Extraction system and method of using secondary amide/alkyl ester composite solvent to separate calcium and extract lithium from brine containing calcium and application thereof

Abstract

The invention discloses an extraction system and method of using a secondary amide / alkyl ester composite solvent to separate calcium and extract lithium from brine containing calcium and application of the extraction method. The extraction system contains secondary amid and alkyl ester, the secondary amid is formed by a single compound of the secondary amid or two or more mixtures, and the alkyl ester is formed by a single compound of the alkyl ester or two or more mixtures. The sum of carbon atoms in molecules of the secondary amid ranges from 12 to 18, and the sum of carbon atoms in molecules of the alkyl ester ranges from 8 to 20. The temperature of the freezing point of the extraction system is smaller than 0 DEG C. The single-stage or multi-stage counter-current extraction is conducted under the condition that the volume ratio of the organic phase to the brine phase is 1-10:1, the density of the brine ranges from 1.30g / cm<3> to 1.56g / cm<3>, the pH value of the brine ranges from 1to 7, and the temperature ranges from 0 DEG C to 50 DEG C; the aqueous phase with the low calcium lithium ratio is obtained through re-extraction; and lithium chloride, lithium carbonate and lithium hydroxide are obtained through concentration, impurity removal and preparation. The extraction system and method of using the secondary amide / alkyl ester composite solvent to separate calcium and extract lithium from the brine containing calcium and the application of the extraction method have the excellent effects that a secondary amide extracting agent is simple in molecular structure and easy to produce, and the properties such as the viscosity of the composite solvent are improved by the alkyl ester; the Li<+> multi-stage extraction rate is high, the lithium calcium separation coefficientis large, and the acid-base consumption of water re-extraction is low; the extraction separation technological process is short, the dissolution loss of the extraction system is few, and the extraction system and method are suitable for oil field brine exploitation.

Description

technical field

[0001] The invention relates to a method for extracting lithium from calcium-containing brine, in particular to an extraction system, an extraction method and an application thereof for separating calcium and extracting lithium from calcium-containing brine with a composite solvent. Background technique

[0002] There is abundant underground brine in oil fields in the Nanyishan area in the west of the Qaidam Basin in Qinghai, my country. Its resource reserves are comparable to those of the salt lake reserves in the Qaidam Basin. It is a rare multi-element coexistence super-large deposit in the world and has great industrial development value. . Among them, there are many useful components such as potassium, boron, lithium and iodine, and the content is high. The resource occurrence status is quite different from that of the developed salt lake resources. It belongs to the calcium chloride type brine in the Sulin classification, showing high salinity, high calc...

Examples

Embodiment 1

[0050] Li in a calcium-containing brine + and Ca 2+ The contents are 3.79g / L and 221.99g / L respectively, and the mass ratio of calcium to lithium is 58.62:1, of which Na + , K + , Mg 2+ , Cl - and B 2 o 3 The contents are 0.83, 5.32, 2.03, 424.10 and 2.42g / L respectively, and the brine density is 1.44g / cm 3 , the pH value of the brine is 5.5, and the ion concentration in the brine is prepared according to the brine composition of an oilfield in Nanyi Mountain, Qaidam Basin, Qinghai. The oilfield brine is degreased by an oil-water separator in advance. Get 6mL of this kind of bittern in the 100mL ground mouth Erlenmeyer flask, then add 21mL N-isooctyl isovaleramide extractant and 9mL ethyl laurate co-extractant therein, the co-extractant accounts for 30% of the organic phase volume, The volume ratio of organic phase to brine is 5:1. Put magnets in the Erlenmeyer flask, insert the matching air condenser into the mouth of the flask to prevent the liquid from splashing out...

Embodiment 2

[0057] Li in a calcium-containing brine + and Ca 2+ The contents are 4.04g / L and 224.03g / L respectively, and the mass ratio of calcium to lithium is 55.46:1, of which Na + , K + and Cl - The contents are 0.88, 5.68 and 423.91g / L respectively, and the brine density is 1.45g / cm 3 , the brine pH value is adjusted to 1.9, and the oil field brine is degreased with an oil-water separator in advance. Get 6mL of this kind of bittern in the 100mL ground mouth Erlenmeyer flask, then add 21mL N-isooctyl isovaleramide extractant and 9mL ethyl laurate co-extractant therein, the co-extractant accounts for 30% of the organic phase volume, The volume ratio of organic phase to brine is 5:1. Put magnets in the Erlenmeyer flask, insert the matching air condenser into the mouth of the flask to prevent the liquid from splashing out, place it in a DF-101S collector type constant temperature heating magnetic stirrer, mix and stir at 20°C, and extract for 20 minutes. Then the mixed liquid was t...

Embodiment 3

[0063] Li in a calcium-containing brine + and Ca 2+ The contents are 3.62g / L and 222.28g / L respectively, and the mass ratio of calcium to lithium is 61.33:1, of which Na + , K + and Cl - The contents are 0.79, 5.09 and 419.79g / L respectively, and the brine density is 1.44g / cm 3 , the pH value of the brine is 1.2, and the oil field brine is degreased with an oil-water separator in advance. Take 6mL of this kind of brine in a 100mL ground-mouth Erlenmeyer flask, then add 21mL N-isooctyl isovaleramide extractant and 9mL ethyl myristate co-extractant, the co-extractant accounts for 30% of the volume of the organic phase , the volume ratio of organic phase to brine is 5:1. Put magnets in the Erlenmeyer flask, insert the matching air condenser into the mouth of the flask to prevent the liquid from splashing out, place it in a DF-101S collector type constant temperature heating magnetic stirrer, mix and stir at 10°C, and extract for 20 minutes. Then the mixed liquid was transfe...

technical field

[0001] The invention relates to a method for extracting lithium from calcium-containing brine, in particular to an extraction system, an extraction method and an application thereof for separating calcium and extracting lithium from calcium-containing brine with a composite solvent. Background technique

[0002] There is abundant underground brine in oil fields in the Nanyishan area in the west of the Qaidam Basin in Qinghai, my country. Its resource reserves are comparable to those of the salt lake reserves in the Qaidam Basin. It is a rare multi-element coexistence super-large deposit in the world and has great industrial development value. . Among them, there are many useful components such as potassium, boron, lithium and iodine, and the content is high. The resource occurrence status is quite different from that of the developed salt lake resources. It belongs to the calcium chloride type brine in the Sulin classification, showing high salinity, high calc...

Examples

Embodiment 1

[0050] Li in a calcium-containing brine + and Ca 2+ The contents are 3.79g / L and 221.99g / L respectively, and the mass ratio of calcium to lithium is 58.62:1, of which Na + , K + , Mg 2+ , Cl - and B 2 o 3 The contents are 0.83, 5.32, 2.03, 424.10 and 2.42g / L respectively, and the brine density is 1.44g / cm 3 , the pH value of the brine is 5.5, and the ion concentration in the brine is prepared according to the brine composition of an oilfield in Nanyi Mountain, Qaidam Basin, Qinghai. The oilfield brine is degreased by an oil-water separator in advance. Get 6mL of this kind of bittern in the 100mL ground mouth Erlenmeyer flask, then add 21mL N-isooctyl isovaleramide extractant and 9mL ethyl laurate co-extractant therein, the co-extractant accounts for 30% of the organic phase volume, The volume ratio of organic phase to brine is 5:1. Put magnets in the Erlenmeyer flask, insert the matching air condenser into the mouth of the flask to prevent the liquid from splashing out...

Embodiment 2

[0057] Li in a calcium-containing brine + and Ca 2+ The contents are 4.04g / L and 224.03g / L respectively, and the mass ratio of calcium to lithium is 55.46:1, of which Na + , K + and Cl - The contents are 0.88, 5.68 and 423.91g / L respectively, and the brine density is 1.45g / cm 3 , the brine pH value is adjusted to 1.9, and the oil field brine is degreased with an oil-water separator in advance. Get 6mL of this kind of bittern in the 100mL ground mouth Erlenmeyer flask, then add 21mL N-isooctyl isovaleramide extractant and 9mL ethyl laurate co-extractant therein, the co-extractant accounts for 30% of the organic phase volume, The volume ratio of organic phase to brine is 5:1. Put magnets in the Erlenmeyer flask, insert the matching air condenser into the mouth of the flask to prevent the liquid from splashing out, place it in a DF-101S collector type constant temperature heating magnetic stirrer, mix and stir at 20°C, and extract for 20 minutes. Then the mixed liquid was t...

Embodiment 3

[0063] Li in a calcium-containing brine + and Ca 2+ The contents are 3.62g / L and 222.28g / L respectively, and the mass ratio of calcium to lithium is 61.33:1, of which Na + , K + and Cl - The contents are 0.79, 5.09 and 419.79g / L respectively, and the brine density is 1.44g / cm 3 , the pH value of the brine is 1.2, and the oil field brine is degreased with an oil-water separator in advance. Take 6mL of this kind of brine in a 100mL ground-mouth Erlenmeyer flask, then add 21mL N-isooctyl isovaleramide extractant and 9mL ethyl myristate co-extractant, the co-extractant accounts for 30% of the volume of the organic phase , the volume ratio of organic phase to brine is 5:1. Put magnets in the Erlenmeyer flask, insert the matching air condenser into the mouth of the flask to prevent the liquid from splashing out, place it in a DF-101S collector type constant temperature heating magnetic stirrer, mix and stir at 10°C, and extract for 20 minutes. Then the mixed liquid was transfe...

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