CN112047525A - Method and system for breaking cyanogen in resin - Google Patents
Method and system for breaking cyanogen in resin Download PDFInfo
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- CN112047525A CN112047525A CN202010896196.2A CN202010896196A CN112047525A CN 112047525 A CN112047525 A CN 112047525A CN 202010896196 A CN202010896196 A CN 202010896196A CN 112047525 A CN112047525 A CN 112047525A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
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Abstract
The embodiment of the application discloses a method and a system for resin cyanogen breaking, wherein the method comprises the following steps: pre-heating the pretreated raw water to 40-50 ℃, wherein the pH value is 3-5, the raw water comprises complex cyanide, and detecting the concentration of the complex cyanide. Injecting the heated raw water into a resin tank, standing for 40-50 hours to enable the resin in the resin tank to adsorb metal ions in the complex cyanide, releasing cyanide ions, combining with sodium ions in the raw water to generate sodium cyanide, injecting the raw water containing the sodium cyanide into a reaction tank, and adding an oxidant, wherein the oxidant reacts with the cyanide ions to generate nitrogen and carbon dioxide gas. Not only the resin is used for adsorbing metal ions in raw water, but also the oxidant is used for converting cyanide ions released from the complex cyanide. Thus removing the complex cyanide in the raw water, improving the treatment effect of the raw water and optimizing the water circulation.
Description
Technical Field
The application relates to a pollutant treatment method in the field of environmental protection, in particular to a method and a system for breaking cyanogen in resin.
Background
High-salt raw water containing cyanogen generated in the process of producing cyanuric chloride is treated in a medium water system through air stripping and chlorine oxidation processes, wherein cyanide in a free state is converted, only cyanide in a complex state (the content is generally in a range of 5-20 mg/l) is remained, and the complex basically exists in the form of an iron-cyanogen complex. The complex has good stability and is not easy to be directly oxidized. At present, the retention time of the iron cyanide complex in the reaction tank is prolonged only by adding more reaction tanks, so that the iron cyanide complex is naturally and slowly hydrolyzed to promote the further conversion of the complex cyanogen.
However, the method has low treatment efficiency and is easily interfered by water quality fluctuation, so that the total cyanogen index of the treated brine can not be effectively controlled. Furthermore, if the treated brine is recycled and used in a chlor-alkali production system, the iron element in the complex cyanide can enter the electrolytic bath along with the brine, so that the ionic membrane in the chlor-alkali production system is polluted. Resulting in the adverse effects of over-rapid increase of power consumption, reduction of service life of the ionic membrane and the like, and increases the operation cost of the chlor-alkali production system.
Disclosure of Invention
The embodiment of the application provides a method and a system for resin cyanogen breaking. The complex cyanide in the raw water is treated, and the purification efficiency and effect of the raw water are improved.
In a first aspect, a method of resin cyanogen breaking, the method comprising the steps of:
s1, preheating the pretreated raw water to 40-50 ℃ to obtain the heated raw water, wherein the raw water comprises a complex cyanide, and the concentration of the complex cyanide is detected to be 1600-2000 mg/L;
s2, injecting heated raw water into the resin tank, wherein the pH value of the heated raw water is 3-5; standing for 40-50 hours to enable the resin in the resin tank to adsorb metal ions in the complex cyanide and release cyanide ions, wherein the cyanide ions are combined with sodium ions in the raw water to generate sodium cyanide, so that raw water containing the sodium cyanide is obtained, and the concentration of the cyanide ions in the raw water containing the sodium cyanide is detected;
s3, if the concentration of the cyanide ions does not match the concentration of the cyanide in the complex state, injecting the raw water containing sodium cyanide into a new resin tank, and repeating the step S2 until the concentration of the cyanide ions matches the concentration of the cyanide in the complex state;
s4, if the raw water is matched with the sodium cyanide, injecting the raw water containing the sodium cyanide into a reaction tank; putting an oxidant with the concentration of 600-800 mg/L into the reaction tank, adding alkali liquor, wherein the pH value of the solution in the reaction tank is more than 10, so that the oxidant reacts with cyanide ions in the sodium cyanide, and the cyanide ions are converted into nitrogen and carbon dioxide gas, wherein the pressure in the reactor is normal pressure, the filling gas is inert gas, and the temperature in the reactor is kept at normal temperature.
Optionally, before preheating the pretreated raw water, the method further includes:
introducing the raw water at the outlet of the pump into a microporous filter at a flow rate of 0.5-1.5m/s so that the microporous filter filters suspended matters in the raw water to obtain pretreated raw water;
wherein the suspended matters in the pretreated raw water meet a preset standard.
Optionally, before the raw water at the outlet of the pump is introduced into the microporous filter, the method further comprises:
and carrying out air stripping and oxidation treatment on the raw water in the brine tank to remove free cyanide ions in the raw water, so that complex cyanide remains in the raw water after air stripping and oxidation treatment.
Optionally, the microporous filter includes an inlet and an outlet, wherein a rotameter is provided to detect raw water flow at the inlet and the outlet, so as to obtain a detected flow;
and adjusting the raw water flow of the inlet and the outlet according to the detection flow and the preset standard.
Optionally, the temperature of the heated raw water is adjusted according to a preset adsorption power of a resin, wherein the resin is any one or more of the following: chelating resins, cation exchange resins, ultra-high crosslinking resins; the pore size of the resin is 0.315-1.25 mm (such as 0.715 mm), and the height of the resin is 1-3 m.
Optionally, before performing step S2, the method further includes:
detecting the dehydration condition of the resin in the resin tank, if the resin is dehydrated, soaking for 30-60 minutes by selecting saline solution with the concentration of 20-30%, wherein the volume height of the saline solution is not lower than the height covering the resin, gradually diluting the concentration of the saline solution to 5-10% (such as 7.8%, and the like), and after diluting and soaking for 20-40 minutes, discharging the saline solution from an outlet of the resin tank.
Optionally, the method further includes:
and detecting the pressure and the temperature in the reactor according to a certain period, and if pressure abnormality and/or temperature abnormality is detected, controlling the outlet valve of the resin tank to be closed, and controlling the oxidant inlet of the reactor to be closed so as to stop adding the oxidant into the reactor.
In a second aspect, a system for resin cyanogen breaking, the system comprising:
the preheater is used for preheating the pretreated raw water to 40-50 ℃ to obtain the heated raw water, the raw water comprises complex cyanide, and the concentration of the complex cyanide is detected, wherein the concentration of the complex cyanide is 1600-2000 mg/L;
the system comprises a resin tank, a water tank and a water tank, wherein the resin tank comprises resin, heated raw water is injected into the resin tank, and the PH value of the heated raw water is 3-5; standing for 40-50 hours to enable the resin to adsorb metal ions in the complex cyanide and release cyanide ions, wherein the cyanide ions are combined with sodium ions in the raw water to generate sodium cyanide, so that the raw water containing the sodium cyanide is obtained, and the concentration of the cyanide ions in the raw water containing the sodium cyanide is detected; if the concentration of the cyanide ions does not match the concentration of the complex-state cyanide, injecting the raw water containing sodium cyanide into a new resin tank so that the resin in the new resin tank adsorbs the metal ions in the complex-state cyanide until the concentration of the cyanide ions matches the concentration of the complex-state cyanide.
A reaction tank, wherein if the concentration of the cyanide ions matches the concentration of the cyanide in a complex state, the raw water containing sodium cyanide is injected into the reaction tank; putting an oxidant with the concentration of 600-800 mg/L into the reaction tank, adding alkali liquor, wherein the pH value of the solution in the reaction tank is more than 10, so that the oxidant reacts with cyanide ions in the sodium cyanide, and the cyanide ions are converted into nitrogen and carbon dioxide gas, wherein the pressure in the reactor is normal pressure, the filling gas is inert gas, and the temperature in the reactor is kept at normal temperature.
Optionally, the system further includes:
the pump is used for introducing the raw water at the outlet of the pump into the microporous filter at the flow velocity of 0.5-1.5m/s so that the microporous filter filters suspended matters in the raw water to obtain pretreated raw water; wherein suspended matters in the pretreated raw water meet a preset standard;
and the microporous filter is used for filtering suspended matters in the raw water to obtain the pretreated raw water.
Optionally, the system further includes:
a brine tank for storing raw water, and/or,
and carrying out air stripping and oxidation treatment on the raw water to remove free cyanide ions in the raw water, so that complex cyanide remains in the raw water after the air stripping and oxidation treatment.
In the present application, the pretreated raw water contains cyanide in a complex state. The complex cyanide is different from free cyanide ions, and has stable property and is not easy to be oxidized. If the stability of the complex cyanide can be destroyed, the cyanide ions are released, and the further treatment of the cyanide ions can be facilitated. Therefore, the pretreated raw water is preheated, and the heated raw water is injected into the resin tank, so that the resin in the resin tank can adsorb metal ions in the complex cyanide to release cyanide ions, and the cyanide ions are combined with sodium ions in the raw water to obtain the raw water containing sodium cyanide. The adsorption effect of the resin is improved by controlling the heating temperature. The raw water containing sodium cyanide is injected into a reaction tank, and an oxidant is fed into the reaction tank so that the oxidant reacts with cyanide ions in the sodium cyanide to convert the cyanide ions into nitrogen gas and carbon dioxide gas. By controlling the concentration of the oxidant, the reaction is more complete and no new impurities are introduced. Not only the resin is used for adsorbing metal ions in raw water, but also the oxidant is used for converting cyanide ions released from the complex cyanide. Thus removing the complex cyanide in the raw water, improving the treatment effect of the raw water and optimizing the water circulation.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a system for breaking cyanogen in resin according to an embodiment of the present disclosure;
FIG. 2 is a schematic flow chart of a method for breaking cyanogen in resin according to an embodiment of the present application;
FIG. 3 is a schematic flow chart of another method for breaking cyanogen in resin according to the embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The terms "first," "second," and the like in the description and claims of the present application and in the above-described drawings are used for distinguishing between different objects and not for describing a particular order. Furthermore, the terms "include" and "have," as well as any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
At present, high-salt raw water containing cyanogen generated in the production of cyanuric chloride is treated in a reclaimed water system through air stripping and chlorine oxidation processes, wherein free cyanogen is converted, only complex cyanides (the content is generally in the range of 5-20 mg/l) are remained, and the complex exists basically in the form of an iron-cyanogen complex. The complex has good stability and is not easy to be directly oxidized. At present, the retention time of the iron cyanide complex in the reaction tank is prolonged only by adding more reaction tanks, so that the iron cyanide complex is naturally and slowly hydrolyzed to promote the further conversion of the complex cyanogen. However, the method has low treatment efficiency and is easily interfered by water quality fluctuation, so that the total cyanogen index of the treated brine can not be effectively controlled.
In order to solve the above problem, embodiments of the present application provide a method for resin cyanogen breaking, which is applied to a system for resin cyanogen breaking. The following detailed description is made with reference to the accompanying drawings.
First, referring to fig. 1, a schematic diagram of a resin cyanogen breaking system 100 may include a brine tank 110, a pump 120, a microporous filter 130, a preheater 140, a resin tank 150, and a reaction tank 160.
Referring to the embodiments of the present application, a system for resin cyanogen breaking, the system comprising:
the preheater is used for preheating the pretreated raw water to 40-50 ℃ to obtain the heated raw water, the raw water comprises complex cyanide, and the concentration of the complex cyanide is detected, wherein the concentration of the complex cyanide is 1600-2000 mg/L;
the system comprises a resin tank, a water tank and a water tank, wherein the resin tank comprises resin, heated raw water is injected into the resin tank, and the PH value of the heated raw water is 3-5; standing for 40-50 hours to enable the resin to adsorb metal ions in the complex cyanide and release cyanide ions, wherein the cyanide ions are combined with sodium ions in the raw water to generate sodium cyanide, so that the raw water containing the sodium cyanide is obtained, and the concentration of the cyanide ions in the raw water containing the sodium cyanide is detected; if the concentration of the cyanide ions does not match the concentration of the complex cyanide, injecting the raw water containing sodium cyanide into a new resin tank so that the resin in the new resin tank adsorbs the metal ions in the complex cyanide until the concentration of the cyanide ions matches the concentration of the complex cyanide
A reaction tank, wherein if the concentration of the cyanide ions matches the concentration of the cyanide in a complex state, the raw water containing sodium cyanide is injected into the reaction tank; putting an oxidant with the concentration of 600-800 mg/L into the reaction tank, adding alkali liquor, wherein the pH value of the solution in the reaction tank is more than 10, so that the oxidant reacts with cyanide ions in the sodium cyanide, and the cyanide ions are converted into nitrogen and carbon dioxide gas, wherein the pressure in the reactor is normal pressure, the filling gas is inert gas, and the temperature in the reactor is kept at normal temperature.
In one possible example, the system further comprises: the pump is used for introducing the raw water at the outlet of the pump into the microporous filter at the flow velocity of 0.5-1.5m/s so that the microporous filter filters suspended matters in the raw water to obtain pretreated raw water; wherein suspended matters in the pretreated raw water meet a preset standard; and the microporous filter is used for filtering suspended matters in the raw water to obtain the pretreated raw water.
In one possible example, the system further comprises: the brine tank is used for storing raw water and/or carrying out air stripping and oxidation treatment on the raw water to remove free cyanide ions in the raw water so as to enable the raw water after air stripping and oxidation treatment to retain complex cyanide.
The technical solution of the embodiment of the present application can be embodied based on the resin cyanogen breaking system or the deformation structure thereof illustrated in fig. 1 as an example.
Referring to fig. 2, fig. 2 is a schematic flow chart of a method for breaking cyanogen in resin according to an embodiment of the present application, which may include, but is not limited to, the following steps:
s1, preheating the pretreated raw water to 40-50 ℃ to obtain the heated raw water, wherein the raw water comprises a complex cyanide, and the concentration of the complex cyanide is detected to be 1600-2000 mg/L.
Specifically, the complex state refers to a chemical form in which the metal in the water body or the soil exists in the form of complex ions or complexes (coordination compounds). By a cyanide in complexed form is understood a chemical substance, such as a ferricyanide complex, in which cyanide ions are complexed with metal ions in the raw water. The complex cyanide has good stability and is not easy to be directly oxidized. The pretreated raw water is preheated, and the preheating can be carried out in a preheater. The specific temperature of heating can be adjusted according to subsequent treatment or according to treatment effect. The heating temperature range of the raw water is preset, so that the subsequent further treatment, such as resin adsorption, is facilitated. Avoid the temperature to hang down and lead to adsorption effect to be influenced, the temperature is too high, destroys the resin structure, further influences adsorption effect.
In addition, the concentration of the complex cyanide can be detected to be 1600mg/L-2000mg/L, so that the mass of the complex cyanide can be calculated conveniently according to the concentration. The concentration detection device can be arranged in the heater or arranged outside the heater, and can automatically sample and obtain a concentration detection sample. Further, the mass of the cyanide ion was calculated. So that whether the subsequent adsorption or reaction is sufficient or not can be detected in a contrast way.
Optionally, the temperature of the heated raw water is adjusted according to a preset adsorption power of a resin, wherein the resin is any one or more of the following: chelating resins, cation exchange resins, ultra-high crosslinking resins; the aperture size of the resin is 0.315-1.25 mm, and the height of the resin is 1-3 m.
In particular, it is understood that different resins have different adsorption powers, or that the same resin has different adsorption powers at different temperatures. Therefore, the adsorption power of the resin can be set in advance according to experiments before the raw water is treated. The adsorption power may be an optimum adsorption power for the resin at a certain temperature or within a certain temperature range. Therefore, the temperature of the heated raw water is adjusted according to the preset adsorption power of the resin, which is beneficial to the adsorption effect of the resin on the metal cations in the complex cyanide.
In addition, due to the variety of resin types, resins can be classified differently according to different criteria. Since the present embodiment is to adsorb metal cations, such as iron ions, in the complex cyanide, the resin for adsorption is any one or more of the following: chelating resin, cation exchange resin and ultrahigh crosslinking resin. And the large-aperture resin with the aperture size of 0.315-1.25 mm is selected, so that the resin has a better adsorption effect on metal cations. In addition, the height of the resin is set to be 1-3m, which is beneficial to quickly and massively adsorbing and treating raw water.
S2, injecting heated raw water into the resin tank, wherein the pH value of the heated raw water is 3-5; and standing for 40-50 hours to enable the resin in the resin tank to adsorb metal ions in the complex cyanide and release cyanide ions, wherein the cyanide ions are combined with sodium ions in the raw water to generate sodium cyanide, so that raw water containing the sodium cyanide is obtained, and the concentration of the cyanide ions in the raw water containing the sodium cyanide is detected.
Specifically, the heated raw water is injected into the resin tank. Standing for 40-50 hrIn time, the adsorption is more sufficient. The standing time is too short, so that the adsorption effect is influenced. The standing time is too long, so that the treatment efficiency of raw water is influenced. The specific standing time can be adjusted according to the treatment amount of raw water (concentration of the cyanide in a complex state). Since the complex cyanide is mainly iron cyanide complex, the pH value of the raw water needs to be adjusted to 3-5 to make the raw water acidic, and the raw water is heated, so that the resin in the resin tank can better adsorb iron ions in the complex cyanide and release Cyanogen (CN)-) Ions destroy the stability of the cyanide in a complex state, so that the cyanide ions are combined with sodium ions in raw water to obtain sodium cyanide.
In addition, the mass of the cyanide element can be calculated by detecting the concentration of the cyanide in the complex state. In this step, the concentration of cyanide ions in the raw water containing sodium cyanide may be detected by a concentration detection device provided in the resin tank, and the mass of the cyanide element may also be calculated. The concentration detection device can also be externally arranged on the resin tank, and can automatically sample and obtain a concentration detection sample. The masses calculated in the two previous and subsequent times are compared to judge the sufficiency of resin adsorption. For example, the mass difference between the two times is calculated to meet a preset standard, for example, 1 ton of raw water, and the mass difference of less than or equal to 1 kilogram (kg) can be regarded as meeting the preset standard, and the subsequent treatment can be carried out.
S3, if the concentration of the cyanide ions does not match the concentration of the cyanide in the complex state, injecting the raw water containing the sodium cyanide into a new resin tank, and repeating the step S2 until the concentration of the cyanide ions matches the concentration of the cyanide in the complex state.
Specifically, it is understood that, if the adsorption of step S2 does not satisfy the predetermined criterion, the raw water containing sodium cyanide is injected into a new resin tank, and step S2 is repeated until the concentration of cyanide ions matches the concentration of cyanide in a complex state.
S4, if the raw water is matched with the sodium cyanide, injecting the raw water containing the sodium cyanide into a reaction tank; putting an oxidant with the concentration of 600-800 mg/L into the reaction tank, adding alkali liquor, wherein the pH value of the solution in the reaction tank is more than 10, so that the oxidant reacts with cyanide ions in the sodium cyanide, and the cyanide ions are converted into nitrogen and carbon dioxide gas, wherein the pressure in the reactor is normal pressure, the filling gas is inert gas, and the temperature in the reactor is kept at normal temperature.
Specifically, the resin adsorbs metal ions of complex cyanide in raw water to release Cyanogen (CN)-) After ionization, the Cyanogen (CN)-) The ions combine with sodium ions in the raw water to produce sodium cyanide. Raw water containing sodium cyanide is injected into the reaction tank to facilitate further treatment of the raw water. In the reaction tank, in order to better treat Cyanogen (CN) in sodium cyanide in raw water-) Ions. Thus, an oxidizing agent is fed into the reaction tank, and an alkali solution is added so that the oxidizing agent reacts with the cyanide ions to convert the cyanide ions into nitrogen (N)2) And carbon dioxide (CO)2) A gas.
The alkali liquor is added mainly for adjusting the pH value in the reaction tank to be more than 10, so that the reaction tank is alkaline, and the reaction condition is met. The alkali liquor can be added into raw water at the outlet pipeline of the resin tank or into the reaction tank. The lye may be a sodium hydroxide (NaOH) solution. Since the concentration of the cyanide ions in the raw water is detected in step S2, the concentration of the oxidizing agent and the flow rate can be adjusted according to the concentration of the cyanide ions, and the concentration range is 600mg/L to 800 mg/L. So that the reaction is more sufficient and new pollution to raw water caused by excessive oxidant is avoided. The oxidizing agent may be a sodium hypochlorite (NaClO) solution.
It can be seen that the pretreated raw water contains cyanide in a complex state. The complex cyanide is different from free cyanide ions, and has stable property and is not easy to be oxidized. If the stability of the complex cyanide can be destroyed, the cyanide ions are released, and the further treatment of the cyanide ions can be facilitated. Therefore, the embodiment of the application preheats the pretreated raw water, and injects the heated raw water into the resin tank, so that the resin in the resin tank can adsorb the metal ions in the complex cyanide, and release the cyanide ions, thereby obtaining the raw water containing sodium cyanide. The resin is acidic by controlling the heating temperature and the pH value of the raw water, so that the adsorption effect of the resin on iron ions in the iron-cyanogen complex is improved. Further, the raw water containing sodium cyanide is injected into a reaction tank. Feeding an oxidant into the reaction tank so that the oxidant reacts with cyanide ions in the sodium cyanide to convert the cyanide ions into nitrogen gas and carbon dioxide gas. By controlling the concentration of the oxidant, the reaction is more complete and no new impurities are introduced. Not only the resin is used for adsorbing metal ions in raw water, but also the oxidant is used for converting cyanide ions released from the complex cyanide. Thus removing the complex cyanide in the raw water, improving the treatment effect of the raw water and optimizing the water circulation.
Furthermore, the treated raw water, namely the purified brine finally obtained, is used as a raw material for producing caustic soda by an ion membrane method. Because the complex cyanide in the raw water is effectively removed, the complex cyanide entering a caustic soda production system can be effectively reduced, the pollution to an ionic membrane (an important component in the caustic soda production system) is reduced, the service life of the ionic membrane is prolonged, and the electric energy consumption is reduced.
Referring to fig. 3, fig. 3 is a schematic flow chart of another resin cyanogen breaking method according to an embodiment of the present application, applied to a resin cyanogen breaking system, consistent with the embodiment shown in fig. 2; the method comprises the following steps:
301. introducing the raw water at the outlet of the pump into a microporous filter at a flow rate of 0.5-1.5m/s so that the microporous filter filters suspended matters in the raw water to obtain pretreated raw water; wherein the suspended matters in the pretreated raw water meet a preset standard.
Specifically, the raw water pretreatment process includes a raw water filtration process. Because suspended matters with different degrees exist in raw water, the subsequent treatment effect of the raw water can be influenced. Therefore, the raw water at the outlet of the pump is introduced into the microporous filter at a flow rate of 0.5-1.5m/s in advance so that the microporous filter filters suspended matters in the raw water. The flow rate is controlled, so that the filtration can be more sufficient. Avoid too fast, the filtration is not enough. Or the flow rate is too fast or too slow, the filtration efficiency is too slow. Suspended matters in the pretreated raw water meet a preset standard. For example, the suspended matter (SS) in the pretreated raw water is less than or equal to 1mg/l, which meets the preset standard. Or suspended matter (SS) in the pretreated raw water is less than or equal to 0.1mg/l, namely the suspended matter meets the preset standard and the like.
Optionally, the microporous filter includes an inlet and an outlet, wherein a rotameter is provided to detect raw water flow at the inlet and the outlet, so as to obtain a detected flow; and adjusting the raw water flow of the inlet and the outlet according to the detection flow and the preset standard.
Specifically, when the microporous filter is used for filtering raw water, the filtering effect can be improved by adjusting the outlet and the flow rate of the raw water at the outlet. The adjustment may be based on the detected flow and a predetermined criterion. The detected flow is obtained by detecting the raw water flow of the inlet and the outlet by the rotor flow meter. The preset standard is the preset content of suspended matters in the pretreated raw water, such as suspended matters (SS) less than or equal to 0.1 mg/l.
302. Preheating the pretreated raw water to 40-50 ℃ to obtain the heated raw water, wherein the raw water comprises a complex cyanide, and the concentration of the complex cyanide is detected to be 1600-2000 mg/L;
303. injecting heated raw water into a resin tank, wherein the pH value of the heated raw water is 3-5; standing for 40-50 hours to enable the resin in the resin tank to adsorb metal ions in the complex cyanide and release cyanide ions, wherein the cyanide ions are combined with sodium ions in the raw water to generate sodium cyanide, so that raw water containing the sodium cyanide is obtained, and the concentration of the cyanide ions in the raw water containing the sodium cyanide is detected;
304. if the concentration of the cyanide ions does not match the concentration of the complex cyanide, injecting the raw water containing sodium cyanide into a new resin tank, and repeating the step S2 until the concentration of the cyanide ions matches the concentration of the complex cyanide;
305. if the raw water is matched with the sodium cyanide, injecting the raw water containing the sodium cyanide into a reaction tank; putting an oxidant with the concentration of 600-800 mg/L into the reaction tank, adding alkali liquor, wherein the pH value of the solution in the reaction tank is more than 10, so that the oxidant reacts with cyanide ions in the sodium cyanide, and the cyanide ions are converted into nitrogen and carbon dioxide gas, wherein the pressure in the reactor is normal pressure, the filling gas is inert gas, and the temperature in the reactor is kept at normal temperature.
The steps 302-305 refer to the above steps S1-S4, which are not described herein again.
It can be seen that, in this application embodiment, at the in-process that carries out the preliminary treatment to raw water, in introducing the raw water of pump export microporous filter, so that microporous filter filters suspended solid in the raw water for suspended solid in the raw water after the preliminary treatment satisfies preset standard. Reducing the interferents in the raw water. Then the complex cyanide contained in the pretreated raw water is treated. Because the complex cyanide is different from free cyanide ions, the property is stable and the cyanide is not easy to be oxidized. If the stability of the complex cyanide can be destroyed, the cyanide ions are released, and the further treatment of the cyanide ions can be facilitated.
Therefore, the embodiment of the application preheats the pretreated raw water, and injects the heated raw water into the resin tank, so that the resin in the resin tank can adsorb the metal ions in the complex cyanide, and release the cyanide ions, thereby obtaining the raw water containing sodium cyanide. The resin is acidic by controlling the heating temperature and the pH value of the raw water, so that the adsorption effect of the resin on iron ions in the iron-cyanogen complex is improved. The adsorption effect of the resin is improved. Injecting the raw water containing sodium cyanide into a reaction tank. Feeding an oxidant into the reaction tank so that the oxidant reacts with cyanide ions in the sodium cyanide to convert the cyanide ions into nitrogen gas and carbon dioxide gas. By controlling the concentration of the oxidant, the reaction is more complete and no new impurities are introduced. Not only the resin is used for adsorbing metal ions in raw water, but also the oxidant is used for converting cyanide ions released from the complex cyanide. Thus removing the complex cyanide in the raw water, improving the treatment effect of the raw water and optimizing the water circulation.
In one possible example, before the introducing the raw water at the pump outlet into the microporous filter, the method further includes: and carrying out air stripping and oxidation treatment on the raw water in the brine tank to remove free cyanide ions in the raw water, so that complex cyanide remains in the raw water after air stripping and oxidation treatment.
Specifically, after high-salt raw water containing cyanogen generated in the production of cyanuric chloride is subjected to air stripping and chlorine oxidation processes in a reclaimed water system, free cyanogen in the raw water is converted, only complex-state cyanides (the content is generally in the range of 5-20 mg/l) are remained, and the complex basically exists in the form of an iron-cyanogen complex. The complex has good stability and is not easy to be directly oxidized. It may be that stripping and oxidation treatment are carried out in a brine tank.
Alternatively, the stripping and oxidation treatment may be performed in a pump. Alternatively, before the raw water enters the brine tank, the raw water may be subjected to stripping and oxidation treatment, so that only the cyanide complex remains in the raw water entering the brine tank.
Therefore, free cyanide ions in raw water are treated by blowing and oxidizing in advance, and the complex cyanide in the raw water can be conveniently treated in a targeted manner. The efficiency and the effect of raw water treatment are improved.
In one possible example, before performing step S2, the method further includes: detecting the dehydration condition of the resin in the resin tank, if the resin is dehydrated, soaking for 30-60 minutes by selecting saline solution with the concentration of 20-30%, wherein the volume height of the saline solution is not lower than the height covering the resin, gradually diluting the concentration of the saline solution to 5-10%, and after diluting and soaking for 20-40 minutes, discharging the saline solution from an outlet of the resin tank.
Specifically, since the resin may be dehydrated during transportation and storage, if the dehydration of the resin in the resin tank is detected, the resin tank is soaked in a salt solution with a concentration of 20-30% for 30-60 minutes. Wherein the volume height of the saline solution is not lower than the height covering the resin, so as to ensure the resin to be completely covered. Then gradually diluting the salt solution to 5-10%, and soaking for 20-40 min after dilution to recover the adsorption force of the resin. After completion of the soaking, the saline solution was discharged from an outlet of the resin tank. After being discharged, the resin can also be washed by proper amount of clear water, thereby ensuring the cleanness of the resin can. The discharged salt solution and clean water can be used in the previous steps.
Therefore, the resin is soaked when the dehydration of the resin is detected, so that the adsorption capacity of the resin is guaranteed.
In one possible example, the method further comprises: and detecting the pressure and the temperature in the reactor according to a certain period, and if pressure abnormality and/or temperature abnormality is detected, controlling the outlet valve of the resin tank to be closed, and controlling the oxidant inlet of the reactor to be closed so as to stop adding the oxidant into the reactor.
Specifically, it can be understood that a pressure detection device and a temperature detection device are also arranged in the resin cyanogen breaking system shown in fig. 1. The pressure and the temperature in the reactor can be detected periodically or in real time, if the pressure abnormality and/or the temperature abnormality is detected, the outlet valve of the resin tank is controlled to be closed, and the oxidant inlet of the reactor is controlled to be closed so as to stop adding the oxidant into the reactor.
Therefore, the pressure and the temperature in the reactor are detected periodically or in real time, the safety of the reaction can be guaranteed, and safety accidents are avoided. Thereby ensuring the treatment effect on the raw water.
It should be noted that, for simplicity of description, the above-mentioned method embodiments are described as a series of acts or combination of acts, but those skilled in the art will recognize that the present application is not limited by the order of acts described, as some steps may occur in other orders or concurrently depending on the application. Further, those skilled in the art will also appreciate that the embodiments described in the specification are presently preferred and that no acts or devices are necessarily required in the present application.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the present disclosure has been described with reference to particular embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present disclosure.
Claims (10)
1. A method for breaking cyanogen in resin, which is characterized by comprising the following steps:
s1, preheating the pretreated raw water to 40-50 ℃ to obtain the heated raw water, wherein the raw water comprises a complex cyanide, and the concentration of the complex cyanide is detected to be 1600-2000 mg/L;
s2, injecting heated raw water into the resin tank, wherein the pH value of the heated raw water is 3-5; standing for 40-50 hours to enable the resin in the resin tank to adsorb metal ions in the complex cyanide and release cyanide ions, wherein the cyanide ions are combined with sodium ions in the raw water to generate sodium cyanide, so that raw water containing the sodium cyanide is obtained, and the concentration of the cyanide ions in the raw water containing the sodium cyanide is detected;
s3, if the concentration of the cyanide ions does not match the concentration of the cyanide in the complex state, injecting the raw water containing sodium cyanide into a new resin tank, and repeating the step S2 until the concentration of the cyanide ions matches the concentration of the cyanide in the complex state;
s4, if the raw water is matched with the sodium cyanide, injecting the raw water containing the sodium cyanide into a reaction tank; putting an oxidant with the concentration of 600-800 mg/L into the reaction tank, adding alkali liquor, wherein the pH value of the solution in the reaction tank is more than 10, so that the oxidant reacts with cyanide ions in the sodium cyanide, and the cyanide ions are converted into nitrogen and carbon dioxide gas, wherein the pressure in the reactor is normal pressure, the filling gas is inert gas, and the temperature in the reactor is kept at normal temperature.
2. The method of claim 1, wherein prior to preheating the pretreated raw water, the method further comprises:
introducing the raw water at the outlet of the pump into a microporous filter at a flow rate of 0.5-1.5m/s so that the microporous filter filters suspended matters in the raw water to obtain pretreated raw water;
wherein the suspended matters in the pretreated raw water meet a preset standard.
3. The method of claim 1, wherein prior to introducing the pump outlet raw water into the microporous filter, the method further comprises:
and carrying out air stripping and oxidation treatment on the raw water in the brine tank to remove free cyanide ions in the raw water, so that complex cyanide remains in the raw water after air stripping and oxidation treatment.
4. The method of claim 2, wherein the microporous filter comprises an inlet and an outlet,
the rotor flow meter is arranged to detect the raw water flow of the inlet and the outlet to obtain a detected flow;
and adjusting the raw water flow of the inlet and the outlet according to the detection flow and the preset standard.
5. The method according to claim 1, wherein the temperature of the heated raw water is adjusted according to a preset adsorption power of a resin, wherein the resin is any one or more of the following: chelating resins, cation exchange resins, ultra-high crosslinking resins; the aperture size of the resin is 0.315-1.25 mm, and the height of the resin is 1-3 m.
6. The method of claim 1, wherein before performing step S2, the method further comprises:
detecting the dehydration condition of the resin in the resin tank, if the resin is dehydrated, soaking for 30-60 minutes by selecting saline solution with the concentration of 20-30%, wherein the volume height of the saline solution is not lower than the height covering the resin, gradually diluting the concentration of the saline solution to 5-10%, and after diluting and soaking for 20-40 minutes, discharging the saline solution from an outlet of the resin tank.
7. The method of claim 1, further comprising:
and detecting the pressure and the temperature in the reactor according to a certain period, and if pressure abnormality and/or temperature abnormality is detected, controlling the outlet valve of the resin tank to be closed, and controlling the oxidant inlet of the reactor to be closed so as to stop adding the oxidant into the reactor.
8. A system for cyanogen removal from a resin, the system comprising:
the preheater is used for preheating the pretreated raw water to 40-50 ℃ to obtain the heated raw water, the raw water comprises complex cyanide, and the concentration of the complex cyanide is detected, wherein the concentration of the complex cyanide is 1600-2000 mg/L;
the system comprises a resin tank, a water tank and a water tank, wherein the resin tank comprises resin, heated raw water is injected into the resin tank, and the PH value of the heated raw water is 3-5; standing for 40-50 hours to enable the resin to adsorb metal ions in the complex cyanide and release cyanide ions, wherein the cyanide ions are combined with sodium ions in the raw water to generate sodium cyanide, so that the raw water containing the sodium cyanide is obtained, and the concentration of the cyanide ions in the raw water containing the sodium cyanide is detected; if the concentration of the cyanide ions does not match the concentration of the complex cyanide, injecting the raw water containing sodium cyanide into a new resin tank so that the resin in the new resin tank adsorbs the metal ions in the complex cyanide until the concentration of the cyanide ions matches the concentration of the complex cyanide
A reaction tank, wherein if the concentration of the cyanide ions matches the concentration of the cyanide in a complex state, the raw water containing sodium cyanide is injected into the reaction tank; putting an oxidant with the concentration of 600-800 mg/L into the reaction tank, adding alkali liquor, wherein the pH value of the solution in the reaction tank is more than 10, so that the oxidant reacts with cyanide ions in the sodium cyanide, and the cyanide ions are converted into nitrogen and carbon dioxide gas, wherein the pressure in the reactor is normal pressure, the filling gas is inert gas, and the temperature in the reactor is kept at normal temperature.
9. The system for resin cyanide breaking of claim 8, wherein the system further comprises:
the pump is used for introducing the raw water at the outlet of the pump into the microporous filter at the flow velocity of 0.5-1.5m/s so that the microporous filter filters suspended matters in the raw water to obtain pretreated raw water; wherein suspended matters in the pretreated raw water meet a preset standard;
and the microporous filter is used for filtering suspended matters in the raw water to obtain the pretreated raw water.
10. The system for resin cyanide breaking of claim 8, wherein the system further comprises:
a brine tank for storing raw water, and/or,
and carrying out air stripping and oxidation treatment on the raw water to remove free cyanide ions in the raw water, so that complex cyanide remains in the raw water after the air stripping and oxidation treatment.
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