CN110790439B - Treatment method of hot galvanizing pickling wastewater - Google Patents
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Abstract
The invention belongs to the technical field of waste liquid recycling, and particularly relates to a treatment method of hot galvanizing pickling wastewater, which comprises the following steps: firstly, adding an oxidant into the pickling waste water to oxidize ferrous ions into ferric ions, wherein the oxidant is excessive, then simultaneously adding alkali and citrate ions into the pickling waste water under a heating condition, fully mixing, filtering, adjusting the pH value of the filtrate, and then treating by chelating resin to realize purification.
Description
Technical Field
The invention belongs to the technical field of waste liquid recycling, and particularly relates to a treatment method of hot galvanizing pickling wastewater.
Background
In the hot galvanizing industry, hydrochloric acid is needed to wash off rust on the surface of a plated part before the plated part enters a galvanizing procedure, hydrochloric acid is needed to deplate when the galvanizing quality of the plated part is unqualified, and a lot of pickling waste water in the hot galvanizing industry is obtained by combining acid solutions after pickling under the two conditions. The main pollution components in the pickling wastewater comprise iron ions (containing ferrous ions), zinc ions and hydrochloric acid.
Wherein, iron ions and zinc ions can be recycled after being recovered, so that the iron ions and the zinc ions in the wastewater are required to be respectively collected.
Disclosure of Invention
The invention provides a treatment method of hot galvanizing pickling waste water, firstly adding oxidant into the pickling waste water to oxidize ferrous iron ions into ferric iron ions, the oxidant is excessive, then simultaneously adding alkali and citrate ions into the pickling waste water under the heating condition, filtering after mixing fully, the obtained filter cake is basically ferric hydroxide, the complex dissolved in the filtrate is basically the complex of zinc ions and citrate ions, after adjusting the pH value of the obtained filtrate, the purification can be realized through the treatment of chelating resin,
wherein, the oxidant is sodium hypochlorite: NaClO +2Fe under acidic condition2++2H+＝2Fe3++NaCl+H2O, sodium hypochlorite is excessive, so that ferrous iron in the wastewater can be fully converted into ferric iron under acidic conditionsAnd (3) dissolving, wherein the molar ratio of sodium hypochlorite to ferrous ions in the wastewater is 1.3-1.8: 2,
the heating temperature is 50 ~ 70 ℃, because sodium hypochlorite is the chemical that takes corrosivity, adopts the heat treatment here, can make excessive sodium hypochlorite be heated and decompose as soon as possible and fall: 2 NaClO-2 NaCl + O2↑
The alkali is sodium hydroxide, on one hand, the residual hydrogen ions in the wastewater can be neutralized by adding the alkali, on the other hand, the alkali can be combined with metal ions in the wastewater for precipitation,
the citrate ions are added in the form of sodium citrate, and can form complexation with metal ions in the wastewater.
The sodium hydroxide can be combined with ferric ions for precipitation and can also be combined with zinc ions for precipitation, and similarly, the sodium citrate can be complexed with the ferric ions and the zinc ions, compared with the stability of the citrate and zinc ion complex which is higher than that of the zinc hydroxide, and the stability of the ferric hydroxide is higher than that of the citrate and iron ions. Therefore, under the condition that ferric ions and zinc ions exist in the wastewater simultaneously, the applicant hopes that sodium hydroxide and sodium citrate are added into the wastewater, so that the sodium hydroxide and the iron ions are combined and precipitated, and the sodium citrate and the zinc ions are complexed and still dissolved in the wastewater, so that the separation of the iron ions and the zinc ions is realized in one step, and the direct reutilization of different types of metal ions is facilitated. However, in practical operation, the applicant found that after sodium citrate and sodium hydroxide are added into wastewater in which ferric ions and zinc ions coexist, ferric hydroxide precipitate, zinc hydroxide precipitate, citrate-ferric ion complex and citrate-zinc ion complex are generated to different degrees, which indicates that competitive binding still exists, and it is difficult to effectively separate zinc ions and iron ions by one-step method,
according to the scheme, on the basis of excessive sodium hypochlorite in the wastewater, the sodium hydroxide and the sodium citrate are heated and added into the wastewater at the same time, the tendency of combination of the sodium hydroxide and ferric ions and the tendency of combination of the sodium citrate and zinc ions are greatly promoted, and as a result, the solid matters of the filter cake obtained after filtering are basically ferric hydroxide, the content of zinc ions is very low, and similarly, the complexes dissolved in the wastewater are basically complexes of zinc ions and citrate radicals, and the content of iron ions is also very low, so that the heavy metal iron ions in the wastewater are removed and the heavy metal zinc ions are captured through a one-step method, the separation of the iron ions and the zinc ions is basically realized after filtering, and the iron ions and the zinc ions can be directly recycled subsequently. The applicant believes that the reason for this should be: the scheme adds sodium hydroxide and sodium citrate into the wastewater for removing or capturing heavy metal precipitates, and simultaneously heats the wastewater system, the heating promotes the dynamic process that oxygen is decomposed from sodium hypochlorite in the wastewater and flows out of the wastewater, the instability of the wastewater system is greatly increased, the reduction of the environmental stability promotes iron ions and zinc ions to further seek a more stable combination mode when selecting which combination reaction to participate, and the basic trend of chemical reaction of 'the reaction tends to be converted from an unstable state to a relatively stable state' is also met.
Detailed Description
Example 1
10 cubic meters of hot galvanizing pickling waste water, wherein the pH value is 0.1, the concentration of ferrous ions is 37g/L, the concentration of ferric ions is 8g/L, the concentration of zinc ions is 12g/L, the concentration of chloride ions is 104g/L,
keeping the stirring speed of 60r/min for the pickling wastewater at normal temperature (25 ℃, the same below), adding 3.5 cubic meters of sodium hypochlorite aqueous solution with the solute mass fraction of 10%, stirring for 10 minutes, heating the wastewater system at the heating speed of 15 ℃/minute, adding 2900kg of sodium citrate (trisodium citrate) solid and 1300kg of sodium hydroxide solid into the wastewater system while starting heating, stopping heating after the wastewater system is heated to 65 ℃, keeping the temperature for 90 minutes to ensure that the bonding reaction in the wastewater system is sufficient, naturally cooling the wastewater system to the normal temperature, stopping stirring and filtering to obtain a filter cake and filtrate.
Wherein the weight of the filter cake after being dried fully at 80 ℃ is 836.7kg, and the filter cake is analyzed and detected by a QL-BS microcomputer multielement analyzer: wherein the mass content of iron is 51.7 percent, the mass content of zinc is 0.61 percent, according to the content, the mass of iron element is 432.57kg and the mass of zinc element is 5.1kg, the total mass of iron element in the original acid washing wastewater is 450kg ((37g/L +8g/L) x 10000L), most of iron element enters the precipitate,
because the iron element in the wastewater is basically in the form of ferric iron after being oxidized by the excessive oxidant, and the zinc, the iron ion and the citrate ion are still dissolved in water after being complexed, the iron element in the precipitated filter cake is basically in the form of ferric hydroxide, and on the basis, the conversion is carried out according to the measured mass of the iron element and the measured mass of the zinc element: the mass of the ferric hydroxide in the precipitated filter cake is 826.5kg, the mass of the zinc hydroxide is only 7.77kg, so the zinc hydroxide is not removed, and the filter cake with the ferric hydroxide content can also be used as a raw material for producing iron oxide red;
because the sodium hydroxide is added in an excessive amount (relative to the hydrogen ions and the heavy metal ions in the pickling wastewater), a certain amount of hydroxide ions still exist in the filtrate, so that free heavy metal ions basically do not exist in the filtrate at the moment, namely, the iron ions and the zinc ions which do not enter the filter cake precipitate are basically complexed by the citrate ions, and according to the detected mass of the zinc element in the filter cake precipitate being 5.4kg (the total mass of the zinc element in the raw acid pickling wastewater being 120kg), most of the zinc element is complexed with the citrate,
in this case, reference is made to the prior art post-processing method: adjusting the pH value of the filtrate to 6-7, then enabling the filtrate to pass through a chromatographic separation column with a stationary phase of chelate resin D463, enabling chelate groups of the chelate resin to form hydrogen bonds with organic molecules of citrate so as to realize adsorption and combination of the citrate and iron and zinc complexes thereof, enabling the concentration of iron element to be 0.8mg/L, the concentration of zinc element to be 0.3mg/L and the concentration of citrate ions to be 3.7mg/L in the filtrate flowing out of the chromatographic separation column, completely meeting the discharge standard, directly discharging the filtrate into a natural water body,
the citrate complex is resolved from the chelating resin by leaching of an eluent, most metal ions in the resolved substance are zinc ions, and the citrate is also an ideal carbon source, so that the resolved substance can be recycled as a precursor of the carbon-supported metal composite material.
Comparative example 1
For the same acid-washing wastewater of example 1, 10 cubic meters: keeping the stirring speed of 60r/min for the pickling wastewater at normal temperature (25 ℃, the same below), adding 3.5 cubic meters of sodium hypochlorite aqueous solution with the solute mass fraction of 10%, stirring for 10 minutes, heating the wastewater system at the heating speed of 15 ℃/minute, stopping heating and keeping the temperature for 90 minutes after the wastewater system is heated to 65 ℃ to fully decompose redundant sodium hypochlorite in the wastewater, simultaneously adding 2900kg of sodium citrate (trisodium citrate) solid and 1300kg of sodium hydroxide solid into the wastewater, continuously reacting for 90 minutes at the temperature of 65 ℃ (fully combining reaction), naturally cooling the wastewater system to normal temperature, stopping stirring and filtering to obtain a filter cake and a filtrate.
Wherein the weight of the filter cake after being dried fully at 80 ℃ is 718.2kg, and the filter cake is analyzed and detected by a QL-BS microcomputer multielement analyzer: wherein the mass content of iron is 48.2%, the mass content of zinc is 5.1%, according to the content, the mass is converted into 346.1kg of iron element and 36.6kg of zinc element,
because the iron element in the wastewater is basically in the form of ferric iron after being oxidized by the excessive oxidant, and the zinc, the iron ion and the citrate ion are still dissolved in water after being complexed, the iron element in the precipitated filter cake is basically in the form of ferric hydroxide (the zinc element is also basically in the form of zinc hydroxide), and on the basis, the measured mass of the iron element and the measured mass of the zinc element are converted: the mass of the precipitated iron hydroxide in the filter cake was 661.2kg and the mass of the zinc hydroxide was 55.7kg, which are typical mixed precipitates.
Comparative example 2
For the same acid-washing wastewater of example 1, 10 cubic meters: keeping the stirring speed of 60r/min for the pickling wastewater at normal temperature (25 ℃, the same below), adding 3.5 cubic meters of sodium hypochlorite aqueous solution with the solute mass fraction of 10%, stirring for 10 minutes, heating the wastewater system at the heating speed of 15 ℃/minute, adding 1300kg of sodium hydroxide solid into the wastewater system while starting heating, stopping heating after the wastewater system is heated to 65 ℃ and keeping the temperature for 90 minutes (fully precipitating), adding 2900kg of sodium citrate (trisodium citrate) solid into the wastewater, keeping the temperature for 90 minutes at 65 ℃ again (precipitating is not reduced), naturally cooling the wastewater system to normal temperature, stopping stirring and filtering to obtain a filter cake and a filtrate.
Wherein the weight of the filter cake after being dried fully at 80 ℃ is 886.4kg, and the filter cake is analyzed and detected by a QL-BS microcomputer multielement analyzer: wherein the mass content of iron is 48.38%, the mass content of zinc is 4.7%, and according to the content, the mass contents are converted into 428.84kg of iron element and 41.66kg of zinc element,
because the iron element in the wastewater is basically in the form of ferric iron after being oxidized by the excessive oxidant, and the zinc, the iron ion and the citrate ion are still dissolved in water after being complexed, the iron element in the precipitated filter cake is basically in the form of ferric hydroxide (the zinc element is also basically in the form of zinc hydroxide), and on the basis, the measured mass of the iron element and the measured mass of the zinc element are converted: the mass of the precipitated iron hydroxide and zinc hydroxide in the filter cake was 819.4kg and 63.45kg, respectively. It can be seen that in this comparative example, the excessive sodium hydroxide is added first to substantially precipitate the iron ions and zinc ions in the wastewater, and the citrate ions added later only dissolve a part of the zinc hydroxide to complex the zinc ions, so that a considerable part of the zinc element still exists in the final filter cake.
Comparative example 3
For the same acid-washing wastewater of example 1, 10 cubic meters: keeping the stirring speed of 60r/min for the pickling wastewater at normal temperature (25 ℃, the same below), adding 3.5 cubic meters of sodium hypochlorite aqueous solution with the solute mass fraction of 10%, stirring for 10 minutes, heating the wastewater system at the heating speed of 15 ℃/minute, adding 2900kg of sodium citrate (trisodium citrate) solid into the wastewater system while starting heating, stopping heating after the wastewater system is heated to 65 ℃ and keeping the temperature for 90 minutes (fully combining the reaction), adding 1300kg of sodium hydroxide solid into the wastewater, keeping the temperature for 90 minutes at 65 ℃ again (fully precipitating), naturally cooling the wastewater system to normal temperature, stopping stirring and filtering to obtain a filter cake and a filtrate.
Wherein, the weight of the filter cake after being dried fully at 80 ℃ is 603.1kg, and the filter cake is analyzed and detected by adopting a QL-BS microcomputer multielement analyzer: wherein the mass content of iron is 48.8%, the mass content of zinc is 3.79%, and according to the contents, the mass contents are converted into 294.3kg of iron element and 22.85kg of zinc element,
because the iron element in the wastewater is basically in the form of ferric iron after being oxidized by the excessive oxidant, and the zinc, the iron ion and the citrate ion are still dissolved in water after being complexed, the iron element in the precipitated filter cake is basically in the form of ferric hydroxide (the zinc element is also basically in the form of zinc hydroxide), and on the basis, the measured mass of the iron element and the measured mass of the zinc element are converted: the mass of the precipitated iron hydroxide and zinc hydroxide in the filter cake was 562.3kg and 34.8kg, respectively.
Comparative example 4
For the same acid-washing wastewater of example 1, 10 cubic meters: keeping the stirring speed of 60r/min for the pickling wastewater at normal temperature (25 ℃, the same below), adding 3.5 cubic meters of sodium hypochlorite aqueous solution with the solute mass fraction of 10%, stirring for 10 minutes, heating the wastewater system at the heating speed of 15 ℃/minute, stopping heating and keeping the temperature for 90 minutes after the wastewater system is heated to 65 ℃ to fully decompose redundant sodium hypochlorite in the wastewater, simultaneously adding 2900kg of sodium citrate (trisodium citrate) solid and 1300kg of sodium hydroxide solid into the wastewater, simultaneously increasing the stirring speed to 150r/min, continuing to react for 90 minutes at the temperature of 65 ℃ (fully combining the reaction), naturally cooling the wastewater system to normal temperature, stopping stirring and filtering to obtain a filter cake and filtrate.
Wherein the weight of the filter cake after being dried fully at 80 ℃ is 724.6kg, and the filter cake is analyzed and detected by a QL-BS microcomputer multielement analyzer: wherein the mass content of iron is 48.7%, the mass content of zinc is 4.4%, and the contents are converted into 352.8kg of iron element mass and 31.88kg of zinc element mass,
because the iron element in the wastewater is basically in the form of ferric iron after being oxidized by the excessive oxidant, and the zinc, the iron ion and the citrate ion are still dissolved in water after being complexed, the iron element in the precipitated filter cake is basically in the form of ferric hydroxide (the zinc element is also basically in the form of zinc hydroxide), and on the basis, the measured mass of the iron element and the measured mass of the zinc element are converted: the mass of the precipitated iron hydroxide and zinc hydroxide in the filter cake was 674.1kg and 48.56kg, respectively.
In comparative example 4, it is expected that the reaction system is made more vigorous by increasing the stirring rate and the degree of instability of the system is increased, but the effect of this method is slight, and the applicant believes that the reason is that: stirring is a regular action after all, and the reaction system can be stabilized again after the stirring speed is met, and sodium hypochlorite is heated and decomposed into oxygen which can move upwards to belong to chemical reaction, so that the reaction system is high in spontaneity and more obvious in randomness, and the instability of the reaction system can be influenced.
Example 2
After experimental experience of the above examples and comparative examples, the amount of sodium hydroxide and sodium citrate can be reduced:
10 cubic meters of hot galvanizing pickling waste water, wherein the pH value is 0.2, the concentration of ferrous ions is 32g/L, the concentration of ferric ions is 12g/L, the concentration of zinc ions is 19g/L, the concentration of chloride ions is 107g/L,
keeping the stirring speed of 60r/min for the pickling wastewater at normal temperature (25 ℃, the same below), adding 4.5 cubic meters of sodium hypochlorite aqueous solution with the solute mass fraction of 10%, stirring for 10 minutes, heating the wastewater system at the heating speed of 15 ℃/minute, adding 950kg of sodium citrate (trisodium citrate) solid and 1000kg of sodium hydroxide solid into the wastewater system while starting heating, stopping heating after the wastewater system is heated to 65 ℃, keeping the temperature for 90 minutes to ensure that the bonding reaction in the wastewater system is sufficient, naturally cooling the wastewater system to normal temperature, stopping stirring and filtering to obtain a filter cake and filtrate.
Wherein the weight of the filter cake after being dried fully at 80 ℃ is 827.3kg, and the filter cake is analyzed and detected by a QL-BS microcomputer multielement analyzer: wherein the mass content of iron is 51.68 percent, the mass content of zinc is 0.7 percent, according to the content, the mass of iron element is 427.6kg and the mass of zinc element is 5.8kg, while the total mass of iron element in the original acid washing wastewater is 440kg, most of iron element enters the precipitate,
because the iron element in the wastewater is basically in the form of ferric iron after being oxidized by the excessive oxidant, and the zinc, the iron ion and the citrate ion are still dissolved in water after being complexed, the iron element in the precipitated filter cake is basically in the form of ferric hydroxide, and on the basis, the conversion is carried out according to the measured mass of the iron element and the measured mass of the zinc element: the mass of the ferric hydroxide in the precipitated filter cake is 817kg, the mass of the zinc hydroxide is only 8.83kg, so the zinc hydroxide is not removed, the filter cake with the ferric hydroxide content can also be used as the raw material for producing the iron oxide red,
according to the detection result of the QL-BS microcomputer multi-element analyzer, the content of the residual iron, zinc and hydroxyl ions in the wastewater system after the sediment removal can be calculated:
iron: (440000g-427600g) ÷ 56g/mol ═ 221.4mol
Zinc: (190000g-5800g) ÷ 65g/mol ═ 2833.8mol
Hydroxyl ion: (1000000 g/40 g/mol) - (427600 g/56 g/mol x 3+5800 g/65 g/mol x 2) - [0.631mol/L x 10000L- (32g/L x 10000L/56 g/mol) ] -1318.8 mol,
wherein "32 g/L × 10000L/56 g/mol" in the above formula is the amount of hydrogen ions (NaClO +2 Fe) consumed in oxidizing divalent iron by sodium hypochlorite2++2H+＝2Fe3++NaCl+H2O), therefore, "", "A" ", a" gene of a gene]"inside meterThe molar quantity of sodium hydroxide required for neutralizing the residual hydrogen ions in the wastewater is calculated,
it can be seen that hydroxide ions in the wastewater system are obviously remained, so that free heavy metal ions are not substantially present in the filtrate at this time, that is, the remaining iron ions and zinc ions in the wastewater system are substantially complexed by citrate ions (the added sodium citrate is excessive relative to the sum of the remaining iron and zinc in the wastewater system), and according to the above detection, the mass of the zinc element in the filter cake precipitate is 5.8kg (the total mass of the zinc element in the raw acid washing wastewater is 190kg), it can be seen that most of the zinc element is complexed with the citrate,
in this case, reference is made to the prior art post-processing method: adjusting the pH value of the filtrate to 6-7, then enabling the filtrate to pass through a chromatographic separation column with a stationary phase of chelate resin D463, enabling chelate groups of the chelate resin to form hydrogen bonds with organic molecules of citrate so as to realize adsorption and combination of the citrate and iron and zinc complexes thereof, enabling the concentration of iron element to be 0.8mg/L, the concentration of zinc element to be 0.2mg/L and the concentration of citrate ions to be 3.5mg/L in the filtrate flowing out of the chromatographic separation column, completely meeting the discharge standard, directly discharging the filtrate into a natural water body,
the citrate complex is resolved from the chelating resin by leaching of an eluent, most metal ions in the resolved substance are zinc ions, and the citrate is also an ideal carbon source, so that the resolved substance can be recycled as a precursor of the carbon-supported metal composite material.
Claims (3)
1. A treatment method of hot galvanizing pickling wastewater is characterized by comprising the following steps: firstly, adding an oxidant into the pickling wastewater to oxidize ferrous ions into ferric ions, wherein the oxidant is excessive, then simultaneously adding alkali and citrate ions into the pickling wastewater under a heating condition, fully mixing and filtering, and the heating temperature is 50-70 ℃;
the oxidant is sodium hypochlorite;
the alkali is sodium hydroxide;
the citrate ions are added in the form of sodium citrate.
2. The method for treating hot galvanizing pickling wastewater according to claim 1, comprising the steps of: the molar ratio of the sodium hypochlorite to the ferrous ions is 1.3-1.8: 2.
3. the method for treating hot galvanizing pickling wastewater according to claim 1, comprising the steps of: adjusting the pH value of the filtrate obtained after filtration, and treating the filtrate by chelating resin.
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| CN1062004A (en) * | 1991-12-13 | 1992-06-17 | 黄石市化工厂 | Produce the novel process of zinc oxide |
| CN104402145A (en) * | 2014-12-08 | 2015-03-11 | 南通大学 | Production method for preparing ferric hydroxide by utilizing ferrite-containing waste water |
| CN106244804A (en) * | 2016-07-29 | 2016-12-21 | 江西理工大学 | Villaumite acid system preferential complexation selectivity sinks the ferrochrome separation method of ferrum |
| CN107986321A (en) * | 2017-12-18 | 2018-05-04 | 东北大学 | A kind of waste water extraction zinc of iron content containing zinc and the method for preparing zinc hydroxide |
| CN110078129A (en) * | 2019-04-28 | 2019-08-02 | 上海大学 | The method for preparing magnetic paint presoma using iron content zinc acid pickle |
| CN110255778A (en) * | 2019-07-18 | 2019-09-20 | 上海电力大学 | Hot galvanizing pickling wastewater recycling method |
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