Iron resource utilization system of hydrometallurgy high iron sulfate system

Abstract

The utility model discloses an iron resource utilization system of a hydrometallurgy high-iron sulfate system, which is characterized in that a discharge hole of an anti-iron waste hydrochloric acid receiving tank in an extraction and separation device for iron ions is connected with a feed hole of a waste hydrochloric acid fluidized bed incinerator in a separation device for extracted iron and hydrochloric acid; a crude hydrochloric acid receiving tank in the extracted iron and hydrochloric acid separation device is connected with a feeding hole of a resin exchange tower in the hydrochloric acid refining device; the other feeding hole of the resin exchange tower in the hydrochloric acid refining device is connected with a pure water pipeline in the iron extraction and separation device; a refined hydrochloric acid collecting tank in the hydrochloric acid refining device is connected with a hydrochloric acid recycling pipeline in the iron extraction and separation device; and a regenerated wastewater collecting tank in the hydrochloric acid refining device is connected with a wastewater collecting and neutralizing tank in the iron extraction and separation device. The system disclosed by the utility model can be used for separating iron in a high-iron sulfate system in the form of dry iron oxide, and the purity of the iron oxide can reach over 99 percent, so that the iron oxide can be completely utilized as a high-added-value product.

Description

Technical Field

[0001] This utility model belongs to the field of hydrometallurgical technology, and relates to the ferric sulfate system, specifically to a hydrometallurgical ferric sulfate system for the utilization of iron resources. Background Technology

[0002] In fields such as hydrometallurgy and comprehensive utilization of waste resources, there is a challenge in separating low-value element iron from high-value elements such as nickel, cobalt, copper, rare earth elements, and aluminum. Many methods have been developed, primarily three: precipitation, ion exchange resin, and solvent extraction. Precipitation is typically used in separation and purification processes where high iron removal efficiency is not required, generally achieving an iron removal rate of 60%, which is insufficient for deep iron removal. During precipitation, other valuable metals inevitably co-precipitate with iron, resulting in losses and the generation of large amounts of hazardous waste such as iron alum containing heavy metals. Ion exchange resins offer high efficiency and selectivity, but due to their relatively low mass transfer rate and limited iron loading capacity, they are unsuitable for separation systems with high iron content; they are only economically feasible when the iron content is relatively low. Solvent extraction offers advantages such as high selectivity and extraction efficiency, large loading capacity, and low energy consumption, but back-extraction of iron requires the use of high-concentration hydrochloric acid. In solvent extraction, organic reagents such as acidic phosphate esters, neutral extractants, and amine extractants perform well in removing iron from solutions. Acidic phosphate ester extractants, such as P204 and P507, are particularly effective in removing iron from solutions containing metal sulfates like nickel, cobalt, and aluminum. However, all these methods remove iron as an impurity, generating a large amount of hazardous waste. For example, in the hydrometallurgical process of nickel, removing 1 ton of iron ions produces more than 4 tons of jaundice slag. The composition of this solid waste varies considerably, containing 18%–25% iron, 10%–13% sulfur, 4%–9% sodium, 1%–4% silicon, 0.05%–7.00% nickel, 0.1%–2.0% cobalt, 0.5%–1.0% copper, and other impurities such as lead, barium, zinc, manganese, calcium, and magnesium, totaling about 1%, making it a typical hazardous waste. While solvent extraction for iron removal reduces solid waste, it generates a large amount of waste hydrochloric acid. Removing one ton of iron produces 25-28 tons of approximately 4N waste hydrochloric acid and a significant amount of wastewater. Given increasingly stringent environmental regulations, solving these problems has become a major challenge for relevant enterprises and technical personnel in hydrometallurgy and environmental protection fields. Summary of the Invention

[0003] In view of the shortcomings of the existing technology, the purpose of this utility model is to provide a system for the utilization of iron resources in the hydrometallurgical ferric sulfate system, and to solve the technical problem that the quality of the separated products in the existing technology needs to be further improved.

[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0005] A hydrometallurgical high-ferric sulfate system for iron resource utilization includes an iron ion extraction and separation device. This device comprises an extraction apparatus with a mixer and separation chamber, divided into an iron extraction section, an anti-iron section, and a washing section. The hydrochloric acid inlet of the anti-iron section is connected to the outlet of a hydrochloric acid mixing tank, whose three inlets are respectively connected to a pure water pipeline, a concentrated hydrochloric acid pipeline, and a recycled hydrochloric acid pipeline. The waste hydrochloric acid outlet of the anti-iron section is connected to the inlet of a waste hydrochloric acid receiving tank. The wastewater outlet of the washing section is connected to the inlet of a wastewater collection and neutralization tank.

[0006] It also includes a separation device for iron and hydrochloric acid after extraction, which includes a waste hydrochloric acid fluidized bed incinerator and a crude hydrochloric acid receiving tank.

[0007] It also includes the hydrochloric acid refining device, which includes at least one resin exchange tower, one outlet of the resin exchange tower being connected to a refined hydrochloric acid collection tank, and the other outlet of the resin exchange tower being connected to a regenerated wastewater collection tank.

[0008] The outlet of the anti-iron waste hydrochloric acid receiving tank is connected to the inlet of the waste hydrochloric acid fluidized bed incinerator.

[0009] The crude hydrochloric acid receiving tank is connected to one of the feed inlets of the resin exchange tower.

[0010] The other inlet of the resin exchange tower is connected to the pure water pipeline; the refined hydrochloric acid collection tank is connected to the recycled hydrochloric acid pipeline; and the regenerated wastewater collection tank is connected to the wastewater collection and neutralization tank.

[0011] The present invention also has the following technical features:

[0012] The iron ion extraction and separation device also includes:

[0013] The inlet of the sulfate solution to be extracted in the iron extraction section is connected to the pH adjustment tank of the sulfate solution to be extracted. One inlet of the pH adjustment tank of the sulfate solution to be extracted is connected to the sulfate solution pipeline, and the other inlet of the pH adjustment tank of the sulfate solution to be extracted is connected to the dilute sulfuric acid pipeline.

[0014] The inlet of the saponification extractant in the iron extraction section is connected to the outlet of the saponification tank. One inlet of the saponification tank is connected to the outlet of the extractant solution tank with kerosene as the solvent, and the other inlet of the saponification tank is connected to the liquid alkali pipeline.

[0015] The outlet of the raffinate from the iron extraction section is connected to the subsequent process.

[0016] The pure water inlet of the washing section is connected to a pure water pipeline.

[0017] The unloading organic phase outlet of the washing section is connected to the inlet of the extractant solution tank using kerosene as a solvent.

[0018] It also includes a triple-effect evaporator, which comprises a first evaporator and a third vapor-liquid separator. The tube-side inlet of the first evaporator is connected to the wastewater collection and neutralization tank for feeding; the liquid outlet of the third vapor-liquid separator is connected to the inlet of the anti-ferrous waste hydrochloric acid receiving tank.

[0019] In the aforementioned triple-effect evaporator, the tube-side outlet of the first evaporator is connected to the inlet of the first vapor-liquid separator, the liquid reflux outlet of the first vapor-liquid separator is connected to the tube-side inlet of the first evaporator for forced circulation, the gas phase outlet of the first vapor-liquid separator is connected to the shell-side inlet of the second evaporator for feeding, and the other liquid phase outlet of the first vapor-liquid separator is connected to the tube-side inlet of the second evaporator for feeding.

[0020] The tube-side outlet of the second evaporator is connected to the inlet of the second vapor-liquid separator, the liquid reflux port of the second vapor-liquid separator is connected to the tube-side inlet of the second evaporator for forced circulation, the gas phase outlet of the second vapor-liquid separator is connected to the shell-side inlet of the third evaporator for feeding, and the other liquid phase outlet of the second vapor-liquid separator is connected to the tube-side inlet of the third evaporator for feeding.

[0021] The tube-side outlet of the third evaporator is connected to the inlet of the third vapor-liquid separator, the liquid reflux port of the third vapor-liquid separator is connected to the tube-side inlet of the third evaporator for forced circulation, and the liquid outlet of the third vapor-liquid separator is connected to the inlet of the anti-iron waste hydrochloric acid receiving tank.

[0022] The recovery steam pipeline in the iron and hydrochloric acid separation device after extraction is connected to the shell-side steam inlet of the first evaporator, and the shell-side condensate outlet of the first evaporator is connected to the recovery condensate pipeline; the gas outlet of the first vapor-liquid separator is connected to the shell-side steam inlet of the second evaporator, and the shell-side condensate outlet of the second evaporator is connected to the recovery condensate pipeline; the gas outlet of the second vapor-liquid separator is connected to the shell-side steam inlet of the third evaporator, and the shell-side condensate outlet of the second vapor-liquid separator is connected to the recovery condensate pipeline; the gas phase outlet of the third vapor-liquid separator is connected to the negative pressure pipeline.

[0023] The outlet of the loaded organic phase in the iron extraction section is connected to the inlet of the anti-iron section; the outlet of the post-anti-iron organic phase in the anti-iron section is connected to the inlet of the washing section.

[0024] The extraction separation device for iron and hydrochloric acid also includes:

[0025] The waste hydrochloric acid fluidized bed incinerator is also connected to a gas pipeline and an air pipeline. The bottom outlet of the waste hydrochloric acid fluidized bed incinerator is connected to an iron oxide spiral discharger. The iron oxide spiral discharger is connected to the inlet of the iron oxide silo. One outlet of the iron oxide silo is connected to the wastewater collection and neutralization tank.

[0026] The top discharge port of the waste hydrochloric acid fluidized bed incinerator is connected to a cyclone dust collector, the solid discharge port of the cyclone dust collector is connected to the furnace of the waste hydrochloric acid fluidized bed incinerator, and the gas outlet of the cyclone dust collector is connected to the tube-side inlet of the waste heat utilization heat exchanger; the tube-side outlet of the waste heat utilization heat exchanger is connected to the inlet of the hydrochloric acid spray absorption tower.

[0027] The outlet of the hydrochloric acid spray absorption tower is connected to the tube-side inlet of the first tail gas cooler, the tube-side outlet of the first tail gas cooler is connected to one inlet of the Venturi dissolved gas reactor, the other inlet of the Venturi dissolved gas reactor is connected to the crude hydrochloric acid receiving tank, the outlet of the Venturi dissolved gas reactor is connected to the tube-side inlet of the second tail gas cooler, and the tube-side outlet of the second tail gas cooler is connected to the exhaust stack.

[0028] The iron oxide screw discharger is equipped with a cooling water pipe. The inlet of the cooling water pipe is connected to a softened water pipe, and the outlet of the cooling water pipe is connected to the shell-side inlet of the waste heat utilization heat exchanger. The shell-side steam outlet of the waste heat utilization heat exchanger is connected to a recovery steam pipe.

[0029] The hydrochloric acid spray absorption tower is also equipped with a spray liquid cooler. The feed end of the spray liquid cooler is connected to the crude hydrochloric acid receiving tank, and the discharge end of the spray liquid cooler is connected to the spray head inside the hydrochloric acid spray absorption tower. The hydrochloric acid recovery port at the bottom of the hydrochloric acid spray absorption tower is connected to the crude hydrochloric acid receiving tank to realize circulating spray cold absorption.

[0030] Compared with the prior art, this utility model has the following technical effects:

[0031] (I) The system of this utility model can separate iron from the ferric sulfate system in the form of dry iron oxide, and the purity of the iron oxide can reach more than 99%, which can be used as a high value-added product.

[0032] (II) The hydrochloric acid obtained by the system of this utility model has high purity and high concentration, and can be completely recycled, which significantly reduces the hydrochloric acid consumption of the system, thus treating waste hydrochloric acid and reducing operating costs.

[0033] (III) The system of this utility model utilizes waste heat to perform multi-effect distillation treatment on wastewater, which not only recovers ferric chloride from the wastewater but also effectively treats the wastewater.

[0034] (IV) The system of this utility model can basically run continuously, which is very beneficial to subsequent automation design. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the overall structure of the hydrometallurgical high-speed ferric sulfate system for iron resource utilization.

[0036] Figure 2(a) is a schematic diagram of the iron ion extraction and separation device.

[0037] Figure 2(b) is an enlarged schematic diagram of the extraction device with a stirring mixer and separation chamber shown in Figure 2(a).

[0038] Figure 2(c) is an enlarged schematic diagram of the right side of the iron extraction section in Figure 2(a).

[0039] Figure 2(d) is a magnified schematic diagram of the middle part where the anti-iron section is located in Figure 2(a).

[0040] Figure 2(e) is an enlarged schematic diagram of the left side where the washing section is located in Figure 2(a).

[0041] Figure 2(f) is an enlarged schematic diagram of the triple-effect evaporator in Figure 2(a).

[0042] Figure 3 This is a schematic diagram of the separation device for iron and hydrochloric acid after extraction.

[0043] Figure 4 This is a schematic diagram of a hydrochloric acid refining device.

[0044] The labels in the diagram represent: 1-Iron ion extraction and separation device, 2-Iron and hydrochloric acid separation device after extraction, 3-Hydrochloric acid purification device, 4-Pipeline, 5-Valve, 6-Transfer pump.

[0045] 101-Iron extraction section, 102-Anti-iron section, 103-Washing section, 104-pH adjustment tank for sulfate solution to be extracted, 105-Sulfate solution pipeline to be extracted, 106-Dilute sulfuric acid pipeline, 107-Saponification tank, 108-Extractant solution tank with kerosene as solvent, 109-Liquid alkali pipeline, 110-Hydrochloric acid mixing tank, 111-Pure water pipeline, 112-Concentrated hydrochloric acid pipeline, 113-Recovered hydrochloric acid pipeline, 114-Anti-iron waste hydrochloric acid receiving tank, 115-Wastewater collection and neutralization tank, 116-Triple-effect evaporator.

[0046] 201-Waste hydrochloric acid fluidized bed incinerator, 202-Gas pipeline, 203-Air pipeline, 204-Iron oxide screw conveyor, 205-Iron oxide silo, 206-Cyclone dust collector, 207-Waste heat recovery heat exchanger, 208-Hydrochloric acid spray absorption tower, 209-First tail gas cooler, 210-Venturi dissolved air tank, 211-Crude hydrochloric acid receiving tank, 212-Second tail gas cooler, 213-Exhaust stack, 214-Cooling water pipeline, 215-Softened water pipeline, 216-Recovered steam pipeline, 217-Spray liquid cooler.

[0047] 301 - Resin exchange tower; 302 - Refined hydrochloric acid collection tank; 303 - Regenerated wastewater collection tank.

[0048] 10101 - Inlet for sulfate solution to be extracted, 10102 - Inlet for saponification extractant, 10103 - Outlet for raffinate.

[0049] 10201 - Hydrochloric acid inlet, 10202 - Antiferroic waste hydrochloric acid outlet.

[0050] 10301 - Pure water inlet, 10302 - Wastewater outlet, 10303 - Unloading organic phase outlet.

[0051] 11601 - First evaporator, 11602 - First vapor-liquid separator, 11603 - Second evaporator, 11604 - Second vapor-liquid separator, 11605 - Third evaporator, 11606 - Third vapor-liquid separator.

[0052] The specific content of this utility model will be further explained in detail below with reference to the embodiments. Detailed Implementation

[0053] It should be noted that, unless otherwise specified, all raw materials and equipment used in this utility model are those known in the prior art.

[0054] Following the above technical solution, the following are specific embodiments of this utility model. It should be noted that this utility model is not limited to the following specific embodiments, and all equivalent modifications made based on the technical solution of this application fall within the protection scope of this utility model.

[0055] Example:

[0056] This embodiment presents a system for the utilization of iron resources in a hydrometallurgical high-ferric sulfate system, such as... Figure 1As shown, the system includes an iron ion extraction and separation device 1, which includes an extraction device with a stirrer and a separation chamber. The extraction device with a stirrer and a separation chamber is divided into an iron extraction section 101, an anti-iron section 102, and a washing section 103. The hydrochloric acid inlet 10201 of the anti-iron section 102 is connected to the outlet of the hydrochloric acid mixing tank 110. The three inlets of the hydrochloric acid mixing tank 110 are respectively connected to the pure water pipeline 111, the concentrated hydrochloric acid pipeline 112, and the recovered hydrochloric acid pipeline 113. The anti-iron waste hydrochloric acid outlet 10202 of the anti-iron section 102 is connected to the inlet of the anti-iron waste hydrochloric acid receiving tank 114. The wastewater outlet 10302 of the washing section 103 is connected to the inlet of the wastewater collection and neutralization tank 115.

[0057] like Figure 1 As shown, it also includes a separation device 2 for iron and hydrochloric acid after extraction, which includes a waste hydrochloric acid fluidized bed incinerator 201 and a crude hydrochloric acid receiving tank 211.

[0058] like Figure 1 As shown, it also includes a hydrochloric acid refining device 3, which includes at least one resin exchange tower 301. One outlet of the resin exchange tower 301 is connected to a refined hydrochloric acid collection tank 302, and the other outlet of the resin exchange tower 301 is connected to a regenerated wastewater collection tank 303.

[0059] like Figure 1 As shown, the outlet of the anti-iron waste hydrochloric acid receiving tank 114 is connected to the inlet of the waste hydrochloric acid fluidized bed incinerator 201.

[0060] like Figure 1 As shown, the crude hydrochloric acid receiving tank 211 is connected to one inlet of the resin exchange tower 301.

[0061] like Figure 1 As shown, another inlet of the resin exchange tower 301 is connected to the pure water pipeline 111; the refined hydrochloric acid collection tank 302 is connected to the recycled hydrochloric acid pipeline 113; and the regenerated wastewater collection tank 303 is connected to the wastewater collection and neutralization tank 115.

[0062] As a preferred embodiment, as shown in Figures 2(a) to 2(f), the outlet of the loaded organic phase of the iron extraction section 101 is connected to the inlet of the anti-iron section 102; the outlet of the anti-iron organic phase of the anti-iron section 102 is connected to the inlet of the washing section 103.

[0063] In this embodiment, the extraction equipment with a stirring mixer and a separation chamber is an extraction equipment with a stirring mixer and a separation chamber known in the art.

[0064] In this embodiment, as Figure 1As shown, the various devices are mainly connected by pipes 4, and valves 5 and delivery pumps 6 are installed on the pipes as needed.

[0065] In this embodiment, the iron extraction section 101, the anti-iron section 102, and the washing section 103 all adopt the countercurrent extraction process.

[0066] In this embodiment, the acidic wastewater is neutralized in the wastewater collection and neutralization tank 115 using iron oxide generated during the process.

[0067] As a further embodiment, the iron ion extraction and separation device 1 also includes:

[0068] As shown in Figures 2(a) to 2(f), the inlet 10101 of the sulfate solution to be extracted in the iron extraction section 101 is connected to the pH adjustment tank 104 of the sulfate solution to be extracted. One inlet of the pH adjustment tank 104 is connected to the sulfate solution pipeline 105, and the other inlet of the pH adjustment tank 104 is connected to the dilute sulfuric acid pipeline 106.

[0069] As shown in Figures 2(a) to 2(f), the saponification extractant inlet 10102 of the iron extraction section 101 is connected to the outlet of the saponification tank 107. One inlet of the saponification tank 107 is connected to the outlet of the extractant solution tank 108 with kerosene as the solvent, and the other inlet of the saponification tank 107 is connected to the liquid alkali pipeline 109.

[0070] As shown in Figures 2(a) to 2(f), the raffinate outlet 10103 of the iron extraction section 101 is connected to the subsequent process.

[0071] As shown in Figures 2(a) to 2(f), the pure water inlet 10301 of the washing section 103 is connected to the pure water pipe 111.

[0072] As shown in Figures 2(a) to 2(f), the unloading organic phase outlet 10303 of the washing section 103 is connected to the inlet of the extractant solution tank 108 with kerosene as the solvent.

[0073] As a preferred embodiment of this invention, as shown in Figures 2(a) to 2(f), a triple-effect evaporator 116 is also included. The triple-effect evaporator 116 includes a first evaporator 11601 and a third vapor-liquid separator 11606. The tube-side inlet of the first evaporator 11601 is connected to the wastewater collection and neutralization tank 115 for feeding. The liquid outlet of the third vapor-liquid separator 11606 is connected to the inlet of the antiferroic waste hydrochloric acid receiving tank 114.

[0074] In a further preferred embodiment, as shown in Figures 2(a) to 2(f), in the triple-effect evaporator 116, the tube-side outlet of the first evaporator 11601 is connected to the inlet of the first vapor-liquid separator 11602, the liquid reflux outlet of the first vapor-liquid separator 11602 is connected to the tube-side inlet of the first evaporator 11601 for forced circulation, the gas phase outlet of the first vapor-liquid separator 11602 is connected to the shell-side inlet of the second evaporator 11603 for feeding, and the other liquid phase outlet of the first vapor-liquid separator is connected to the tube-side inlet of the second evaporator for feeding.

[0075] The tube-side outlet of the second evaporator 11603 is connected to the inlet of the second vapor-liquid separator 11604. The liquid reflux outlet of the second vapor-liquid separator 11604 is connected to the tube-side inlet of the second evaporator 11603. The gas phase outlet of the second vapor-liquid separator 11604 is connected to the shell-side inlet of the third evaporator 11605 for feeding. The other liquid phase outlet of the second vapor-liquid separator is connected to the tube-side inlet of the third evaporator for feeding.

[0076] The tube-side outlet of the third evaporator 11605 is connected to the inlet of the third vapor-liquid separator 11606. The liquid reflux port of the third vapor-liquid separator 11606 is connected to the tube-side inlet of the third evaporator 11605 for forced circulation. The liquid outlet of the third vapor-liquid separator 11606 is connected to the inlet of the anti-iron waste hydrochloric acid receiving tank 114.

[0077] More preferably, as shown in Figures 2(a) to 2(f), the recovery steam pipe 216 in the iron and hydrochloric acid separation device 2 after extraction is connected to the shell-side steam inlet of the first evaporator 11601, and the shell-side condensate outlet of the first evaporator 11601 is connected to the recovery condensate; the gas outlet of the first vapor-liquid separator 11602 is connected to the shell-side steam inlet of the second evaporator 11603, and the shell-side condensate outlet of the second evaporator 11603 is connected to the recovery condensate; the gas outlet of the second vapor-liquid separator 11604 is connected to the shell-side steam inlet of the third evaporator 11605, and the shell-side condensate outlet of the second vapor-liquid separator 11604 is connected to the recovery condensate; the gas outlet of the third vapor-liquid separator 11606 is connected to the negative pressure pipe.

[0078] As a further embodiment, the separation device 2 for iron and hydrochloric acid after extraction also includes:

[0079] like Figure 3 As shown, the waste hydrochloric acid fluidized bed incinerator 201 is also connected to the gas pipeline 202 and the air pipeline 203. The bottom discharge port of the waste hydrochloric acid fluidized bed incinerator 201 is connected to the iron oxide spiral discharge device 204, and the iron oxide spiral discharge device 204 is connected to the inlet of the iron oxide silo 205. One discharge port of the iron oxide silo 205 is connected to the wastewater collection and neutralization tank 115.

[0080] like Figure 3 As shown, the top discharge port of the waste hydrochloric acid fluidized bed incinerator 201 is connected to the cyclone dust collector 206, the solid discharge port of the cyclone dust collector 206 is connected to the furnace of the waste hydrochloric acid fluidized bed incinerator 201, the gas outlet of the cyclone dust collector 206 is connected to the tube-side air inlet of the waste heat utilization heat exchanger 207, and the tube-side air outlet of the waste heat utilization heat exchanger 207 is connected to the air inlet of the hydrochloric acid spray absorption tower 208.

[0081] like Figure 3 As shown, the outlet of the hydrochloric acid spray absorption tower 208 is connected to the tube-side inlet of the first tail gas cooler 209, the tube-side outlet of the first tail gas cooler 209 is connected to one inlet of the Venturi dissolved gas reactor 210, the other inlet of the Venturi dissolved gas reactor 210 is connected to the crude hydrochloric acid receiving tank 211, the outlet of the Venturi dissolved gas reactor 210 is connected to the tube-side inlet of the second tail gas cooler 212, and the tube-side outlet of the second tail gas cooler 212 is connected to the exhaust stack 213.

[0082] As a preferred embodiment of this invention, such as Figure 3 As shown, the iron oxide screw feeder 204 is equipped with a cooling water pipe 214. The inlet of the cooling water pipe 214 is connected to the softened water pipe 215, and the outlet of the cooling water pipe 214 is connected to the shell-side inlet of the waste heat utilization heat exchanger 207. The shell-side steam outlet of the waste heat utilization heat exchanger 207 is connected to the recovery steam pipe 216.

[0083] As a preferred embodiment of this invention, such as Figure 3 As shown, the hydrochloric acid spray absorption tower 208 is also equipped with a spray liquid cooler 217. The tube side inlet of the spray liquid cooler 217 is connected to the crude hydrochloric acid receiving tank 211, and the tube side outlet of the spray liquid cooler 217 is connected to the spray head inside the hydrochloric acid spray absorption tower 208. The hydrochloric acid recovery port at the bottom of the hydrochloric acid spray absorption tower 208 is connected to the crude hydrochloric acid receiving tank 211 to realize circulating spray cold absorption.

[0084] As a further solution in this embodiment, such as Figure 4 As shown, there are three resin exchange towers 301, operating in a two-on-one-standby mode, absorbing the crude hydrochloric acid produced through thermal decomposition. The two open resin exchange towers 301 are connected in series, with the bottom outlet of the first tower connected to the top inlet of the second tower, and the bottom outlet of the second tower connected to the refined hydrochloric acid collection tank 302.

[0085] This embodiment also provides a process for the hydrometallurgical ferric sulfate system for iron resource utilization based on this embodiment. The process uses an iron ion extraction and separation device 1 to perform the iron ion extraction process of the ferric sulfate system; an extraction iron and hydrochloric acid separation device 2 to perform the extraction iron and hydrochloric acid separation process; and a hydrochloric acid purification device 3 to perform the hydrochloric acid purification process.

[0086] The specific process includes the following steps:

[0087] Step 1: Extraction process of iron ions in the ferric sulfate system:

[0088] Step S11: Adjust the pH value of the sulfate solution to be extracted in pH adjustment tank 104, and perform multi-stage extraction in iron extraction section 101 using saponified extractant with kerosene as solvent to extract iron ions from the sulfate solution to be extracted into the organic phase, thereby obtaining a loaded organic phase. The raffinate is then used in subsequent processes.

[0089] In step S11, the pH of the sulfate solution to be extracted is adjusted to 1-3.

[0090] In step S11, the extractant is P204 extractant (i.e., di(2-ethylhexyl) phosphate; bis(2-ethylhexyl) phosphate) or P507 extractant (i.e., 2-ethylhexyl phosphate mono-2-ethylhexyl ester); the kerosene is petroleum fractionated hydrogenated kerosene or coal-derived kerosene; the mass ratio of extractant to kerosene is 1:(3-4).

[0091] In step S11, the saponification rate of the extractant is 50-70%, and the oil-water ratio is 1:(1-3).

[0092] In step S11, the number of extraction stages is 6 to 10.

[0093] Step S12: The loaded organic phase obtained in step S11 is subjected to multi-stage back-extraction with hydrochloric acid in the anti-iron section 102 to obtain the anti-iron organic phase and the ferric chloride solution containing hydrochloric acid.

[0094] In step S12, the number of back-extraction stages is 4 to 6.

[0095] In step S13, the antiferroic organic phase obtained in step S12 is washed in multiple stages with pure water in the washing section 103 to obtain the unloaded organic phase and ferric chloride wastewater containing hydrochloric acid; the unloaded organic phase is recycled to the extractant solution tank 108 with kerosene as solvent.

[0096] In step S13, the washing stages are 4 to 6.

[0097] Step S14: The ferric chloride wastewater containing hydrochloric acid obtained in step S13 is neutralized in wastewater collection and neutralization tank 115 using the iron oxide obtained in step two to obtain ferric chloride wastewater.

[0098] In step S14, the neutralized pH is 3.5 to 4.

[0099] In step S15, the wastewater containing ferric chloride obtained in step S14 is further concentrated by passing it through a triple-effect evaporator 116 to obtain a concentrated ferric chloride solution. The concentrated ferric chloride solution is then combined with the ferric chloride solution containing hydrochloric acid obtained in step S12 to form a combined liquid, which is then transported to the antiferric waste hydrochloric acid receiving tank 114.

[0100] In step S15, the concentration of the concentrated ferric chloride solution is 325 g to 432 g / L.

[0101] Step 2, the separation process of iron and hydrochloric acid after extraction:

[0102] In step S21, the combined liquid obtained in step S15 is sprayed into the furnace of the waste hydrochloric acid fluidized bed incinerator 201, so that the hydrochloric acid and water in the combined liquid are vaporized, the ferric chloride in the combined liquid reacts with water to generate ferric oxide and hydrogen chloride, and the ferric oxide grows into particles and is cooled and discharged by the ferric oxide screw discharger 204 to obtain the ferric oxide product.

[0103] In step S21, the temperature of the furnace chamber of the waste hydrochloric acid fluidized bed incinerator 201 is 800℃~900℃.

[0104] In step S22, the hydrogen chloride and water vapor generated in step S21 are separated by cyclone dust collector 206 to obtain mixed gas and iron oxide dust. The iron oxide dust is returned to the furnace of waste hydrochloric acid fluidized bed incinerator 201 to be melted and grown into particles again. The mixed gas recovers heat through waste heat recovery heat exchanger 207 to obtain cooled mixed gas.

[0105] In step S23, the cooled mixed gas obtained in step S22 is sprayed and absorbed in hydrochloric acid spray absorption tower 208 to obtain crude hydrochloric acid and primary tail gas; the crude hydrochloric acid is transported to crude hydrochloric acid receiving tank 211.

[0106] In step S24, the primary exhaust gas obtained in step S23 is cooled by the first exhaust gas cooler 209 and then enters the Venturi dissolved gas reactor 210 for reabsorption to obtain hydrochloric acid and secondary exhaust gas. The secondary exhaust gas is cooled by the second exhaust gas cooler 212 and then discharged from the exhaust stack 213. The crude hydrochloric acid is transported to the crude hydrochloric acid receiving tank 211.

[0107] Step 3, the refining process of hydrochloric acid:

[0108] Step S31: The crude hydrochloric acid obtained in step two is added to the resin exchange tower 301 for ion exchange, and the residual iron ions in the crude hydrochloric acid are further removed through the resin exchange tower 301 to obtain refined hydrochloric acid and regenerated wastewater containing residual iron ions.

[0109] In step S31, the exchange resin in the resin exchange tower 301 is a strong basic anion exchange resin with an exchange capacity ≥3.5mmol / g and an exchange temperature of room temperature to 45℃.

[0110] In step S32, refined hydrochloric acid is finally obtained and transported to the refined hydrochloric acid collection tank 302, and then returned to the hydrochloric acid mixing tank 110 for recycling.

[0111] In step S33, the regenerated wastewater containing residual iron ions is transported to the regenerated wastewater collection tank 303 and then returned to the wastewater collection and neutralization tank 115 for recycling.

Claims

1. A hydrometallurgical high-iron sulfate system iron resource utilization system, the system comprising an iron ion extraction separation device (1), the iron ion extraction separation device (1) comprising an extraction equipment with a stirring mixer and a separation chamber, the extraction equipment with a stirring mixer and a separation chamber being divided into an iron extraction section (101), an anti-iron section (102) and a washing section (103); characterized in that, The hydrochloric acid feeding port (10201) of the reverse iron section (102) is connected with the discharge port of the hydrochloric acid preparation tank (110), and the three feeding ports of the hydrochloric acid preparation tank (110) are respectively connected with the pure water pipeline (111), the concentrated hydrochloric acid pipeline (112) and the recovered hydrochloric acid pipeline (113); the reverse iron waste hydrochloric acid discharge port (10202) of the reverse iron section (102) is connected with the feeding port of the reverse iron waste hydrochloric acid receiving tank (114); the waste water discharge port (10302) of the washing section (103) is connected with the feeding port of the waste water collecting tank (115); It also comprises a separation device (2) for the extracted iron and hydrochloric acid, wherein the separation device (2) comprises a waste hydrochloric acid fluidized bed incinerator (201) and a crude hydrochloric acid receiving tank (211); It also comprises a refining device (3) for the hydrochloric acid, wherein the refining device (3) comprises at least one resin exchange tower (301), one discharge port of the resin exchange tower (301) is connected with a refined hydrochloric acid collecting tank (302), and another discharge port of the resin exchange tower (301) is connected with a regenerated waste water collecting tank (303); The discharge port of the reverse iron waste hydrochloric acid receiving tank (114) is connected with the feeding port of the waste hydrochloric acid fluidized bed incinerator (201); The crude hydrochloric acid receiving tank (211) is connected with one feeding port of the resin exchange tower (301); Another feeding port of the resin exchange tower (301) is connected with the pure water pipeline (111); the refined hydrochloric acid collecting tank (302) is connected with the recovered hydrochloric acid pipeline (113); and the regenerated waste water collecting tank (303) is connected with the waste water collecting tank (115).

2. The hydrometallurgical high-iron sulfate system iron resource utilization system according to claim 1, characterized in that, The iron ion extraction separation device (1) further comprises: The to-be-extracted sulfate solution feeding port (10101) of the iron extraction section (101) is connected with a to-be-extracted sulfate solution pH adjusting tank (104), one inlet of the to-be-extracted sulfate solution pH adjusting tank (104) is connected with a to-be-extracted sulfate solution pipeline (105), and another feeding port of the to-be-extracted sulfate solution pH adjusting tank (104) is connected with a dilute sulfuric acid pipeline (106); The saponification extractant feeding port (10102) of the iron extraction section (101) is connected with the discharge port of a saponification tank (107), one feeding port of the saponification tank (107) is connected with the discharge port of a kerosene-solvent-based extractant solution tank (108), and another feeding port of the saponification tank (107) is connected with a liquid alkali pipeline (109); The raffinate outlet (10103) of the iron extraction section (101) is connected with a subsequent process; The pure water feeding port (10301) of the washing section (103) is connected with the pure water pipeline (111); The unloaded organic phase discharge port (10303) of the washing section (103) is connected with the feeding port of the kerosene-solvent-based extractant solution tank (108).

3. The hydrometallurgical high-iron sulfate system iron resource utilization system according to claim 1, characterized in that, The three-effect evaporator (116) comprises a first evaporator (11601) and a third vapor-liquid separator (11606), and a tube side feed inlet of the first evaporator (11601) is connected with the wastewater collecting tank (115).

4. The hydrometallurgical high-iron sulfate system iron resource utilization system according to claim 3, characterized by, In the three-effect evaporator (116), a tube side outlet of the first evaporator (11601) is connected with a feed inlet of a first vapor-liquid separator (11602), a liquid reflux outlet of the first vapor-liquid separator (11602) is connected with the tube side feed inlet of the first evaporator (11601) for forced circulation, a gas phase outlet of the first vapor-liquid separator (11602) is connected with a shell side feed inlet of a second evaporator (11603), and another liquid phase outlet of the first vapor-liquid separator (11602) is connected with a tube side feed inlet of the second evaporator (11603). A tube side outlet of the second evaporator (11603) is connected with a feed inlet of a second vapor-liquid separator (11604), a liquid reflux outlet of the second vapor-liquid separator (11604) is connected with the tube side feed inlet of the second evaporator (11603) for forced circulation, a gas phase outlet of the second vapor-liquid separator (11604) is connected with a shell side feed inlet of a third evaporator (11605), and another liquid phase outlet of the second vapor-liquid separator (11604) is connected with a tube side feed inlet of the third evaporator (11605). A tube side outlet of the third evaporator (11605) is connected with a feed inlet of a third vapor-liquid separator (11606), a liquid reflux outlet of the third vapor-liquid separator (11606) is connected with the tube side feed inlet of the third evaporator (11605) for forced circulation, and a liquid outlet of the third vapor-liquid separator (11606) is connected with the feed inlet of the anti-iron waste hydrochloric acid receiving tank (114).

5. The hydrometallurgical high-iron sulfate system iron resource utilization system according to claim 4, characterized in that, A recovery steam pipeline (216) in the iron and hydrochloric acid separation device (2) is connected with a shell side steam inlet of the first evaporator (11601), a shell side condensate outlet of the first evaporator (11601) is connected with a recovery condensate pipeline, a gas outlet of the first vapor-liquid separator (11602) is connected with a shell side steam inlet of the second evaporator (11603), a shell side condensate outlet of the second evaporator (11603) is connected with the recovery condensate pipeline, a gas outlet of the second vapor-liquid separator (11604) is connected with a shell side steam inlet of the third evaporator (11605), and a shell side condensate outlet of the second vapor-liquid separator (11604) is connected with the recovery condensate pipeline.

6. The hydrometallurgical high-iron-sulphate system iron resource utilization system according to claim 1, characterized in that, A loaded organic phase outlet of the iron extraction section (101) is connected with a feed inlet of the anti-iron section (102), and an anti-iron organic phase outlet of the anti-iron section (102) is connected with a feed inlet of the washing section (103).

7. The hydrometallurgical high-iron-sulphate system iron resource utilization system according to claim 1, characterized by, The separation device (2) for iron and hydrochloric acid after extraction further comprises: The fluidized bed incinerator (201) is connected with a gas pipeline (202) and an air pipeline (203), the bottom discharge port of the fluidized bed incinerator (201) is connected with the iron oxide screw discharger (204), the iron oxide screw discharger (204) is connected with the feed inlet of the iron oxide storage bin (205), and one discharge port of the iron oxide storage bin (205) is connected with the wastewater collecting and concentrating tank (115). The top discharge port of the fluidized bed incinerator (201) is connected with the cyclone dust collector (206), the solid discharge port of the cyclone dust collector (206) is connected with the hearth of the fluidized bed incinerator (201), and the gas outlet of the cyclone dust collector (206) is connected with the tube-side gas inlet of the waste heat utilization heat exchanger (207). The gas outlet of the hydrochloric acid spray absorption tower (208) is connected with the tube-side inlet of the first tail gas cooler (209), one inlet of the Venturi gas dissolver (210) is connected with the crude hydrochloric acid receiving tank (211), the outlet of the Venturi gas dissolver (210) is connected with the tube-side inlet of the second tail gas cooler (212), and the tube-side outlet of the second tail gas cooler (212) is connected with the exhaust cylinder (213).

8. The hydrometallurgical high-iron sulfate system iron resource utilization system according to claim 7, characterized in that, The iron oxide screw discharger (204) is provided with a cooling water pipeline (214), the water inlet end of the cooling water pipeline (214) is connected with the softened water pipeline (215), the outlet of the cooling water pipeline (214) is connected with the shell-side inlet of the waste heat utilization heat exchanger (207), and the shell-side steam outlet of the waste heat utilization heat exchanger (207) is connected with the recovered steam pipeline (216).

9. The hydrometallurgical high-iron sulfate system iron resource utilization system according to claim 7, characterized in that, The hydrochloric acid spray absorption tower (208) is further provided with a spray liquid cooler (217), the tube-side feed end of the spray liquid cooler (217) is connected with the crude hydrochloric acid receiving tank (211), the tube-side discharge end of the spray liquid cooler (217) is connected with the spray head inside the hydrochloric acid spray absorption tower (208), the hydrochloric acid recovery port at the bottom of the hydrochloric acid spray absorption tower (208) is connected with the crude hydrochloric acid receiving tank (211), and the circulating spray cold absorption is realized.

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