CN115849625A - Resource utilization method of stainless steel pickling wastewater - Google Patents
Resource utilization method of stainless steel pickling wastewater Download PDFInfo
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- CN115849625A CN115849625A CN202211644302.3A CN202211644302A CN115849625A CN 115849625 A CN115849625 A CN 115849625A CN 202211644302 A CN202211644302 A CN 202211644302A CN 115849625 A CN115849625 A CN 115849625A
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Abstract
The invention discloses a resource utilization method of stainless steel pickling wastewater, which comprises the following steps: (1) Providing stainless steel pickling wastewater containing iron, chromium and nickel elements, and adjusting the pH value to 3-6; (2) Adding an oxidant into the stainless steel pickling wastewater to remove Fe in the stainless steel pickling wastewater 2+ Oxidation to Fe 3+ (ii) a (3) Adding Fe into the oxidized stainless steel pickling wastewater 2 O 3 Reacting the solid to obtain a mixed solution; (4) Transferring the mixed solution into a reaction kettle for hydrothermal reaction, and performing solid-liquid separation to obtain solid-phase precipitate and a liquid phase; (5) Washing and drying the solid phase precipitateAnd (3) drying to obtain an iron-chromium-nickel compound, adjusting the pH value of the liquid phase to 7-8, carrying out solid-liquid separation after reaction, and carrying out evaporative crystallization to obtain ammonium sulfate. The resource utilization method avoids adding calcium salt, has no secondary wastewater discharge in the whole process, greatly reduces the sludge treatment capacity, and simultaneously, the recycled iron-chromium-nickel solid product and ammonium salt have the economic benefit of recycling.
Description
Technical Field
The invention relates to the technical field of stainless steel pickling wastewater treatment, in particular to a resource utilization method of stainless steel pickling wastewater.
Background
The stainless steel pickling wastewater contains a large amount of H + And Fe 2+ 、Cr 3+ 、Ni 2+ The heavy metal ions are listed in the national hazardous waste list. The prior art mainly adopts a neutralization precipitation method to treat the stainless steel pickling wastewater, and the method has the advantages of simple process, small investment, easy operation and the like, but can generate a large amount of heavy metal sludge, and the heavy metal sludge has higher treatment cost and larger threat to the environment, and does not have a reasonable utilization way at present.
In patent CN102659274A, it is proposed that waste acid in acid washing wastewater is removed by resin adsorption, and a two-step method for neutralizing, precipitating and separating metal ions and fluorine ions realizes resource recovery of inorganic acid and nickel, but iron, chromium and fluorine ion sediments generated in the first step of precipitation are not recovered, so that resource waste is caused. Patent CN101269889A proposes to replace lime with sodium hydroxide and deposite alone as the neutralizer to the heavy metal in the waste water, then adds lime defluorination again, realizes the separation of metal ion and calcium fluoride, and heavy metal mud has the condition of returning to the furnace, but the cost of replacing lime with sodium hydroxide improves greatly to can bring the high salt waste water treatment difficult problem. Patent CN108928953A proposesAdding calcium-containing neutralizer and sodium-containing neutralizer at different time, and adding Fe, cr, ni and F in the wastewater respectively as Fe (OH) 3 、Cr(OH) 3 、Ni(OH) 2 And CaF 2 The solid-liquid separation of the sludge and the liquid phase, which also brings about the difficult problem of high-salt wastewater treatment.
Therefore, how to economically and efficiently realize the resource utilization of Fe, cr and Ni elements in the stainless steel pickling wastewater and the reasonable utilization of waste acid are two key problems of the resource utilization of the stainless steel pickling wastewater.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a resource utilization method of stainless steel pickling wastewater, so as to realize resource utilization of Fe, cr and Ni elements in the stainless steel pickling wastewater and reasonable utilization of waste acid, and provide an effective way for comprehensive utilization of the stainless steel pickling wastewater.
The invention provides a resource utilization method of stainless steel pickling wastewater, which comprises the following steps: (1) Providing stainless steel pickling wastewater containing iron, chromium and nickel elements, and adjusting the pH value to 3-6;
(2) Adding an oxidant into the stainless steel pickling wastewater obtained in the step (1) to remove Fe in the stainless steel pickling wastewater 2+ Oxidation to Fe 3+ ；
(3) Adding Fe into the stainless steel pickling wastewater oxidized in the step (2) 2 O 3 Reacting the solid to obtain a mixed solution;
(4) Transferring the mixed solution in the step (3) into a reaction kettle for hydrothermal reaction, and performing solid-liquid separation to obtain solid-phase precipitate and a liquid phase;
(5) And (4) washing and drying the solid-phase precipitate in the step (4) to obtain an iron-chromium-nickel compound, adjusting the pH of the liquid phase to 7-8, and performing solid-liquid separation, evaporation and crystallization after reaction to obtain ammonium sulfate.
Compared with the prior art, the resource utilization method provided by the invention is realized by adding Fe into stainless steel pickling wastewater 2 O 3 Solid, reasonably adjusts pH, avoids adding calcium salt, can effectively treat stainless steel pickling wastewater, and has no secondary wastewater discharge in the whole processAnd moreover, the problem of high-salinity wastewater is avoided, the sludge treatment capacity can be greatly reduced, and the recycled iron-chromium-nickel solid product and ammonium salt have economic benefits of recycling.
Drawings
Fig. 1 is a flow chart of a resource utilization method of stainless steel pickling wastewater according to an embodiment of the present invention.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Referring to fig. 1, an embodiment of the present invention provides a method for recycling stainless steel pickling wastewater, including the following steps:
(1) Providing stainless steel pickling wastewater containing iron, chromium and nickel elements, and adjusting the pH value to 3-6;
(2) Adding an oxidant into the stainless steel pickling wastewater obtained in the step (1) to remove Fe in the stainless steel pickling wastewater 2+ Oxidation to Fe 3+ ；
(3) Adding Fe into the stainless steel pickling wastewater oxidized in the step (2) 2 O 3 Reacting the solid to obtain a mixed solution;
(4) Transferring the mixed solution in the step (3) into a reaction kettle for hydrothermal reaction, and performing solid-liquid separation to obtain solid-phase precipitate and a liquid phase;
(5) And (4) washing and drying the solid-phase precipitate in the step (4) to obtain an iron-chromium-nickel compound, adjusting the pH of the liquid phase to 7-8, and performing solid-liquid separation, evaporation and crystallization after reaction to obtain ammonium sulfate.
The invention oxidizes Fe in stainless steel pickling wastewater 2+ Is Fe 3+ Adding Fe 2 O 3 Solid bodyThen inducing Fe under specific conditions through hydrothermal reaction 3+ And converting into iron crystals, and simultaneously transferring Cr and Ni elements into the iron crystals to obtain the iron-chromium-nickel solid compound. And moreover, by adjusting the pH value, the subsequent liquid phase can be used for preparing ammonium salt, so that the problem of secondary wastewater treatment is avoided.
Researches show that the stainless steel pickling wastewater is not added with Fe 2 O 3 When solid, the iron element in the wastewater can not be induced to Fe 2 O 3 And the transformation results in slow crystallization speed and low efficiency of iron element in the wastewater. And moreover, by regulating and controlling the pH values in the step (1) and the step (5), iron, chromium and nickel elements can be fully reacted and precipitated, and the purity of the finally obtained ammonium sulfate product is improved.
In some embodiments, it is preferred in step (1) to adjust the pH to 4 to 5.
Fe added when the pH is 4-5 2 O 3 The solid can fully induce Fe in the stainless steel pickling wastewater 3+ To Fe 2 O 3 The crystal is transformed, and the slag amount is small after the pH is adjusted to 7-8 for the subsequent second time.
In some embodiments, the oxidant added in step (2) is hydrogen peroxide.
The amount of the oxidant added is herein controlled by controlling the Oxidation Reduction Potential (ORP). In the actual operation process, the oxidation-reduction electrode is inserted into the stainless steel pickling wastewater, the ORP numerical value is observed while the oxidant is added, and the ORP suddenly and greatly rises at a certain time point, and the oxidant is stopped adding at the moment.
In some embodiments, the Fe added in step (3) 2 O 3 The mass of the iron is 1 to 10 percent of the total iron mass in the stainless steel pickling wastewater.
Preferably, fe added in step (3) 2 O 3 The mass of the iron content is 2 percent of the total iron mass in the stainless steel pickling wastewater.
In some embodiments, the hydrothermal reaction in step (4) is carried out at a temperature of 150 to 200 ℃ for 3 to 9 hours.
Preferably, the temperature of the hydrothermal reaction in the step (4) is 175 ℃ and the time is 6h.
In some embodiments, the reagent used to adjust the pH in steps (1) and (5) is, independently, one of aqueous ammonia, liquid ammonia, ammonium carbonate, or ammonium bicarbonate.
Preferably, the reagent used to adjust the pH in step (1) is aqueous ammonia.
Wherein, the solid slag obtained by solid-phase separation after the liquid-phase reaction in the step (5) mainly contains metallic elements such as Fe, cr, ni and the like, and can be used for preparing pigments, alloys and the like so as to realize the utilization of resources.
The method for recycling stainless steel pickling waste water according to the present invention will be described below with reference to specific examples. In the specific embodiment of the invention, the stainless steel pickling wastewater is obtained from Anematococcus Kogyo (Guangzhou) stainless steel Co., ltd, and the total iron mass is Fe 50g/L, cr 4.5g/L and Ni44.3mg/L.
Example 1
(1) Providing 100mL of stainless steel pickling wastewater containing iron, chromium and nickel elements, and adding ammonia water to adjust the pH value to 4.0;
(2) Adding 6mL of hydrogen peroxide into the stainless steel pickling wastewater obtained in the step (1) by controlling the ORP potential, and fully stirring for 1h;
(3) Adding 0.1g of Fe into the stainless steel pickling wastewater oxidized in the step (2) 2 O 3 Fully stirring the powder for 0.5h to obtain a mixed solution;
(4) Transferring the mixed solution obtained in the step (3) into a reaction kettle for hydrothermal reaction, reacting for 6 hours at 175 ℃ under a closed condition, and performing centrifugal solid-liquid separation to obtain solid-phase precipitate and a liquid phase;
(5) And (4) washing and drying the solid-phase precipitate in the step (4) to obtain the iron-chromium-nickel composite. Adding ammonia water to adjust the pH value of the liquid phase to 7-8, stirring for reaction for 2 hours, carrying out solid-liquid separation, and evaporating and crystallizing the liquid to obtain ammonium sulfate.
Tests show that the liquid obtained after the reaction in the reaction kettle in the step (4) contains a large amount of Fe, cr and Ni elements, and the Fe is added when the pH value of the solution is adjusted to 3 2 O 3 The powder can not sufficiently induce the iron ions in the stainless steel pickling wastewater to Fe 2 O 3 Crystallization ofAnd (4) carrying out bulk transformation. And the secondary addition of ammonia water to adjust the pH value to 7-8, stirring and reacting for 2h, and then the slag amount is large.
Table 1 shows the contents of the components in the ammonium sulfate product obtained in example 1, which meet the standard of fertilizer-grade ammonium sulfate (GB/T535-2020).
Table 1 table for measuring contents of components of ammonium sulfate product in example 1
Example 2
Example 2 differs from example 1 in that ammonia was added to the step (1) to adjust the pH to 4.0, and the rest of the steps were the same.
Tests show that the liquid obtained after the reaction in the reaction kettle in the step (4) is clear and transparent, which shows that the liquid contains a very small amount of Fe, cr and Ni elements at the moment, and that the added Fe is added when the pH of the solution is adjusted to 4 2 O 3 The powder can fully induce the iron ions in the stainless steel pickling wastewater to be Fe 2 O 3 And (4) crystal transformation. The ammonia water is added for the second time to adjust the pH value to 7-8, and the slag amount is very small after the stirring reaction is carried out for 2 hours.
Table 2 shows the contents of the components in the ammonium sulfate product obtained in example 2, which meet the standard of fertilizer-grade ammonium sulfate (GB/T535-2020).
Table 2 table for measuring contents of components of ammonium sulfate product in example 2
Example 3
Example 3 differs from example 1 in that ammonia was added to the step (1) to adjust the pH to 5.0, and the rest of the steps were the same.
Tests prove that the liquid obtained after the reaction in the reaction kettle in the step (4) is clear and transparent, which shows that the liquid contains a very small amount ofFe. Cr and Ni elements, indicating that Fe is added when the pH of the solution is adjusted to 5 2 O 3 The powder can fully induce the iron ions in the stainless steel pickling wastewater to be Fe 2 O 3 And (4) crystal transformation. And adding ammonia water for the second time to adjust the pH value to 7-8, stirring and reacting for 2 hours, wherein the amount of slag is very small.
Table 3 shows the contents of the components in the ammonium sulfate product obtained in example 3, which meet the standard of fertilizer-grade ammonium sulfate (GB/T535-2020).
Table 3 table for measuring contents of components of ammonium sulfate product in example 3
Example 4
Example 4 differs from example 1 in that ammonia was added in step (1) to adjust the pH to 4.0 and 0.2g Fe was added in step (3) 2 O 3 Powder, the rest steps are the same.
Table 4 shows the content of the components in the ammonium sulfate product obtained in example 4, which reaches the standard of fertilizer grade ammonium sulfate (GB/T535-2020).
Table 4 table for measuring contents of components of ammonium sulfate product in example 4
Example 5
Example 5 differs from example 1 in that ammonia was added in step (1) to adjust the pH to 4.0, the reaction temperature in step (4) was 150 ℃, and the rest of the steps were the same.
Tests show that the liquid obtained after the reaction in the reaction kettle in the step (4) is light green, which shows that the liquid contains a large amount of unreacted Fe, cr and Ni elements, and shows that the added Fe is 2 O 3 The powder does not sufficiently induce the iron ions in the stainless steel pickling wastewater to Fe 2 O 3 And (4) crystal transformation. And adding ammonia water for the second time to adjust the pH value to 7-8, stirring and reacting for 2 hours, wherein the slag amount is large.
Table 5 shows the content of the components in the ammonium sulfate product obtained in example 5, which reaches the standard of fertilizer grade ammonium sulfate (GB/T535-2020).
Table 5 table for measuring contents of components of ammonium sulfate product in example 5
Example 6
Example 6 differs from example 1 in that ammonia was added in step (1) to adjust the pH to 3.0, the reaction temperature in step (4) was 175 ℃, and the rest of the steps were the same.
Tests show that the liquid obtained after the reaction in the reaction kettle in the step (4) is clear and transparent, and the content of Fe, cr and Ni elements in the liquid is extremely low, which shows that Fe is added at 175 DEG C 2 O 3 The powder can fully induce the iron ions in the stainless steel pickling wastewater to be Fe 2 O 3 And (4) crystal transformation. And adding ammonia water for the second time to adjust the pH value to 7-8, stirring and reacting for 2 hours, wherein the amount of slag is very small.
Table 6 shows the content of the components in the ammonium sulfate product obtained in example 6, which reaches the standard of fertilizer grade ammonium sulfate (GB/T535-2020).
Table 6 table for measuring contents of components in ammonium sulfate product in example 6
Comparative example 1
Comparative example 1 differs from example 1 in that ammonia was added to adjust the pH to 4.0 in step (1) and no Fe was added in step (3) 2 O 3 Powder, the rest steps are the same.
Tests show that the solid powder obtained after the reaction in the reaction kettle in the step (4) is very little, the solution is dark green, and the contents of Fe, cr and Ni elements in the liquid are very high. As shown in Table 7, it was found that Fe 2 O 3 Powder-induced Fe in stainless steel pickling wastewater 2+ To Fe 2 O 3 Necessity of crystal transformation. The secondary addition of ammonia water to adjust the pH value to 7-8, stirring and reacting for 2 hours, and then the slag amount is maximum, which shows thatThe content of Fe, cr and Ni elements in the wastewater is highest under the condition.
It should be noted that, because a large amount of ammonia water is added to adjust the pH (about 30 mL) in step (1), the concentrations of Fe, cr and Ni elements are reduced, i.e. although the values in table 7 are much reduced compared to the original concentrations (Fe 50g/L, cr 4.5g/L and Ni44.3 mg/L), the actual total mass is not significantly reduced.
TABLE 7 contents of Fe, cr and Ni elements in the liquid phase obtained after the reaction of step (4)
| Element(s) | Fe(g/L) | Cr(g/L) | Ni(g/L) |
| Content (wt.) | 28.1 | 2.4 | 0.019 |
In summary, in the present application, fe is added to the oxidized stainless steel pickling wastewater 2 O 3 Powder capable of sufficiently inducing iron ions in the stainless steel pickling wastewater to Fe 2 O 3 And (3) crystal transformation, namely obtaining high-purity iron-chromium-nickel solid and ammonium sulfate products by regulating and controlling the pH value and the reaction temperature. In the whole process, calcium salt is avoided being added, secondary wastewater discharge is avoided, the problem of high-salinity wastewater is avoided, the sludge treatment capacity can be greatly reduced, and the recycled iron-chromium-nickel solid product and ammonium salt have the economic benefit of recycling.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A resource utilization method of stainless steel pickling wastewater is characterized by comprising the following steps:
(1) Providing stainless steel pickling wastewater containing iron, chromium and nickel elements, and adjusting the pH value to 3-6;
(2) Adding an oxidant into the stainless steel pickling wastewater obtained in the step (1) to remove Fe in the stainless steel pickling wastewater 2+ Oxidation to Fe 3+ ；
(3) Adding Fe into the stainless steel pickling wastewater oxidized in the step (2) 2 O 3 Reacting the solid to obtain a mixed solution;
(4) Transferring the mixed solution in the step (3) into a reaction kettle for hydrothermal reaction, and performing solid-liquid separation to obtain solid-phase precipitate and a liquid phase;
(5) And (4) washing and drying the solid-phase precipitate in the step (4) to obtain an iron-chromium-nickel compound, adjusting the pH of the liquid phase to 7-8, and performing solid-liquid separation, evaporation and crystallization after reaction to obtain an ammonium sulfate product.
2. The resource utilization method according to claim 1, wherein the pH is adjusted to 4 to 5 in step (1).
3. A resource utilization method as claimed in claim 1, wherein the oxidant added in the step (2) is hydrogen peroxide.
4. A resource utilization method as claimed in claim 3, wherein the step (2) specifically includes the steps of:
and (3) slowly adding hydrogen peroxide into the stainless steel pickling wastewater, measuring the oxidation-reduction potential of the stainless steel pickling wastewater, and stopping adding the hydrogen peroxide when the numerical value of the oxidation-reduction potential changes suddenly.
5. The resource utilization method according to claim 1, wherein Fe added in the step (3) 2 O 3 The mass of the iron is 1-10% of the total iron mass in the stainless steel pickling wastewater.
6. A resource utilization method according to claim 5, wherein Fe added in step (3) 2 O 3 The mass of the iron content is 5 percent of the total iron mass in the stainless steel pickling wastewater.
7. The resource utilization method according to claim 1, wherein the temperature of the hydrothermal reaction in the step (4) is 120 to 200 ℃ and the time is 3 to 9 hours.
8. A resource utilization method as claimed in claim 7, wherein the hydrothermal reaction in step (4) is carried out at 175 ℃ for 6 hours.
9. A resource utilization method as claimed in claim 1, wherein the reagent used for adjusting the pH in step (1) and step (5) is one of ammonia, liquid ammonia, ammonium carbonate or ammonium bicarbonate, respectively.
10. The resource utilization method according to claim 9, wherein the reagent used for adjusting the pH in step (1) is ammonia water.
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