阅读说明：本技术 一种镀锌三价铬彩色钝化液的除杂装置及除杂方法 (Impurity removal device and impurity removal method for zinc-plated trivalent chromium color passivation solution ) 是由 侯继斌 张小勇 韩秀台 曹聚涛 刘新伟 王伟党 李丰 鲁显礼 李达 潘雄 李艳娜 于 2019-11-15 设计创作，主要内容包括：本发明公开一种镀锌三价铬彩色钝化液的除杂装置,涉及金属钝化处理技术领域,包括离子交换器,离子交换器上设置有与钝化槽管道连接的钝化液入口和钝化液出口,纯水进水管道与离子交换器上的纯水入口连接,三价铬离子废水池通过管道与离子交换器上的废水出口连接,再生液容器通过两根管道分别与离子交换器上的再生液入口和再生液出口连接,离子交换器与钝化槽、纯水进水管道、三价铬离子废水池和再生液容器的连接管道上均设有至少一个阀门,离子交换器中填充有强酸性阳离子树脂,再生液容器内装设有强酸,再生液容器与离子交换器的连接管道上设有液压泵。本发明能有效除去三价铬钝化液中的Fe<Sup>3+</Sup>、用锌络合剂除去钝化液中积累过的Zn<Sup>2+</Sup>等杂质离子。(The invention discloses an impurity removing device for zinc-plated trivalent chromium color passivation solution, which relates to the technical field of metal passivation treatment and comprises an ion exchanger, wherein a passivation solution inlet and a passivation solution outlet which are connected with a passivation tank pipeline are arranged on the ion exchanger, a pure water inlet pipeline is connected with a pure water inlet on the ion exchanger, a trivalent chromium ion wastewater pool is connected with a wastewater outlet on the ion exchanger through a pipeline, a regeneration solution container is respectively connected with a regeneration solution inlet and a regeneration solution outlet on the ion exchanger through two pipelines, and the ion exchanger is connected with a passivation tank, a pure water inlet pipeline and a trivalent chromium ionAt least one valve is arranged on the connecting pipeline of the sub wastewater pond and the regenerated liquid container, strong acid cation resin is filled in the ion exchanger, strong acid is filled in the regenerated liquid container, and a hydraulic pump is arranged on the connecting pipeline of the regenerated liquid container and the ion exchanger. The method can effectively remove Fe in the trivalent chromium passivation solution 3+ Removing Zn accumulated in the passivation solution by using a zinc complexing agent 2+ And plasma impurity ions.)

1. An impurity removal device for zinc-plated trivalent chromium color passivation solution is characterized by comprising an ion exchanger (1), wherein a passivation solution inlet and a passivation solution outlet which are connected with a passivation tank (2) through pipelines are arranged on the ion exchanger (1), a pure water inlet pipeline (3) is connected with a pure water inlet on the ion exchanger (1), a trivalent chromium ion wastewater pool (4) is connected with a wastewater outlet on the ion exchanger (1) through a pipeline, a regeneration solution container (5) is respectively connected with a regeneration solution inlet and a regeneration solution outlet on the ion exchanger (1) through two pipelines, at least one valve is arranged on the connecting pipelines of the ion exchanger (1), the passivation tank (2), the pure water inlet pipeline (3), the trivalent chromium ion wastewater pool (4) and the regeneration solution container (5), and strong acid cation resin is filled in the ion exchanger (1), strong acid is filled in the regenerated liquid container (5), and a hydraulic pump is arranged on a connecting pipeline of the regenerated liquid container (5) and the ion exchanger (1).

2. The impurity removing device for the zinc-plated trivalent chromium color passivating solution according to claim 1, wherein the passivating solution inlet, the waste water outlet and the regenerating solution outlet are all arranged at the bottom of the ion exchanger (1), and the passivating solution outlet, the pure water inlet and the regenerating solution inlet are all arranged at the top of the ion exchanger.

3. The impurity removing device for the zinc-plated trivalent chromium color passivating solution according to claim 2, wherein the filling degree of the strong acid cation resin in the ion exchanger (1) is not more than 90%.

4. The impurity removal device for the zinc-plated trivalent chromium color passivation solution according to claim 3, further comprising a control device (6), wherein the ion exchanger (1), the passivation tank (2), the pure water inlet pipeline (3), the trivalent chromium ion wastewater pool (4) and the regeneration solution container (5) are respectively connected with valves comprising at least one electromagnetic valve, and the signal input ends of all the electromagnetic valves are respectively connected with the signal input end of the control device (6).

5. The impurity removing device for the zinc-plated trivalent chromium color passivating solution according to claim 4, wherein the control device (6) is a PLC.

6. The impurity removing device for the zinc-plated trivalent chromium color passivation solution according to claim 1 or 5, wherein a temperature detection device and a pH detection device are arranged in the passivation tank (2).

7. An impurity removal method of a zinc-plated trivalent chromium color passivation solution, which is based on the impurity removal device of the zinc-plated trivalent chromium color passivation solution of any one of claims 1 to 6, and is characterized by comprising the following steps:

s1: sampling passivation solution which needs to be input into the ion exchanger (1);

s2: inputting the passivation solution into an ion exchanger (1);

s3: purifying the passivation solution input in the S2 by strong acid cation resin, and outputting the passivation solution to a passivation tank (2);

s4: sampling passivation solution output from the ion exchanger (1) to the passivation tank (2);

s5: fe sampled in S4³⁺Content of Fe sampled in S1³⁺The content is analyzed and compared to obtain Fe³⁺And setting a threshold point, Fe³⁺The loss rate is above the threshold, repeating the steps S1-S4, Fe³⁺If the loss rate does not exceed the threshold point, performing step S6 and the following steps;

s6: stopping the steps from S1 to S4, inputting pure water into the ion exchanger (1) from a pure water inlet pipeline (3), and outputting the treated wastewater to a trivalent chromium ion wastewater pool (4);

s7: stopping the step of S6, inputting the regeneration liquid from the regeneration liquid container (5) to the ion exchanger (1), and outputting the regeneration liquid from the regeneration liquid outlet to the regeneration liquid container (5);

s8: the step of S7 is stopped, and the step of S6 is executed again;

s9: the step of S8 is stopped, and the steps of S1 to S5 are performed again.

8. The impurity removal method for the trivalent chromium color passivating solution for galvanization of claim 7, wherein the control device (6) controls the electromagnetic valve to execute the steps from S1 to S9.

9. The impurity removal method for the zinc-plated trivalent chromium color passivation solution according to claim 8, wherein the regeneration solution is hydrochloric acid, the concentration of the hydrochloric acid is 20-45% VOL, and the ratio of the hydrochloric acid to water is 1: 2.

10. the impurity removal method for the zinc-plated trivalent chromium color passivation solution according to claim 9, further comprising the following steps of:

t1: for Zn in the passivation tank (2)²⁺Analyzing the content and setting a threshold value point;

T2：Zn²⁺when the content does not exceed the threshold value point, the passivation tank (2) continues to work;

T3：Zn²⁺when the content exceeds a threshold point, adding a zinc complexing agent into the passivation tank (2);

t4: filtering the passivation solution in the passivation tank (2).

Technical Field

The invention relates to the technical field of metal passivation treatment, in particular to an impurity removal device and an impurity removal method for a zinc-plated trivalent chromium color passivation solution.

Background

Clean production has become an international trend in the world today and is the only way to achieve social sustainable development. The clean production is carried out in an all-around and multi-angle way, and comprises the measures of improving design, using clean energy and raw materials, adopting advanced process technology and equipment, improving management, comprehensively utilizing and the like, reducing pollution from the source, improving the utilization efficiency of resources, reducing or improving the generation and emission of pollutants in the processes of production, service and product use, and reducing or eliminating the harm to human health.

Trivalent chromium passivation is a common passivation treatment process for zinc coatings. According to the forming mechanism of trivalent chromium passivation film, the passivation area is increased and the passivation solution is inThe zinc ions are continuously accumulated and increased. Practice proves that the concentration of zinc ions in the passivation solution is more than 10g/L, and the salt spray performance of a workpiece is influenced; fe of passivation solution³⁺Concentrations greater than 120mg/L first affect the appearance of the passive film (the color of the passive film gradually yellows with excessive accumulation of ferric iron) and also make the corrosion resistance worse than normal.

In practical production, after the passivating solution is used for a period of time, the passivating solution is accompanied by Fe in the passivating solution³⁺、Zn²⁺The accumulation of the (C) component (B) can lead the appearance of the passive film to be yellow and the salt spray performance to be poor (the requirements of no white rust for 96h and no red rust for 144h are not met), and the addition of the concentrated solution can not lead the passive solution to be recovered to the normal state, so that part of the solution or all the solution has to be replaced. The scrapped trivalent chromium passivation solution contains Fe³⁺、Zn²⁺、Cr³⁺、Co²⁺And the waste water can be discharged after reaching the standard. The cost of new grooving of trivalent chromium passivation solution and the cost of wastewater treatment increase the cost of electroplating. In production practice, it is found that when the trivalent chromium passivation solution contains impurity ions (such as Fe)³⁺、Zn²⁺) Beyond a certain range, the film quality can be affected.

Disclosure of Invention

In order to solve the problems, prolong the service life of the trivalent chromium passivation solution and reduce the discharge of the trivalent chromium wastewater, the content of impurity ions (Fe) is controlled within a certain range³⁺、Zn²⁺The content of (b) is lower than 120mg/L and 10g/L, respectively). Ion exchange is one of the commonly used techniques for removing impurity ions from a solution and has the advantage of selective adsorption. The invention adopts a strong acid cation resin exchange method to remove Fe in trivalent chromium passivation solution³⁺Removing Zn accumulated in the passivation solution by using a zinc complexing agent²⁺And the impurity ions are subjected to plasma treatment to prolong the service cycle of the trivalent chromium passivation solution, reduce the discharge of wastewater on the premise of ensuring the product quality and achieve the purposes of environmental protection, energy conservation, emission reduction and cost saving.

The technical purpose of the invention is realized by the following technical scheme:

the utility model provides an edulcoration device of colored passivation solution of zinc-plated trivalent chromium, including ion exchanger, be provided with passivation solution entry and passivation solution export with passivation groove pipe connection on the ion exchanger, the pure water inlet channel is connected with the pure water entry on the ion exchanger, trivalent chromium ion wastewater disposal basin passes through the waste water exit linkage on pipeline and the ion exchanger, the regeneration liquid container passes through two pipelines respectively with regeneration liquid entry and regeneration liquid exit linkage on the ion exchanger, ion exchanger and passivation groove, the pure water inlet channel, all be equipped with at least one valve on the connecting tube of trivalent chromium ion wastewater disposal basin and regeneration liquid container, it has strong acid cation resin to fill in the ion exchanger, the built-in strong acid that is equipped with of regeneration liquid container, be equipped with the hydraulic pump on the connecting tube of regeneration liquid container and ion exchanger.

By adopting the technical scheme, in the passivation treatment process, Fe³⁺Gradually increasing concentration, removing impurities from the passivation solution, opening the output valve of the passivation solution, introducing the passivation solution into an ion exchanger, and treating Fe with strong acid cation resin³⁺Adsorbing, guiding the treated passivation solution into a passivation tank again, and continuing to perform passivation treatment; after repeating this operation a plurality of times and the iron ion loss rate is lower than a certain level, the strongly acidic cation resin needs to be subjected to a regeneration treatment: firstly, opening an input valve of pure water, introducing the pure water into an ion exchanger from a pure water inlet pipeline, removing air bubbles and passivation liquid in the strong-acid cation resin, introducing wastewater into a trivalent chromium ion wastewater pool, introducing a regeneration liquid into the ion exchanger from a regeneration liquid container, recovering the ion exchange function of the acid cation resin, introducing the derived regeneration liquid back into the regeneration liquid container, introducing the pure water, cleaning the strong-acid regeneration liquid in the ion exchanger, using the regeneration liquid for 3-5 times, and judging whether the resin needs to be prepared again or not by the loss rate of ferric iron adsorption on the resin so as to ensure the regeneration effect of the resin.

The technical scheme can prolong the service cycle of the trivalent chromium passivation solution, reduce the discharge of waste water on the premise of ensuring the product quality, and achieve the purposes of environmental protection, energy conservation, emission reduction and cost saving.

As a preferred scheme, the passivation liquid inlet, the waste water outlet and the regeneration liquid outlet are all arranged at the bottom of the ion exchanger, and the passivation liquid outlet, the pure water inlet and the regeneration liquid inlet are all arranged at the top of the ion exchanger.

By adopting the technical scheme, Fe in the passivation solution³⁺Can be well adsorbed by the strong acid cation resin, and simultaneously ensures the cleaning effect of pure water and the regeneration effect of regeneration liquid. The iron ions of the passivation solution are stabilized below 120mg/L, and the salt spray performance of the coating is ensured.

As a preferable mode, the filling degree of the strong acid cation resin in the ion exchanger is not more than 90%.

At least 10% of the space needs to be reserved because the strong acid cation resin can expand when meeting the passivating solution.

As a preferred scheme, the impurity removal device for the zinc-plated trivalent chromium color passivation solution further comprises a control device, the ion exchanger and the passivation tank, the pure water inlet pipeline, the trivalent chromium ion wastewater pool and the regeneration liquid container are respectively connected with valves which respectively comprise at least one electromagnetic valve, and the signal input ends of all the electromagnetic valves are respectively connected with the signal input end of the control device.

By adopting the technical scheme, the automation of the device can be improved, and the labor cost is reduced.

As a preferred scheme, the control device is a PLC or a single chip microcomputer, and when the PLC is used, the model of the PLC can be selected from Siemens S7-200.

By adopting the technical scheme, taking PLC as an example, the opening and closing time points of the corresponding electromagnetic valves are respectively controlled by setting a time delay program, and Fe of the tank liquor of the production line passivation tank is passivated by an operator³⁺The concentration is analyzed periodically, and the bath solution Fe³⁺And after the process range is exceeded, the equipment is immediately started, the adsorption process is started, and the control is carried out by combining a time delay program, so that the full-automatic treatment is realized.

Preferably, a temperature detection device and a pH detection device are arranged in the passivation tank.

By adopting the technical scheme, the Zn in the passivation solution needs to be treated by using a zinc complexing agent²⁺The concentration is regulated, the temperature is controlled to be more than 60 ℃ in order to prevent cobalt in the passivation solution from precipitating, and when the zinc complexing agent is added into the passivation solution, the pH value of the passivation solution is reduced (the higher the temperature is, the higher the p isH to lower), which affects the passivation process, so it is necessary to cool down to the process range, and after filtration, normal passivation can be resumed by adjusting the pH to the rear of the process range with 10% pure sodium hydroxide or sodium carbonate.

As a preferred scheme, the pure water inlet pipeline is connected with a reserved water outlet.

By adopting the technical scheme, if hydrochloric acid splashes on the skin when the regeneration liquid is prepared, water is required to be used for washing immediately, so that the reserved water outlet ensures the construction safety of the site.

An impurity removal method of a zinc-plated trivalent chromium color passivation solution is based on the impurity removal device of the zinc-plated trivalent chromium color passivation solution, and comprises the following steps:

s1: sampling passivation solution needing to be input into an ion exchanger;

s2: inputting the passivation solution into an ion exchanger;

s3: purifying the passivation solution input in the S2 by strong acid cation resin, and outputting the passivation solution to a passivation tank;

s4: sampling the passivation solution output from the ion exchanger to the passivation tank;

s5: fe sampled in S4³⁺Content of Fe sampled in S1³⁺The content is analyzed and compared to obtain Fe³⁺And setting a threshold point, Fe³⁺The loss rate is above the threshold, repeating the steps S1-S4, Fe³⁺If the loss rate does not exceed the threshold point, performing step S6 and the following steps;

s6: stopping the steps from S1 to S4, inputting pure water into the ion exchanger from a pure water inlet pipeline, and outputting the treated wastewater to a trivalent chromium ion wastewater pool;

s7: stopping the step of S6, inputting the regeneration liquid into the ion exchanger from the regeneration liquid container, and outputting the regeneration liquid to the regeneration liquid container from the regeneration liquid outlet;

s8: the step of S7 is stopped, and the step of S6 is executed again;

s9: the step of S8 is stopped, and the steps of S1 to S5 are performed again.

By adopting the technical scheme, the sampling is carried out in S1 and S5, the sampling can be carried out manually, and thenPerforming assay analysis to obtain Fe³⁺And in the process of multiple experiments, the threshold point of the loss rate is set to be about 70%, the effect can be optimal, and the optimal proportion of the regeneration times and the impurity removal effect is obtained.

Preferably, the control device controls the solenoid valve to perform steps S1 to S9.

As a preferable scheme, the regeneration liquid is hydrochloric acid, the concentration of the hydrochloric acid is 20-45% VOL, and the ratio of the hydrochloric acid to water is 1: 2.

as a preferable scheme, the method further comprises the following steps:

t1: for Zn in passivation tank²⁺Monitoring the content and setting a threshold value point;

T2：Zn²⁺when the content does not exceed the threshold point, the passivation tank continues to work;

T3：Zn²⁺adding a zinc complexing agent into the passivation tank when the content exceeds a threshold point;

t4: and filtering the passivation solution in the passivation tank.

In conclusion, the invention has the following beneficial effects:

the method can effectively remove Fe in the trivalent chromium passivation solution³⁺Removing Zn accumulated in the passivation solution by using a zinc complexing agent²⁺And the impurity ions are subjected to plasma treatment to prolong the service cycle of the trivalent chromium passivation solution, reduce the discharge of wastewater on the premise of ensuring the product quality and achieve the purposes of environmental protection, energy conservation, emission reduction and cost saving.

Drawings

FIG. 1 is a schematic structural diagram of an impurity removal device for a trivalent chromium color galvanization passivation solution according to an embodiment of the invention;

wherein:

1. an ion exchanger; 2. a passivation tank; 3. a pure water inlet pipe; 4. a trivalent chromium ion wastewater pond; 5. a regeneration liquid container; 6. a control device; 7. an acid-base wastewater pool; 8. and reserving a water outlet.

Detailed Description

The present invention will be described in further detail below.