溶剂萃取基本原理 - Phil
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• Acid - residual acid after leaching affects economics of SX copper recovery. 酸－浸出后的残留酸影响溶剂萃取铜的回收经济。
• Iron - can be transferred to EW, affecting EW efficiency. 铁－能够被传递到电积，影响电积效率
Spent Electrolyte 废电积液
Cu
Cu
Cu
Cu
Acid
LEACH
EXTRACT
STRIP
EW
酸
铜浸出
铜萃取
铜反萃
PLS 料液
Loaded Organic 负载有机相
Strong Electrolyte 电积富液
Cu2+
Emulsion mixing and separation – OC 乳状液混合和分相－有机相连续
世界上第一个铜溶剂萃取厂在1968年投产， Ranchers Exploration Bluebird mine，使 用的是LIX 64N.
Copper Solvent Extraction 铜溶剂萃取
Today, about ¼ of the world‘s copper is produced by SX
Organic weir
有机堰
Launders
பைடு நூலகம்
流槽
Organic in 有机进入
Settler
Aqueous in 水相进入
Organic out 有机出口
Aqueous out 水相出口
In the mixer, the two phases form an
emulsion which separates in the settler 在混合室，两相形成一个乳状液在澄清 室分离
• Most important species include copper, acid, iron, chloride, manganese, nitrate, dissolved silica and solids. 最重要的种类包括的是铜、酸、铁、氯、锰、硝酸根、被溶解的硅和固体颗 粒。
• Copper - the desired pure product. 铜－想得到纯铜
负债有机相 +电积贫液 反萃有机相 + 电积液
• 酸的浓度应适合于电积
Solvent Extraction Equipment – The Mixer Settler
溶剂萃取设备－混合室澄清室
Pump mixer Secondary mixer 抽吸混和室 二级混和室
Distribution fence 分散栅栏
今天世界上大约有1/4的铜是通 过溶剂萃取的方法生产的
Ranchers Bluebird Mine SX-EW Plant 溶剂萃取电积厂
Uranium Solvent Extraction
Today, about ¾ of the world‘s uranium is produced by SX
Australia
Aqueous continuous emulsion – AC 水相连续乳状液
Organic droplets surrounded by aqueous phase 有机小液滴被水相包围
Aqueous Continuous emulsion 水相连续乳状液
Desired Mixer Emulsion conditions 期望的混合室乳状液条件
E2 二萃
S.O.反萃有机相
S1 反萃
L.O. 负载有机相
Each stage uses a mixer – settler 每一段使用一个混合室－澄清室系列
OVERALL LEACH - SX - EW PROCESS
全部的浸出－溶剂萃取－电积工艺
H+
Raffinate 萃余液
Stripped Organic 反萃有机相
eg. Counter-current circuit for Cu Extraction
2 Extract x 1 Strip (2E x 1S) 例如. 铜逆流萃取 2萃1反（ 2E x 1S ）
PLS 料液
Raffinate 萃余液 Spent废电积液
E.W. 电积
Strong 电积富液
E1 一萃
< 1.5
Autoclave/agitation加压浸出/搅浸 2 – 20
pH 1.5 – 2.2 1–2 1–2 <1 - 2
However, the PLS always contains some undesirable impurities 然而，料液仍然含有一些不想要的杂质
Typical PLS constituents 典型的料液成分
E1 AC if no crud – to minimise PLS entrainment in LO.
…..But, if crud present, then run OC 一萃 水相如果没有第三相－将料液夹带入负载有机相降到最 低。
E2 OC – to minimise organic entrainment in raffinate. 二萃 有机相连续－将有机夹带入萃余液降到最低。
industry were used in processing uranium ores. 在采矿和冶炼工业中第一个被商业运营的萃取剂是用于铀矿石的处理。
• First developed in the 1950’s, D2EHPA (Dapex process) was replaced by
Alamine® 336 tertiary amine in 1958 due to better efficiency. 在五十年代被发展， 由于更高效，在1958D2EHPA被Alamine ®336叔胺所取 代。
Basic Principles of
Solvent Extraction 溶剂萃取基本原理
Historical development 历史发展
• The first commercial extractants developed for the mining and metallurgical
Specific gravity of organic phase ~ 0.8 有机相比重～0.8
Aqueous droplets surrounded by organic phase Organic Continuous emulsion 水相小液滴被有机相包裹 有机相连续乳状液
Specific gravity of aqueous phase > 1.0 水相比重～1.0
• Nitrate - can degrade organic (particularly modified reagents). 硝酸根－能够降解有机相（特别是改型的萃取剂）
• Silica and suspended solids - causes crud formation and accentuates physical transfer of impurities to EW. 硅和悬浮颗粒－导致第三相的形成和会加剧杂质传递到电积
Scrub AC – to minimise aqueous entrainment in WLO. 洗涤段 水相连续－将水相夹带入洗涤负载有机相降到最低。
Strip OC – to minimise organic entrainment to EW. 反萃 有机相连续－将有机夹带入电积降到最低。
Typical PLS Cu concentration from different
Leach process sources 来自不同浸出工艺的典型料液铜浓度
PLS source 料液来源
料液 PLS Cu, g/l
Oxide ore 氧化矿
3–8
Chalcocite辉铜矿
1.5 – 4
Chalcopyrite (dump)黄铜矿
R2Cu + H2SO4
Loaded Organic + Spent Electrolyte
→ 2RH + CuSO4
Stripped Organic + Strong Electrolyte
• Acid concentration should be suitable for Electrowinning (EW)
Cu Solvent Extraction Chemistry
• Hydroxyoxime reagents are used to selectively EXTRACT copper from the PLS into the organic phase;
2RH + CuSO4 → R2Cu + H2SO4
Stripped Organic + PLS Loaded Organic + Raffinate
Organic recycled to Extraction • Strong acid is used to STRIP copper from the organic phase
back into an aqueous phase (eg, electrolyte suitable for EW);
Typical oxide copper leach solution Typical sulphide copper leach solution
典型的氧化铜浸出液
典型的硫化铜浸出液
Mainly copper, low iron 主要是铜，低铁
Mainly iron, low copper 主要是铁，低铜
• Chloride - can be transferred to EW, affecting EW and the environment. 氯－能够被传递到电积，影响电积和环境
• Manganese – can be transferred to EW and can degrade the organic phase in SX. 锰－能够被传递到电积，能够在溶剂萃取中降解有机相
process a few years later, in the 1960‘s.
随后在六十年代，相同的科学家也设计出了铜萃取工艺（CuSX）。
• The first Cu SX plant was commissioned in 1968 in the S.W. USA, Ranchers
Exploration Bluebird mine, using LIX 64N.
• Alamine was developed by General Mills Chemicals Inc., now Cognis
Corporation.
Alamine是由通用矿物公司发明的，现属于科宁公司。
• The same scientists conceived of the copper solvent extraction (CuSX)
铜溶剂萃取 – 化学
• 羟基肟萃取剂被用于从料液中选择性的萃取铜进入有机相;
2RH + CuSO4 → R2Cu + H2SO4
反萃有机相 + 料液
负债有机相 + 萃余液
回收有机去萃取 • 强酸被用于从有机相中反萃铜进入水相 (如, 适合于电积的电积
贫液);
R2Cu + H2SO4 → 2RH + CuSO4
今天世界上大约有3/4的铀是通过溶 剂萃取的方法生产的
Olympic Dam SX Plants 溶剂萃取厂
The Aim of Copper Solvent Extraction (SX) 铜溶剂萃取的目标
“To PURIFY and UPGRADE the copper content of an aqueous solution suitable for end product processing.” “来净化和浓缩液相溶液中的铜浓度使之适合于最终产品 生产”
The process always uses leaching before SX, and usually uses Electro-Winning (EW) following SX. 工艺在溶剂萃取之前始终使用浸出，并且在溶剂萃取之后 使用电积。
Leaching produces an impure Pregnant Leach Solution (PLS). 浸出产生不纯的浸出母液。
• Iron - can be transferred to EW, affecting EW efficiency. 铁－能够被传递到电积，影响电积效率
Spent Electrolyte 废电积液
Cu
Cu
Cu
Cu
Acid
LEACH
EXTRACT
STRIP
EW
酸
铜浸出
铜萃取
铜反萃
PLS 料液
Loaded Organic 负载有机相
Strong Electrolyte 电积富液
Cu2+
Emulsion mixing and separation – OC 乳状液混合和分相－有机相连续
世界上第一个铜溶剂萃取厂在1968年投产， Ranchers Exploration Bluebird mine，使 用的是LIX 64N.
Copper Solvent Extraction 铜溶剂萃取
Today, about ¼ of the world‘s copper is produced by SX
Organic weir
有机堰
Launders
பைடு நூலகம்
流槽
Organic in 有机进入
Settler
Aqueous in 水相进入
Organic out 有机出口
Aqueous out 水相出口
In the mixer, the two phases form an
emulsion which separates in the settler 在混合室，两相形成一个乳状液在澄清 室分离
• Most important species include copper, acid, iron, chloride, manganese, nitrate, dissolved silica and solids. 最重要的种类包括的是铜、酸、铁、氯、锰、硝酸根、被溶解的硅和固体颗 粒。
• Copper - the desired pure product. 铜－想得到纯铜
负债有机相 +电积贫液 反萃有机相 + 电积液
• 酸的浓度应适合于电积
Solvent Extraction Equipment – The Mixer Settler
溶剂萃取设备－混合室澄清室
Pump mixer Secondary mixer 抽吸混和室 二级混和室
Distribution fence 分散栅栏
今天世界上大约有1/4的铜是通 过溶剂萃取的方法生产的
Ranchers Bluebird Mine SX-EW Plant 溶剂萃取电积厂
Uranium Solvent Extraction
Today, about ¾ of the world‘s uranium is produced by SX
Australia
Aqueous continuous emulsion – AC 水相连续乳状液
Organic droplets surrounded by aqueous phase 有机小液滴被水相包围
Aqueous Continuous emulsion 水相连续乳状液
Desired Mixer Emulsion conditions 期望的混合室乳状液条件
E2 二萃
S.O.反萃有机相
S1 反萃
L.O. 负载有机相
Each stage uses a mixer – settler 每一段使用一个混合室－澄清室系列
OVERALL LEACH - SX - EW PROCESS
全部的浸出－溶剂萃取－电积工艺
H+
Raffinate 萃余液
Stripped Organic 反萃有机相
eg. Counter-current circuit for Cu Extraction
2 Extract x 1 Strip (2E x 1S) 例如. 铜逆流萃取 2萃1反（ 2E x 1S ）
PLS 料液
Raffinate 萃余液 Spent废电积液
E.W. 电积
Strong 电积富液
E1 一萃
< 1.5
Autoclave/agitation加压浸出/搅浸 2 – 20
pH 1.5 – 2.2 1–2 1–2 <1 - 2
However, the PLS always contains some undesirable impurities 然而，料液仍然含有一些不想要的杂质
Typical PLS constituents 典型的料液成分
E1 AC if no crud – to minimise PLS entrainment in LO.
…..But, if crud present, then run OC 一萃 水相如果没有第三相－将料液夹带入负载有机相降到最 低。
E2 OC – to minimise organic entrainment in raffinate. 二萃 有机相连续－将有机夹带入萃余液降到最低。
industry were used in processing uranium ores. 在采矿和冶炼工业中第一个被商业运营的萃取剂是用于铀矿石的处理。
• First developed in the 1950’s, D2EHPA (Dapex process) was replaced by
Alamine® 336 tertiary amine in 1958 due to better efficiency. 在五十年代被发展， 由于更高效，在1958D2EHPA被Alamine ®336叔胺所取 代。
Basic Principles of
Solvent Extraction 溶剂萃取基本原理
Historical development 历史发展
• The first commercial extractants developed for the mining and metallurgical
Specific gravity of organic phase ~ 0.8 有机相比重～0.8
Aqueous droplets surrounded by organic phase Organic Continuous emulsion 水相小液滴被有机相包裹 有机相连续乳状液
Specific gravity of aqueous phase > 1.0 水相比重～1.0
• Nitrate - can degrade organic (particularly modified reagents). 硝酸根－能够降解有机相（特别是改型的萃取剂）
• Silica and suspended solids - causes crud formation and accentuates physical transfer of impurities to EW. 硅和悬浮颗粒－导致第三相的形成和会加剧杂质传递到电积
Scrub AC – to minimise aqueous entrainment in WLO. 洗涤段 水相连续－将水相夹带入洗涤负载有机相降到最低。
Strip OC – to minimise organic entrainment to EW. 反萃 有机相连续－将有机夹带入电积降到最低。
Typical PLS Cu concentration from different
Leach process sources 来自不同浸出工艺的典型料液铜浓度
PLS source 料液来源
料液 PLS Cu, g/l
Oxide ore 氧化矿
3–8
Chalcocite辉铜矿
1.5 – 4
Chalcopyrite (dump)黄铜矿
R2Cu + H2SO4
Loaded Organic + Spent Electrolyte
→ 2RH + CuSO4
Stripped Organic + Strong Electrolyte
• Acid concentration should be suitable for Electrowinning (EW)
Cu Solvent Extraction Chemistry
• Hydroxyoxime reagents are used to selectively EXTRACT copper from the PLS into the organic phase;
2RH + CuSO4 → R2Cu + H2SO4
Stripped Organic + PLS Loaded Organic + Raffinate
Organic recycled to Extraction • Strong acid is used to STRIP copper from the organic phase
back into an aqueous phase (eg, electrolyte suitable for EW);
Typical oxide copper leach solution Typical sulphide copper leach solution
典型的氧化铜浸出液
典型的硫化铜浸出液
Mainly copper, low iron 主要是铜，低铁
Mainly iron, low copper 主要是铁，低铜
• Chloride - can be transferred to EW, affecting EW and the environment. 氯－能够被传递到电积，影响电积和环境
• Manganese – can be transferred to EW and can degrade the organic phase in SX. 锰－能够被传递到电积，能够在溶剂萃取中降解有机相
process a few years later, in the 1960‘s.
随后在六十年代，相同的科学家也设计出了铜萃取工艺（CuSX）。
• The first Cu SX plant was commissioned in 1968 in the S.W. USA, Ranchers
Exploration Bluebird mine, using LIX 64N.
• Alamine was developed by General Mills Chemicals Inc., now Cognis
Corporation.
Alamine是由通用矿物公司发明的，现属于科宁公司。
• The same scientists conceived of the copper solvent extraction (CuSX)
铜溶剂萃取 – 化学
• 羟基肟萃取剂被用于从料液中选择性的萃取铜进入有机相;
2RH + CuSO4 → R2Cu + H2SO4
反萃有机相 + 料液
负债有机相 + 萃余液
回收有机去萃取 • 强酸被用于从有机相中反萃铜进入水相 (如, 适合于电积的电积
贫液);
R2Cu + H2SO4 → 2RH + CuSO4
今天世界上大约有3/4的铀是通过溶 剂萃取的方法生产的
Olympic Dam SX Plants 溶剂萃取厂
The Aim of Copper Solvent Extraction (SX) 铜溶剂萃取的目标
“To PURIFY and UPGRADE the copper content of an aqueous solution suitable for end product processing.” “来净化和浓缩液相溶液中的铜浓度使之适合于最终产品 生产”
The process always uses leaching before SX, and usually uses Electro-Winning (EW) following SX. 工艺在溶剂萃取之前始终使用浸出，并且在溶剂萃取之后 使用电积。
Leaching produces an impure Pregnant Leach Solution (PLS). 浸出产生不纯的浸出母液。