AU2022304960A1 - PROCESS FOR THE RECOVERY OF RARE EARTH METALS FROM WASTE RESIDUES FROM TiO2 PRODUCTION - Google Patents

PROCESS FOR THE RECOVERY OF RARE EARTH METALS FROM WASTE RESIDUES FROM TiO2 PRODUCTION Download PDF

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AU2022304960A1
AU2022304960A1 AU2022304960A AU2022304960A AU2022304960A1 AU 2022304960 A1 AU2022304960 A1 AU 2022304960A1 AU 2022304960 A AU2022304960 A AU 2022304960A AU 2022304960 A AU2022304960 A AU 2022304960A AU 2022304960 A1 AU2022304960 A1 AU 2022304960A1
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calcium
sulphate
rare earth
scandium
process according
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Terence MAKANYIRE
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G S A Environmental Ltd
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    • 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
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/282—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • 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
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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
    • 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
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A process is provided for recovery of scandium and certain other rare earth metals from titanium dioxide production residue The process comprises treating the residue with a calcium source at a temperature below 30°C to selectively co-precipitate calcium sulphate, scandium and other metals from solution. The precipitate can then be filtered and treated with dilute acid to leach the scandium into solution for separation by selective precipitation.

Description

PROCESS FOR THE RECOVERY OF RARE EARTH METALS FROM WASTE RESIDUES FROM T1O2 PRODUCTION
Field of the Invention
[0001] This invention relates to the recovery of metals such as scandium and certain other rare earth elements from residues generated during production of T1O2 using the sulphate process.
Background to the Invention
[0002] The production of T1O2 using the sulphate process results in huge volumes of sulphate waste containing up to 25 v/v% free acid and 45 grams per litre ferrous iron among other metal ions. The waste is typically neutralised us ing slaked lime or limestone before landfilling or disposal by other means. With in the sulphate waste are valuable and/or strategic metals such as vanadium, scandium, zirconium and niobium, which could be recovered for establishing a circular economy, while improving the sustainability and environmental creden tials of the T1O2 industry. As one of the most valuable of the present metals, scandium has been the focus of most research, and due to its low concentration (up to 20 ppm), established processes utilise solvent extraction or ion exchange for its recovery. Solvent extraction and ion exchange processes are very ex pensive to operate for such low concentrations and huge volumes of waste, therefore a concentration enhancement step, or alternative technologies are re quired for making a scandium recovery process greener and sustainable. Scan dium is normally soluble below pH 4. It has now been found that scandium and other rare earth metals can be selectively co-precipitated with calcium sulphate by addition of calcium ions to a rare earth element-containing sulphate solution, thereby permitting precipitation below pH 4 and even where the pH is below 0. This is important where sulphate waste can be generated at a pH below 0, typi cally about pH -0.5 for a material having >23% free H2SO4.
[0003] US2253590 discloses the use of calcium sulphate at temperatures of
90°C and above to remove “objectionable rare earth impurities” which cause discoloration from residual acid liquor in titanium dioxide pigment manufacture. RU2716693C1 discloses processing titanium dioxide production waste and mentions adding milk of lime to neutralise and produce gypsum for building ma terials. It explains that a disadvantage of this is that some rare-earth metals such as scandium are “irretrievably lost”. To overcome this, it proposes the use of an extractant containing di(2-ethylhexyl) phosphoric acid and tributyl phos phate. No information is disclosed on the efficacy of this. CN102275969B dis closes a method of processing titanium dioxide production residue by adding calcium chloride, thereby forming calcium sulphate. The document is silent con cerning rare earth metals.
Summary of the Invention
[0004] According to the invention, a process for recovery from acidic sul phate waste from titanium dioxide production of at least one rare earth metal from the group consisting of scandium, cerium, lanthanum, neodymium, prase odymium and yttrium, comprises treating the sulphate waste with at least one calcium compound selected from calcium chloride, calcium hydroxide, calcium carbonate, calcium chlorate, calcium nitrate and calcium hypochlorite at a tem perature below 30°C thereby selectively co-precipitating calcium sulphate and rare earth metals from solution, filtering the precipitate from the solution, and extracting the rare earth metals from the filtered precipitate.
[0005] Other rare earth elements - dysprosium, erbium, europium, gadolini um, holmium, lutetium, samarium, terbium and thulium - remain in solution for recovery through pH adjustment at later processing stages.
[0006] The precipitation step is preferably carried out at low temperatures, suitably 20°C. The sulphate waste solution preferably contains at least 10 v/v% free acid. The precipitated calcium sulphate/rare earth element residue is fil tered and washed in water, preferably cold water. For effective extraction of scandium, an intermediate leaching step using sodium carbonate may be car ried out first. The solid calcium sulphate is converted by the sodium carbonate solution into solid calcium carbonate. The scandium remains at this stage in the solids and sodium sulphate solution is filtered off. Dilute sulphuric acid is then preferably used for re-dissolving the rare earth elements from the calcium car- bonate, leaving a calcium sulphate residue. The acid level is controlled so that the scandium remains in solution at this stage. Conventional methods for pre cipitation and/or purification can then be employed for obtaining a pure scandi um product. Other rare earth elements present in the residue can be re dissolved and selectively precipitated using conventional methods and rea gents.
Brief Description of the Figures
[0007] Figure 1 shows the fraction of scandium precipitated when different amounts of calcium or barium ions are introduced to a scandium containing sul phate solution at 20°C and stirred for 30 minutes; and
[0008] Figure 2 is a flow chart illustrating the steps in the process described hereinafter in the Examples.
Detailed Description of the Illustrated Embodiment
[0009] Production of TiC>2 by the sulphate process results in toxic acidic resi dues, which are made less hazardous by neutralisation with limestone or slaked lime before disposal at landfill sites. If not recovered, scandium and other rare earth elements (“REE”) follow the neutralised ions to form a filter cake for land fill.
[0010] Although generally soluble below pH 4, scandium can co-precipitate with calcium sulphate when a source of calcium is added to waste sulphate liq uor below pH 0. This is carried out at room temperature, with up to 5 w/v% cal cium ions. A scandium-rich precipitate is then filtered and leached, first in a so dium carbonate solution and then in dilute sulphuric acid to form a scandium- rich solution, leaving behind a calcium sulphate residue.
[0011] The invention is illustrated by the following Examples:
Example 1
[0012] A 100 ml sample of residual acid liquor from the production of T1O2 by the sulphate process (hereinafter referred to as “TiC>2 sulphate waste”) is mixed with 13 g CaCl2 in a beaker. The mixture is stirred for 30 minutes and filtered. Over 97 % of the scandium in initial sulphate solution co-precipitates with calci- um sulphate. The filtered precipitate is then washed using water and leached in hot dilute sulphuric acid at 70°C to achieve an overall recovery of over 95 %.
Example 2
[0013] A 100 ml sample of T1O2 sulphate waste is mixed with 18.5 g CaCC>3 in a beaker. The mixture is then stirred for 30 minutes and filtered. Over 55 % of the scandium in initial sulphate solution co-precipitates with calcium sulphate. The precipitate is then washed with cold water and leached in hot dilute sul phuric acid to achieve an overall recovery of over 52 %.
Example 3 [0014] A 100 ml sample of T1O2 sulphate waste is mixed with 15 g Ca(OH)2 in a beaker. The mixture is then stirred for 30 minutes and filtered. Over 80 % of the scandium in initial sulphate solution will have co-precipitated with calcium sulphate. The precipitate is then washed with water and leached in dilute sul phuric acid at 70°C to achieve an overall recovery of over 75 %. Example 4
[0015] A 100 ml sample of T1O2 sulphate waste is mixed with 15 g CaS04 in a beaker. The mixture is then stirred for 30 minutes and filtered. Over 15 % of the scandium in initial sulphate solution will have adsorbed to the calcium sul phate. The precipitate is then washed with cold water and leached in hot dilute sulphuric acid to achieve an overall recovery of about 10 %.
Example 5
[0016] To a litre of T1O2 sulphate waste at room temperature, 60g of calcium chloride powder were added for scandium and rare earth metals recovery. The mixture was stirred for a total of 60 minutes at room temperature before filtering and analysing the filtrate by ICP OES. Analysis of the filtrate show that the con centrations of Scandium (Sc); Cerium (Ce); Lanthanum (La); Neodymium (Nd); praseodymium (Pr) and Yttrium (Y) dropped by between 65% and 99%, while concentration of other rare earths (Dy; Er; Eu; Gd; Ho; Lu; Sm; Tb and Tm) re mains unchanged. Example 6
[0017] To a litre of T1O2 sulphate waste at room temperature, 38g of calcium hydroxide powder were added for scandium and rare earth metals recovery. The mixture was stirred for a total of 60 minutes at room temperature before fil tering and analysing the filtrate by ICP OES. Analysis of the filtrate show that the amount of Scandium (Sc); Cerium (Ce); Lanthanum (La); Neodymium (Nd); praseodymium (Pr) and Yttrium (Y) dropped by between 55% and 96%, while concentration of other rare earths (Dy; Er; Eu; Gd; Ho; Lu; Sm; Tb and Tm) re duce by a maximum of 2%.
Example 7
[0018] To a litre of T1O2 sulphate waste at room temperature, 50g of calcium carbonate powder were added for scandium and rare earth metals recovery. The mixture was stirred for a total of 60 minutes at room temperature before fil tering and analysing the filtrate by ICP OES. Analysis of the filtrate show that the amount of Scandium (Sc); Cerium (Ce); Lanthanum (La); Neodymium (Nd); praseodymium (Pr) and Yttrium (Y) dropped by between 40% and 80%, while concentration of other rare earths (Dy; Er; Eu; Gd; Ho; Lu; Sm; Tb and Tm) re duce by a maximum of 10%.
Example 8
[0019] To a litre of T1O2 sulphate waste at room temperature, 1800g of calci um chloride powder were added for scandium and rare earth metals recovery. The mixture was stirred for a total of 60 minutes at room temperature before fil tering and analysing the filtrate by ICP OES. Analysis of the filtrate show that the concentrations of Scandium (Sc); Cerium (Ce); Lanthanum (La); Neodymi um (Nd); praseodymium (Pr) and Yttrium (Y) dropped by 100%, while concen tration of other rare earths (Dy; Er; Eu; Gd; Ho; Lu; Sm; Tb and Tm) remains unchanged.
Example 9
[0020] Repeating Example 5 at 50°C, 70°C and 90°C resulted in reduction of amount of scandium precipitated, with a maximum of 32% precipitated at 50°C, 28% at 70°C and 12% at 90°C. The other rare earth metals follow a different trend wherein the fraction precipitated increased with temperature to a maxi mum of 100% at 90°C. Using calcium hydroxide (similar to Example 6) and cal cium carbonate (similar to Example 7) instead of calcium chloride at 50°C, 70°C and 90°C yielded similar trends to Example 8.
[0021] The following Examples are included for comparison and are not with in the scope of the invention:
Comparative Example 1
[0022] A 100 ml sample of T1O2 sulphate waste is mixed with 15 g BaCl2 in a beaker. The mixture is then stirred for 30 minutes and filtered. No scandium co precipitates with barium sulphate.
Comparative Example 2
[0023] To a litre of T1O2 sulphate waste at 90°C containing up to 30 mg/L scandium as an oxide and up to 50mg/L rare earth metals calculated as mixed oxides, 0.45g of calcium sulphate hemihydrate (CaSC>4.1/2H20) were added for scandium and rare earth metals recovery. The residual acid liquor originates from a hydrolysis reaction used for selectively precipitating Ti02 pigment after digestion of T1O2 from typical feedstock. The free acid concentration was ap proximately 25%. The mixture was stirred for a total of 60 minutes at tempera ture before filtering and analysing the filtrate by ICP OES.
[0024] Analysis of the filtrate showed that the concentration of scandium and all rare earth metals remained unchanged, indicating that the process is not ef fective for recovering scandium or other rare earth metals.
Comparative Example 3
[0025] To a litre of T1O2 sulphate waste at 90°C, 45g of calcium sulphate hemihydrate were added for scandium and rare earth metals recovery. The mix ture was stirred for a total of 60 minutes at temperature before filtering and ana lysing the filtrate by ICP OES. Analysis of the filtrate show that the concentra tions of Scandium dropped by up to 10%, while concentration of other rare earth elements drops by up to 100%. Comparative Example 4
[0026] To a litre of T1O2 sulphate waste at 90°C, 200g of calcium sulphate hemihydrate were added for scandium and rare earth metals recovery. The mix ture was stirred for a total of 60 minutes at temperature before filtering and ana- lysing the filtrate by ICP OES. Analysis of the filtrate show that the concentra tions of Scandium dropped by up to 30 %, while concentration of other rare earth elements dropped by up to 100%.
Comparative Example 5
[0027] To a litre of T1O2 sulphate waste at 90°C, 50mg of insoluble calcium sulphate anhydrite and 400mg of calcium sulphate dihydrate were added over 30 minutes. The system was stirred for a total of 60 minutes at temperature be fore filtering and analysing the filtrate by ICP OES. Analysis of the filtrate show that the concentration of scandium and all rare earth metals remained un changed, indicating that the process is not effective for recovering scandium or other rare earth metals at the concentrations investigated.
Comparative Example 6
[0028] To a litre of T1O2 sulphate waste at 90°C, 5g of insoluble calcium sul phate anhydrite and 40g of calcium sulphate dihydrate were added over 30 minutes. The system was stirred for a total of 60 minutes at temperature before filtering and analysing the filtrate by ICP OES. Analysis of the filtrate show that the concentrations of Scandium dropped by up to 17 %, while concentration of other rare earth elements drops by up to 100%.
Comparative Example 7
[0029] To a litre of T1O2 sulphate waste at 90°C, 20g of insoluble calcium sulphate anhydrite and 180g of calcium sulphate dihydrate were added over 30 minutes. The system was stirred for a total of 60 minutes at temperature before filtering and analysing the filtrate by ICP OES. Analysis of the filtrate show that the concentrations of Scandium dropped by up to 33 %, while concentration of other rare earth elements drops by up to 100%. [0030] Comparative Examples 3 to 7 show that higher temperature treatment with calcium sulphate can be used to fully precipitate REE such as Cerium, Lan thanum, Neodymium, Praseodymium and Yttrium, but Scandium is only partially precipitated, with a significant proportion of that present in the waste remaining in solution. By contrast, with the process of the invention, Scandium is fully pre cipitated along with Ce, La, Nd, Pr and Y, with other REE remaining in solution.

Claims (9)

1. A process for recovery from acidic sulphate waste from titanium dioxide production of at least one rare earth metal from the group consisting of scandium, cerium, lanthanum, neodymium, praseodymium and yttrium , com- prising treating the sulphate waste with at least one calcium compound selected from calcium chloride, calcium hydroxide, calcium carbonate, calcium chlorate, calcium nitrate and calcium hypochlorite at a temperature below 30°C thereby selectively co-precipitating calcium sulphate and rare earth metals from solu tion, filtering the precipitate from the solution, and extracting the rare earth met- als from the filtered precipitate.
2. A process according to Claim 1 , wherein the sulphate residue comprises more than 2 % free acid (H2SO4).
3. A process according to Claim 1 or 2, wherein the pH value of the titanium dioxide production residue is below 4.
4. A process according to Claim 3, wherein the pH value of the tita nium dioxide production residue is below 0.
5. A process according to any preceding claim, further comprising washing the filtered precipitate in water.
6. A process according to Claim 5, wherein the temperature of the wash water is below 30°C
7. A process according to preceding claim, wherein the extraction step comprises treating the filtered precipitate with dilute acid to leach the rare earth metals into solution and then selectively precipitating scandium and other metals from the resulting solution.
8. A process according to Claim 7, comprising treating the filtered precipitate with a sodium carbonate solution to convert the precipitated calcium sulphate into calcium carbonate, prior to the treatment with dilute acid.
9. A process according to Claim 7 or 8, wherein the dilute acid is sulphuric acid.
AU2022304960A 2021-06-30 2022-06-23 PROCESS FOR THE RECOVERY OF RARE EARTH METALS FROM WASTE RESIDUES FROM TiO2 PRODUCTION Pending AU2022304960A1 (en)

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PCT/EP2022/067186 WO2023274838A1 (en) 2021-06-30 2022-06-23 PROCESS FOR THE RECOVERY OF RARE EARTH METALS FROM WASTE RESIDUES FROM TiO2 PRODUCTION

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2253590A (en) * 1939-04-20 1941-08-26 Du Pont Purification of acidic liquors
CN102275969B (en) * 2011-05-20 2013-04-17 攀枝花市尚亿科技有限责任公司 Comprehensive utilization method of titanium dioxide waste
CN102976527B (en) * 2012-12-14 2014-06-25 中国有色集团（广西）平桂飞碟股份有限公司 Method for obtaining scandium-rich material from acidic wastewater of titanium dioxide environment-friendly workshop
CN103540752B (en) * 2013-10-14 2015-12-23 广西冶金研究院 One is scandium-enriched, titanium and vanadium and useless acid-treated method thereof from titanium dioxide waste acid by sulfuric acid process
US10190507B2 (en) * 2016-12-16 2019-01-29 Ford Global Technologies, Llc Systems and methods for a split exhaust engine system
GB201817904D0 (en) * 2018-11-01 2018-12-19 Grimley Smith Associates Env Ltd Metals recovery
RU2716693C1 (en) * 2018-11-27 2020-03-13 Федеральное государственное автономное образовательное учреждение высшего образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" Hydrolysic acid processing method
CN109825711A (en) * 2019-03-14 2019-05-31 何耀 A kind of titanium dioxide waste acid by sulfuric acid process resource utilization method
CN110983044B (en) * 2019-09-03 2021-07-30 河南荣佳钪钒科技有限公司 Method for recycling scandium and vanadium from titanium white wastewater produced by chlorination process

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