CN216513279U - Hydrometallurgy extraction piece-rate system runs off online recovery unit of organic phase - Google Patents
Hydrometallurgy extraction piece-rate system runs off online recovery unit of organic phase Download PDFInfo
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Abstract
The utility model discloses an online recovery device for a lost organic phase of a hydrometallurgy extraction separation system, which comprises a product water phase or waste water phase lost organic phase recovery sub-device and a lost organic phase recovery sub-device in acid mist waste gas; wherein, the upper inlets of the fiber ball adsorption tower and the active carbon adsorption tower are respectively connected with a liquid carbon dioxide pipeline with a flowmeter; the bottom valves of the fiber ball adsorption tower and the active carbon adsorption tower are connected with an organic matter recovery tank. The method adopts an online recovery process in the main organic phase loss link of the hydrometallurgy extraction separation system, thereby not only ensuring the purity of the product, removing water pollution and atmospheric pollution, recovering the extractant, avoiding frequent replacement of the adsorption material, ensuring that the production process is more stable and environment-friendly, and obviously improving the production efficiency. The utility model adopts the supercritical carbon dioxide extraction technology, so that the recovered organic matters can be completely returned to the system for reuse without chemical change.
Description
Technical Field
The utility model belongs to the technical field of wet metallurgy, relates to an extraction separation system, and particularly relates to an online recovery device for lost organic phases of a wet metallurgy extraction separation system.
Background
Hydrometallurgy is a metallurgical technology which is rapidly developed during world war ii as an independent technology, and because traditional pyrometallurgy cannot be adopted when some mineral substances such as uranium and the like are extracted, separation and purification can be carried out only in chemical solution, and the method for extracting metals is hydrometallurgy. In recent decades, with the development of rare earth and nonferrous metal industries, people have higher and higher requirements on the purity and the accurate proportion of materials, the separation technology of similar metals develops very rapidly, and particularly, the extraction separation technology is utilized to ensure that the purity of the metals is higher and the proportion of alloy materials is more accurate, so that more excellent new materials, such as corrosion-resistant and high-temperature-resistant alloys, power battery anode materials and the like, are produced. However, in hydrometallurgical extraction separation processes a considerable portion of the organic extractant is lost with the aqueous phase, which on the one hand increases the production costs and on the other hand affects the product quality and causes environmental pollution. The lost organic phase mainly goes to three aspects, firstly, along with the loss of the product phase, the product is dissolved in water in a certain salt form such as sulfate after separation is finished, and then the next procedure is carried out, wherein the organic matters emulsified and dissolved in the product solution are usually firstly demulsification to remove bright oil, then oil removing materials such as fiber balls are used for absorbing and emulsifying and dissolving a part of organic phase in the water phase, and then a large amount of active carbon is used for carrying out deep treatment; on the other hand, the organic phase lost with the wastewater is high-salinity wastewater with the salt content of more than 5 percent, such as wastewater containing sodium sulfate, the COD (chemical oxygen demand) is usually as high as more than 2000mg/L, although the concentration of the organic matters lost in the wastewater is not high, the total amount of the organic phase lost is considerable due to the large amount of the wastewater in the extraction section; the third aspect is the organic phase which volatilizes along with the acid mist, because the extraction usually repeatedly carries out acid-base reaction at a certain temperature so as to selectively distribute metal ions in the water phase and the organic phase, and the acid mist is generated, the current mature extraction equipment is a polyvinyl chloride plastic tank, and absolute sealing cannot be realized, so that the acid mist in the extraction tank needs to be organized to be led out of a system in order to improve the operating environment, and thus, a part of solvent is volatilized to cause pollution of VOCs (volatile organic compounds).
Regarding the organic phase lost during the extraction process, which is not currently recovered efficiently by the production units, in fact this part of the organic phase is still a good raw material, only dissolved in the aqueous phase or volatilized, which is regarded as an impurity, waste, pollutant by some means in view of the product quality and the environmental pressures, which on the one hand results in the loss of expensive extractant, and more importantly as a waste disposal which is labour and time consuming and which generates new pollution, in fact converting one form of pollution into another environmentally acceptable form.
The series of problems finally cause the loss of a large amount of extraction organic phase, the product purity is not high, the wastewater treatment difficulty is high, the waste residue amount is large, the waste salt is difficult to dispose, the whole process is difficult to realize the automation completely, the labor intensity of workers is high, the production efficiency is low, the cost is high, and the improvement of the wet metallurgy capacity and the modernization of the production are severely restricted. To address these problems, many modifications have been made by those skilled in the art of hydrometallurgy.
Wuqing Han et al systematically introduced the organic phase loss and corresponding disposal method in the extraction section of the hydrometallurgy industry at present in the text of 'analysis and prevention of pollution sources of nickel and cobalt hydrometallurgy' (J, world nonferrous metals, 2019, 3 months, P4-8), generally adopt methods such as emulsion breaking phase separation, fiber ball adsorption and the like to recover organic matters as far as possible for emulsified organic phases, but for volatile organic matters and organic matters dissolved in water phase (product phase and waste water phase), the common process is to regard the organic matters as pollutants and use activated carbon adsorption or use other methods to oxidize and decompose the organic matters, thereby achieving the purpose of reducing COD and VOCs.
Chinese patents with application numbers of CN201910255859.X, CN201811419673.5, CN201810909767.4, CN201510684466.2 and the like disclose a method for treating hydrometallurgy wastewater, which mainly comprises the steps of carrying out oxidative decomposition on organic matters dissolved in high-salt wastewater by means of electrocatalytic oxidation, ozone oxidation, hydrogen peroxide oxidation and the like, and even carrying out deep treatment by adsorption on activated carbon after oxidation, so that COD (chemical oxygen demand) in the water is reduced to prepare for next desalting.
Chinese patents CN201820163953.3, CN201810091845.4, etc. disclose oil-containing acid mist treatment processes in hydrometallurgical extraction process, mainly adopt alkaline water to absorb and neutralize, and then perform oil-water separation, the method has better treatment effect on acid mist, but is not ideal for volatile oil treatment, on one hand, the purpose of treating VOCs cannot be achieved, and in addition, COD in absorption wastewater is increased, so that VOCs pollution is changed into water pollution, and the treatment cost is increased.
In the prior art, the hydrometallurgy extraction separation process can not realize the whole-process continuity, the organic impurities in the products are high, the COD in the waste water is high, the VOCs in the acid mist exceeds the standard, and the like, which influence the production cost and the quality of the products.
Through the technical analysis reported in the prior art, the methods in the prior art have a wrong area, namely the organic phases emulsified and dissolved in the water phase or volatilized along with acid mist are regarded as impurities and wastes and abandoned for recycling, the starting point is wrong, the treatment method is not ideal, and in fact, the organic phases are still good raw materials, if the organic phases can be effectively recycled and returned to a system for reuse, the production cost is reduced, and the pollution problem is also solved.
Disclosure of Invention
Aiming at the defects in the prior art, the utility model aims to provide an online recovery device for the loss organic phase of a hydrometallurgy extraction separation system, and solve the technical problem that the organic phase is not recovered in the hydrometallurgy extraction separation process in the prior art.
In order to solve the technical problems, the utility model adopts the following technical scheme:
an online recovery device for a lost organic phase of a hydrometallurgy extraction separation system comprises a product water phase or waste water phase lost organic phase recovery sub-device and a lost organic phase recovery sub-device in acid mist waste gas;
the product water phase or waste water phase loss organic phase recovery device comprises a temporary storage tank connected with a product water phase or waste water phase pipeline in a hydrometallurgy extraction separation system, the temporary storage tank is connected with a liquid inlet of an ultrasonic emulsion breaker through a water pump, a liquid outlet of the ultrasonic emulsion breaker is connected with a feed inlet of a super oleophobic hydrophilic membrane separator, an organic phase outlet at the upper end of the super oleophobic hydrophilic membrane separator is connected with an organic phase collecting tank, a water phase outlet at the lower end of the super oleophobic hydrophilic membrane separator is connected with a bottom valve of a fiber ball adsorption tower, a discharge port at the upper end of the fiber ball adsorption tower is connected with a bottom valve of a first active carbon adsorption tower, and a discharge port at the upper end of the first active carbon adsorption tower is connected with a pipeline of the next process in the hydrometallurgy extraction separation system;
the upper end inlets of the fiber ball adsorption tower and the first active carbon adsorption tower are respectively connected with a first liquid carbon dioxide pipeline with a first flowmeter; the bottom valve of the fiber ball adsorption tower is connected with a first organic matter recovery tank, and the bottom valve of the first activated carbon adsorption tower is connected with a second organic matter recovery tank;
the acid mist waste gas loss organic phase recovery sub-device comprises a second activated carbon adsorption tower, wherein a bottom valve of the second activated carbon adsorption tower is used for being connected with a pipeline of acid mist waste gas in an induced draft system in a hydrometallurgy extraction separation system, and a discharge port at the upper end of the second activated carbon adsorption tower is connected with a pipeline of an acid mist absorption process in the hydrometallurgy extraction separation system;
an inlet at the upper end of the second activated carbon adsorption tower is connected with a second liquid carbon dioxide pipeline with a second flowmeter; and a bottom valve of the second activated carbon adsorption tower is connected with a third organic matter recovery tank.
The utility model also has the following technical characteristics:
and a return pipe is also arranged between the ultrasonic demulsifying device and the temporary storage tank.
And the upper end inlets of the fiber ball adsorption tower and the first active carbon adsorption tower are respectively communicated with a first gaseous carbon dioxide pipeline.
The fiber ball adsorption tower, the first active carbon adsorption tower and the second active carbon adsorption tower are all arranged in parallel one by one and one by two.
And an inlet at the upper end of the second activated carbon adsorption tower is also connected with a second gaseous carbon dioxide pipeline.
The fiber ball adsorption tower, the first active carbon adsorption tower, the second active carbon adsorption tower, the first organic matter recovery tank, the second organic matter recovery tank and the third organic matter recovery tank are respectively provided with a temperature control jacket, a thermometer, a pressure gauge, a safety valve and/or an emptying valve, and a heating belt is arranged behind the emptying valve.
Compared with the prior art, the utility model has the following technical effects:
in the utility model, an online recovery process is adopted in the main organic phase loss links (product water phase, raffinate, saponification wastewater and acid mist system) of the hydrometallurgy extraction separation system, so that the purity of the product is ensured, water pollution and air pollution are removed, the extractant is recovered, frequent replacement of the adsorption material is avoided, the production process is more stable and environment-friendly, and the production efficiency is obviously improved.
The utility model adopts ultrasonic demulsification and super oleophobic hydrophilic membrane separation technology to fully separate emulsified and insoluble organic phases, thereby reducing the pressure and saturation frequency of an adsorption link, and compared with the traditional separation technology which utilizes the difference of specific gravity, the super oleophobic hydrophilic membrane separation technology is more thorough in separation and is not influenced by an oil-water interface.
The utility model (III) adopts the supercritical carbon dioxide extraction technology, so that the recovered organic matters can be completely returned to the system for reuse without chemical change.
(IV) the utility model has better product quality because the organic phase is recycled thoroughly, and COD and VOCs in the waste water and the waste gas directly meet the requirements of the next procedure.
(V) the regeneration effect of the supercritical carbon dioxide on the adsorption material fiber balls and the activated carbon is superior to that of other regeneration technologies.
Drawings
FIG. 1 is a schematic diagram of the structure of a product water phase or waste water phase loss organic phase recovery sub-unit according to the present invention.
FIG. 2 is a schematic diagram of the structure of the recovery sub-device for the loss of organic phase in the acid mist waste gas.
The meaning of the individual reference symbols in the figures is: 1-a product water phase or waste water phase loss organic phase recovery sub-device, 2-a product water phase or waste water phase loss organic phase recovery sub-device, 3-a product water phase or waste water phase pipeline, 4-a next procedure pipeline, 5-an acid mist waste gas pipeline in an induced air system, and 6-an acid mist absorption procedure pipeline;
101-a temporary storage tank, 102-a water pump, 103-an ultrasonic emulsion breaker, 104-an ultra-oleophobic hydrophilic membrane separator, 105-an organic phase collecting tank, 106-a fiber ball adsorption tower, 107-a first activated carbon adsorption tower, 108-a first flowmeter, 109-a first liquid carbon dioxide pipeline, 110-a first organic matter recovery tank, 111-a second organic matter recovery tank, 112-a return pipe and 113-a first gaseous carbon dioxide pipeline;
201-a second activated carbon adsorption tower, 202-a second flowmeter, 203-a second liquid carbon dioxide pipeline, 204-a third organic matter recovery tank, 205-a second gaseous carbon dioxide pipeline.
The present invention will be explained in further detail with reference to examples.
Detailed Description
From the above background analysis, there are three major aspects of hydrometallurgical extraction stage organic phase loss. The organic phase lost along with the water phase of the product enters the product, which inevitably affects the product quality, and the organic phase can only be treated by a physical method which can not generate secondary pollution to the product, so that the aim of removing organic impurities is successfully achieved by the combined adsorption of oil absorption resin such as fiber balls and activated carbon in industry, but the regeneration process of the oil absorption resin is relatively complicated, the replaced resin is generally regenerated by methods such as distillation, the waste activated carbon is treated as waste by a qualification unit, the labor and the time are wasted, the cost is higher, and the problem of recovering the lost organic phase is not fundamentally solved. The organic phase lost with the wastewater is mainly dissolved organic matters, because the pH value of the wastewater is generally close to neutral, the phosphate extractant is dissolved in the water in the form of sodium salt, the extractant cannot be recovered through oil-water separation, and the added concentration is relatively low, the wastewater amount is relatively large, the production unit generally treats the phosphate extractant as waste, but the high-salt wastewater cannot be treated by a low-cost method such as biochemistry and the like, and can only be treated by an oxidation decomposition method such as electrochemical oxidation, ozone oxidation, hydrogen peroxide oxidation and the like, so that the treatment cost is greatly increased, in fact, if the pH value of the wastewater is adjusted to be about 3.5, the effect of adsorbing the organic matters in the wastewater by using the active carbon is very good, like removing the organic matters in the product, COD can be reduced from thousands of mg/L to below 50mg/L, because the extractant is reduced to the original state from the state of the sodium salt at the pH value of 3.5, the adsorption efficiency of the activated carbon is the best at the moment, and can reach more than 98%, but the amount of the waste activated carbon generated by the larger waste water amount is also larger, and the disposal cost is also higher, which is also the reason that production units are not willing to adopt the method. The organic matter volatilized with the acid mist is mainly solvent kerosene, only part of kerosene can be condensed by an alkali liquor absorption method for treating the acid mist, part of VOCs still do not reach the standard, and COD in absorbed water exceeds the standard, so that the conventional method firstly uses activated carbon to absorb volatile oil, then uses alkali water to absorb the acid mist, and the waste activated carbon is difficult to regenerate by methods such as steam heating and the like due to the high boiling point of the adsorbed kerosene and can only be discarded.
From the analysis, the adsorption of the adsorption fiber balls and the activated carbon for the three lost organic phases can meet the requirements of product quality and environmental protection, but the adsorption capacity of the adsorption fiber balls and the activated carbon is limited, the adsorption fiber balls and the activated carbon are saturated and failed soon and need to be replaced, and the disposal of the replaced adsorption fiber balls and the replaced activated carbon becomes a problem. In fact, the organic matter dispersed and dissolved in the water phase mainly has two states, one is oil drops with different grain diameters emulsified in the water phase; the other is organic matter dissolved in the aqueous phase. The method is characterized in that emulsion breaking split phases are used for recovering partial organic matters in water as much as possible for emulsified organic matters, so that the replacement frequency of adsorption fiber balls and activated carbon is reduced, and for the fiber balls and the activated carbon which are saturated in adsorption, if the fiber balls and the activated carbon can be regenerated, the on-line regeneration can be realized, and meanwhile, the key for solving the problems is realized by recovering lost organic matters. As for the emulsified organic phase, common emulsion breaking methods include an ultrasonic method, an air floatation method and a chemical emulsion breaker, the simplest and most simple method without secondary pollution is the ultrasonic method, but ultrasonic is not absolute, and the method can break emulsion and accelerate the emulsification, so that the frequency and the residence time are generally controlled to only enable small oil drops to be aggregated into large oil drops, and then a part of organic phase is separated by utilizing the specific gravity difference, but the separation is not very thorough, and the oil-water interface is not well judged. With respect to adsorbent fiber ball regeneration, the data show that distillation is the primary method, and although it is feasible, on-line regeneration requires separate disposal instead, which is labor and time consuming. The regeneration of waste activated carbon is usually carried out by heating, activating and regenerating with steam or high-temperature roasting, and the organic substances used for extraction are all high boiling point substances which cannot be activated by heating with steam, so that the purpose of activating and regenerating can be achieved by oxidizing, decomposing and adsorbing the organic substances by roasting at high temperature, but the investment and operation cost is high, and the purpose of recovering the lost organic phase is not achieved, so that the method is not preferable.
The utility model provides an online recovery device and process for lost organic phase of a hydrometallurgy extraction separation system, aiming at the defects of the prior art and process, especially aiming at the higher requirements on quality, safety, environmental protection and industrial automation in the current economic form. Firstly, ultrasonic oscillation demulsification is adopted, then a super-oleophobic hydrophilic membrane is adopted, more than 95% of oil drops can be separated on line, the residual oil drops and dissolved organic matters are absorbed by the combination of adsorption fiber balls and activated carbon, and only one of the oil drops can be used according to working conditions. The adsorption process adopts A, B line combination without stopping production, and utilizes supercritical carbon dioxide extraction technology to recover the lost organic matters adsorbed on the fiber balls and the active carbon on line, and achieves on-line activation adsorptionThe purpose of the fiber balls and the activated carbon is to make them reusable. The supercritical carbon dioxide extraction technology is adopted to elute organic matters such as extractant, solvent kerosene and the like from the adsorption fiber balls and the active carbon at room temperature, the organic matters can not be destroyed and can be returned to the system for reuse, the purpose of regenerating and adsorbing the fiber balls and the active carbon can be completely achieved due to the super-strong solubility and penetrability of the supercritical carbon dioxide, and even the adsorption capacity of the regenerated fiber balls and the active carbon is stronger. The product quality treated by the process is better, the oil content of the treated product solution is less than 0.5ppm, the COD is less than 30mg/L, the COD in the waste water can be reduced to be below 30mg/L, and the VOCs in the waste gas can be reduced to be 50mg/m3The following. The whole process of the process is to operate liquid phase or gas phase fluid, so that automation is very easy to realize, and a foundation is laid for online recovery of lost organic phase.
According to the utility model, the supercritical carbon dioxide extraction technology is adopted in the hydrometallurgy extraction separation system to recover the lost organic phase on line, the whole process can realize automatic production control, the production efficiency is improved, more importantly, the lost raw materials are recovered, the production cost is reduced, the product quality is improved, and meanwhile, the COD of the waste water and the VOCs in the waste gas are reduced to the level required by environmental protection.
It should be noted that carbon dioxide is in a non-gaseous and non-liquid state at a temperature above 31.1 ℃ and a pressure above 7.39MPa, which is a supercritical state, and is a supercritical carbon dioxide fluid.
It is to be noted that all components and equipment in the present invention, unless otherwise specified, all employ components and equipment known in the art, for example, a hydrometallurgical extraction separation system as known in the art. The organic phase in the utility model is the common organic phase in a hydrometallurgy extraction separation system. Valves are arranged on all the pipelines.
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1:
the embodiment provides an online recovery device for a lost organic phase of a hydrometallurgy extraction separation system, which comprises a product water phase or waste water phase lost organic phase recovery sub-device 1 and/or a lost organic phase recovery sub-device 2 in acid mist waste gas.
As shown in fig. 1, the organic phase recycling device 1 for product water phase or waste water phase loss comprises a temporary storage tank 101 connected to a pipeline 3 of the product water phase or waste water phase in the hydrometallurgy extraction separation system, the temporary storage tank 101 is connected to a liquid inlet of an ultrasonic emulsion breaker 103 through a water pump 102, a liquid outlet of the ultrasonic emulsion breaker 103 is connected to a feed inlet of a superoleophobic hydrophilic membrane separator 104, an organic phase outlet at the upper end of the superoleophobic hydrophilic membrane separator 104 is connected to an organic phase collecting tank 105, a water phase outlet at the lower end of the superoleophobic hydrophilic membrane separator 104 is connected to a bottom valve of a fiber ball adsorption tower 106, a discharge outlet at the upper end of the fiber ball adsorption tower 106 is connected to a bottom valve of a first activated carbon adsorption tower 107, and a discharge outlet at the upper end of the first activated carbon adsorption tower 107 is connected to a pipeline 4 of a next process in the hydrometallurgy extraction separation system;
the upper inlets of the fiber ball adsorption tower 106 and the first activated carbon adsorption tower 107 are respectively connected with a first liquid carbon dioxide pipeline 109 with a first flow meter 108; the bottom valve of the fiber ball adsorption tower 106 is connected with a first organic matter recovery tank 110, and the bottom valve of the first activated carbon adsorption tower 107 is connected with a second organic matter recovery tank 111;
as shown in fig. 2, the lost organic phase recovery sub-device 2 in the acid mist waste gas comprises a second activated carbon adsorption tower 201, a bottom valve of the second activated carbon adsorption tower 201 is used for being connected with a pipeline 5 of the acid mist waste gas in an induced draft system in the hydrometallurgy extraction separation system, and a discharge port at the upper end of the second activated carbon adsorption tower 201 is connected with a pipeline 6 of an acid mist absorption process in the hydrometallurgy extraction separation system;
the inlet at the upper end of the second activated carbon adsorption tower 201 is connected with a second liquid carbon dioxide pipeline 203 with a second flow meter 202; the bottom valve of the second activated carbon adsorption tower 201 is connected with a third organic matter recovery tank 204.
In a preferred embodiment, a return pipe 112 is further provided between the ultrasonic demulsifying device 103 and the temporary storage tank 101.
As a preferable scheme of this embodiment, the upper end inlets of the fiber ball adsorption tower 106 and the first activated carbon adsorption tower 107 are also respectively communicated with a first gaseous carbon dioxide pipeline 113. The inlet of the upper end of the second activated carbon adsorption tower 201 is also connected with a second gaseous carbon dioxide pipeline 205. And before the supercritical carbon dioxide extraction regeneration process, discharging residual water in the relevant equipment in the product water phase or waste water phase loss organic phase recovery sub-device 1 and/or the loss organic phase recovery sub-device 2 in the acid mist waste gas by adopting gaseous carbon dioxide.
As a preferable scheme of this embodiment, the fiber ball adsorption tower 106, the first activated carbon adsorption tower 107 and the second activated carbon adsorption tower 201 are all arranged in parallel one by one.
As a preferable scheme of this embodiment, the fiber ball adsorption tower 106, the first activated carbon adsorption tower 107, the second activated carbon adsorption tower 201, the first organic matter recovery tank 110, the second organic matter recovery tank 111, and the third organic matter recovery tank 204 are respectively provided with a temperature control jacket, a thermometer, a pressure gauge, a safety valve, and/or an atmospheric valve, and a heating tape is disposed behind the atmospheric valve.
Example 2:
the embodiment provides an online recovery process of a loss organic phase of a hydrometallurgy extraction separation system, which comprises a recovery process of a loss organic phase in a product water phase, a recovery process of a loss organic phase in a waste water phase and/or a recovery process of a loss organic phase in acid mist waste gas;
the process for recovering the organic phase lost in the product water phase is the same as the process for recovering the organic phase lost in the wastewater phase, and the product water phase or the wastewater phase lost organic phase recovery sub-device 1 provided in the embodiment 1 is adopted;
after a product water phase or a wastewater phase enters a temporary storage tank 101, the product water phase or the wastewater phase is sent into an ultrasonic emulsion breaker 103 through a water pump 102 for emulsion breaking, then enters a superoleophobic hydrophilic membrane separator 104 for separation of an organic phase and a water phase, the organic phase enters an organic phase collecting tank 105, the water phase enters a fiber ball adsorption tower 106 and a first activated carbon adsorption tower 107 for adsorption of organic matters in the water phase, and the water phase after passing through the first activated carbon adsorption tower 107 enters the next process in a hydrometallurgy extraction separation system;
when regeneration is needed after adsorption is completed, gaseous carbon dioxide is firstly adopted to discharge water and air remained in relevant equipment in the product water phase or waste water phase loss organic phase recovery sub-device 1. Then, liquid carbon dioxide is introduced into the fiber ball adsorption tower 106 and the first active carbon adsorption tower 107, the liquid carbon dioxide is adjusted to a supercritical state in the fiber ball adsorption tower 106 and the first active carbon adsorption tower 107, organic matters adsorbed in the fiber ball adsorption tower 106 and the first active carbon adsorption tower 107 are extracted by adopting carbon dioxide supercritical so that the fiber balls in the fiber ball adsorption tower 106 and the active carbon in the first active carbon adsorption tower 107 are regenerated, and the organic matters obtained by extraction enter the first organic matter recovery tank 110 and the second organic matter recovery tank 111;
the recovery process of the loss organic phase in the acid mist waste gas adopts a loss organic phase recovery sub-device 2 in the acid mist waste gas given in the embodiment 1;
the acid mist waste gas enters a second activated carbon adsorption tower 201 to adsorb organic matters in the acid mist waste gas, and the acid mist waste gas after passing through the second activated carbon adsorption tower 201 enters an acid mist absorption process in a hydrometallurgy extraction separation system;
when regeneration is needed after adsorption is completed, the gas carbon dioxide is firstly adopted to discharge water and air remained in the relevant equipment in the loss organic phase recovery sub-device 2 in the acid mist waste gas. Liquid carbon dioxide is introduced into the second activated carbon adsorption tower 201, the liquid carbon dioxide is adjusted to a supercritical state in the second activated carbon adsorption tower 201, organic matters adsorbed in the second activated carbon adsorption tower 201 are extracted by carbon dioxide supercritical, so that the activated carbon in the second activated carbon adsorption tower 201 is regenerated, and the extracted organic matters enter the third organic matter recovery tank 204.
As a preferred scheme of this embodiment, the ultrasonic demulsification process conditions in the ultrasonic demulsification device 103 are as follows: the frequency of the ultrasonic waves is 20-25 KHz, the retention time of the product water phase or the wastewater phase in the ultrasonic emulsion breaker 103 is less than 15min, and the flow velocity of the product water phase or the wastewater phase and the position of an overflow port of the product water phase or the wastewater phase are controlled to adjust.
As a preferable scheme of the embodiment, the pore diameter of the super oleophobic hydrophilic membrane in the super oleophobic hydrophilic membrane separator 104 is 0.5-15 microns.
As a preferred scheme of this embodiment, the process conditions of the carbon dioxide supercritical extraction regeneration are as follows: the pressure is 7.39-15.9 Mpa, the temperature is 31.1-65 ℃, and the supercritical carbon dioxide extraction residence time is 15-180 min.
Example 3:
this embodiment provides an online recovery process of an organic phase lost in a hydrometallurgical extraction separation system, which is based on embodiment 2, and the process includes a recovery process of an organic phase lost in a product aqueous phase, where the product aqueous phase in this embodiment is a cobalt sulfate aqueous solution, that is, the online recovery process of an organic phase lost in a cobalt sulfate aqueous solution in a hydrometallurgical extraction separation system is provided in this embodiment.
In this example, the aqueous cobalt sulfate solution from the extraction line contains the extractant P507 and the solvent kerosene, and is recovered on-line by the process of example 2. Wherein, the fiber ball adsorption tower 106 and the active carbon adsorption tower 107 are one-off and one-standby, the organic matters contained in the cobalt sulfate aqueous solution after flowing out according to the process are separated and adsorbed by sections, the organic matters contained in the cobalt sulfate aqueous phase at the outlet is less than or equal to 0.5ppm, and the COD is less than or equal to 30 mg/L.
Example 4:
this example shows an online recovery process of an organic phase lost in a hydrometallurgical extraction separation system, which includes a recovery process of an organic phase lost in a waste water phase, where the waste water phase in this example is a raffinate, i.e., the online recovery process of an organic phase lost in a hydrometallurgical extraction separation system is shown in this example.
In this example, the raffinate was adjusted to pH 3.5 prior to processing.
The same method as that of example 3 is adopted for on-line recovery, and the COD of the water phase at the outlet after treatment is less than or equal to 30 mg/L.
Example 5:
this example shows an on-line recovery process for the organic phase lost from hydrometallurgical extraction separation system based on example 2, which includes recovery of the organic phase lost from acid mist exhaust.
The process of example 2 was used for on-line recovery. The VOCs at the outlet of the acid mist waste gas in the extraction section after the acid mist waste gas is subjected to activated carbon adsorption treatment is less than or equal to 25mg/m3。
Example 6:
this example shows an on-line recovery process of the lost organic phase in a hydrometallurgical extraction separation system based on example 2, which includes on-line regeneration of the fiber balls in the fiber ball adsorption tower 106.
When the fiber ball is saturated (whether the fiber ball is saturated or not can be known by detecting COD of the solution before and after the fiber ball adsorption tower), the organic matters needing to be regenerated on line and adsorbed by the fiber ball are recovered.
The corresponding valve was closed and opened, and the aqueous phase remaining in the fiber ball adsorption column 106 was slowly pressed out by gaseous carbon dioxide and the pressure was raised to 0.8 Mpa. Then liquid carbon dioxide is led in to 8Mpa, the temperature of the system is kept to be 35 ℃, the carbon dioxide in the system is in a supercritical state at the moment, the density is 0.4, the state is kept for 1h, then the temperature of the system is reduced to 20 ℃, the carbon dioxide is in a liquid state at the moment, the density is 0.8, the carbon dioxide with the organic matters extracted falls into the first organic matter recovery tank 110 in a liquid state due to the fact that the first organic matter recovery tank 110 is larger than the volume of the adsorption tower, a stop valve between the fiber ball adsorption tower 106 and the first organic matter recovery tank 110 is closed, the temperature is kept to be 20-25 ℃, carbon dioxide is discharged through an emptying valve of the first organic matter recovery tank 110 (meanwhile, a heating belt is started to ensure that the carbon dioxide is not frozen in the releasing process), the extracted organic matters remain in the first organic matter recovery tank 110, and the extracted organic matters are discharged through a bottom valve and returned to the system.
Then closing the vent valve and the bottom valve, opening a stop valve between the fiber ball adsorption tower 106 and the first organic matter recovery tank 110, continuously feeding liquid carbon dioxide into the fiber ball adsorption tower 106 to 8Mpa, keeping the system temperature at 35 ℃, keeping the carbon dioxide in the system in a supercritical state, keeping the state for 1h, then cooling the system to 20 ℃, dropping the carbon dioxide with the organic matters extracted for the second time into the first organic matter recovery tank 110 in a liquid state, closing the stop valve between the fiber ball adsorption tower 106 and the first organic matter recovery tank 110, keeping the temperature at 20-25 ℃, discharging the carbon dioxide through the vent valve of the first organic matter recovery tank 110, discharging the extracted organic matters in the first organic matter recovery tank 110, and returning the extracted organic matters to the system through the bottom valve. And opening an emptying valve to discharge residual carbon dioxide in the fiber ball adsorption tower 106, and finishing the fiber ball regeneration process for later use.
The content of organic matters in the regenerated fiber balls is 0.35 percent, the content of organic matters in untreated adsorption saturated fiber balls is 9.5 percent, and the deoiling rate is 96.3 percent.
Examples 7 to 9:
this example shows an on-line recovery process for the lost organic phase of a hydrometallurgical extractive separation system based on example 2, which includes on-line regeneration of the fiber balls in the fiber ball adsorption tower 106.
The process of this example is substantially the same as example 6, except that the specific process conditions are different, as shown in table 1 below.
Table 1 removal of organic materials from fiber balls under different conditions in examples 7 to 9
| Examples | Extraction Change temperature (. degree.C.) | Extraction pressure (Mpa) | Extraction time (min.) | Deoiling Rate (%) |
| 7 | 40→20 | 9→8 | 120 | 96.6 |
| 8 | 50→20 | 15→8 | 60 | 96.5 |
| 9 | 75→20 | 20→8 | 30 | 96.1 |
Examples 10 to 15:
this example shows an on-line recovery process for the spent organic phase of a hydrometallurgical extractive separation system based on example 2, which includes on-line regeneration of activated carbon in the first activated carbon adsorption column 107.
When the activated carbon is adsorbed and saturated (whether the activated carbon is saturated or not can be known by detecting COD (chemical oxygen demand) of the solution before and after the activated carbon adsorption tower or whether the activated carbon adsorption tower is saturated or not can be known by detecting VOCs (volatile organic compounds) in acid mist before and after the activated carbon adsorption tower), the organic matters adsorbed by the activated carbon adsorption tower are required to be regenerated on line and recovered.
The process of this example is substantially the same as that of example 6, except that the regeneration target in this example is activated carbon, and the specific process conditions are different, as shown in table 2 below.
TABLE 2 results of regeneration of activated carbon under various conditions in examples 10 to 15
| Examples | 0 | 10 | 11 | 12 | 13 | 14 | 15 |
| Number of regenerations | 0 | 1 | 2 | 3 | 4 | 5 | 6 |
| Adsorption capacity | 15.0 | 16.35 | 15.15 | 15.01 | 14.85 | 14.7 | 14.5 |
| Rate of change | 1.0 | 1.07 | 1.01 | 1.00 | 0.99 | 0.98 | 0.97 |
Note: the adsorption capacity is the extractant/activated carbon × 100%.
Claims (6)
1. An online recovery device for a lost organic phase of a hydrometallurgy extraction separation system is characterized by comprising a product water phase or waste water phase lost organic phase recovery sub-device (1) and a lost organic phase recovery sub-device (2) in acid mist waste gas;
the product water phase or waste water phase loss organic phase recovery sub-device (1) comprises a temporary storage tank (101) connected with a pipeline (3) of the product water phase or waste water phase in the hydrometallurgy extraction separation system, a temporary storage tank (101) is connected with a liquid inlet of an ultrasonic emulsion breaker (103) through a water pump (102), a liquid outlet of the ultrasonic emulsion breaker (103) is connected with a feed inlet of a super-oleophobic hydrophilic membrane separator (104), an organic phase outlet at the upper end of the super-oleophobic hydrophilic membrane separator (104) is connected with an organic phase collecting tank (105), a water phase outlet at the lower end of the super-oleophobic hydrophilic membrane separator (104) is connected with a bottom valve of a fiber ball adsorption tower (106), a discharge outlet at the upper end of the fiber ball adsorption tower (106) is connected with a bottom valve of a first active carbon adsorption tower (107), and a discharge outlet at the upper end of the first active carbon adsorption tower (107) is connected with a pipeline (4) of the next process in the hydrometallurgy extraction separation system;
the upper end inlets of the fiber ball adsorption tower (106) and the first activated carbon adsorption tower (107) are respectively connected with a first liquid carbon dioxide pipeline (109) with a first flow meter (108); the bottom valve of the fiber ball adsorption tower (106) is connected with a first organic matter recovery tank (110), and the bottom valve of the first activated carbon adsorption tower (107) is connected with a second organic matter recovery tank (111);
the acid mist waste gas loss organic phase recovery sub-device (2) comprises a second activated carbon adsorption tower (201), a bottom valve of the second activated carbon adsorption tower (201) is used for being connected with a pipeline (5) of acid mist waste gas in an induced draft system in a hydrometallurgy extraction separation system, and a discharge port at the upper end of the second activated carbon adsorption tower (201) is connected with a pipeline (6) of an acid mist absorption process in the hydrometallurgy extraction separation system;
the upper end inlet of the second activated carbon adsorption tower (201) is connected with a second liquid carbon dioxide pipeline (203) with a second flow meter (202); and the bottom valve of the second activated carbon adsorption tower (201) is connected with a third organic matter recovery tank (204).
2. The online recovery device for the lost organic phase in the hydrometallurgical extraction separation system of claim 1, characterized in that a return pipe (112) is further arranged between the ultrasonic demulsifying device (103) and the temporary storage tank (101).
3. The online recovery device for the lost organic phase in the hydrometallurgical extraction separation system of claim 1, wherein the upper inlets of the fiber ball adsorption tower (106) and the first activated carbon adsorption tower (107) are respectively communicated with the first gaseous carbon dioxide pipeline (113).
4. The hydrometallurgical extraction separation system lost organic phase on-line recovery device of claim 1, wherein the upper inlet of the second activated carbon adsorption column (201) is further connected to a second gaseous carbon dioxide line (205).
5. The online recovery device for the lost organic phase in the hydrometallurgical extraction separation system of claim 1, wherein the fiber ball adsorption tower (106), the first activated carbon adsorption tower (107) and the second activated carbon adsorption tower (201) are all arranged in parallel with one another for one use and one spare.
6. The online recovery device for the lost organic phase in the hydrometallurgical extraction separation system of claim 1, wherein the fiber ball adsorption tower (106), the first activated carbon adsorption tower (107), the second activated carbon adsorption tower (201), the first organic matter recovery tank (110), the second organic matter recovery tank (111) and the third organic matter recovery tank (204) are respectively provided with a temperature control jacket, a thermometer, a pressure gauge, a safety valve and/or an atmospheric valve, and a heating belt is arranged behind the atmospheric valve.
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