CN109811138A - A method of from recycling iridium in organic liquid waste containing iridium - Google Patents
A method of from recycling iridium in organic liquid waste containing iridium Download PDFInfo
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- CN109811138A CN109811138A CN201910119310.8A CN201910119310A CN109811138A CN 109811138 A CN109811138 A CN 109811138A CN 201910119310 A CN201910119310 A CN 201910119310A CN 109811138 A CN109811138 A CN 109811138A
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- 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
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Abstract
The method that the invention discloses a kind of to recycle iridium from organic liquid waste containing iridium, it is characterized in that, adjust the pH value of the organic liquid waste containing iridium, it is charged with defoaming agent, waste liquid and solid reductant are subjected to reduction reaction, the iridic compound in waste liquid is reduced to metal iridium precipitating, filtering, washing obtains iridium powder after dry.Present invention process is simple, and recovery efficiency is high, strong to adaptability to raw material, can handle a variety of organic liquid wastes containing iridium.
Description
Technical field
The present invention relates to the recovery methods of iridium, and in particular to a method of from recycling iridium in organic liquid waste containing iridium.
Background technique
The organic compound of iridium, such as acetylacetone,2,4-pentanedione iridium, two (Phenylphosphine) carbonyl iridium chlorides, acetic acid iridium are a kind of important
OLED iridium phosphorescent molecules material, homogeneous catalyst, Metallo-Organic Chemical Vapor deposition precursor compound.In having for iridium
In machine compound preparation of the production process, since product yield is lower, there is substantial portion of iridium by-product to enter containing large amount of organic
Waste liquid in.Fine Chemical S-metolachlor synthesis 1,5- cyclo-octadiene iridium chloride homogeneous catalyst, low-pressure methanol
Carbonylation acetic acid Cativa technique produces process of acetic acid acetic acid iridium catalyst [Ir3(O2CCH3)6-μ3-O(H2O)3]
O2CCH3A large amount of organic waste materials containing iridium are generated after failure, are generated in OLED iridium phosphorescent molecules material preparation process and are largely contained iridium
Organic liquid waste, the organic liquid waste containing iridium that triphenylphosphine iridium chloride preparation process generates, such organic liquid waste is mainly by organic phase, water
Equal composition.
It is seldom for the recovery method report of iridium in organic liquid waste.Currently, there are mainly two types of iridium in organic waste materials containing iridium
Method: conventional incineration method and oxidation dissolution method.Conventional incineration method is to remove organic matter by burning, and generates the oxygen of metal iridium or iridium
Then iridium is transferred to after solution by the methods of medium temperature chlorination, oxidation alkali fusion or sulfonium trapping-aluminothermy activation and is mentioned again by compound
Pure, conventional incineration method iridium volatilization loss in the podzolic process of organic matter containing iridium is big, while can generate a large amount of toxic exhaust emission,
Operating process is not easy to control.Oxidation dissolution method is the stabilization of the organic matter destroyed under given conditions in solution with strong oxidizer
Property, so that it is aoxidized or is decomposed, is transferred to iridium in inorganic phase and carries out recycling purification.As needle has research to contain levulinic to certain
The waste liquid containing iridium of the organic matters such as ketone, alcohol recycles iridium using oxidation dissolution, uses chloroazotic acid Oxidative demage organic matter first, realizes molten
The transition of liquid medium makes iridium be converted into the hydrochloric acid solution of iridium, hydrochloric acid is added after the completion of oxidation and catches up with nitre, can remove remnants by hydrolysis
Organic matter and most soluble-salt exchange aluminium, the copper, iron, magnesium, calcium removed in iridium solution using strong acid type cationic resin
Equal base metal impurities, iridium are not easy to form hydrated cation, obtain condensing crystallizing after the solution purification containing iridium, obtain chloro-iridic acid, directly
Connect calcining, hydrogen reduction produces high-purity iridium powder.
Since iridium exists in the form of organo-iridium compounds in organic waste materials containing iridium, it is difficult using conventional reducing agent from having
Body system direct-reduction recycling iridium；Meanwhile containing volatile iridic compound in these organic liquid wastes, it directly heats or calcines
It will cause the loss of iridium.It, can be with for relatively simple organic liquid waste system when handling organic liquid waste containing iridium using the above method
It is recycled by oxidation dissolution method；But it is big for the recovery difficult of iridium in complex system, it needs by burning-medium temperature chloride-oxidation
A series of many and diverse process such as alkali fusion or sulfonium trapping-aluminothermy activation, be just able to achieve the recycling of iridium, and it is difficult to ensure that iridium
The rate of recovery.
Summary of the invention
The purpose of the present invention is the existing method from organic liquid waste recycling iridium there are aiming at the problem that, propose a kind of from containing
The method of iridium is recycled in iridium organic liquid waste.
It is of the present invention it is a kind of from organic liquid waste recycle iridium method include:
A. defoaming agent tributyl phosphate is added into this waste liquid for the pH value 7~10 for adjusting the organic liquid waste containing iridium, and quality is added
Than being 0.05~0.1%；
B. the resulting organic liquid waste of step A is slowly added into and is filled in solid sodium borohydride/potassium reactor, stirred,
Until generating without obvious bubble, the iridic compound in waste liquid is reduced to metallic state and is precipitated out, wherein sodium borohydride/potassium with have
The molar ratio of contained iridium is 5~30 in machine waste liquid；
C. dehydrated alcohol, 80 DEG C of deionized water washings is respectively adopted in the resulting iridium precipitating of step B, then in tube furnace
In 250~300 DEG C of temperature, stream of nitrogen gas after drying, iridium powder is obtained.
The beneficial effects of the present invention are existing incineration method, oxidation dissolution method are required to destroy organic-compound system, make
At the loss of removal process iridium, organic matter is destroyed.The present invention will contain iridium organic liquid waste directly adopt strong reductant sodium borohydride/
Potassium is handled, and is precipitated out iridium component with metallic forms, and the organic constituents after separation can carry out other recovery processings.This
Invention needs not move through the processing such as burning, oxidation, and waste liquor PH is adjusted to 7~10, ensure that stability of the reducing agent in system,
Reduce its dosage；Addition tributyl phosphate effectively inhibits the generation of a large amount of bubbles in reaction process, is not in lead because emitting slot
Cause the loss of iridium.Present invention process is simple, and recovery efficiency is high, strong to adaptability to raw material, can handle a variety of (iridium of organic liquid waste containing iridium
Mass fraction 0.01~3%).
Specific embodiment
Embodiment 1 takes waste reaction solution 5000g (the iridium content for preparing the generation of 1,5- cyclo-octadiene iridium chloride dimer process
0.24%) its pH value 10, is adjusted, the tributyl phosphate of 5g is added, waste liquid is slowly added into and fills 50g solid reductant boron hydrogen
In the reactor for changing sodium, reaction is sufficiently stirred, until bubble-free generates；Iridium precipitating is isolated to after reaction, be filtered under diminished pressure,
Dehydrated alcohol is respectively adopted, 80 DEG C of deionized waters are sufficiently washed, filtering, then iridium is deposited in tube furnace in 300 DEG C, nitrogen
Under air-flow after drying, iridium powder 10.82g, the rate of recovery 90.17% of iridium are obtained.
Embodiment 2 takes the waste reaction solution 2000g (iridium content 0.08%) for preparing the generation of acetylacetone,2,4-pentanedione dicarbapentaborane iridium process, adjusts
Its whole pH value 10, is added the tributyl phosphate of 1.5g, and waste liquid is slowly added into and fills the anti-of 25g solid reductant potassium borohydride
It answers in device, reaction is sufficiently stirred, until bubble-free generates；Iridium precipitating is isolated to after reaction, be filtered under diminished pressure, is respectively adopted
Dehydrated alcohol, 80 DEG C of deionized waters are sufficiently washed, and obtained iridium is deposited in tube furnace under 300 DEG C, stream of nitrogen gas by filtering
After drying, iridium powder 1.43g, the rate of recovery 89.37% of iridium are obtained.
Embodiment 3 takes the waste reaction solution for preparing the generation of 1,5- cyclo-octadiene iridium chloride dimer process to be concentrated through vacuum distillation
Concentrate 3000g (iridium content 2.19%) afterwards, adjusts its pH value 7, the tributyl phosphate of 3g is added, waste liquid is slowly added into
In the reactor for filling 150g solid reductant sodium borohydride, reaction is sufficiently stirred, until bubble-free generates；To the end of reacting
Afterwards, it is filtered under diminished pressure and isolates iridium precipitating, dehydrated alcohol is respectively adopted, 80 DEG C of deionized waters are sufficiently washed, filtering, the iridium that will be obtained
It is deposited in tube furnace under 300 DEG C, stream of nitrogen gas after drying, obtains iridium powder 62.00g, the rate of recovery 94.36% of iridium.
Embodiment 4 prepares waste reaction solution 1000g (the iridium content that organic iridium phosphorescent molecules material mating object process generates
0.52%) its pH value 8, is adjusted, the tributyl phosphate of 1g is added, waste liquid is slowly added into and fills 30g solid reductant boron hydrogen
In the reactor for changing sodium, reaction is sufficiently stirred, until bubble-free generates；Iridium precipitating is isolated to after reaction, be filtered under diminished pressure,
Dehydrated alcohol is respectively adopted, 80 DEG C of deionized waters are sufficiently washed, filtering, obtained iridium is deposited in tube furnace in 300 DEG C, nitrogen
Under gas air-flow after drying, iridium powder 4.70g, the rate of recovery 90.38% of iridium are obtained.
Claims (4)
1. a kind of method for recycling iridium from organic liquid waste containing iridium, it is characterised in that step includes: adjustment organic liquid waste containing iridium
PH value is charged with defoaming agent, waste liquid and solid reductant is carried out reduction reaction, the iridic compound in waste liquid is reduced to
Metal iridium precipitating, is filtered, and washing obtains iridium powder after dry.
2. a kind of method for recycling iridium from organic liquid waste containing iridium, which is characterized in that sequentially include the following steps:
A. the pH value 7~10 for adjusting the organic liquid waste containing iridium is charged with the defoaming agent tricresyl phosphate that mass ratio is 0.05~0.1%
Butyl ester；
B. the resulting organic liquid waste of step A is slowly added into and is filled in solid sodium borohydride/potassium reactor, stirred, until
No obvious bubble generates, and the iridium in waste liquid is reduced to metallic state and is precipitated out, wherein sodium borohydride/potassium and institute in organic liquid waste
Molar ratio containing iridium is 5~30；
C. by dehydrated alcohol is respectively adopted in the resulting iridium precipitating of step B, 80 DEG C of deionized waters are washed to neutrality, then in tube furnace
It is interior at a temperature of 250~300 DEG C, it is dry in stream of nitrogen gas after, obtain iridium powder.
3. a kind of method for recycling iridium from organic liquid waste containing iridium described in accordance with the claim 1, which is characterized in that this method institute
The organic liquid waste containing iridium of processing is that hydrated iridium trichloride prepares 1,5- cyclo-octadiene iridium chloride dimer, acetylacetone,2,4-pentanedione dicarbapentaborane
Iridium, carbonyl three are triphenylphosphine iridium chloride, carbonyl double i.e. triphenylphosphine iridium chloride, organic iridium phosphorescent molecules material mating objects etc.
Any one or more in waste reaction solution, wherein the content of iridium is 0.01~3%.
4. a kind of method for recycling iridium from organic liquid waste containing iridium, which is characterized in that sequentially include the following steps:
Take preparation 1, the waste reaction solution 5000g that 5- cyclo-octadiene iridium chloride dimer process generates, iridium content 0.24% in waste liquid,
Its pH value 10 is adjusted, the tributyl phosphate of 5g is added, waste liquid is slowly added into and fills the anti-of 50g solid reductant sodium borohydride
It answers in device, reaction is sufficiently stirred, until bubble-free generates；Iridium precipitating is isolated to after reaction, be filtered under diminished pressure, is respectively adopted
Dehydrated alcohol, 80 DEG C of deionized waters are sufficiently washed, then iridium is deposited in tube furnace and does under 300 DEG C, stream of nitrogen gas by filtering
After dry, iridium powder 10.82g, the rate of recovery 90.17% of iridium are obtained.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196836A (en) * | 2021-12-07 | 2022-03-18 | 泸西县扩铂贵金属有限公司 | Method for removing noble metal impurities in iridium-containing feed liquid |
| CN115043883A (en) * | 2022-05-25 | 2022-09-13 | 昆明贵金属研究所 | Preparation method of acetylacetonatodicarbonyl iridium (I) |
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| CN114196836A (en) * | 2021-12-07 | 2022-03-18 | 泸西县扩铂贵金属有限公司 | Method for removing noble metal impurities in iridium-containing feed liquid |
| CN115043883A (en) * | 2022-05-25 | 2022-09-13 | 昆明贵金属研究所 | Preparation method of acetylacetonatodicarbonyl iridium (I) |
| CN115043883B (en) * | 2022-05-25 | 2024-05-07 | 昆明贵金属研究所 | Preparation method of iridium (I) acetylacetonate dicarbonyl |
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