Resourceful treatment device for copper raffinate and treatment system for copper ore charge

Abstract

The utility model belongs to the field of water treatment, and provides a resourceful treatment device for copper raffinate and a treatment system for copper ore charge. The resourceful treatment device for the copper raffinate comprises a pretreatment unit, a membrane concentration unit and an acid separation and recovery unit, wherein the pretreatment unit is used for pretreating the copper raffinate to obtain pretreated produced water; the membrane concentration unit comprises an acid-resistant reverse osmosis device and is used for performing reverse osmosis treatment on the pretreated produced water to obtain reverse osmosis concentrated water and reverse osmosis produced water; and the acid separation and recovery unit comprises a resin device filled with strongly basic anion resin. According to the resourceful treatment device, effective separation of acid and salt in the copper raffinate can be achieved, effective purification, concentration and recovery of the acid are achieved, and water expansion of a system is avoided.

Description

TECHNICAL FIELD

[0001] The utility model belongs to the field of water treatment, specifically, relate to a kind of copper raffinate's resource processing device and copper ore processing system. BACKGROUND

[0002] Congo (Kinshasa) copper belt has the world's largest high-grade copper ore and its cobalt by-product, the area buried with high-grade oxidized copper cobalt ore, rich resources attract the mining enterprises of all countries to go to development. Currently, oxidized copper cobalt ore metallurgical process is mostly hydrometallurgical process, main process includes: leaching, extraction, electrodeposition, iron removal and cobalt precipitation.

[0003] Since most of the oxidized copper ore is copper-cobalt associated ore, a reducing agent is generally added to improve the metal leaching rate during copper leaching. After copper in leaching solution is extracted, cobalt remains in copper raffinate, and cobalt is gradually accumulated with the circulation of copper raffinate. According to the reaction equilibrium principle of copper extraction agent, copper is extracted into the organic phase, and H + is replaced into the aqueous solution, therefore, the pH of the leaching solution continuously decreases during the extraction of copper, and the H2SO4 concentration of the raffinate is generally between 10-20 g / L. The yield of copper raffinate is extremely large in the process of copper smelting by hydrometallurgy, and the traditional treatment method of copper raffinate is to neutralize the raffinate with lime, which results in that the H2SO4 in the raffinate cannot be effectively utilized, and the use amount of neutralizing agent is greatly increased, which leads to high cobalt recovery cost, and a large amount of waste residue is generated, which is not conducive to the long-term management of tailings pond.

[0004] CN107460315A discloses a method for recovering copper and cobalt from copper raffinate, which utilizes nanofiltration membrane assembly to concentrate and separate the copper raffinate, and the copper, cobalt, iron, aluminum, arsenic and magnesium in the copper raffinate are retained in the concentrated solution, and the valuable metals cobalt and copper are recovered by chemical precipitation treatment, and the dialysis solution (sulfuric acid solution) is returned to the leaching system to achieve resource recovery and utilization of acid and valuable metals in the raffinate. The method can recover 60%-70% of H2SO4 by nanofiltration membrane concentration and separation, and reduces the amount of reagent in the neutralization process, but the method has the following disadvantages: ① the volume of nanofiltration dialysis solution is 75%-80% of the volume of the original raffinate, a large amount of low-concentration acid (10-12 g / L) carries most of the water back to acid leaching, and only 20%-25% of the water is discharged from the system through the neutralization path, which inevitably exacerbates the water swelling problem in the system and increases the system load; ② in the method, the nanofiltration membrane enriches metals at the same time, and part of the acid is also concentrated, so the separation efficiency of the system is low, and to improve the separation efficiency, additional separation systems need to be added, which leads to high device cost.

[0005] In summary, the traditional copper raffinate treatment system and process cannot effectively recycle the acid, and the recovery of the acid carries a large amount of water, resulting in water swelling of the system and increasing the load of the system. Utility model content

[0006] The utility model aims at solving one of the technical problems in the related art at least to some extent.

[0007] The utility model provides a kind of copper raffinate's resource processing device, and the resource processing device includes pretreatment unit, membrane concentration unit and acid separation recovery unit;Wherein,

[0008] The pretreatment unit is used to pretreat the copper raffinate, to obtain pretreatment water, and includes multiple medium filter, oil removal filter and precision filter connected in sequence;

[0009] The membrane concentration unit includes acid-resistant reverse osmosis device, for the reverse osmosis treatment of pretreatment water, to obtain reverse osmosis concentrated water and reverse osmosis water, and the water inlet of the acid-resistant reverse osmosis device is connected with the water outlet of the precision filter;

[0010] The acid separation recovery unit includes resin device filled with strong alkaline anion resin, and the first feed liquid outlet and the second feed liquid outlet are provided on the resin device;

[0011] The first feed liquid outlet is connected with the concentrated water outlet of the acid-resistant reverse osmosis device, so that the reverse osmosis concentrated water can enter the resin device for acid adsorption treatment, to obtain deacidification raffinate;

[0012] The second feed liquid outlet is connected with the water outlet of the acid-resistant reverse osmosis device, so that the reverse osmosis water is used as elution water for acid elution treatment, to obtain elution liquid.

[0013] The resource processing device for copper raffinate provided by the utility model has simple structure, adopts acid-resistant reverse osmosis device and specific resin device for membrane concentration separation treatment and acid separation recovery treatment respectively, realizes effective separation of acid and salt in copper raffinate, recovers sulfuric acid in raffinate, and effectively purifies and concentrates acid. Further, the acid-resistant reverse osmosis device and the resin device are effectively coupled, the elution water comes from reverse osmosis water, avoids introducing a large amount of water from outside the system during the acid elution process in the resin device, and effectively avoids the aggravation of the system water swelling problem.

[0014] According to some embodiments of the utility model, the acid-resistant reverse osmosis device includes acid-resistant reverse osmosis membrane, and the maximum operating pressure of the acid-resistant reverse osmosis membrane is 60-80 bar.

[0015] According to some embodiments of the present application, the acid-resistant reverse osmosis device is a single membrane module system, the single membrane module system comprises a shell and a membrane module installed in the shell, and the membrane module comprises one membrane element or a plurality of membrane elements connected in series.

[0016] According to some embodiments of the present application, the acid-resistant reverse osmosis device is a multi-membrane module system, the multi-membrane module system comprises a shell and a plurality of membrane modules installed in parallel in the shell, and each membrane module is formed by connecting a plurality of membrane elements in series.

[0017] According to some embodiments of the present application, the multi-medium filter is an anthracite filter or a garnet filter.

[0018] According to some embodiments of the present application, the resin device is a fixed-bed vertical resin device, the first feed liquid inlet and outlet is located at the bottom of the resin device, and the second feed liquid inlet and outlet is located at the top of the resin device.

[0019] The present application also provides a copper ore processing system, which comprises the copper raffinate resource processing device according to the first aspect of the present application.

[0020] The processing system according to the present application comprises the resource processing device, which can not only realize effective recovery and utilization of acid, but also can avoid consumption of a large amount of neutralizing agent in subsequent neutralization treatment, and almost no metal discharge loss, so that the processing system can improve the cobalt product content and effectively avoid water swelling and impurity enrichment problems.

[0021] According to some embodiments of the present application, the processing system further comprises an acid leaching unit, and the first feed liquid inlet and outlet of the resin device is further connected with the acid leaching unit, so that the elution liquid is used for acid leaching treatment of the copper ore. The backflow utilization of the elution liquid can not only realize utilization of acid and avoid loss of the acid due to neutralization process, but also a small amount of valuable metal ions (such as Cu and Co) contained in the elution liquid can return to the processing system with the reuse of the acid, so that the whole system basically does not cause loss of valuable metal ions.

[0022] According to some embodiments of the present application, the processing system further comprises an extraction unit, the extraction unit is connected with the acid leaching unit, and is used for extracting the material liquid obtained after acid leaching treatment to obtain a copper raffinate.

[0023] According to some embodiments of the present application, the processing system further comprises a metal recovery unit, the metal recovery unit comprises an iron removal unit, a copper precipitation unit and a cobalt precipitation unit connected in sequence, and the second feed liquid inlet and outlet of the resin device is further connected with the iron removal unit, so that the deacidification raffinate can be sequentially subjected to iron removal, copper precipitation and cobalt precipitation treatment.

[0024] Further, the treatment system further comprises a heavy metal removal unit, which is connected with the cobalt precipitation unit, so that the cobalt precipitation unit can be treated by the heavy metal removal unit to obtain product water.

[0025] Additional aspects and advantages of the present application will be made apparent from the following description of embodiments of the present application, given by way of example only, and from the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0026] The above and / or additional aspects and advantages of the present application will become apparent and more readily appreciated from the following description of embodiments, taken in conjunction with the accompanying drawings, in which:

[0027] Figure 1 is a schematic diagram of a resource treatment device according to an embodiment of the present application;

[0028] Figure 2 is a schematic diagram of a pretreatment unit according to an embodiment of the present application;

[0029] Figure 3 is a schematic diagram of a membrane concentration unit according to an embodiment of the present application, wherein (a) is a single membrane module system and (b) is a multiple membrane module system;

[0030] Figure 4 is a schematic diagram of an acid separation and recovery unit according to an embodiment of the present application;

[0031] Figure 5 is a schematic diagram of a treatment system according to an embodiment of the present application.

[0032] BRIEF DESCRIPTION OF DRAWINGS

[0033] 100: pretreatment unit; 200: membrane concentration unit;

[0034] 300: acid separation and recovery unit; 400: acid leaching unit;

[0035] 500: extraction unit; 600: electrodeposition unit;

[0036] 710: iron removal unit; 720: copper precipitation unit;

[0037] 730: cobalt precipitation unit; 800: heavy metal removal unit;

[0038] 101: multi-media filter; 111: multi-media filtrate storage tank;

[0039] 102: oil removal filter; 112: post-oil removal liquid storage tank;

[0040] 103: precision filter; 104: raw water pump;

[0041] 105: first feed pump; 106: second feed pump;

[0042] 107: booster pump; 201: acid-resistant reverse osmosis device;

[0043] 2011: membrane element 301: resin device;

[0044] 302: feed pump; 303: water pump; 700: metal recovery unit. DETAILED DESCRIPTION

[0045] The embodiments of the present application will be described in detail below. The embodiments described below are exemplary and are only used to explain the present application and cannot be understood as a limitation of the present application.

[0046] The range disclosed by the present application is limited in the form of lower limit and / or upper limit, and the given range is limited by selecting a lower limit and / or an upper limit. The range limited in this way can include or not include the end value, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range not explicitly recited, and any lower limit can be combined with other lower limits to form a range not explicitly recited, and any upper limit can be combined with any other upper limit to form a range not explicitly recited. In addition, each individually disclosed point or single value can be combined with any other point or single value as a lower limit or upper limit or combined with other lower limits or upper limits to form a range not explicitly recited.

[0047] It should be noted that the terms "first", "second" are only used for description purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Therefore, the features limited by "first", "second" can explicitly or implicitly include one or more features. In the description of the present application, the meaning of "multiple" is two or more, unless otherwise specifically limited.

[0048] In the present application, unless otherwise specifically defined and limited, the terms "connected", "connected" and the like should be broadly understood, for example, it can be fixedly connected, or it can be detachably connected, or it can be integrated; it can be directly connected, or it can be indirectly connected through an intermediate medium (such as a pump, a valve, a liquid storage tank), it can be the communication between two elements or the interaction relationship between two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0049] In the description of the present specification, the description referring to the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. Furthermore, the person skilled in the art can combine and combine the different embodiments or examples described in the present specification and the features of the different embodiments or examples, without contradiction.

[0050] In a first aspect, the present application provides a copper raffinate resource treatment device. According to some embodiments, as shown in Figures 1 to 4 The resource treatment device includes a pretreatment unit 100, a membrane concentration unit 200, and an acid separation and recovery unit 300.

[0051] According to the present application, the pretreatment unit 100 is used for pretreating the copper raffinate to obtain pretreated water. Through the pretreatment, the oil, suspended matter and colloid in the copper raffinate can be removed, and the mechanical damage and pollution of the copper raffinate to the membrane concentration unit 200 can be reduced. According to the material flow direction, the pretreatment unit 100 includes a multi-medium filter 101, an oil removal filter 102 and a precision filter 103 connected in sequence. The membrane concentration unit 200 includes an acid-resistant reverse osmosis device 201.

[0052] According to the present application, the multi-medium filter 101 is intended to remove larger suspended particulate impurities and part of oil substances in the copper raffinate. In some embodiments, the multi-medium filter 101 is an anthracite filter or a garnet filter.

[0053] According to the present application, the oil removal filter 102 is a filter provided with an oil removal filter element to remove organic solvents and other oil phases in the raffinate after multi-medium filtration.

[0054] According to the present application, the precision filter 103 is intended to remove fine suspended matter and colloid.

[0055] Further, as shown in Figure 2 The pretreatment unit 100 further includes a raw water pump 104, a multi-medium filtrate storage tank 111, a first material conveying pump 105, an oil removal liquid storage tank 112, a second material conveying pump 106 and a booster pump 107; wherein,

[0056] The raw water pump 104 is connected with the water inlet of the multi-medium filter 101, so that the copper raffinate is pumped into the multi-medium filter 101 by the raw water pump 104;

[0057] The outlet of the multi-medium filter 101, the multi-medium filtrate storage tank 111, the inlet of the oil removal filter 102 and the first feed pump 105 are sequentially connected, so that the feed liquid treated by the multi-medium filter 101 is pumped to the oil removal filter 102 through the first feed pump 105 after being buffered in the multi-medium filtrate storage tank 111.

[0058] The outlet of the oil removal filter 102, the oil-removed liquid storage tank 112, the second feed pump 106 and the inlet of the precision filter 103 are sequentially connected, so that the feed liquid treated by the oil removal filter 102 is pumped to the precision filter 103 through the second feed pump 106 after being buffered in the oil-removed liquid storage tank 112.

[0059] The outlet of the precision filter 103, the booster pump 107 and the inlet of the acid-resistant reverse osmosis device 201 are sequentially connected, so that the feed liquid from the precision filter 103 is pressurized by the booster pump 107 and then enters the acid-resistant reverse osmosis device 201.

[0060] In some embodiments, the removal rate of colloids and suspensions in the copper raffinate is greater than or equal to 90% through the pretreatment.

[0061] According to the utility model, in the membrane concentration unit 200, the pretreated water from the pretreatment unit 100 is treated by the acid-resistant reverse osmosis device 201 to obtain reverse osmosis concentrated water (RO concentrated water) and reverse osmosis produced water (RO produced water). The copper raffinate after pretreatment (i.e., pretreatment produced water) enters the acid-resistant reverse osmosis device 201, and various ions (SO4 2- and metal ions) in the raffinate are enriched under the interception of the acid-resistant reverse osmosis membrane to obtain RO concentrated water; and most of the water molecules permeate through the acid-resistant reverse osmosis membrane under the action of pressure driving to obtain RO produced water, and the water quality of the RO produced water is close to pure water and can be used as the elution water in the acid separation and recovery unit 300.

[0062] According to the utility model, the acid-resistant reverse osmosis membrane in the acid-resistant reverse osmosis device refers to a reverse osmosis membrane that can be used for low-pH feed liquid (such as acidic wastewater), which can usually have a multi-layer composite structure, such as a polyester reinforced non-woven fabric layer at the bottom, a polysulfone porous support layer in the middle and an acid-resistant polymer layer (acid-resistant polymers such as polysulfonamide, sulfonated polymer, polyelectrolyte or triazine ring polymer) at the top. Preferably, the acid-resistant reverse osmosis membrane is a high-pressure acid-resistant reverse osmosis membrane. In some embodiments, the maximum operating pressure of the acid-resistant reverse osmosis membrane is 60-80 bar, for example, 70 bar, 80 bar, etc.

[0063] According to the utility model, the acid-resistant reverse osmosis device 201 can be a single-membrane assembly system or a multi-membrane assembly system, and the number of membrane elements in the system and the connection mode thereof can be selected according to the water treatment capacity.

[0064] In some embodiments, the acid-resistant reverse osmosis device 201 is a single membrane module system. The single membrane module system comprises a housing and a membrane module installed in the housing, and the membrane module comprises one spiral membrane element or multiple (not more than 6, for example 3, 4, 5, 6) spiral membrane elements connected in series. As shown in Figure 3 (a), the single membrane module system comprises a membrane module composed of 5 membrane elements 2011 connected in series.

[0065] In other embodiments, the acid-resistant reverse osmosis device 201 is a multiple membrane module system. The multiple membrane module system comprises a housing and multiple (such as two or more) membrane modules installed in the housing in parallel, and each membrane module is composed of multiple spiral membrane elements connected in series. As shown in Figure 3 (b), the multiple membrane module system comprises three or more membrane modules (the "..." represents optional membrane modules) connected in parallel, and each membrane module is composed of 5 membrane elements 2011 connected in series.

[0066] According to the present application, the membrane element used in the acid-resistant reverse osmosis device can be an acid-resistant spiral membrane element, for example, the AR RO1 series of permeation membrane elements of UNISOL Company, such as AR RO 4040, AR RO 8040, etc.

[0067] As some examples, when treating the pretreated product water, the operating pressure of the acid-resistant reverse osmosis device is 45-70 bar, the membrane flux is 8-10 LMH, and the product water recovery rate is 40%-60%.

[0068] According to the present application, the acid separation and recovery unit 300 comprises a resin device 301 filled with strong alkaline anion resin. The resin device 301 is provided with a first feed liquid inlet and a second feed liquid inlet; the first feed liquid inlet is connected with the concentrated water outlet of the acid-resistant reverse osmosis device 201, so that the RO concentrated water can enter the resin device 301 for acid adsorption treatment to obtain deacidification raffinate; and the second feed liquid inlet is connected with the product water outlet of the acid-resistant reverse osmosis device 201, so that the RO product water is used as elution water for acid elution treatment to obtain eluate.

[0069] According to the present application, the strong alkaline anion resin achieves the effect of blocking acid by utilizing its delayed action on acid, and can realize effective separation of acid and metal in the RO concentrated water. Acid and salt are separated by anion exchange resin based on Donnan equilibrium. During the separation process, the center of the anion resin is a positively charged group, which repels the same charged ions, i.e. metal cations, H + And when the resin separates two types of ions, the outer layer of the resin forms a chromatography membrane similar to a semi-permeable membrane, and there are a large number of H + and part of the metal ions outside the membrane, in order to maintain the charge balance on both sides of the membrane, H +The resin center and H + SO4 2- To achieve electrical neutrality, while the metal cations and small amounts of SO4 2- Will be the first out of the resin column, namely, the deacidification raffinate. After the resin is loaded with acid, the resin column can be washed with RO water to obtain a sulfuric acid solution (eluate).

[0070] As some examples, the strong basic anion resin can be A-853E product of Tulsimer Company, 201x7 anion resin, etc.

[0071] In some embodiments, the resin device 301 is a fixed bed vertical resin device, the first feed liquid inlet is located at the bottom of the resin device 301, and the second feed liquid inlet is located at the top of the resin device 302. This arrangement can on the one hand make the RO concentrated water enter the resin device from bottom to top for acid and metal ion separation; on the other hand, the RO water can enter the resin device from top to bottom as elution water to elute the acid adsorbed by the resin.

[0072] According to the present application, the first feed liquid inlet is the inlet of the RO concentrated water and the outlet of the eluate, and the second feed liquid inlet is the inlet of the RO water and the outlet of the deacidification raffinate. It can be understood that the "feed liquid inlet" can be one port or multiple ports, i.e. at least one inlet and at least one outlet. When the feed liquid inlet is one port, the pipelines of different feed liquids are connected in parallel to the inlet, and valves are provided on the corresponding pipelines to control the operation sequence of each feed liquid. When the feed liquid inlet is multiple ports, different feed liquids can be connected to their corresponding ports through pipelines to achieve the entry or discharge of the feed liquid as required.

[0073] Further, as shown in Figure 4 The acid separation and recovery unit 300 further comprises a feed pump 302 and a water pump 303, wherein the feed pump 302 is arranged on the connecting pipeline between the concentrated water outlet of the acid-resistant reverse osmosis device 201 and the first feed and discharge port, and the water pump 303 is arranged on the connecting pipeline between the concentrated water outlet of the acid-resistant reverse osmosis device 201 and the second feed and discharge port. By arranging the feed pump 302 and the water pump 303, the water inlet pressure of the RO concentrated water and the RO water can be increased respectively. The feed pump 302 and the water pump 303 may, for example, be magnetic pumps respectively.

[0074] The copper raffinate resource treatment device provided by the utility model can be directly connected through pipelines between components, or a pump and a valve can be arranged on a connecting pipeline related to a corresponding step according to the process operation condition and operation sequence requirement. For example, when the acid-resistant reverse osmosis requires a higher water inlet pressure, a booster pump can be arranged on the connecting pipeline between the water outlet of the precision filter and the water inlet of the acid-resistant reverse osmosis device, so that the pretreated water is pumped into the reverse osmosis device according to the process required water inlet pressure; for another example, when the RO concentrated water and the resolving liquid to be treated need to enter and discharge the resin device through the same inlet and outlet, respectively, valves can be arranged on the RO concentrated water outlet and the first material liquid inlet and outlet and the drain pipeline of the first material liquid inlet and outlet, respectively, to control the operation of the material liquid. In the case that the utility model introduces each treatment unit and the material treatment mode, the above-mentioned arrangement is well known in the art, and will not be described here.

[0075] According to some specific embodiments, referring to Figures 1 to 4 , the copper raffinate resource treatment device is used for the treatment process of the copper raffinate, which includes the following processes:

[0076] The copper raffinate is introduced into the pretreatment unit to remove oil, suspended matter, colloid and the like in the copper raffinate, and pretreated water is obtained;

[0077] The pretreated water is concentrated by the acid-resistant reverse osmosis device in the membrane concentration unit, and two liquids, RO concentrated liquid and RO water (also referred to as "dialysis liquid"), are obtained;

[0078] The RO concentrated liquid enters the resin device through the first material liquid inlet and outlet at the bottom, flows through the resin bed layer from bottom to top, adsorbs acid, and the deacidification raffinate is discharged from the second material liquid outlet at the top of the device;

[0079] The RO water enters the resin device through the second material liquid inlet and outlet at the top, flows through the resin bed layer in which acid is adsorbed from top to bottom, resolves acid, and the resolving liquid is discharged from the first material liquid outlet at the bottom of the device.

[0080] In the second aspect, the utility model provides a kind of copper ore processing system. As Figure 5 The processing system includes the copper raffinate resource treatment device of the first aspect of the utility model.

[0081] In some embodiments, the processing system further includes an acid leaching unit 400, and the first inlet and outlet material liquid port of the resin device is connected with the acid leaching unit 400. In this way, the obtained resolving liquid returns to the acid leaching unit, realizes the recycling of acid and the recycling of a small amount of metal contained therein, and avoids metal loss.

[0082] In some embodiments, the processing system further comprises an extraction unit 500 connected with the acid leaching unit 400, for extracting the material liquid after the acid leaching treatment to obtain a copper raffinate.

[0083] In some embodiments, the processing system further comprises an electrodeposition unit 600 connected with the extraction unit 400, for electrodeposition treatment of the crude copper material generated by the acid leaching treatment to produce electrodeposition copper.

[0084] In some embodiments, the processing system further comprises a metal recovery unit 700 comprising a de-ironing unit 710, a copper precipitation unit 720 and a cobalt precipitation unit 730 connected in sequence. The second inlet and outlet of the resin device 301 is connected with the de-ironing unit 710, so that the de-acid raffinate can be sequentially subjected to de-ironing, copper precipitation and cobalt precipitation treatment. Generally, the de-ironing process can include adjusting the pH of the de-acid raffinate to 3.5-4 using a neutralizing agent (such as lime); the copper precipitation process can include adjusting the pH of the de-ironed material liquid to 5.5-6 using a neutralizing agent (such as lime); and the cobalt precipitation process can include adjusting the pH of the copper precipitated material liquid to 7.8-8.5 using a neutralizing agent (such as magnesium oxide).

[0085] Further, the processing system further comprises a heavy metal impurity removal unit 800 connected with the cobalt precipitation unit 730, so that the material liquid obtained by the cobalt precipitation unit can be subjected to heavy metal impurity removal treatment to obtain the required effluent water. Generally, the heavy metal impurity removal process can include treating with a neutralizing agent (such as lime) to remove impurities such as Mn in the heavy metal.

[0086] In the processing system of the present application, the first aspect of the resource processing device is used to effectively separate the acid and the salt in the copper raffinate, and at the same time of recycling the sulfuric acid in the raffinate, the small amount of valuable metal ions (Cu, Co) contained in the acid can also be returned to the system with the reuse of the acid, and the whole process basically does not cause the loss of valuable metal ions. In some embodiments, the valuable metals (Cu, Co) in the de-acid raffinate are recovered by copper precipitation and cobalt precipitation, and the remaining metal ions can also be removed from the system through the segmented neutralization process, the alkali consumption in the neutralization process can be greatly reduced, and at the same time, the water volume requirement of the system is also guaranteed, which helps to solve the problem of water swelling of the system.

[0087] Additional aspects and advantages of the present application will be partially given in the following description, some of which will become apparent from the following description, or will be understood through practice of the present application.

[0088] The following describes the embodiments of the present application. The embodiments described below are exemplary and are only used to explain the present application, and cannot be understood as a limitation of the present application.

[0089] Embodiments 1-3 are combined Figures 1 to 5 The process for treating copper raffinate using the resource recovery device of the present application and the application effect thereof on the entire treatment system are described, wherein,

[0090] The acid-resistant reverse osmosis device is a single-component system using an acid-resistant spiral membrane element, and the membrane element is AR RO1 4040 of UNISOL company, and the maximum operating pressure is 80 bar.

[0091] Resin device: a fixed bed vertical resin device is used, and the strong basic anion resin filled in the resin device is A-853E of Du Sheng company, the first inlet and outlet of the resin device is located at the bottom of the device, and is used for introducing RO concentrated water and discharging eluate; the second inlet and outlet is located at the top of the device, and is used for introducing RO product water and discharging deacidification raffinate.

[0092] The calculation formula of the acid recovery rate of the device is:

[0093] Acid recovery rate = [total acid content (T2) of the eluate recovered by the device per day / total acid content (T1) of the copper raffinate treated by the device per day] x 100%.

[0094] Embodiment 1

[0095] The copper raffinate of a certain copper hydrometallurgy plant in Congo (Kinshasa) is taken as the treated liquid.

[0096] Pretreatment: the treated liquid is sequentially subjected to the pretreatment process of the anthratlite filter, the oil removal filter and the precision filter to remove impurities such as oil, colloid and suspended matter in the solution, and the pretreated product water is obtained;

[0097] High-pressure reverse osmosis concentration treatment: the pretreated product water is pumped into the acid-resistant reverse osmosis device for concentration separation, and RO concentrated liquid and RO product water are obtained, in the concentration process, the recovery rate is controlled at 55%, the membrane flux is maintained at 8 LMH, and the system operating pressure is 65 bar;

[0098] Acid separation and recovery treatment: the RO concentrated liquid is used as the feed liquid of the resin device, the single feed volume is 1.2 BV (600 L), the feed flow rate is 4 BV / h (2 m 3 / h), and the acid-resistant reverse osmosis device is used for the acid separation and recovery treatment, and the deacidification raffinate is obtained;

[0099] The RO product water is used as the elution water of the resin device, the single feed volume of the elution water is 1.4 BV (700 L), the elution flow rate is 4 BV / h (2 m 3 / h), and the acid is eluted by the magnetic pump from top to bottom, and the eluate is obtained. The related liquid water quality is shown in Table 1.

[0100] Table 1

[0101]

[0102] Note: The metal concentration refers to the concentration of metal ions.

[0103] The treatment capacity of the acid-resistant reverse osmosis device was 10 m 3 / d, and the reverse osmosis water production was 5.5 m 3 / d, and the reverse osmosis concentrated water was 4.5 m 3 / d; after treatment by the resin device, 4.5 m 3 / d of deacidification raffinate and 5.5 m 3 / d of elution solution were obtained.

[0104] As can be seen from Table 1, the acid-resistant reverse osmosis concentration treatment has a H2SO4 interception rate of 89.64%, a Cu interception rate of 98.64%, a Co interception rate of 97.92%, and a Fe interception rate of 97.8%, and both the acid and the metal are enriched; the deacidification rate of the resin device is 86.12%, which can greatly save the amount of neutralizing agent used in the subsequent staged neutralization process (iron removal + copper precipitation + cobalt precipitation + metal impurity removal), and the metal in the deacidification raffinate is enriched, which helps to improve the recovery efficiency of Co and other metals.

[0105] The H2SO4 recycling rate in the raffinate of the device was calculated as follows:

[0106] T1 = 10 m 3 / d x 20.18 g / L = 201.8 kg / d; T2 = 5.5 m 3 / d x 31.99 g / L = 175.945 kg / d;

[0107] (T2 / T1) x 100% = 87.19%.

[0108] As can be seen, the H2SO4 recycling rate in the raffinate of the entire treatment system including the resource treatment device is 87.19%, which avoids the waste of acid resources.

[0109] In addition, the deacidification raffinate of the entire treatment system including the resource treatment device is 4.5 m 3 / d, and after the part of the raffinate enters the subsequent process to recover the corresponding metal, it is discharged outside the system, and the water discharged from the system accounts for 45% of the system treatment capacity, which will effectively avoid the problem of water expansion and impurity enrichment in the system.

[0110] Example 2

[0111] Congo (DRC) cobalt-containing copper raffinate from a certain copper hydrometallurgical smelter was taken as the treated liquid.

[0112] Pretreatment: the liquid to be treated is sequentially subjected to a filter with anthracite, an oil removal filter and a precision filter to remove oil, colloid and suspended impurities in the solution to obtain pretreated water;

[0113] High-pressure reverse osmosis concentration treatment: the pretreated water is pumped into an acid-resistant reverse osmosis device for concentration separation to obtain RO concentrate and RO water, wherein the recovery rate is controlled at 50% during the concentration process, the membrane flux is maintained at 8 LMH, and the system operating pressure is 62 bar;

[0114] Acid separation and recovery treatment: the RO concentrate is used as the feed liquid of the resin device, the single feed volume is 1.2 BV (600 L), the feed flow rate is 4 BV / h (2 m 3 / h), the acid is separated from the resin device from bottom to top by a magnetic pump, and the deacidification raffinate is obtained by adsorbing the acid by a strong alkaline anion exchange resin;

[0115] The RO water is used as the elution water of the resin device, the single feed volume of the elution water is 1.2 BV (600 L), the elution flow rate is 4 BV / h (2 m 3 / h), the acid is eluted from the resin device from top to bottom by a magnetic pump, and the elution liquid is obtained. The relevant liquid water quality is shown in Table 2.

[0116] Table 2

[0117]

[0118] Note: The metal concentration refers to the metal ion concentration.

[0119] The treatment capacity of the acid-resistant reverse osmosis device is 11.5 m 3 / d, the reverse osmosis water is 5.75 m 3 / d, the reverse osmosis concentrated water is 5.75 m 3 / d, the deacidification raffinate is 5.75 m 3 / d, and the elution liquid (sulfuric acid solution) is 5.75 m 3 / d after the resin device treatment;

[0120] As can be seen from Table 2, the H2SO4 retention rate of the acid-resistant high-pressure reverse osmosis concentration treatment is 90%, the Cu retention rate is 97.62%, the Co retention rate is 97.76%, and the Fe retention rate is 98.03%, and the acid and the metal are enriched; the deacidification rate of the resin device is 77.16%, which can greatly save the neutralizing agent usage in the subsequent staged neutralization process (iron removal + copper precipitation + cobalt precipitation + metal impurity removal), and the metal in the deacidification raffinate is enriched, which helps to improve the recovery efficiency of Co and other metals.

[0121] The H2SO4 recycling rate in the resin device raffinate is calculated as follows:

[0122] T1 = 11.5m 3 / d×21.18g / L=243.57kg / d; T2=5.75m3 / d×32.73g / L=188.2kg / d;

[0123] (T2 / T1)×100%=77.27%;

[0124] It can be seen that the H2SO4 recovery rate in the raffinate of the entire treatment system, including the resource recovery device, reaches 77.27%, thus avoiding the waste of acid resources.

[0125] In addition, the deacidification extraction residue of the entire processing system, including this resource recovery unit, is 5.75m. 3 / d, after the raffinate enters the subsequent process of the treatment system to recover the corresponding metals, it is discharged from the system. The amount of water discharged from the system accounts for 50% of the system's processing capacity, which will effectively avoid the problems of water expansion and impurity accumulation in the system.

[0126] Example 3

[0127] Cobalt-containing copper raffinate from a hydrometallurgical copper smelting plant in the Democratic Republic of Congo was used as the liquid to be treated.

[0128] Pretreatment: The liquid to be treated is sequentially passed through an anthracite filter, an oil removal filter, and a precision filter to remove oil, colloids, and suspended impurities from the solution, resulting in pretreated permeable water;

[0129] High-pressure reverse osmosis concentration treatment: The pretreated permeate is pumped into the acid-resistant reverse osmosis unit for concentration and separation to obtain RO concentrate and RO permeate. During the concentration process, the recovery rate is controlled at 50%, the membrane flux is maintained at 12 LMH, and the system operating pressure is 45 bar.

[0130] Acid separation and recovery treatment: RO concentrate is used as feed liquid for the resin unit, with a single feed volume of 1.2 BV (600 L) and a feed flow rate of 4 BV / h (2 m³ / h). 3 / h), the acid is pumped from bottom to top into the resin device by a magnetic pump, and the acid is adsorbed by a strong basic anion exchange resin to obtain the deacidified raffinate.

[0131] The RO permeate is used as the stripping water for the resin unit. The single feed volume of the stripping water is 1.2 BV (600 L), and the stripping flow rate is 4 BV / h (2 m³ / h). 3 The acid is pumped from top to bottom into the resin unit via a magnetic pump ( / h) to decompose the acid and obtain the eluent. The relevant feed solution water quality is shown in Table 3.

[0132] Table 3

[0133]

[0134] Note: The metal concentration refers to the concentration of metal ions.

[0135] The treatment capacity of the acid-resistant high-pressure reverse osmosis device was 17 m 3 / d, and the reverse osmosis water was 8.5 m 3 / d, and the reverse osmosis concentrated water was 8.5 m 3 / d; after treatment by the resin device, 8.5 m 3 / d of deacidification raffinate and 8.5 m 3 / d of elution liquid (sulfuric acid solution) were obtained.

[0136] As can be seen from Table 3, the acid-resistant high-pressure reverse osmosis concentrated H2SO4 rejection rate was 90%, the Cu rejection rate was 98.18%, the Co rejection rate was 98.51%, and the Fe rejection rate was 97.9%, and the acid and metals were enriched; the deacidification rate of the resin device was 82.26%, which can greatly save the neutralizing agent consumption in the subsequent staged neutralization process (iron removal + copper precipitation + cobalt precipitation + metal impurity removal), and the metals in the deacidification raffinate are enriched, which helps to improve the recovery efficiency of Co and other metals.

[0137] The H2SO4 recycling rate in the raffinate of the device was calculated as follows:

[0138] T1 = 17 m 3 / d x 10.89 g / L = 185.13 kg / d; T2 = 8.5 m 3 / d x 17.82 g / L = 151.47 kg / d;

[0139] (T2 / T1) x 100% = 81.82%;

[0140] As can be seen, the H2SO4 recycling rate in the raffinate of the device is 81.82%, which avoids the waste of acid resources in the system.

[0141] In addition, the deacidification raffinate of the entire treatment system including the resource treatment device is 8.5 m 3 / d, and this part of the raffinate will be discharged from the system after recovering the corresponding metals in the subsequent process, and the water discharged from the system accounts for 50% of the system treatment capacity, which will effectively avoid the water expansion problem and impurity enrichment problem of the system.

[0142] It should be finally pointed out that: the above examples are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application, and they should all be covered in the scope of the claims and the specification of the present application. In particular, as long as there is no structural conflict, the various technical features mentioned in the embodiments can be combined in any way. The present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

Claims

1. A device for the resource recovery of copper raffinate, characterized in that, The device comprises a pretreatment unit, a membrane concentration unit and an acid separation and recovery unit. The pretreatment unit is used for pretreating the copper raffinate to obtain pretreated water and comprises a multi-medium filter, an oil removal filter and a precision filter connected in sequence. The membrane concentration unit comprises an acid-resistant reverse osmosis device used for reverse osmosis treatment of the pretreated water to obtain reverse osmosis concentrated water and reverse osmosis water, and the water inlet of the acid-resistant reverse osmosis device is connected with the water outlet of the precision filter. The acid separation and recovery unit comprises a resin device filled with strong basic anion resin, and the resin device is provided with a first feed liquid inlet and a second feed liquid inlet. The first feed liquid inlet is connected with the concentrated water outlet of the acid-resistant reverse osmosis device, so that the reverse osmosis concentrated water can enter the resin device for acid adsorption treatment to obtain deacidification raffinate. The second feed liquid inlet is connected with the water outlet of the acid-resistant reverse osmosis device, so that the reverse osmosis water can be used as elution water for acid elution treatment to obtain elution liquid.

2. The resource processing apparatus of claim 1, wherein, The acid-resistant reverse osmosis device comprises an acid-resistant reverse osmosis membrane, and the maximum operating pressure of the acid-resistant reverse osmosis membrane is 60-80 bar.

3. The resource processing apparatus of claim 1, wherein, The acid-resistant reverse osmosis device is a single membrane module system, wherein the single membrane module system comprises a shell and a membrane module installed in the shell, and the membrane module comprises one or a plurality of series-connected spiral membrane elements.

4. The resource processing apparatus of claim 1, wherein The acid-resistant reverse osmosis device is a multi-membrane module system, wherein the multi-membrane module system comprises a shell and a plurality of parallel membrane modules installed in the shell, and each membrane module is formed by a plurality of series-connected spiral membrane elements.

5. The resource processing apparatus of claim 1, wherein, The multi-medium filter is an anthracite filter or a garnet filter.

6. The resource processing apparatus of claim 1, wherein The resin device is a fixed bed vertical resin device, the first feed liquid inlet is located at the bottom of the resin device, and the second feed liquid inlet is located at the top of the resin device.

7. A system for the treatment of copper ore material, characterized in that The device for resourceful treatment of the copper raffinate of any one of claims 1-6.

8. The processing system of claim 7, wherein, The device further comprises an acid leaching unit, the first feed liquid inlet of the resin device is further connected with the acid leaching unit, so that the elution liquid is used for acid leaching treatment of copper ore; The treatment system further comprises an extraction unit connected with the acid leaching unit, which is used for extracting the obtained liquid after acid leaching treatment to obtain copper raffinate.

9. The processing system according to claim 7 or 8, characterized in that The device further comprises a metal recovery unit, the metal recovery unit comprises a deironing unit, a copper precipitation unit and a cobalt precipitation unit connected in sequence, and the second feed liquid inlet of the resin device is further connected with the deironing unit, so that the deacidification raffinate can be sequentially subjected to deironing, copper precipitation and cobalt precipitation.

10. The processing system of claim 9, wherein, The device further comprises a heavy metal impurity removal unit connected with the cobalt precipitation unit, so that the liquid obtained from the cobalt precipitation unit can be subjected to heavy metal impurity removal treatment to obtain water.

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