CN116477679B - Method for preparing chloroiridium acid by recycling and purifying iridium catalyst with alumina carrier - Google Patents
Method for preparing chloroiridium acid by recycling and purifying iridium catalyst with alumina carrier Download PDFInfo
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- CN116477679B CN116477679B CN202310726610.9A CN202310726610A CN116477679B CN 116477679 B CN116477679 B CN 116477679B CN 202310726610 A CN202310726610 A CN 202310726610A CN 116477679 B CN116477679 B CN 116477679B
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- iridium
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 86
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002253 acid Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004064 recycling Methods 0.000 title claims abstract description 12
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 title claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 238000011084 recovery Methods 0.000 claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 238000003795 desorption Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 11
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 229920001429 chelating resin Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 35
- 238000001816 cooling Methods 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000011978 dissolution method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- -1 platinum group metals Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a method for preparing chloroiridium acid by recycling and purifying an alumina carrier iridium catalyst, which comprises the steps of carrying out high-temperature melting and acid dissolution precipitation on filter residues obtained after normal-pressure acid dissolution of alumina carrier iridium catalyst powder, enriching more than 90% iridium, and carrying out absorption, resin desorption and precipitation on filtrate obtained after normal-pressure acid dissolution of the alumina carrier iridium catalyst powder by chelating resin to collect the rest iridium metal; and then combining and dissolving the ammonium chloroiridate precipitates respectively to obtain the chloroiridic acid. The method has low requirement on iridium recovery equipment, low energy consumption and high recovery rate, and the comprehensive recovery rate reaches 96%.
Description
Technical Field
The invention relates to the technical field of recovery and separation of platinum group metal iridium, in particular to a method for preparing chloroiridium acid by utilizing recovery and purification of an alumina carrier iridium catalyst.
Background
The alumina carrier iridium catalyst is mainly used for purifying automobile exhaust, decomposing hydrazine, hydrogenating unsaturated hydrocarbon and the like. The iridium metal belongs to extremely rare noble metal types worldwide, and the iridium metal has good economic value when recovered and purified from the catalyst and reused.
Iridium has extremely strong corrosion resistance, so that the iridium is difficult to dissolve and produce liquid at normal temperature and normal pressure, the recovery and separation difficulty is high, and the recovery rate is low. Thus, there are few reports of methods for directly recovering and purifying iridium from alumina-supported iridium catalysts, and relatively many methods for recovering alumina-supported platinum and palladium catalysts are disclosed in patent (CN 103276215B), which discloses a method for recovering noble metals from spent catalysts, which requires high-pressure dissolution, and patent (CN 103194606 a), which discloses a method for enriching platinum group metals from alumina-based spent catalysts, and the above disclosed methods are mainly applicable to recovery of platinum and palladium-alumina-supported catalysts.
The traditional method for recovering iridium from granular alumina carrier iridium catalyst is generally divided into an alkali dissolution method and an acid dissolution method, sodium peroxide can convert iridium into iridium oxide in a high-temperature melting method, sodium hydroxide can convert indissolvable alumina in the catalyst into sodium metaaluminate, but a large amount of aluminum dissolution can cause difficulty in iridium separation, iridium precipitation is difficult to avoid inclusion of aluminum metal, and subsequent purification difficulty is increased. Although most of the alumina as a carrier can be dissolved by the acid dissolution method, a small amount of iridium metal can be dissolved to cause loss, and the recovery rate is low.
Disclosure of Invention
Aiming at the defects existing in the prior art, the main purpose of the invention is to provide a method for preparing chloroiridic acid by recycling and purifying an alumina carrier iridium catalyst, which comprises two steps, namely, the first step is to perform high-temperature melting on filter residues obtained by performing normal-pressure acid dissolution on alumina carrier iridium catalyst powder, the acid dissolution precipitation step is to enrich more than 90% of iridium, and the second step is to perform absorption on filtrate obtained by performing normal-pressure acid dissolution on the alumina carrier iridium catalyst powder through chelating resin, resin desorption and precipitation to collect the rest iridium metals; and then combining and dissolving the ammonium chloroiridate precipitates respectively to obtain the chloroiridic acid. The method has low requirement on iridium recovery equipment, low energy consumption and high recovery rate, and the comprehensive recovery rate reaches 96%.
In order to achieve the above object, the present invention provides a method for preparing chloroiridic acid by recovery and purification of an alumina-supported iridium catalyst.
The method for preparing chloroiridium acid by recycling and purifying the alumina-supported iridium catalyst comprises the following steps:
acid-soluble under normal pressure: heating alumina carrier iridium catalyst powder with sulfuric acid under normal pressure for reaction, diluting and filtering, and washing the obtained insoluble substances to obtain filtrate and filter residues;
high-temperature melting: melting the filter residue at high temperature by adopting a mixture of sodium hydroxide and sodium peroxide to obtain a molten product;
acid-soluble precipitation: dissolving the fused product by hydrochloric acid, oxidizing by nitric acid, and then adding a saturated ammonium chloride solution to precipitate iridium to obtain a first ammonium chloroiridate crystal;
resin adsorption: adsorbing the filtrate after standing by using propanethiol resin;
and (3) resin desorption: desorbing by adopting a hydrochloric acid solution containing thiourea, adding the desorbed solution into a concentrated sulfuric acid solution for heating and concentrating, dissolving the obtained precipitate by adopting aqua regia, and adding a saturated ammonium chloride solution to precipitate iridium to obtain a second ammonium chloroiridate crystal;
and mixing the first ammonium chloroiridate crystal and the second ammonium chloroiridate crystal, and then adding aqua regia to dissolve to prepare the chloroiridic acid.
Further, the method also comprises ball milling and crushing: ball milling is carried out on the alumina carrier iridium catalyst to obtain alumina carrier iridium catalyst powder.
Further, the granularity of the alumina carrier iridium catalyst powder is 50-100 meshes.
Further, in the normal pressure acid dissolution step, the mass fraction of the sulfuric acid is 30-40%, the heating temperature is 80-100 ℃, and the continuous reaction time is 2-4 hours; washing insoluble substances with hot water for several times to obtain the filtrate and the filter residue.
Further, in the high-temperature melting step, the mass ratio of the sodium hydroxide to the sodium peroxide is 1:3, the high-temperature melting temperature is 700+/-50 ℃;
the mass ratio of the filter residue to the mixture of the sodium hydroxide and the sodium peroxide is 1: (3-5).
In the resin adsorption step, the filtrate passes through the propanethiol resin at a speed of 50-200 ml/min.
Further, the propanethiol resin is 1-propanethiol resin or 1, 3-propanedithiol resin.
In the resin desorption step, a hydrochloric acid solution containing 2-5% of thiourea is adopted for desorption; the mass fraction of the concentrated sulfuric acid solution is 40-60%; the heating concentration temperature is 100-130 ℃ and the time is 3-5 h.
Further, the mass fraction of the hydrochloric acid solution is 5-20%.
Further, the mass fraction of iridium in the alumina-supported iridium catalyst is 5-40%.
The invention provides a method for recycling and preparing chloroiridic acid by using an alumina carrier iridium catalyst, which realizes recycling and reutilization of iridium in the alumina carrier iridium catalyst.
The recovery purification preparation method has low requirement on iridium recovery equipment, low energy consumption and high recovery rate, and the comprehensive recovery rate reaches 96%.
The recovery purification preparation method is suitable for the alumina carrier catalyst with the iridium content of 5-40%, and has more obvious effect on the catalyst with lower iridium content.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to designate like parts throughout the figures. In the drawings:
FIG. 1 is a flow chart of a method for preparing chloroiridic acid by recycling and purifying an alumina-supported iridium catalyst in an embodiment provided by the invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
According to the specific embodiment of the invention, a method for preparing chloroiridic acid by recycling and purifying an alumina carrier iridium catalyst is provided.
The method for preparing chloroiridic acid by recycling and purifying the iridium catalyst with the alumina carrier is suitable for the alumina carrier catalyst with the iridium content of 5-40% in mass fraction, and has more obvious effect on the catalyst with lower iridium content.
Of course, the method can also be applied to the recovery and purification of the catalyst with higher iridium content to prepare chloroiridium acid.
The method for preparing chloroiridium acid by recycling and purifying the alumina carrier iridium catalyst in the invention specifically comprises the following steps:
ball milling and crushing: ball milling is carried out on the alumina carrier iridium catalyst to obtain alumina carrier iridium catalyst powder.
In the embodiment of the invention, the granularity of the alumina-supported iridium catalyst powder is 50-100 meshes.
Acid-soluble under normal pressure: adding the iridium catalyst powder with the alumina carrier into an atmospheric pressure reaction kettle, adding sulfuric acid with the mass fraction of 30-40% for heating reaction, wherein the heating temperature is 80-100 ℃, and the continuous reaction time is 2-4 hours; cooling after the reaction is finished, adding high-purity water for dilution, filtering supernatant, centrifuging the insoluble matters at the lower layer, filtering, and washing the insoluble matters with hot water for a plurality of times, such as three times, to effectively remove aluminum sulfate on the surface of the insoluble matters, thereby obtaining filtrate and filter residues.
In the present invention, the filter residue mainly includes iridium metal and iridium oxide, and since iridium ions are contained in the filtrate, the filtrate is collected and subjected to subsequent treatment in order to achieve efficient recovery of iridium.
In an embodiment of the invention, the filtrate comprises a supernatant fluid after dilution filtration, an insoluble centrifugal filtrate and a washing liquid to ensure efficient recovery of iridium.
High-temperature melting: and (3) adopting a mixture of sodium hydroxide and sodium peroxide to carry out high-temperature melting on the filter residues to obtain a melted product.
In the embodiment of the invention, the mass ratio of sodium hydroxide to sodium peroxide is 1:3, the high-temperature melting temperature is 700+/-50 ℃.
As one embodiment of the invention, the mass ratio of the filter residue to the mixture of sodium hydroxide and sodium peroxide is 1 (3-5).
Acid-soluble precipitation: and (3) cooling and crushing the molten product, transferring the crushed molten product into a reaction kettle, adding high-purity water, pulping and stirring, adding hydrochloric acid to dissolve the molten product, and adding nitric acid to oxidize. And adding a saturated ammonium chloride solution to precipitate iridium to obtain blackish brown first ammonium chloroiridate crystals, cooling and filtering the crystals.
The quality, concentration, etc. of the hydrochloric acid, nitric acid and saturated ammonium chloride solution added in the acid-soluble precipitation step of the present invention may be adjusted and selected according to actual needs, and are not particularly limited.
Resin adsorption: the filtrate was adsorbed using propanethiol resin.
It should be noted that the filtrate needs to be left for a certain period of time before the resin adsorption is performed, for example, after 24 hours.
In the embodiment of the invention, the filtrate passes through the propanethiol resin column at a speed of 50-200 ml/min.
As an embodiment of the present invention, the propanethiol resin may be a 1-propanethiol resin or a 1, 3-propanedithiol resin.
And (3) resin desorption: and (3) desorbing by adopting a hydrochloric acid solution containing thiourea, then adding the desorbed solution into a concentrated sulfuric acid solution, heating, concentrating and precipitating iridium, wherein the heating, concentrating temperature is 100-130 ℃ and the time is 3-5 hours, obtaining a precipitate, filtering the precipitate, adding aqua regia for dissolving, then adding a saturated ammonium chloride solution for precipitating iridium, obtaining a second ammonium chloroiridate crystal, and filtering.
In the embodiment of the invention, the desorption is carried out by adopting a hydrochloric acid solution containing 2-5% (in mass fraction) of thiourea.
As one embodiment of the invention, the mass fraction of the hydrochloric acid solution is 5-20%.
In the embodiment of the invention, in the resin desorption process, the mass fraction of the concentrated sulfuric acid solution is 40-60%.
Finally, mixing the first ammonium chloroiridate crystal and the second ammonium chloroiridate crystal, and adding aqua regia to dissolve to prepare the chloroiridic acid.
The concentration and the addition amount of aqua regia may be designed according to actual needs, and are not particularly limited.
The method provided by the invention has low requirements on iridium recovery equipment, low energy consumption and high recovery rate, and the comprehensive recovery rate reaches 96%.
The method for producing chloroiridic acid by recovery and purification using an alumina-supported iridium catalyst in the present invention will be described in detail by way of specific examples.
Example 1:
ball milling and crushing: 1000g of an iridium catalyst with an iridium content of 35% on an alumina support were ball-milled to a 60 mesh powder.
Acid-soluble under normal pressure: adding the powder into a 10L normal pressure reaction kettle, adding 3L of 40% sulfuric acid, heating to 95 ℃ for continuous reaction for 3 hours, cooling to room temperature after the reaction is finished, adding 5L of high-purity water for dilution, standing for 24 hours, filtering supernatant, centrifuging the insoluble matters at the lower layer, filtering, and washing the insoluble matters with 1L of hot water for three times each time to obtain filtrate and filter residues.
High-temperature melting: and (3) drying and weighing the obtained filter residues, wherein the weight is 351g, adding 1500g of a mixture of sodium hydroxide and sodium peroxide (1:3), uniformly mixing, and carrying out high-temperature melting in a muffle furnace at the temperature of 700 ℃ to obtain a molten product.
Acid-soluble precipitation: and (3) cooling the molten product, transferring the molten product into a reaction kettle, adding 2L of high-purity water, stirring, adding 5L of hydrochloric acid for dissolution, and adding 1.5L of nitric acid for oxidation. Then, 3.3L of saturated ammonium chloride solution was added to precipitate iridium to obtain blackish brown ammonium chloroiridate crystals, which were cooled, filtered and dried to weight 732g.
Resin adsorption: 10.3L of the filtrate obtained in the normal pressure acid-dissolution step was adsorbed by 500mL of a 1-propanethiol resin column at a rate of 60 mL/min.
And (3) resin desorption: 1.1L of hydrochloric acid solution containing 5% thiourea is used for resin desorption, the concentration of the hydrochloric acid solution is 10%, desorption solution is added into 1L of 60% concentrated sulfuric acid solution, the solution is heated to 120 ℃ for concentrating for 3 hours to precipitate iridium, precipitate is obtained, aqua regia is added after the precipitate is filtered to dissolve the precipitate, 500mL of saturated ammonium chloride solution is added to precipitate iridium, ammonium chloroiridate crystal is obtained, and the solution is filtered and dried, and the weight is 43g.
And combining ammonium chloroiridate crystals obtained in the acid-soluble precipitation step and the resin desorption step, and adding 6L of aqua regia for dissolution to obtain 963.2g of 35% chloroiridic acid, wherein the comprehensive yield is 96.3%.
Example 2:
ball milling and crushing: 4000g of an iridium catalyst with 5% iridium content on an alumina support were ball-milled to a 100 mesh powder.
Acid-soluble under normal pressure: adding the powder into a 20L normal pressure reaction kettle, adding 15L of 30% sulfuric acid, heating to 80 ℃ for continuous reaction for 4 hours, cooling to room temperature after the reaction is finished, adding 23L of high-purity water for dilution, standing for 10 hours, filtering supernatant, centrifuging the insoluble matters at the lower layer, filtering in two batches, and washing the insoluble matters with 1L of hot water for three times in each batch to obtain filtrate and filter residues.
High-temperature melting: and (3) drying and weighing the filter residues to obtain 203g, adding 800g of a mixture of sodium hydroxide and sodium peroxide (1:3), uniformly mixing, and melting at a high temperature of 700 ℃ to obtain a molten product.
Acid-soluble precipitation: and (3) cooling the molten product, transferring the molten product into a reaction kettle, adding 1.2L of high-purity water, stirring, adding 3L of hydrochloric acid for dissolution, and adding 1L of nitric acid for oxidation. Then, 2.1L of saturated ammonium chloride solution was added to precipitate iridium to obtain blackish brown ammonium chloroiridate crystals, which were cooled and then filtered to dry the crystals, and the weight of the crystals was 413g.
Resin adsorption: 39.5L of the filtrate obtained in the normal pressure acid-dissolution step was adsorbed by a 1L 1, 3-propanethiol resin column at a rate of 100 mL/min.
And (3) resin desorption: 2.4L of hydrochloric acid solution containing 3% thiourea is used for resin desorption, the concentration of the hydrochloric acid solution is 15%, desorption liquid is slowly added into 1L of 40% concentrated sulfuric acid solution, the temperature is heated to 110 ℃ for concentrating for 5 hours to precipitate iridium, precipitate is obtained, aqua regia is added after the precipitate is filtered to dissolve the precipitate, 300mL of saturated ammonium chloride solution is added to precipitate iridium, ammonium chloroiridate crystal is obtained, and the solution is filtered and dried, and the weight is 29g.
And combining ammonium chloroiridate crystals obtained in the acid dissolution and precipitation step and the resin desorption step, and adding 4L of aqua regia for dissolution to obtain 549.3g of 35% chloroiridate, wherein the comprehensive yield is 96.1%.
It should be noted that the term "comprising" in the description of the invention and in the claims, as well as any variants thereof, is intended to cover a non-exclusive inclusion, for example, comprising a series of elements not necessarily limited to those elements explicitly listed, but may include other elements not explicitly listed or inherent to elements.
The description of "first," "second," etc. in this disclosure is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature.
In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (3)
1. The method for preparing chloroiridium acid by recycling and purifying the alumina-supported iridium catalyst is characterized by comprising the following steps of:
ball milling and crushing: ball milling is carried out on the alumina carrier iridium catalyst to obtain alumina carrier iridium catalyst powder; the particle size of the alumina carrier iridium catalyst powder is 50-100 meshes, and the mass fraction of iridium in the alumina carrier iridium catalyst is 5-40%;
acid-soluble under normal pressure: heating the alumina carrier iridium catalyst powder with sulfuric acid at normal pressure for reaction, wherein the mass fraction of the sulfuric acid is 30-40%, the heating temperature is 80-100 ℃, and the continuous reaction time is 2-4 hours; diluting and filtering, washing the obtained insoluble matters, and washing the insoluble matters for a plurality of times by adopting hot water to obtain filtrate and filter residues;
high-temperature melting: melting the filter residue at high temperature by adopting a mixture of sodium hydroxide and sodium peroxide to obtain a molten product;
acid-soluble precipitation: dissolving the fused product by hydrochloric acid, oxidizing by nitric acid, and then adding a saturated ammonium chloride solution to precipitate iridium to obtain a first ammonium chloroiridate crystal;
resin adsorption: adsorbing the filtrate after standing by using propanethiol resin; wherein the filtrate passes through the propanethiol resin at a speed of 50-200 ml/min;
and (3) resin desorption: desorbing by using a hydrochloric acid solution containing 2-5% of thiourea, wherein the mass fraction of the hydrochloric acid solution is 5-20%, adding the desorbed solution into a concentrated sulfuric acid solution for heating and concentrating, dissolving the obtained precipitate by using aqua regia, and adding a saturated ammonium chloride solution to precipitate iridium to obtain a second ammonium chloroiridate crystal; wherein the mass fraction of the concentrated sulfuric acid solution is 40-60%; heating and concentrating at 100-130 ℃ for 3-5 hours;
and mixing the first ammonium chloroiridate crystal and the second ammonium chloroiridate crystal, and then adding aqua regia to dissolve to prepare the chloroiridic acid.
2. The method for producing chloroiridic acid by recovery and purification using alumina-supported iridium catalyst according to claim 1, wherein in the high-temperature melting step, the mass ratio of sodium hydroxide to sodium peroxide is 1:3, the high-temperature melting temperature is 700+/-50 ℃;
the mass ratio of the filter residue to the mixture of the sodium hydroxide and the sodium peroxide is 1 (3-5).
3. The method for producing chloroiridium acid by recovery and purification using an alumina-supported iridium catalyst according to claim 1, wherein the propanethiol resin is a 1-propanethiol resin or a 1, 3-propanedithiol resin.
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| CN101445872A (en) * | 2007-11-27 | 2009-06-03 | 中国蓝星（集团）股份有限公司 | Method for extracting noble metal iridium from mixed oxide containing ruthenium, iridium, titanium, tin, zirconium and palladium |
| WO2010057582A1 (en) * | 2008-11-18 | 2010-05-27 | Oxea Gmbh | Method for reclaiming rhodium from aqueous solutions comprising rhodium complex bonds |
| CN112357979A (en) * | 2020-11-16 | 2021-02-12 | 沈阳有色金属研究院有限公司 | Method for directly preparing chloro-iridic acid from iridium-containing waste material |
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| CN101445872A (en) * | 2007-11-27 | 2009-06-03 | 中国蓝星（集团）股份有限公司 | Method for extracting noble metal iridium from mixed oxide containing ruthenium, iridium, titanium, tin, zirconium and palladium |
| WO2010057582A1 (en) * | 2008-11-18 | 2010-05-27 | Oxea Gmbh | Method for reclaiming rhodium from aqueous solutions comprising rhodium complex bonds |
| CN112357979A (en) * | 2020-11-16 | 2021-02-12 | 沈阳有色金属研究院有限公司 | Method for directly preparing chloro-iridic acid from iridium-containing waste material |
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