a second acid concentration detector and a second metal salt concentration detector of the outlet pipeline at the bottom end of the resin bed detect the concentration of solution in the outlet pipeline at the bottom end at the same time, whether the solution flows into an acid tank or a regenerated acid collecting tank is judged again according to the detection result, or the resin is completely desorbed, and the pumping of water to the resin bed is stopped.
Preferably, when the concentration of the solution in the top outlet pipe is detected, three conditions are classified according to the resin adsorption process: s1, the acid concentration and the metal salt concentration are 0, and the solution at the top outlet pipeline returns to the water tank; s2, the acid concentration is 0, the metal salt concentration is more than 0, and the wastewater containing the metal salt enters a wastewater collection tank; s3, the acid concentration and the metal salt concentration are both greater than 0, which means that the resin in the resin bed is adsorbed and saturated, and the free acid starts to penetrate the resin, and then the adsorption is ended, and the pumping of acid to the resin bed is stopped.
Preferably, when the concentration of the solution in the bottom outlet pipeline is detected, three conditions are classified according to the resin desorption process: s1, the concentration of acid and the concentration of metal salt are both more than 0, and the solution at the outlet pipeline at the bottom end returns to an acid tank;
s2, enabling the acid concentration to be more than 0 and the metal salt concentration to be 0, and enabling eluted free acid to enter a regenerated acid collecting tank; s3, the acid concentration and the metal salt concentration are both 0, which means that the resin in the resin bed is completely desorbed, and then the resin bed is at the desorption end point, and the water pumping to the resin bed is stopped, so that the next adsorption-desorption cycle can be started.
The invention has the following beneficial effects:
the method can detect the concentration of the solution acid and the concentration of the metal salt in the adsorption/desorption process of the resin bed in real time, and determine the adsorption endpoint and desorption endpoint according to the detected concentration; the method can be suitable for recycling the waste acid liquid with larger concentration variation, and can adjust the adsorption acid consumption and desorption water consumption in real time according to different waste acid liquid concentrations, thereby improving the recycling efficiency and reducing the industrial water consumption and the wastewater production.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of an on-line adjustable acid liquor recovery device according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention provides an on-line adjustable acid liquor recovery method, which comprises an adsorption step and a desorption step, wherein the adsorption step comprises the steps that acid liquor in an acid tank 3 is pumped into a resin bed 1 from the bottom of the resin bed 1 from bottom to top, free acid is adsorbed by resin, waste water containing metal salt flows out from an outlet pipeline 20 at the top end of the resin bed 1, and in the process, a first acid concentration detector 4 and a first metal salt concentration detector 5 of the outlet pipeline 20 at the top end of the resin bed 1 detect the concentration of the solution in the outlet pipeline 20 at the top end at the same time, and the method is divided into three conditions according to the resin adsorption process: s1, the acid concentration and the metal salt concentration are 0, and the solution at the top outlet pipeline returns to the water tank 2; s2, the acid concentration is 0, the metal salt concentration is more than 0, and the metal salt-containing wastewater 22 enters a wastewater collection tank; s3, the acid concentration and the metal salt concentration are both greater than 0, which means that the resin in the resin bed 1 is adsorbed and saturated, and the free acid starts to penetrate the resin, and then the adsorption is ended, and the acid pumping to the resin bed 1 is stopped;
the desorption step comprises pumping water in a water tank 2 into the resin bed 1 from top to bottom of the resin bed 1, desorbing and eluting the adsorbed free acid, and flowing out from a bottom outlet pipeline 21 of the resin bed 1, wherein a second acid concentration detector 6 and a second metal salt concentration detector 7 of the bottom outlet pipeline 21 of the resin bed simultaneously detect the concentration of the solution in the bottom outlet pipeline 21, and the desorption step is divided into three cases according to the resin desorption process: s1, the acid concentration and the metal salt concentration are both more than 0, and the bottom outlet pipeline solution returns to the acid tank 3; s2, enabling the acid concentration to be more than 0 and the metal salt concentration to be 0, and enabling the eluted free acid (regenerated acid 23) to enter a regenerated acid collecting tank; s3, the acid concentration and the metal salt concentration are both 0, which means that the resin in the resin bed 1 is completely desorbed, and the resin bed is at the desorption end point, and the water pumping to the resin bed is stopped, so that the next adsorption-desorption cycle can be started.
The on-line adjustable acid liquor recovery method provided by the embodiment of the invention is based on an on-line adjustable acid liquor recovery device as shown in fig. 1, the device comprises a resin bed 1, a water tank 2 and an acid tank 3, wherein the acid tank 3 is communicated with the bottom of the resin bed 1 through a pipeline, the water tank 2 is communicated with the top of the resin bed 1 through a pipeline, a first acid concentration detector 4 and a first metal salt concentration detector 5 are arranged on a top end outlet pipeline 20 of the resin bed 1, the tail end of the top end outlet pipeline 20 is communicated with the water tank 2 through a pipeline with a third automatic valve 10, the tail end of the top end outlet pipeline 20 is communicated with a wastewater collection tank (not shown) through a pipeline with a seventh automatic valve 14, the wastewater collection tank is used for inflow of metal salt-containing wastewater 22, a second acid concentration detector 6 and a second metal salt concentration detector 7 are arranged on a bottom end outlet pipeline 21 of the resin bed 1, the tail end of the bottom end outlet pipeline 21 is communicated with the acid tank 3 through a pipeline with a fifth automatic valve 12, and the tail end outlet pipeline 21 is communicated with a regeneration acid collection tank (not shown) through an eighth acid collection tank (not shown) through an elution valve).
The bottom of the acid tank 3 is communicated with a pump through a pipeline with a sixth automatic valve 13, the bottom of the resin bed 1 is communicated with the pump through a pipeline with a second automatic valve 9, and the pipeline with the sixth automatic valve 13 and the pipeline with the second automatic valve 9 form an acid liquor inlet pipeline for pumping the acid liquor in the acid tank 3 into the resin bed 1. The acid liquor in the acid tank 3 is pumped into the resin bed 1 from bottom to top from the bottom of the resin bed 1, free acid is adsorbed by the resin, and wastewater containing metal salt flows out from an outlet pipeline 20 at the top end of the resin bed 1.
The bottom of the water tank 2 is communicated with the pump through a pipeline with a fourth automatic valve 11, the top of the resin bed 1 is communicated with the pump through a pipeline with a first automatic valve 8, and the pipeline with the fourth automatic valve 11 and the pipeline with the first automatic valve 8 form a water inlet pipeline for pumping the water in the water tank 2 into the resin bed 1. The water in the water tank 2 is pumped into the resin bed 1 from top to bottom from the top of the resin bed 1, adsorbed free acid is desorbed and eluted, and flows out from the outlet pipeline 21 at the bottom end of the resin bed 1.
The first acid concentration detector 4 and the first metal salt concentration detector 5 of the outlet pipe 20 at the top end of the resin bed 1 detect the concentration of the solution in the outlet pipe 20 at the top end, and judge whether the solution flows into the water tank 2 or the wastewater collection tank or the resin is saturated by adsorption according to the detection result, and stop pumping acid to the resin bed 1.
The second acid concentration detector 6 and the second metal salt concentration detector 7 of the bottom outlet pipe 21 of the resin bed 1 detect the concentration of the solution in the bottom outlet pipe 21 at the same time, and judge whether the solution flows into the acid tank 3 or the regenerated acid collecting tank or the resin is completely desorbed according to the detection result, and stop pumping water to the resin bed 1.
The resin bed 1 is filled with a resin having an acid retarding effect. The resin can adsorb free acid in solution, and metal salt in solution can directly penetrate the resin. The water tank 2 is communicated with a pipeline into which the industrial water 19 flows, and a ninth automatic valve 16 is arranged on the pipeline into which the industrial water 19 flows. The acid tank 3 is communicated with a pipeline into which the waste acid 18 flows, and a tenth automatic valve 17 is arranged on the pipeline into which the waste acid 18 flows.
The invention provides an on-line adjustable acid liquor recovery device which comprises a resin bed 1, an acid tank 3, a water tank 2, a first acid concentration detector 4, a first metal salt concentration detector 5, a second acid concentration detector 6 and a second metal salt concentration detector 7. The acid concentration detector and the metal salt concentration detector are respectively arranged at the top outlet pipeline and the bottom outlet pipeline of the resin bed 1, and the production amount of wastewater and regenerated acid is controlled according to the real-time detection results of the acid concentration detector and the metal salt concentration detector. The invention aims to determine the adsorption acid consumption and desorption water consumption by detecting the acid concentration and the metal salt concentration of a solution in real time, improve the acid recovery efficiency and simultaneously reduce the industrial water consumption and the wastewater production.
The resin bed 1 is filled with a resin having an acid retarding effect, which resin adsorbs the free acid in the solution, and the metal salt in the solution is directly permeable to the resin. The operation process of the acid liquor recovery device mainly comprises two steps of adsorption and desorption.
Adsorption: the acid liquor in the acid tank 3 is pumped into the resin bed 1 from bottom to top from the bottom of the resin bed 1, free acid is adsorbed by the resin, and wastewater containing metal salt flows out from an outlet pipeline 20 at the top end of the resin bed 1. In this process, the first acid concentration detector 4 and the first metal salt concentration detector 5 of the top outlet pipe 20 of the resin bed 1 detect the concentration of the solution in the top outlet pipe 20 at the same time, and the three conditions are classified according to the resin adsorption process: (1) when the acid concentration and the metal salt concentration are both 0, the valve 10 is opened, the valve 14 is closed, and the top outlet pipeline solution returns to the water tank 2; (2) when the acid concentration is 0 and the metal salt concentration is more than 0, the valve 10 is closed, the valve 14 is opened, and the wastewater containing the metal salt enters a wastewater collection tank; (3) the acid concentration and the metal salt concentration are both greater than 0, which indicates that the resin is saturated by adsorption, and the free acid starts to penetrate the resin, and at this time, the adsorption is terminated, and the pumping of acid to the resin bed 1 is stopped.
And (3) a desorption step: the water in the water tank 2 is pumped into the resin bed 1 from top to bottom from the top of the resin bed 1, adsorbed free acid is desorbed and eluted, and flows out from the outlet pipeline 21 at the bottom end of the resin bed 1. The second acid concentration detector 6 and the second metal salt concentration detector 7 of the bottom outlet pipe 21 of the resin bed in this process detect the concentration of the solution in the bottom outlet pipe at the same time, and are classified into three cases according to the resin desorption process: (1) when the acid concentration and the metal salt concentration are both greater than 0, the valve 12 is opened, the valve 15 is closed, and the bottom outlet pipeline solution returns to the acid tank 3; (2) when the acid concentration is more than 0 and the metal salt concentration is 0, the valve 12 is closed, the valve 15 is opened, and the eluted free acid enters a regenerated acid collecting tank; (3) the acid concentration and the metal salt concentration are both 0, which indicates that the resin is completely desorbed, and the desorption is ended at this time, and the water pumping to the resin bed is stopped, so that the next adsorption-desorption cycle can be started.
The on-line adjustable acid liquor recovery device and the method provided by the invention can be used for treating and recovering waste acid, so that the environmental pollution and the resource waste are avoided, and the recovery efficiency is improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (1)
1. An on-line adjustable acid liquor recovery method is characterized in that: the method comprises an adsorption step and a desorption step, wherein acid liquor in an acid tank is pumped into a resin bed from bottom to top, free acid is adsorbed by resin, waste water containing metal salt flows out of an outlet pipeline at the top end of the resin bed, a first acid concentration detector and a first metal salt concentration detector of the outlet pipeline at the top end of the resin bed detect the concentration of the solution in the outlet pipeline at the top end simultaneously, and the acid is pumped into a water tank or a waste water collecting tank according to the detection result, or the resin is adsorbed and saturated, so that acid pumping to the resin bed is stopped; pumping water in a water tank into a resin bed from the top of the resin bed from top to bottom, desorbing and eluting the adsorbed free acid, and flowing out of an outlet pipeline at the bottom end of the resin bed, wherein in the process, a second acid concentration detector and a second metal salt concentration detector of the outlet pipeline at the bottom end of the resin bed detect the concentration of the solution in the outlet pipeline at the bottom end at the same time, and judging whether the solution flows into an acid tank or a regenerated acid collecting tank or the resin is completely desorbed according to the detection result, and stopping pumping water to the resin bed; in the adsorption step: when the concentration of the solution in the top outlet pipeline is detected, three conditions are classified according to the resin adsorption process: s1, the acid concentration and the metal salt concentration are 0, and the solution at the top outlet pipeline returns to the water tank; s2, the acid concentration is 0, the metal salt concentration is more than 0, and the wastewater containing the metal salt enters a wastewater collection tank; s3, the acid concentration and the metal salt concentration are both greater than 0, which indicates that the resin in the resin bed is adsorbed and saturated, and the free acid starts to penetrate the resin, and then the adsorption is ended, and the pumping of acid to the resin bed is stopped; in the desorption step: when the concentration of the solution in the bottom outlet pipeline is detected, three conditions are classified according to the resin desorption process: s1, the concentration of acid and the concentration of metal salt are both more than 0, and the solution at the outlet pipeline at the bottom end returns to an acid tank; s2, enabling the acid concentration to be more than 0 and the metal salt concentration to be 0, and enabling eluted free acid to enter a regenerated acid collecting tank; s3, the acid concentration and the metal salt concentration are both 0, which means that the resin in the resin bed is completely desorbed, and then the resin bed is at the desorption end point, and the water pumping to the resin bed is stopped, so that the next adsorption-desorption cycle can be started.
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| CN202111262859.6A CN114150328B (en) | 2021-10-28 | 2021-10-28 | Online adjustable acid liquor recovery method |
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| CN202111262859.6A CN114150328B (en) | 2021-10-28 | 2021-10-28 | Online adjustable acid liquor recovery method |
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| CN114150328B true CN114150328B (en) | 2023-08-25 |
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