Method for producing iron oxide black and manganese carbonate by using iron-containing waste hydrochloric acid

Abstract

The invention relates to the technical field of waste acid resource utilization, and provides a method for producing iron oxide black and manganese carbonate by using iron-containing waste hydrochloric acid, which comprises the following steps: S1, adding ferrous oxide waste mud into ferrous chloride-containing waste hydrochloric acid, and extracting to obtain an organic phase and a water phase; s2, hydrochloric acid and first manganese oxide mineral powder are added into the 70 wt% water phase, and first filtrate and first filter residues are obtained; s3, adding a first alkaline material into the first filtrate to obtain a ferric oxide and manganous chloride solution; s4, mixing ferric oxide with the remaining water phase, and adding a second alkaline material to obtain iron oxide black; s5, manganese dioxide mineral powder and sodium sulfide are added into the manganous chloride solution, and second filtrate and second filter residues are obtained; and S6, adding sodium carbonate into the second filtrate to obtain a manganese carbonate and sodium chloride solution. According to the technical scheme, the problems of low purity and poor resource utilization effect of the iron oxide black obtained from the iron-containing waste hydrochloric acid in related technologies are solved.

Description

Technical Field

[0001] The invention relates to the technical field of waste acid resource utilization, and in particular to a method for producing black iron oxide and manganese carbonate by using iron-containing waste hydrochloric acid. Background Art

[0002] Pickling is a common method for cleaning metal surfaces and a necessary process for steel production and processing. Its purpose is to remove oxides from the metal surface. The discharged pickling waste liquid not only contains high-concentration waste acid, but also contains a large amount of heavy metal ions, which are highly corrosive and will cause serious pollution and harm to the surrounding environment. The hydrochloric acid cleaning agent for general steel pickling usually has a hydrochloric acid content of 5%~15%. Although the hydrochloric acid concentration in the pickling waste liquid discharged after pickling will be reduced to 3%~5%, the iron ion concentration will usually increase to 60~120g / L. Therefore, it is necessary to treat the acid-containing waste liquid to achieve the purpose of resource utilization.

[0003] The main methods for resource treatment of pickling waste liquid include high-temperature roasting, evaporation crystallization, ion exchange, chemical conversion, membrane treatment technology, etc. Among them, the high-temperature roasting method has a high resource recovery rate and the best treatment effect, but it also has the defects of large initial investment, high energy consumption, and high process and equipment requirements, which limits its application in small and medium-sized enterprises; ion exchange and membrane treatment technology can effectively separate metal ions from acids, and the equipment is simple, but its application is limited by the concentration of metal ions and there is a problem of easy contamination of resin and membrane components, so it is also restricted in practical applications; evaporation crystallization is simple to operate and has low treatment costs, but it has the disadvantages of high evaporation temperature, difficult equipment maintenance, and the residual iron content of the effluent cannot meet the standard. Therefore, it is necessary to propose a new technology for resource utilization of pickling waste liquid, which can further realize the efficient recovery of iron in the pickling waste liquid while utilizing the acid in the pickling waste liquid, and obtain iron compounds with higher purity, which is of great significance for resource utilization. Summary of the invention

[0004] The invention provides a method for producing black iron oxide and manganese carbonate by using waste hydrochloric acid containing iron, which solves the problems of low purity and poor resource utilization effect of black iron oxide obtained from waste hydrochloric acid containing iron in the related art.

[0005] The technical solution of the present invention is as follows: The present invention provides a method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid, comprising the following steps: S1. Adding ferrous oxide waste mud to waste hydrochloric acid containing ferrous chloride to obtain a mixed solution, and extracting the mixed solution to obtain an organic phase and an aqueous phase; S2, taking 70 wt% of the aqueous phase, adding hydrochloric acid and the first manganese oxide ore powder to the 70 wt% aqueous phase, reacting, filtering, and obtaining a first filtrate and a first filter residue; S3, adding a first alkaline material to the first filtrate, reacting, and separating to obtain ferric oxide and manganous chloride solution; S4, after countercurrent washing and impurity removal, the ferric oxide is mixed with the remaining water in step S1 to obtain a mixed solution, a second alkaline material is added, filtered, countercurrent washed, and dried to obtain black iron oxide; S5, adding a second manganese oxide ore powder and sodium sulfide to the manganous chloride solution, reacting, filtering, and obtaining a second filtrate and a second filter residue; S6, adding sodium carbonate to the second filtrate, reacting, and separating to obtain manganese carbonate and sodium chloride solution; The first manganese oxide ore powder and the second manganese oxide ore powder each independently include psilomelane ore powder.

[0006] As a further technical solution, in step S1, the pH value of the waste hydrochloric acid containing ferrous chloride is 2-3, and the amount of ferrous oxide waste sludge added is calculated based on the pH value of the mixed solution being 6-7.

[0007] As a further technical solution, in step S1, during the extraction, the extractant includes one or more of neodecanoic acid, tributyl phosphate, di(2-ethylhexyl) phosphate, 2-ethylhexyl phosphonic acid mono(2-ethylhexyl) ester, and bis(2,4,4-trimethylpentyl)phosphonic acid.

[0008] In the present invention, the mixed solution after neutralization with hydrochloric acid is extracted with an extractant, and zinc ions, chromium ions, aluminum ions, manganese ions, calcium ions and magnesium ions in the mixed solution can be effectively extracted and removed. The organic phase after extraction is then back-extracted with hydrochloric acid, sulfuric acid, phosphoric acid or other organic acids to obtain corresponding salts. The extractant can be one or more of neodecanoic acid, tributyl phosphate, di(2-ethylhexyl) phosphate, 2-ethylhexyl phosphonic acid mono(2-ethylhexyl) ester, and bis(2,4,4-trimethylpentyl)phosphonic acid, preferably tributyl phosphate.

[0009] As a further technical solution, in step S2, when hydrochloric acid is added, the pH value of the 70wt% aqueous phase is less than 1.

[0010] As a further technical solution, in step S2, the hydrochloric acid is a hydrochloric acid solution with a mass fraction of 6% to 10%.

[0011] As a further technical solution, in step S2, the reaction is a stirring reaction, and the reaction time is 2 to 4 hours.

[0012] In the present invention, the main component of the first filter residue obtained in step S2 is silicon dioxide, which can be used to produce an iron oxide room-temperature desulfurization agent after being combined with ferrous sulfate and lime.

[0013] As a further technical solution, in step S2, the mass volume ratio of the first manganese oxide ore to the waste hydrochloric acid containing ferrous chloride is 1-3 g:10 mL.

[0014] As a further technical solution, the first manganese oxide ore powder also includes brown manganese ore powder and black manganese ore powder.

[0015] In the present invention, when the first manganese oxide ore powder further includes brown manganese ore powder and henry manganese ore powder, the brown manganese ore powder, henry manganese ore powder and pyrolusite powder can be used together to further improve the manganese oxide ore powder's effect on Fe. 2+ The oxidizing property of Fe in the waste hydrochloric acid containing ferrous chloride is further promoted. 2+ Converted into black iron oxide, thereby further obtaining black iron oxide with higher purity.

[0016] As a further technical solution, the mass ratio of the brown manganese ore powder and the henmanganese ore powder to the psilomelane powder is 1:4-9.

[0017] When the mass ratio of brown manganese ore powder and black manganese ore powder to psilomelane powder is less than 1:4-9, excessive psilomelane powder will hinder the oxidizability of the overall manganese oxide ore powder, and when the mass ratio of brown manganese ore powder and black manganese ore powder to psilomelane powder is greater than 1:4-9, excessive brown manganese ore powder and black manganese ore powder will increase the possibility of side reactions, thereby reducing the oxidizability of manganese oxide ore powder, and when the mass ratio of brown manganese ore powder and black manganese ore powder to psilomelane powder is 1:4-9, the three are synergistically compounded to maximize the overall oxidizability, thereby further improving the purity of black iron oxide prepared using waste hydrochloric acid containing ferrous chloride.

[0018] As a further technical solution, the mass ratio of the brown manganese ore powder to the black manganese ore powder is 1:1.

[0019] As a further technical solution, in step S3, the first alkaline material includes one or more of sodium hydroxide, potassium hydroxide, ammonia water, ammonium carbonate, liquid ammonia, manganese oxide, manganese carbonate, calcium oxide, and magnesium oxide; the mass volume ratio of the first alkaline material to the waste hydrochloric acid containing ferrous chloride is 1~2g:10mL.

[0020] As a further technical solution, in step S4, when the second alkaline material is added, the pH value of the mixed solution is 10-11; The second alkaline material includes one or more of sodium hydroxide, potassium hydroxide, ammonia water, and liquid ammonia.

[0021] As a further technical solution, in step S4, the temperature during the reaction is 50-70°C.

[0022] As a further technical solution, in step S5, the mass volume ratio of the second manganese oxide ore powder to the waste hydrochloric acid containing ferrous chloride is 0.5~1g:10mL; the mass ratio of the sodium sulfide to the second manganese oxide ore powder is 0.01:1; the mass ratio of the first manganese oxide ore powder and the second manganese oxide ore powder to the sodium carbonate is 1:1~1.1.

[0023] The working principle and beneficial effects of the present invention are: In the present invention, waste hydrochloric acid containing ferrous chloride is used to produce black iron oxide and manganese carbonate, and the ferrous chloride in the waste hydrochloric acid can be converted into black iron oxide with economic value, while reducing the discharge of waste hydrochloric acid, low carbon and low energy consumption, and recycling of resources are achieved. Among them, by utilizing the reducibility of ferrous ions in the waste hydrochloric acid containing ferrous chloride and the oxidizability of manganese oxide ore, the manganese oxide ore includes pyrolusite powder, the divalent iron ions in the system can be oxidized into trivalent iron ions under a mild environment, and finally black iron oxide is generated, thereby improving the purity of black iron oxide, and at the same time, the manganese ions introduced into the system can be converted into manganese carbonate with economic value. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0025] Example 1 A method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid comprises the following steps: S1, in 100mL of waste hydrochloric acid containing ferrous chloride (Fe 2+ Add ferrous oxide waste sludge into the mixture (containing 160 g / L of ferrous oxide and 10% of hydrochloric acid by mass) to obtain a mixed solution with a pH value of 6, and extract the mixed solution with tributyl phosphate to obtain an organic phase and an aqueous phase; S2, taking 70wt% of the aqueous phase, adding 8% hydrochloric acid solution by mass fraction to the 70wt% aqueous phase until the pH value of the aqueous phase is 0.5, adding 10g of pyrolusite powder, stirring and reacting for 2h, filtering, and obtaining a first filtrate and a first filter residue; S3, adding 10g of manganese oxide to the first filtrate, reacting, and separating to obtain ferric oxide and manganous chloride solution; S4, after countercurrent washing and impurity removal, the ferric oxide is mixed with the remaining water in step S1 to obtain a mixed solution, sodium hydroxide is added at 50° C. until the pH value of the mixed solution is 10, filtered, countercurrent washed, and dried to obtain iron oxide black; S5, adding 5 g of psilomelane powder and 0.05 g of sodium sulfide to the manganous chloride solution, reacting, filtering, and obtaining a second filtrate and a second filter residue; S6. Add 15 g of sodium carbonate to the second filtrate, react, and separate to obtain manganese carbonate and sodium chloride solution; After testing, the purity of black iron oxide was 94.3% and the purity of manganese carbonate was 96.7%.

[0026] Example 2 A method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid comprises the following steps: S1, in 100mL of waste hydrochloric acid containing ferrous chloride (Fe 2+ Add ferrous oxide waste sludge into the mixture (containing 160 g / L of ferrous oxide and 10% of hydrochloric acid by mass) to obtain a mixed solution with a pH value of 7, and extract the mixed solution with tributyl phosphate to obtain an organic phase and an aqueous phase; S2, taking 70wt% of the aqueous phase, adding 8% hydrochloric acid solution by mass fraction to the 70wt% aqueous phase until the pH value of the aqueous phase is 0.5, adding 20g of pyrolusite powder, stirring and reacting for 4h, filtering, and obtaining a first filtrate and a first filter residue; S3, adding 15g of manganese oxide to the first filtrate, reacting, and separating to obtain ferric oxide and manganous chloride solution; S4, after countercurrent washing and impurity removal, the ferric oxide is mixed with the remaining water in step S1 to obtain a mixed solution, sodium hydroxide is added at 60° C. until the pH value of the mixed solution is 10, filtered, countercurrent washed, and dried to obtain iron oxide black; S5, adding 8 g of psilomelane powder and 0.08 g of sodium sulfide to the manganous chloride solution, reacting, filtering, and obtaining a second filtrate and a second filter residue; S6. Add 28 g of sodium carbonate to the second filtrate, react, and separate to obtain manganese carbonate and sodium chloride solution; After testing, the purity of black iron oxide was 95.5% and the purity of manganese carbonate was 97.3%.

[0027] Example 3 A method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid comprises the following steps: S1, in 100mL of waste hydrochloric acid containing ferrous chloride (Fe 2+ Add ferrous oxide waste sludge into the mixture (containing 160 g / L of ferrous oxide and 10% of hydrochloric acid by mass) to obtain a mixed solution with a pH value of 7, and extract the mixed solution with tributyl phosphate to obtain an organic phase and an aqueous phase; S2, taking 70wt% of the aqueous phase, adding 8% hydrochloric acid solution by mass fraction to the 70wt% aqueous phase until the pH value of the aqueous phase is 0.5, adding 30g of pyrolusite powder, stirring and reacting for 4h, filtering, and obtaining a first filtrate and a first filter residue; S3, adding 20g of manganese oxide to the first filtrate, reacting, and separating to obtain ferric oxide and manganous chloride solution; S4, after countercurrent washing and impurity removal, the ferric oxide is mixed with the remaining water in step S1 to obtain a mixed solution, sodium hydroxide is added at 70° C. until the pH value of the mixed solution is 11, filtered, countercurrent washed, and dried to obtain iron oxide black; S5, adding 10 g of psilomelane powder and 0.1 g of sodium sulfide to the manganous chloride solution, reacting, filtering, and obtaining a second filtrate and a second filter residue; S6. Add 40 g of sodium carbonate to the second filtrate, react, and separate to obtain manganese carbonate and sodium chloride solution; After testing, the purity of black iron oxide was 96.2% and the purity of manganese carbonate was 97.7%.

[0028] Example 4 The only difference between this embodiment and embodiment 2 is that, in this embodiment, the first manganese oxide ore includes 6 g of brown manganese ore powder and 14 g of psilomelane powder; after testing, the purity of black iron oxide is 96.8%, and the purity of manganese carbonate is 97.9%.

[0029] Example 5 The only difference between this embodiment and embodiment 2 is that, in this embodiment, the first manganese oxide ore includes 6 g of henostachysinite powder and 14 g of psilomelane powder; after testing, the purity of black iron oxide is 97.1%, and the purity of manganese carbonate is 97.8%.

[0030] Example 6 The only difference between this embodiment and embodiment 2 is that, in this embodiment, the first manganese oxide ore includes 3g of brown manganese ore powder, 3g of black manganese ore powder and 14g of pyrolusite powder; after testing, the purity of black iron oxide is 98.4%, and the purity of manganese carbonate is 98.0%.

[0031] Example 7 The only difference between this embodiment and embodiment 6 is that, in this embodiment, the first manganese oxide ore includes 0.5g of brown manganese ore powder, 0.5g of black manganese ore powder and 19g of pyrolusite powder; after testing, the purity of black iron oxide is 98.8%, and the purity of manganese carbonate is 97.9%.

[0032] Example 8 The only difference between this embodiment and embodiment 6 is that, in this embodiment, the first manganese oxide ore includes 1g of brown manganese ore powder, 1g of black manganese ore powder and 18g of pyrolusite powder; after testing, the purity of black iron oxide is 99.6%, and the purity of manganese carbonate is 98.1%.

[0033] Example 9 The only difference between this embodiment and embodiment 6 is that, in this embodiment, the first manganese oxide ore includes 2g of brown manganese ore powder, 2g of black manganese ore powder and 16g of psilomelane powder; after testing, the purity of black iron oxide is 99.9%, and the purity of manganese carbonate is 98.2%.

[0034] Comparative Example 1 The difference between this comparative example and Example 1 is that in this comparative example, in step S2, the psilomelane powder is replaced with an equal amount of hydrogen peroxide; after testing, the purity of black iron oxide is 73.3%, and the purity of manganese carbonate is 96.9%.

[0035] Comparative Example 2 The only difference between this comparative example and Example 1 is that in this comparative example, in step S2, the pyrolusite powder is replaced by an equal amount of sodium hypochlorite; after testing, the purity of black iron oxide is 70.5%, and the purity of manganese carbonate is 96.8%.

[0036] Comparative Example 3 The difference between this comparative example and Example 1 is that in this comparative example, in step S2, the pyrolusite powder is replaced by an equal amount of pyrolusite powder; after testing, the purity of black iron oxide is 79.9%, and the purity of manganese carbonate is 96.9%.

[0037] Comparative Example 4 The difference between this comparative example and Example 1 is that in this comparative example, in step S2, the pyrolusite powder is replaced by an equal amount of brown manganese ore powder; after testing, the purity of black iron oxide is 78.8%, and the purity of manganese carbonate is 96.8%.

[0038] Comparative Example 5 The difference between this comparative example and Example 1 is that in this comparative example, in step S2, the pyrolusite powder is replaced by an equal amount of henolite powder; after testing, the purity of black iron oxide is 79.3%, and the purity of manganese carbonate is 96.9%.

[0039] It can be seen from Examples 1 to 3 that in this scheme, the purity of black iron oxide can reach more than 89%, and the purity of manganese carbonate can reach 96%, indicating that this scheme can effectively convert Fe in waste hydrochloric acid into 2+ It is converted into black iron oxide and manganese ions are effectively recovered to obtain black iron oxide and manganese carbonate with higher purity.

[0040] Compared with Comparative Examples 1 to 5, the purity of the black iron oxide in Example 1 is significantly improved, indicating that when the first manganese oxide ore powder is psilomelane powder, it has a good oxidation effect and can significantly improve the purity of the black iron oxide prepared using waste hydrochloric acid containing ferrous chloride.

[0041] Compared with Example 2 and Examples 4 to 5, the purity of the black iron oxide in Examples 6 to 9 is improved, indicating that when the first manganese oxide ore powder also includes brown manganese ore powder and henluorimane ore powder, the brown manganese ore powder, the henluorimane ore powder and the psilomelane powder have a synergistic effect, which can further improve the purity of the black iron oxide prepared using waste hydrochloric acid containing ferrous chloride.

[0042] Compared with Examples 6 to 7, the purity of the black iron oxide in Examples 8 to 9 is improved, indicating that when the mass ratio of the brown manganese ore powder and the black manganese ore powder to the mass ratio of the hard manganese ore powder is 1:4 to 9, the synergistic effect of the three is optimal, which can further improve the purity of the black iron oxide prepared using waste hydrochloric acid containing ferrous chloride.

[0043] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid, characterized in that: The following steps are involved: S1. Adding ferrous oxide waste mud to waste hydrochloric acid containing ferrous chloride to obtain a mixed solution, and extracting the mixed solution to obtain an organic phase and an aqueous phase; S2, taking 70 wt% of the aqueous phase, adding hydrochloric acid and the first manganese oxide ore powder to the 70 wt% aqueous phase, reacting, filtering, and obtaining a first filtrate and a first filter residue; S3, adding a first alkaline material to the first filtrate, reacting, and separating to obtain ferric oxide and manganous chloride solution; S4, after countercurrent washing and impurity removal, the ferric oxide is mixed with the remaining water in step S1 to obtain a mixed solution, a second alkaline material is added, filtered, countercurrent washed, and dried to obtain black iron oxide; S5, adding a second manganese oxide ore powder and sodium sulfide to the manganous chloride solution, reacting, filtering, and obtaining a second filtrate and a second filter residue; S6, adding sodium carbonate to the second filtrate, reacting, and separating to obtain manganese carbonate and sodium chloride solution; The first manganese oxide ore powder and the second manganese oxide ore powder each independently include psilomelane ore powder.

2. A method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid according to claim 1, characterized in that: In step S1, the pH value of the waste hydrochloric acid containing ferrous chloride is 2-3, and the amount of ferrous oxide waste sludge added is calculated based on the pH value of the mixed solution being 6-7.

3. A method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid according to claim 1, characterized in that: In step S1, during the extraction, the extractant includes one or more of neodecanoic acid, tributyl phosphate, di(2-ethylhexyl) phosphate, 2-ethylhexyl phosphonic acid mono(2-ethylhexyl) ester, and bis(2,4,4-trimethylpentyl)phosphonic acid.

4. The method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid according to claim 1, characterized in that: In step S2, when hydrochloric acid is added, the pH value of the 70wt% aqueous phase is less than 1.

5. The method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid according to claim 1, characterized in that: In step S2, the mass volume ratio of the first manganese oxide ore powder to the waste hydrochloric acid containing ferrous chloride is 1-3 g:10 mL.

6. The method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid according to claim 1, characterized in that: The first manganese oxide ore powder also includes brown manganese ore powder and henry manganese ore powder.

7. A method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid according to claim 6, characterized in that: The mass ratio of the brown manganese ore powder and the black manganese ore powder to the mass ratio of the psilomelane powder is 1:4-9.

8. The method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid according to claim 1, characterized in that: In step S3, the first alkaline material includes one or more of sodium hydroxide, potassium hydroxide, ammonia water, ammonium carbonate, liquid ammonia, manganese oxide, manganese carbonate, calcium oxide, and magnesium oxide; the mass volume ratio of the first alkaline material to the waste hydrochloric acid containing ferrous chloride is 1-2 g:10 mL.

9. The method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid according to claim 1, characterized in that: In step S4, when the second alkaline material is added, the pH value of the mixed solution is adjusted to 10-11; The second alkaline material includes one or more of sodium hydroxide, potassium hydroxide, ammonia water and liquid ammonia.

10. The method for producing black iron oxide and manganese carbonate using iron-containing waste hydrochloric acid according to claim 1, characterized in that: In step S5, the mass volume ratio of the second manganese oxide ore powder to the waste hydrochloric acid containing ferrous chloride is 0.5~1g:10mL; the mass ratio of the sodium sulfide to the second manganese oxide ore powder is 0.01:1; the mass ratio of the first manganese oxide ore powder and the second manganese oxide ore powder to the sodium carbonate is 1:1~1.1.