CN117025985B - Method for recycling rare earth elements from red mud by utilizing acidophilic thermophilic red algae and application - Google Patents
Method for recycling rare earth elements from red mud by utilizing acidophilic thermophilic red algae and application Download PDFInfo
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- 238000002386 leaching Methods 0.000 claims abstract description 36
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- 238000011084 recovery Methods 0.000 claims abstract description 27
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- 239000000463 material Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000011081 inoculation Methods 0.000 description 3
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- 239000010936 titanium Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 241000883968 Galdieria sulphuraria Species 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
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- 229910052772 Samarium Inorganic materials 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
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- 230000019522 cellular metabolic process Effects 0.000 description 2
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- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
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- 241001474374 Blennius Species 0.000 description 1
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 241001282804 Sargassum fluitans Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Metallurgy (AREA)
- Geology (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Geochemistry & Mineralogy (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recycling rare earth elements from red mud by utilizing acidophilic thermophilic red algae and application thereof, and belongs to the technical field of resource recycling. The method comprises the steps of mixing red mud leaching liquor, acidophilic thermophilic red algae seed liquor and a carbon source to obtain a treatment liquor to be recovered; and recycling the rare earth elements in the treatment liquid to be recycled by utilizing acidophilic thermophilic red algae, wherein the unicellular acidophilic thermophilic red algae is G.sulfophiaria. Compared with other microalgae recovery technologies, the method for recovering the rare earth elements in the red mud can effectively avoid the pollution and interference of mixed bacteria, and simultaneously avoid complicated sterilization procedures. The method of the invention has the advantages of easy implementation, high treatment efficiency, good absorption effect, low cost and environmental protection.
Description
Technical Field
The invention belongs to the technical field of resource recycling, and particularly relates to a method for recycling rare earth elements from red mud by utilizing acidophilic thermophilic red algae and application thereof.
Background
The red mud is a solid waste discharged after alumina is extracted from bauxite, and researches show that the red mud is produced by about 1-2 tons per 1 ton of alumina on average, and the annual red mud production amount is about 1.5 hundred million tons worldwide. The alumina yield in China exceeds 2500 ten thousand tons, the red mud yield exceeds 4000 ten thousand tons, but the comprehensive utilization rate of the red mud is only 4%, and the accumulated stockpiling amount of the red mud is over 2 hundred million tons. On one hand, a large amount of stacking of the red mud occupies a large amount of land, construction and maintenance of a storage yard consume a large amount of funds, and the pollution of polluted soil, underground water and atmosphere is easily caused due to improper storage, so that the ecological environment is further deteriorated; on the other hand, the red mud contains a large amount of renewable metal elements, especially contains abundant valuable metals such as iron, aluminum, calcium, titanium, rare earth and other metal elements. Rare earth elements are considered as key important metals of many high-tech materials, are called as industrial gold, and have wide application in the fields of new energy, metallurgy, petrochemical industry, glass ceramic, aerospace and the like, so the demand for rare earth elements is continuously growing. Therefore, the recycling of rare earth metals from the red mud not only can realize the recycling of resources, but also is more beneficial to reducing environmental pollution and helping ecological civilization construction.
At present, three processes are mainly adopted in the method for recovering rare earth elements from red mud, one is to directly leach the rare earth elements in the red mud by inorganic acid, so that cerium, calcium, titanium and other elements generate soluble salts, the soluble salts belong to a strong acid leaching process, and the process has the problems of large acid consumption and complex separation steps; the second method is that rare earth elements are leached after the red mud is sulfated and roasted, the sulfuric acid concentration is high, and the roasting temperature involved in the sulfuric acid acidification process is high; the third is a means of combining physical separation with chemical dissolution, such as iron removal by reduction roasting-magnetic separation, silicon removal by acid leaching, aluminum removal by sodium hydroxide solution leaching to obtain rare earth elements. However, whichever process is adopted, the problems of high energy consumption, high carbon emission and environmental pollution caused by high acid and alkali are all faced.
In recent years, environmental and wastewater bioremediation by biotechnology has received increasing attention due to low cost, low carbon, environmental friendliness, multiple varieties and excellent performance. In this case, the recovery of rare earth elements in the liquid phase by algae is a potential biotechnological means. As early as 1997, hao et al (1997) studied the process of enriching rare earth elements in living Chlorella. In 2002, palnieri et al used dried gulfweed (Sargassum fluitans) to remove La 3+ . In 2017, jacinto et al reported for the first time that living macroalgae can remove and recover rare earths. Although algae have the potential to be diluteThe removal of soil provides sustainable materials, but its efficiency, controllability and convenience in the recycling process still need to be greatly improved. Especially, most of the existing organisms cannot adapt to the low-pH and high-concentration metal environment of the red mud extract, so that the application and popularization of the technology for recycling rare earth elements from the red mud by algae are restricted.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for recovering rare earth elements from red mud by utilizing acidophilic thermophilic red algae and application thereof, and the method and the application of the method utilize the characteristic that acidophilic thermophilic microalgae can survive in extreme environments, so that the acidophilic thermophilic microalgae survive in red mud acid leaching wastewater and absorb the rare earth elements, thereby realizing recovery and secondary utilization of the rare earth metal elements.
The invention provides a method for recycling rare earth elements from red mud by utilizing acidophilic thermophilic red algae, which is characterized in that red mud leaching liquor is mixed with acidophilic thermophilic red algae seed liquor to obtain treatment liquor to be recycled, the treatment liquor to be recycled is recycled and cultivated, the acidophilic thermophilic red algae is utilized to purify the treatment liquor to be recycled, so that the recovery of the rare earth elements in the red mud is realized, the acidophilic thermophilic red algae seed liquor is a red algae liquor rich in unicellular red algae G.sulforhodoria, the algae seed number is G.sulforhodoria UTEX 2919, the method can survive in unfavorable ecological environments such as acid hot sulphur springs, sulphur pores, open mines and endogenetic rocks, and can resist various extreme environments such as high temperature (up to 63 ℃), strong acid (pH is 0-4.0), high osmotic pressure (9% salinity) and high concentration heavy metals (such as chromium and nickel), and the method has good large-scale adsorptivity to heavy metals and the like, and can be used as heavy metal biological adsorbents.
Further, the method comprises the following steps: mixing red mud with the extracting solution, oscillating, centrifuging, taking supernatant to obtain red mud leaching solution, mixing the red mud leaching solution, acidophilic thermophilic red algae seed solution and a carbon source to obtain treatment solution to be recovered, recovering and culturing the treatment solution to be recovered, centrifugally settling and separating acidophilic thermophilic red algae adsorbed with rare earth elements, washing for 2-3 times with deionized water, adding a desorption agent, oscillating, and realizing enrichment and recovery of the rare earth elements in the red mud.
Further, the desorbing agent is HNO with the concentration of 0.1mol/L 3 。
Further, the preparation method of the acidophilic thermophilic red algae seed liquid comprises the following steps: inoculating single-cell red algae G.sulfauraria into a conical flask containing BG11 culture medium at room temperature for pre-culture, wherein the initial inoculation concentration is 0.44g/L, the culture time is 7 days, the illumination intensity is 2500lx, and the light-dark ratio is 12h to 12h, so as to obtain acidophilic thermophilic red algae seed liquid.
Further, the extracting solution is nitric acid solution with the volume fraction of 10%, and the solid-liquid ratio of the red mud to the extracting solution is 1 kg:50L.
Further, after shaking at room temperature for 10 hours, centrifugation was performed at 2000g for 10 minutes.
Further, in the treatment liquid to be recovered, the volume of the red mud leaching liquid is 10%.
Further, the carbon source comprises one or two of glycerin and glucose, and the addition amount of the carbon source in the treatment liquid to be recovered is 20-40g/L.
Further, in the treatment solution to be recovered, the initial cell density of the acidophilic thermophilic red algae is 1.8X10 6 cells/mL。
Further, the recovery culture temperature is 40 ℃, the humidity is 50-70%, the time is 5-10d, the pH is 2.5-4, and preferably, the pH is 3.5.
Further, the recovery culture is carried out under illumination (full spectrum LED lamp), the illumination intensity is 8000-12000 Lx, and the light-dark period ratio is 16h to 8h.
The invention also provides application of the method in red mud recovery treatment.
Compared with the prior art, the invention has the following advantages and technical effects:
the invention can realize the rapid absorption of rare earth elements in red mud by utilizing the special absorption performance of single-cell acidophilic thermophilic red algae on rare earth elements. The method provided by the invention is used for recovering rare earth elements in red mud, and compared with other microalgae recovery technologies, the method can effectively avoid pollution and interference of mixed bacteria and avoid complicated sterilization procedures because the pH value is 2.5-4 and the temperature is 40 ℃. The method of the invention has the advantages of easy implementation, high treatment efficiency, good absorption effect, low cost and environmental protection.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and explain the application and are not to be construed as limiting the application. In the drawings:
FIG. 1 is an optical picture of red alga G.sulfariia;
FIG. 2 shows growth curves of G.sulfaria cultured in control and RM groups;
FIG. 3 shows the results of measuring the total rare earth element content in cells at different pH values in examples 1 to 4;
FIG. 4 is the concentration results of absorption enriched single rare earth elements of example 5 (RM) and comparative example 1 (control);
FIG. 5 is the total rare earth element concentration results of the absorption enrichment of example 5 (RM) and comparative example 1 (control);
fig. 6 is a graph showing the cumulative total rare earth element concentration results for g.sulfauraria in examples 3, 5, 6 and comparative examples 2-4.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The invention provides a method for recycling rare earth elements from red mud by utilizing acidophilic thermophilic red algae, which is characterized in that red mud leaching liquor is mixed with acidophilic thermophilic red algae seed liquor, recycling culture is carried out, the recycling of the rare earth elements in the red mud is realized, the acidophilic thermophilic red algae seed liquor is a single-cell red algae-enriched G.sulfophia algae liquid, the algae seed number is G.sulfophia UTEX 2919, the acidophilic red algae is purchased from a university of Texas algae seed library (UTEX) in U.S. and the optical picture is shown in figure 1, the acidophilic thermophilic red algae leaching liquor can survive in unfavorable ecological environments such as acid hot sulphur springs, sulphur pores, open mines, interior rocks and the like, can endure various extreme environments such as high temperature (up to 63 ℃), strong acid (pH 0-4.0), high osmotic pressure (9% salinity) and high concentration heavy metals (such as chromium and nickel), has good large-scale adsorptivity to heavy metals and the like, and can be used as heavy metal biological adsorbents in mass production without modification or pretreatment.
In the embodiment of the invention, the method for recovering the rare earth elements from the red mud by utilizing the acidophilic thermophilic red algae specifically comprises the following steps:
(1) Mixing red mud with the extracting solution, oscillating, centrifuging, and taking supernatant to obtain red mud leaching solution;
(2) Mixing the red mud leaching solution, acidophilic thermophilic red algae seed solution and a carbon source to obtain a treatment solution to be recovered;
(3) And (3) recovering and culturing the treatment liquid to be recovered, centrifugally settling and separating the acidophilic thermophilic red algae adsorbed with the rare earth elements, flushing for 2-3 times by using deionized water, adding a desorption agent, oscillating, and purifying the treatment liquid to be recovered by using the acidophilic thermophilic red algae (G.sulfalaria), thereby recovering the rare earth elements in the red mud.
Preferably, the desorbing agent is HNO with the concentration of 0.1mol/L 3 。
Preferably, the preparation method of the acidophilic thermophilic red algae seed liquid in the embodiment of the invention comprises the following steps: inoculating unicellular red algae G.sulfauraria into a conical flask containing BG-11 culture medium (the culture medium components are shown in table 1) at room temperature for pre-culture, wherein the initial inoculation concentration is 0.44g/L, the culture time is 7 days, the illumination intensity is 2500lx, and the light-dark ratio is 12h to 12h, so as to obtain acidophilic thermophilic red algae seed liquid.
Preferably, the extracting solution is a 10% nitric acid solution, and the solid-liquid ratio of the red mud to the extracting solution is 1 kg:50L. The purpose of leaching the red mud with nitric acid is: rare earth elements such as scandium, titanium and the like in the red mud enter into the pickle liquor in an ionic form, so that acidophilic thermophilic red algae can conveniently enrich the rare earth elements through cell metabolism, and the recovery of the rare earth elements is realized.
Preferably, in step (1), after shaking at room temperature for 10 hours, centrifugation is performed at 2000g for 10 minutes. After oscillation and centrifugation treatment, most of rare earth elements in the red mud can be transferred into a liquid phase in an ionic form under the acid leaching condition.
Preferably, in the treatment solution to be recovered, the volume of the red mud leaching solution is 10%.
Preferably, the carbon source comprises one or two of glycerol and glucose, and the addition amount of the carbon source in the treatment liquid to be recovered is 20-40g/L. The carbon source is added to enable the microalgae to grow heterotrophically or concurrently by using the additional carbon source, so that the growth metabolism of the microalgae can be promoted, and the enrichment rate of the microalgae on rare earth elements can be improved.
Preferably, in the treatment solution to be recovered, the initial cell density of the acidophilic thermophilic red algae is 1.8X10 6 cells/mL. The method is used for controlling the initial cell density of the acidophilic thermophilic red algae, and aims to control the biomass concentration of the acidophilic thermophilic red algae, wherein the excessive concentration can lead to the competition of the acidophilic thermophilic red algae to substances such as illumination, nutrients and the like, inhibit the growth of microalgae, and the too low concentration can lead to the reduction of the enrichment efficiency of the acidophilic thermophilic red algae on rare earth elements.
Preferably, the recovery culture is performed at a temperature of 40 ℃, a humidity of 50 to 70%, a time of 5 to 10d, and a pH of 2.5 to 4, preferably, a pH of 3.5. The key point of the recovery culture process is that proper culture conditions are adjusted to realize the maximum enrichment rate of the acidophilic thermophilic red algae on rare earth elements.
Preferably, the recovery culture is performed under illumination (full spectrum LED lamp), the illumination intensity is 8000-12000 Lx, and the light-dark period ratio is 16h:8h. Under the condition of illumination, the acidophilic thermophilic red algae enriches rare earth elements through cell metabolism.
The raw materials used in the examples of the present invention are all commercially available.
In the embodiment of the invention, the room temperature is 25+/-2 ℃.
In the embodiment of the invention, the red mud is collected from a red mud yard of an alumina production enterprise in a certain city.
Resistance of Sulphuraria to Red mud leach liquor
The red mud and the extracting solution (nitric acid solution with the volume fraction of 10 percent) are mixed according to the solid-liquid ratio of 1:50 (kg.L) -1 ) Mixing, oscillating for 10 hours at room temperature, centrifuging for 10 minutes under 2000g, and taking supernatant to obtain red mud leaching liquor; inoculating acidophilic thermophilic red algae seed solution (G.sulfophia) into 300mL 2MA culture medium (culture medium composition is shown in Table 2, red mud extract (30 mL) containing red mud extract (RM)) as RM group, and determining initial OD 700 The culture conditions were 40℃and 10000Lx of aeration culture under light. After inoculation, the OD of the red algae cultures was detected daily 700 The value of the sum of the values,a growth curve was prepared, and the tolerance of G.Sulphuraria to red mud leaching solution was observed by using 2MA medium to directly culture acidophilic thermophilic red algae seed solution (G.Sulphuraria) as a control group, and the result of the growth curve is shown in FIG. 2.
TABLE 2 composition of 2MA Medium
As can be seen from fig. 2, the growth curve (control group) of g.sulfaaria cultured in 2MA medium is not much different from the growth curve (RM group) cultured in 2MA medium added with red mud leaching liquor (RM), and it is seen that g.sulfaaria has relatively high tolerance to red mud leaching liquor (RM), so that g.sulfaaria can be applied to red mud recovery treatment, and the technical scheme of the present invention will be further described by way of examples. Specific examples are as follows:
example 1
(1) The red mud and the extracting solution (nitric acid solution with the volume fraction of 10 percent) are mixed according to the solid-liquid ratio of 1:50 (kg.L) -1 ) Mixing, oscillating for 10 hours at room temperature, centrifuging for 10 minutes under 2000g, and collecting supernatant to obtain red mud leaching liquor;
(2) Mixing the red mud leaching solution, the acidophilic thermophilic red algae seed solution and a carbon source (glucose, the adding amount of the glucose in the treatment solution to be recovered is 40 g/L) to obtain the treatment solution to be recovered, wherein the volume of the red mud leaching solution in the treatment solution to be recovered is 10%, and the initial cell density of the acidophilic thermophilic red algae is 1.8x10% 6 cells/mL；
(3) Recovering and culturing the treatment liquid to be recovered, wherein the temperature is 40 ℃, the humidity is 70%, the time is 10d, the pH is 2.5, the treatment liquid is carried out under a full spectrum LED lamp, the illumination intensity is 10000Lx, the light-dark period ratio is 16h to 8h, recovering the acidophilic thermophilic red algae enriched with rare earth elements by a centrifugal sedimentation method, washing for 2-3 times by deionized water, and using HNO of 0.1mol/L 3 Mixing with acidophilic thermophilic red algae as desorption agent, oscillating thoroughly, desorbing rare earth ions enriched in algae cells, purifying the treated solution to be recovered by using acidophilic thermophilic red algae (G.sulfophiaria), and recovering rare earth elements in red mud。
In the embodiment, rare earth elements in the red mud in the treatment fluid to be recovered are enriched through acidophilic thermophilic red algae (G.sulfophuraria), and are further separated, so that the recovery of the rare earth elements in the red mud is realized.
Example 2
The only difference from example 1 is that the pH of the recovery culture was 3.
Example 3
The only difference from example 1 is that the pH of the recovery culture was 3.5.
Example 4
The only difference from example 1 is that the pH of the recovery culture was 4.
Example 5
(1) The red mud and the extracting solution (nitric acid solution with volume fraction of 10 percent and solid-liquid ratio of 1:50 (kg.L) -1 ) After shaking for 10 hours at room temperature, centrifuging for 10 minutes under 2000g, and taking supernatant to obtain red mud leaching liquor;
(2) Mixing the red mud leaching solution, acidophilic thermophilic red algae seed solution and carbon source (glucose, the adding amount of the treated solution to be recovered is 40 g/L) to obtain the treated solution to be recovered, wherein the volume of the red mud leaching solution in the treated solution to be recovered is 10%, and the initial cell density of the acidophilic thermophilic red algae is 1.8X10% 6 cells/mL；
(3) Recovering and culturing the treatment solution to be recovered, wherein the temperature is 40 ℃, the humidity is 50%, the time is 10d, the pH is 3.5, the treatment solution is carried out under a full spectrum LED lamp, the illumination intensity is 10000Lx, the light-dark period ratio is 16h to 8h, recovering the acidophilic thermophilic red algae enriched with rare earth elements by a centrifugal sedimentation method, washing for 2-3 times by deionized water, and using HNO of 0.1mol/L 3 Mixing and fully oscillating the solution as a desorption agent with acidophilic thermophilic red algae, desorbing rare earth ions enriched in algae cells, and purifying the treatment solution to be recovered by utilizing acidophilic thermophilic red algae (G.sulfophiaria), thereby realizing the recovery of rare earth elements in red mud.
Example 6
(1) Mixing red mud with an extracting solution (nitric acid solution with volume fraction of 10% and solid-liquid ratio of 1:50 (kg/L)), oscillating for 10 hours at room temperature, centrifuging for 10 minutes under 2000g condition, and collecting supernatant to obtain red mud leaching solution;
(2) Mixing the red mud leaching solution, the acidophilic thermophilic red algae seed solution and a carbon source (glucose, the adding amount of the glucose in the treatment solution to be recovered is 40 g/L) to obtain the treatment solution to be recovered, wherein the volume of the red mud leaching solution in the treatment solution to be recovered is 10%, and the initial cell density of the acidophilic thermophilic red algae is 1.8x10% 6 cells/mL；
(3) Recovering and culturing the treated liquid to be recovered, wherein the temperature is 40 ℃, the humidity is 60%, the time is 10d, the pH is 3.5, the treatment liquid is carried out under a full spectrum LED lamp, the illumination intensity is 12000Lx, the light-dark period ratio is 16h:8h, recovering the acidophilic thermophilic red algae enriched with rare earth elements by a centrifugal sedimentation method, washing the acidophilic thermophilic red algae for 2-3 times by deionized water, and using HNO of 0.1mol/L 3 Mixing and fully oscillating the solution as a desorption agent with acidophilic thermophilic red algae, desorbing rare earth ions enriched in algae cells, and purifying the treatment solution to be recovered by utilizing acidophilic thermophilic red algae (G.sulfophiaria), thereby realizing the recovery of rare earth elements in red mud.
Comparative example 1
The only difference from example 5 is that no red mud leaching solution was added: mixing the acidophilic thermophilic red algae seed solution with carbon source (glucose, 40g/L of the additive amount of the treatment solution to be recovered) to obtain the treatment solution to be recovered, wherein the initial cell density of acidophilic thermophilic red algae is 1.8X10% 6 cells/mL; and (3) recycling and culturing the treatment liquid to be recycled, wherein the temperature is 40 ℃, the humidity is 50%, the time is 10d, the pH is 3.5, the treatment liquid is performed under a full spectrum LED lamp, the illumination intensity is 10000Lx, and the light-dark period ratio is 16h to 8h.
Comparative example 2
The difference from example 5 was that the amount of glucose added to the treatment liquid to be recovered was 15g/L.
Comparative example 3
The difference from example 5 is that the recovery culture in step (3) is performed under full spectrum LED lamp with illumination intensity of 10000Lx and light-dark cycle ratio of 16h to 8h at a temperature of 40 deg.C, humidity of 50%, time of 10d and pH of 3.5 for 4 d.
Comparative example 4
The difference from example 6 is that the light intensity was 15000Lx, the temperature of recovery culture was 40 ℃, the humidity was 60%, the time was 10d, the pH was 3.5, and the light-dark cycle ratio was 16h:8h.
Performance testing
After growth into the stationary phase, algal cells in examples and comparative examples were collected by centrifugation at 2000g, respectively, and absorption of enriched rare earth elements in red algae was detected by ICP-MS.
The experimental results of examples 1-4 show that red algae has enrichment effect on cerium (Ce), lanthanum (La), yttrium (Y), neodymium (Nd), praseodymium (Pr), samarium (Sm) and gadolinium (Gd) when the culture pH is between 2.5-4.0, and in addition, the measurement results of the total rare earth element content in cells under different pH of examples 1-4 are shown in FIG. 3, and as can be seen from FIG. 3, the enrichment efficiency is highest when the pH value is 3.5; at pH 2.5, the enrichment efficiency is lower. Therefore, the optimal pH value for culturing red algae to recover rare earth elements from red mud is about 3.5.
The results of measuring the concentration of the single rare earth element enriched by absorption of example 5 and comparative example 1 (control/control) are shown in fig. 4 and table 3.
TABLE 3 enrichment Effect of example 5 and comparative example 1 on rare earth elements (. Mu.g/g dry weight)
| Y | La | Ce | Pr | Nd | Sm | Eu | Gd | Tb | Dy | Er | Tm | Yb | |
| Comparative example 1 | 0.21 | 0.22 | 0.35 | 0.34 | 0.35 | 0.30 | 0.25 | 0.41 | 0.23 | 0.33 | 0.42 | 0.53 | 1.12 |
| Example 5 | 10.31 | 10.74 | 26.42 | 4.82 | 16.14 | 3.42 | 1.24 | 3.11 | 0.54 | 2.83 | 1.51 | 0.33 | 2.32 |
As can be seen from fig. 4 and table 3, g.sulfaria has an absorption and enrichment effect on cerium (Ce), lanthanum (La), yttrium (Y), neodymium (Nd), praseodymium (Pr), samarium (Sm), gadolinium (Gd), and has a better absorption effect on Ce, nd, la and Y.
The result of measuring the total rare earth element concentration of the absorption enrichment of the example 5 and the comparative example 1 (control/control) is shown in fig. 5, and as can be seen from fig. 5, the total rare earth element concentration accumulated in the g.sulfaria biomass in the example 5, compared with the comparative example 1, the concentration of the rare earth absorbed in algae cells reaches 121.5 mug/g dry weight, which proves that the red algae can survive in the acidic red mud leaching solution and has good enrichment effect on the rare earth metals in the red mud leaching solution.
The results of the total rare earth element concentration accumulated in the g.sulfaria biomass in the methods of example 3, example 5, example 6 and comparative examples 2-4 are shown in fig. 6. The total rare earth element concentration accumulated in G.sulfophia biomass in the example 5 is slightly lower than that in the example 3, the concentration of the rare earth absorbed in alga cells in the example 3 and the example 5 reaches 125.1 mug/g and 121.5 mug/g dry weight respectively, and the red alga can realize higher enrichment efficiency under the culture condition that the humidity is 50-70%; the total rare earth element concentration accumulated in G.sulfophuraria biomass in the example 5 is far higher than that of the comparative examples 2 and 3, which shows that the red algae has low rare earth element enrichment efficiency under the culture condition that the carbon source (glucose) addition amount is lower than 20g/L or the culture time is less than 5d, and the proper culture condition of the red algae is proved to be that the carbon source addition amount is 20-40g/L and the culture time is 5-10d; the concentration of total rare earth elements accumulated in G.sulfophia biomass in example 6 is far higher than that in comparative example 4, and it is proved that when the illumination intensity is higher than 12000Lx, the enrichment efficiency of acidophilic thermophilic red algae is reduced, and the proper culture condition of the red algae is carried out under a full spectrum LED lamp, the illumination intensity is 8000-12000 Lx, and the light-dark period ratio is 16h to 8h.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (5)
1. A method for recycling rare earth elements from red mud by utilizing acidophilic thermophilic red algae is characterized in that red mud leaching liquor is mixed with acidophilic thermophilic red algae seed liquor, and the acidophilic thermophilic red algae seed liquor is used for purifying to realize recycling of the rare earth elements in the red mud, wherein the acidophilic thermophilic red algae seed liquor is an algae liquor rich in unicellular red algae G.sulfophiaria; the method specifically comprises the following steps:
mixing red mud with an extracting solution, oscillating, centrifuging, taking a supernatant to obtain a red mud leaching solution, mixing the red mud leaching solution, acidophilic thermophilic red algae seed solution and a carbon source to obtain a treatment solution to be recovered, recovering and culturing the treatment solution to be recovered, centrifugally settling and separating acidophilic thermophilic red algae adsorbed with rare earth elements, washing, adding a desorption agent, oscillating, and realizing enrichment and recovery of the rare earth elements in the red mud;
the extracting solution is nitric acid solution with the volume fraction of 10%, and the solid-liquid ratio of the red mud to the extracting solution is 1 kg:50L;
the carbon source comprises one or two of glycerol and glucose, and the addition amount of the carbon source in the treatment liquid to be recovered is 20-40g/L;
the pH value of the recovery culture is 3-4;
the temperature of the recovery culture is 40 ℃, the humidity is 50-70%, and the time is 5-10d;
the recovery culture is carried out under illumination, the illumination intensity is 8000-12000 Lx, and the light-dark period ratio is 16h to 8h.
2. The method for recovering rare earth elements from red mud using acidophilic thermophilic red algae according to claim 1, wherein after shaking for 10 hours at room temperature, centrifugation is performed for 10 minutes at 2000 g.
3. The method for recycling rare earth elements from red mud by utilizing acidophilic thermophilic red algae according to claim 1, wherein the volume of the red mud leaching solution in the treatment solution to be recycled is 10%.
4. The method for recovering rare earth elements from red mud by utilizing acidophilic thermophilic red algae according to claim 1, wherein the initial cell density of acidophilic thermophilic red algae in the treatment liquid to be recovered is 1.8x10 6 cells/mL。
5. Use of the process of any one of claims 1 to 4 in red mud recovery treatment.
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