CN112760484B - Normal-temperature chlorination and dissolution treatment method for waste platinum-rhodium thermocouples - Google Patents
Normal-temperature chlorination and dissolution treatment method for waste platinum-rhodium thermocouples Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 75
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 33
- 238000004090 dissolution Methods 0.000 title claims abstract description 31
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 82
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 43
- 239000010948 rhodium Substances 0.000 claims abstract description 43
- 239000002608 ionic liquid Substances 0.000 claims abstract description 41
- 229910052742 iron Inorganic materials 0.000 claims abstract description 41
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 37
- -1 rhodium ions Chemical class 0.000 claims abstract description 36
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- PLWSZOQYWKLNIL-UHFFFAOYSA-N 1-butyl-2-chloro-3-methyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1Cl PLWSZOQYWKLNIL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 39
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000000460 chlorine Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000629 Rh alloy Inorganic materials 0.000 abstract description 31
- 230000008569 process Effects 0.000 abstract description 29
- 239000000956 alloy Substances 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 6
- 238000009529 body temperature measurement Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 4
- 229910001260 Pt alloy Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011978 dissolution method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical group CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 101150108975 Rhd gene Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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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
- 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
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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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
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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
- 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
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Abstract
The invention relates to the field of chemical engineering, in particular to a normal-temperature chlorination and dissolution treatment method of waste platinum-rhodium thermocouples, which comprises the following steps: 1) preparing iron-based ionic liquid; 2) chloridizing and dissolving the waste platinum-rhodium thermocouple at normal temperature; 3) and purifying and separating the simple substance rhodium and the simple substance platinum. The invention utilizes Cl at normal temperature2The oxidation of the catalyst and the generated hypochlorous acid dissolve platinum-rhodium alloy materials, 1-butyl-3-methyl chloroimidazole and ferric chloride hexahydrate are used for synthesizing iron-based ionic liquid to enrich platinum and rhodium ions and accelerate the dissolution of the platinum-rhodium alloy materials, the platinum and rhodium can be enriched and recovered only by uniformly stirring, and high-temperature conditions are not needed, so that the energy consumption is saved, the process cost is reduced, the harmless and recycling treatment of the waste platinum-rhodium alloy is realized, the waste thermocouple treated by the method can reach the direct yield of more than 98 percent, the method accords with sustainable development roads advocated by China and the era theme of the world at present.
Description
Technical Field
The invention relates to the field of chemical engineering, in particular to a normal-temperature chlorination and dissolution treatment method of waste platinum-rhodium thermocouples.
Background
Along with the development of temperature measurement technology, the performance of measuring instruments and measuring systems is continuously improved, and the requirements on temperature measurement precision and accuracy are more and more strict. The thermocouple can directly convert temperature into electric quantity during temperature measurement, is particularly suitable for automatic adjustment and automatic control of temperature, and is widely applied to medium temperatures of gas, liquid, steam and the like at minus 200-2500 ℃. In large-scale temperature measurement, thermocouples are widely used in industries of power plants, manufacturing enterprises, scientific research institutions and other departments due to their small size, high sensitivity and stable output signals.
At present, a low-cost K-type nickel-chromium thermocouple is generally adopted for measuring high temperature, but the measurement can be stably carried out for a long time only at the temperature below 700 ℃, and the service life is shortened or even damaged sharply due to oxidation in the temperature environment above 700 ℃ for a long time; if the temperature above 1000 ℃ needs to be measured stably for a long time, only the thermocouple made of the platinum-rhodium precious metal material with high cost can be adopted. Thermocouples made of noble metals such as platinum group and alloys thereof are called noble metal thermocouples, and have many advantages such as wide temperature measurement range (0-1800 ℃), high measurement accuracy, sensitive temperature change, long service life, and the like, compared with inexpensive metal thermocouples. The platinum-rhodium alloy has the excellent characteristics of good catalytic activity, stable thermoelectric property, good creep resistance, high-temperature endurance strength, good corrosion resistance, strong high-temperature oxidation resistance and the like, so that the platinum-rhodium alloy is widely applied to the fields of thermocouples and the like. Because the platinum-rhodium precious metal has excellent performance and wide application prospect, under the background of extremely deficient platinum-group metal resources, the dissolution and recovery of waste platinum-rhodium alloy arouses the interest of a plurality of foreign researchers, and develops a plurality of new recovery methods and new technologies.
At present, the enrichment of platinum group metals mainly comprises two processes, namely a fire process and a wet process. The pyrogenic process comprises plasma smelting, metal trapping, dry chlorination and other technologies; wet process is used in carrier dissolving process, active component dissolving process, full dissolving process, pressurized cyaniding process and other technological processes. As the pyrometallurgical process has the defects of high energy consumption, long production period, difficult post-treatment of part of generated slag, large investment and the like, the wet process is generally adopted in industry to dissolve platinum group metals.
The waste platinum-rhodium thermocouples are generally dissolved and recovered directly by an active component dissolving method, wherein the active component dissolving method mainly comprises an aqueous solution chlorination dissolving method and an electrochemical dissolving method. Because the electrochemical dissolution method has low dissolution speed and complex operation and is less applied to the industry, the aqueous solution chlorination dissolution method is mainly adopted to dissolve the platinum-rhodium alloy. The aqueous solution chlorination dissolving method comprises HCl-HNO3、HCl-Cl2、HCl-NaClO3The constant-strength acid oxidation system is widely applied to the present time and is HCl-HNO3And (5) processing.
HCl-HNO3The process can have a good dissolving effect on the platinum-rhodium alloy, but has the defects of long dissolving period, need of heating to a certain temperature, insoluble slag generation when the rhodium content in the platinum-rhodium alloy is more than 5 percent and the like, so related researchers in HCl-HNO3The process is improved, for example, aluminum is added under the condition of high temperature for alloying activation, and then aqua regia is used for dissolution, thereby improving the dissolution rate of rhodium; or by reaction in HCl-HNO3In the process, H is added2O2And heated to boiling to enhance the dissolution of rhodium. The HCl-HNO after the above improvement3Although the process can better dissolve the platinum-rhodium alloy, the process needs to be carried out at higher temperature, and NO which is difficult to treat is generatedxPollutants and subsequent complex operations such as denitration and the like cannot achieve the purposes of energy conservation and environmental protection. HCl-NaClO3The process is also related to reports, or HCl-NaClO is adopted3The process recovers platinum and palladium from silver electrolysis anode mud, or adopts HCl-NaClO3Rhodium powder is dissolved in the four processes, although the four processes have good dissolving effect, high-temperature heating is needed, the energy consumption is serious, the process cost is increased, and the problem to be solved at present is to find an energy-saving and environment-friendly process capable of efficiently dissolving platinum-rhodium alloy at normal temperature.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a normal-temperature chlorination and dissolution treatment method for waste platinum-rhodium thermocouples.
The purpose of the invention is realized by adopting the following scheme: a normal-temperature chlorination and dissolution treatment method for waste platinum-rhodium thermocouples comprises the following steps:
1) preparing an iron-based ionic liquid:
1-1) Synthesis of 1-butyl-3-methylchloroimidazole solution:
uniformly mixing N-methylimidazole and N-butyl chloride according to a molar ratio of 1:1, and fully reacting to obtain a 1-butyl-3-methylimidazole chloride solution, wherein the reaction formula of the process is as follows:
1-2) synthesis of iron-based ionic liquid:
mixing the 1-butyl-3-methyl imidazole chloride solution obtained in the step 1-1) with FeCl3·6H2Mixing O uniformly according to a molar ratio of 1:2, fully reacting, and standing for liquid separation to obtain an iron-based ionic liquid;
the reaction formula of the process is as follows:
2) chloridizing and dissolving the waste platinum-rhodium thermocouple at normal temperature:
2-1) uniformly mixing the iron-based ionic liquid and hydrochloric acid to obtain a mixed solution, wherein the volume ratio of the iron-based ionic liquid to the hydrochloric acid in the mixed solution is 2-4: 15-20;
2-2) putting crushed waste platinum-rhodium thermocouple particles into the mixed solution to be submerged, continuously introducing chlorine into the mixed solution, stirring the mixed solution, and respectively oxidizing platinum ions and rhodium ions to +4 and +3 by using [ Cl ] generated by the chlorine so as to realize the dissolution of platinum and rhodium;
2-3) carrying out sampling detection analysis on the mixed solution for multiple times, stopping introducing chlorine when the contents of platinum ions and rhodium ions in the mixed solution are not less than 98%, and stopping stirring;
3) purifying and separating simple substance rhodium and simple substance platinum:
adding NaOH into a mixed solution with the contents of platinum ions and rhodium ions being more than or equal to 98 percent for precipitating rhodium, purifying and separating simple substance rhodium, taking out the simple substance rhodium, and adding NH into the mixed solution4And precipitating the platinum by using Cl, purifying and separating the simple substance platinum, and taking out the simple substance platinum.
In the step 1-1), impurities in the 1-butyl-3-methyl imidazole chloride solution are removed by adopting an impurity removal method.
The impurity removal method adopts the following steps to remove impurities in the 1-butyl-3-methyl imidazole chloride solution in the step 1-1):
adding ethyl acetate into the 1-butyl-3-methyl imidazole chloride solution obtained in the step 1-1), placing the solution in a rotary evaporator, setting the operating temperature to be 70 ℃, evaporating and removing the ethyl acetate in the 1-butyl-3-methyl imidazole chloride solution, and then placing the 1-butyl-3-methyl imidazole chloride solution in a vacuum drying oven at 70 ℃ for drying.
In the step 1-1), the N-methylimidazole and N-butyl chloride are fully reacted by adopting the following method: under the condition of room temperature, uniformly mixing N-methylimidazole and N-butane chloride according to the molar ratio of 1:1, putting the mixture into a constant-temperature magnetic stirrer, and continuously stirring for at least 72 hours, wherein the temperature in the constant-temperature magnetic stirrer is 65-75 ℃.
In the step 1-2), 1-butyl-3-methylimidazole chloride solution and FeCl are mixed by the following method3·6H2And (3) fully reacting O: under the condition of room temperature, 1-butyl-3-methyl imidazole chloride solution and FeCl3·6H2And (3) uniformly mixing the O according to the molar ratio of 1:2, placing the mixture into a constant-temperature stirrer, and setting the reaction temperature to be 70 ℃ to continuously stir and react for 24 hours.
The iron-based ionic liquid is obtained by adopting the following steps of standing and liquid separation in the step 1-2): mixing the 1-butyl-3-methyl imidazole chloride solution obtained in the step 1-1) with FeCl3·6H2O is uniformly mixed according to the molar ratio of 1:2 and fully reacted, then the mixture is put into a separating funnel and stands until the solution is separated into two phases, and after the liquid at the lower layer is drained from the lower port of the separating funnel, the dark green liquid at the upper layer, namely the iron-based ionic liquid, is collected from the upper port;
and 2) washing the waste platinum-rhodium thermocouple with ethanol and deionized water to remove surface stains before crushing.
The structural formula of the iron-based ionic liquid is as follows:
the concentration of the hydrochloric acid in the step 2-1) is 4-14 mol/L.
The concentration of the iron-based ionic liquid in the step 2-1) is 2-8 mol/L.
The invention has the following beneficial effects: when the waste platinum-rhodium thermocouple is dissolved, the dissolution rate of rhodium which is an insoluble matter of aqua regia is improved by using the iron-based ionic liquid, the dissolution rate of platinum-rhodium alloy is greatly promoted, the dissolution time is greatly shortened, the dissolution rate and the dissolution speed reach the international advanced level, and the method has great industrial application potential.
The invention can also find out the optimal reaction condition by adjusting the stirring speed, the hydrochloric acid concentration, the chlorine gas introduction amount, the reaction time, the concentration of the iron-based ionic liquid and the like to influence the dissolution efficiency of the waste platinum-rhodium thermocouple.
Because the rhodium content is more than 5 percent, the platinum-rhodium alloy can not be dissolved by methods such as aqua regia dissolution method, and the like, but the invention can dissolve the platinum-rhodium alloy with the rhodium content of more than 5 percent, and can not generate aqua regia insoluble slag and NOxPollutants are dissolved by the aid of iron-based ionic liquid, and the platinum-rhodium alloy can be continuously and rapidly dissolved at normal temperature by introducing chlorine.
The invention has the advantages that 1-butyl-3-methyl imidazole chloride and ferric trichloride hexahydrate are used for synthesizing the iron-based ionic liquid, and the platinum-rhodium ions are enriched to accelerate the dissolution of the platinum-rhodium alloy by adding the iron-based ionic liquid into a device for dissolving the platinum-rhodium alloy in the waste platinum-rhodium thermocouple.
The optimal reaction condition can be found out by influencing the dissolution effect of the platinum-rhodium alloy by different conditions such as pH, hydrochloric acid concentration, chlorine gas introduction amount, reaction time, ionic liquid concentration and the like, the operation is simple, the investment cost is low, and the guarantee is provided for industrialization.
In summary, the invention provides a normal-temperature chlorination and dissolution treatment method for waste platinum-rhodium thermocouples, which utilizes Cl at normal temperature2The oxidation of the catalyst and the generated hypochlorous acid dissolve platinum-rhodium alloy materials, 1-butyl-3-methyl chloroimidazole and ferric chloride hexahydrate are used for synthesizing iron-based ionic liquid for enriching platinum and rhodium ions to accelerate the dissolution of the platinum-rhodium alloy materials, and the platinum-rhodium alloy materials can be enriched and recovered only by uniformly stirringThe method has the advantages that platinum and rhodium are collected, energy consumption is saved, process cost is reduced, the adopted chlorine is convenient to recycle, harmless recycling and resource treatment of waste platinum and rhodium alloys are realized, the direct yield of the waste thermocouple treated by the method is over 98 percent, the method accords with sustainable development roads advocated by China and the era theme of the world at present.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a graph showing the effect of acidity on platinum-rhodium alloy dissolution according to the present invention;
FIG. 3 is a graph showing the effect of the amount of oxidant used in the present invention on the dissolution of a platinum-rhodium alloy;
FIG. 4 is a graph showing the effect of the dosage of the iron-based ionic liquid on the dissolution of the platinum-rhodium alloy.
Detailed Description
As shown in fig. 1 to 4, a normal temperature chlorination and dissolution treatment method for waste platinum-rhodium thermocouples comprises the following steps:
1) preparing an iron-based ionic liquid:
1-1) Synthesis of 1-butyl-3-methylchloroimidazole solution:
uniformly mixing N-methylimidazole and N-butyl chloride according to a molar ratio of 1:1, and fully reacting to obtain a 1-butyl-3-methylimidazole chloride solution, wherein the reaction formula of the process is as follows:
in the step 1-1), impurities in the 1-butyl-3-methyl imidazole chloride solution are removed by adopting an impurity removal method.
The impurity removal method adopts the following steps to remove impurities in the 1-butyl-3-methyl imidazole chloride solution in the step 1-1):
adding ethyl acetate into the 1-butyl-3-methyl imidazole chloride solution obtained in the step 1-1), placing the solution in a rotary evaporator, setting the operating temperature to be 70 ℃, evaporating and removing the ethyl acetate in the 1-butyl-3-methyl imidazole chloride solution, and then placing the 1-butyl-3-methyl imidazole chloride solution in a vacuum drying oven at 70 ℃ for drying.
In the step 1-1), the N-methylimidazole and N-butyl chloride are fully reacted by adopting the following method: under the condition of room temperature, uniformly mixing N-methylimidazole and N-butane chloride according to the molar ratio of 1:1, putting the mixture into a constant-temperature magnetic stirrer, and continuously stirring for at least 72 hours, wherein the temperature in the constant-temperature magnetic stirrer is 65-75 ℃.
1-2) synthesis of iron-based ionic liquid:
mixing the 1-butyl-3-methyl imidazole chloride solution obtained in the step 1-1) with FeCl3·6H2Mixing O uniformly according to a molar ratio of 1:2, fully reacting, standing, separating to obtain an iron-based ionic liquid, wherein the chemical formula of the 1-butyl-3-methylimidazolium chloride is [ Bmim ]]Cl, the chemical formula of the iron-based ionic liquid is [ Bmim ]][FeCl4]；
The reaction formula of the process is as follows:
the structural formula of the iron-based ionic liquid is as follows:
in the step 1-2), the 1-butyl-3-methyl imidazole chloride solution and FeCl are mixed by the following method3·6H2And (3) fully reacting O: under the condition of room temperature, 1-butyl-3-methylimidazole chloride solution and FeCl3·6H2And (3) uniformly mixing the O according to the molar ratio of 1:2, placing the mixture into a constant-temperature stirrer, and setting the reaction temperature to be 70 ℃ to continuously stir and react for 24 hours.
The iron-based ionic liquid is obtained by adopting the following steps of standing and liquid separation in the step 1-2): mixing the 1-butyl-3-methyl imidazole chloride solution obtained in the step 1-1) with FeCl3·6H2Mixing O at a molar ratio of 1:2, reacting, placing into a separating funnel, standing until the solution is separated into two phases, draining the lower layer liquid from the lower port of the separating funnel, and collecting the upper layer dark green liquid, i.e. iron-based liquidIonic liquid;
2) chloridizing and dissolving the waste platinum-rhodium thermocouple at normal temperature:
2-1) uniformly mixing the iron-based ionic liquid and hydrochloric acid to obtain a mixed solution, wherein the volume ratio of the iron-based ionic liquid to the hydrochloric acid in the mixed solution is 2-4: 15-20;
the concentration of the hydrochloric acid in the step 2-1) is 4-14 mol/L.
The concentration of the iron-based ionic liquid in the step 2-1) is 2-8 mol/L.
2-2) putting crushed waste platinum-rhodium thermocouple particles into the mixed solution to be submerged, continuously introducing chlorine into the mixed solution, stirring the mixed solution, and respectively oxidizing platinum ions and rhodium ions to +4 and +3 by using [ Cl ] generated by the chlorine so as to realize the dissolution of platinum and rhodium;
2-3) carrying out sampling detection analysis on the mixed solution for multiple times, stopping introducing chlorine when the contents of platinum ions and rhodium ions in the mixed solution are not less than 98%, and stopping stirring;
in the embodiment, the mixed solution is sampled every 15min, and an icp-aes analyzer is used for detecting to obtain the content of platinum ions and rhodium ions in the mixed solution.
3) Purifying and separating simple substance rhodium and simple substance platinum:
adding NaOH into a mixed solution with the contents of platinum ions and rhodium ions being more than or equal to 98 percent for precipitating rhodium, purifying and separating simple substance rhodium, taking out the simple substance rhodium, and adding NH into the mixed solution4And precipitating the platinum by using Cl, purifying and separating the simple substance platinum, and taking out the simple substance platinum.
The invention comprises the following steps of performing chlorination and dissolution treatment on waste platinum-rhodium thermocouple particles at normal temperature:
example 1:
1500mL of hydrochloric acid with the concentration of 4mol/L and 200mL of iron-based ionic liquid with the concentration of 8mol/L which is prepared in advance are mixed, 200g of waste platinum-rhodium thermocouple particles (number 1: Pt90 wt%, Rh10 wt%) which are cleaned in advance are weighed and placed in a mixed solution, then chlorine is introduced at the speed of 2L/min to saturate the chlorine in the mixed solution, 5mL of the mixed solution is sampled every 15min after uniform stirring, and an icp-aes analyzer is used for detecting the contents of platinum ions and rhodium ions in the mixed solution. Stopping stirring when the content of platinum ions and rhodium ions in the mixed solution reaches 98%, and stopping introducing chlorine; the reagent consumption in the present example for dissolving platinum rhodium alloy is shown in table 1.
Example 2:
1500mL of hydrochloric acid with the concentration of 8mol/L and 300mL of iron-based ionic liquid with the concentration of 4mol/L which is prepared in advance are mixed, 200g of waste platinum-rhodium thermocouple particles (number 1: Pt80 wt%, Rh20 wt%) which are pretreated and cleaned are weighed and placed in a mixed solution, then chlorine is introduced at the speed of 2L/min to saturate the chlorine in the mixed solution, 5mL of the mixed solution is sampled every 15min after uniform stirring, and an icp-aes analyzer is used for detecting the contents of platinum ions and rhodium ions in the mixed solution. Stopping stirring when the content of platinum ions and rhodium ions in the mixed solution reaches 98%, and stopping introducing chlorine; the reagent consumed for dissolving the platinum-rhodium alloy in the present example is shown in Table 1.
Example 3:
1500mL of hydrochloric acid with the concentration of 12mol/L and 400mL of iron-based ionic liquid with the concentration of 2mol/L, which is prepared in advance, are mixed, 200g of waste and old platinum-rhodium thermocouple particles (number 1: Pt70 wt% and Rh30 wt%) which are pretreated and cleaned are weighed and placed in a mixed solution, then chlorine is introduced at the speed of 2L/min to saturate the chlorine in the mixed solution, 5mL of mixed solution is sampled every 15min after uniform stirring, and an icp-aes analyzer is used for detecting the contents of platinum ions and rhodium ions in the mixed solution. Stopping stirring when the content of platinum ions and rhodium ions in the mixed solution reaches 98%, and stopping introducing chlorine; the reagent consumed for dissolving the platinum-rhodium alloy in the present example is shown in Table 1.
TABLE 1 materials consumed in examples 1-3
In summary, the present invention utilizes Cl at normal temperature2The oxidation of (2) and the generated hypochlorous acid dissolve the platinum-rhodium alloy material andthe method for synthesizing the iron-based ionic liquid by using the 1-butyl-3-methyl imidazole chloride and the ferric trichloride hexahydrate to enrich platinum and rhodium ions and accelerate dissolution of platinum and rhodium alloy materials has the advantages that the platinum and rhodium can be enriched and recovered only by uniformly stirring, the energy consumption is saved, the process cost is reduced, the harmless and recycling treatment of the recovered waste platinum and rhodium alloy is realized, the direct yield of the waste thermocouple treated by the method is over 98 percent, the method accords with the sustainable development road advocated in China and the era theme of the world at present.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and modifications of the present invention by those skilled in the art can be made without departing from the spirit of the present invention.
Claims (10)
1. A normal-temperature chlorination and dissolution treatment method of waste platinum-rhodium thermocouples is characterized by comprising the following steps:
1) preparing an iron-based ionic liquid:
1-1) Synthesis of 1-butyl-3-methylchloroimidazole solution:
uniformly mixing N-methylimidazole and N-butyl chloride according to the molar ratio of 1:1, and fully reacting to obtain a 1-butyl-3-methylimidazole chloride solution;
1-2) synthesis of iron-based ionic liquid:
mixing the 1-butyl-3-methyl imidazole chloride solution obtained in the step 1-1) with FeCl3·6H2Mixing O uniformly according to a molar ratio of 1:2, fully reacting, and standing for liquid separation to obtain an iron-based ionic liquid;
2) chloridizing and dissolving the waste platinum-rhodium thermocouple at normal temperature:
2-1) uniformly mixing the iron-based ionic liquid and hydrochloric acid to obtain a mixed solution, wherein the volume ratio of the iron-based ionic liquid to the hydrochloric acid in the mixed solution is 2-4: 15-20;
2-2) putting crushed waste platinum-rhodium thermocouple particles into the mixed solution to be submerged, continuously introducing chlorine into the mixed solution, and stirring the mixed solution;
2-3) carrying out sampling detection analysis on the mixed solution for multiple times, stopping introducing chlorine when the contents of platinum ions and rhodium ions in the mixed solution are not less than 98%, and stopping stirring;
3) purifying and separating simple substance rhodium and simple substance platinum:
adding NaOH into a mixed solution with the contents of platinum ions and rhodium ions being more than or equal to 98 percent for precipitating rhodium, purifying and separating simple substance rhodium, taking out the simple substance rhodium, and adding NH into the mixed solution4And precipitating the platinum by using Cl, purifying and separating the simple substance platinum, and taking out the simple substance platinum.
2. The method of claim 1, wherein: in the step 1-1), impurities in the 1-butyl-3-methyl imidazole chloride solution are removed by adopting an impurity removal method.
3. The method of claim 2, wherein: the impurity removal method adopts the following steps to remove impurities in the 1-butyl-3-methylimidazole chloride solution in the step 1-1):
adding ethyl acetate into the 1-butyl-3-methyl imidazole chloride solution obtained in the step 1-1), placing the solution in a rotary evaporator, setting the operating temperature to be 70 ℃, evaporating and removing the ethyl acetate in the 1-butyl-3-methyl imidazole chloride solution, and then placing the 1-butyl-3-methyl imidazole chloride solution in a vacuum drying oven at 70 ℃ for drying.
4. The method of claim 1, wherein: in the step 1-1), the N-methylimidazole and N-butyl chloride are fully reacted by adopting the following method: under the condition of room temperature, uniformly mixing N-methylimidazole and N-butane chloride according to the molar ratio of 1:1, putting the mixture into a constant-temperature magnetic stirrer, and continuously stirring for at least 72 hours, wherein the temperature in the constant-temperature magnetic stirrer is 65-75 ℃.
5. The method of claim 1, wherein: in the step 1-2), the 1-butyl-3-methyl imidazole chloride solution and FeCl are mixed by the following method3·6H2And (3) fully reacting: under the condition of room temperature, 1-butyl-3-methyl imidazole chloride solution and FeCl3·6H2Mixing O uniformly according to the molar ratio of 1:2, and placing the mixture in a constant-temperature stirrerThe reaction temperature was set at 70 ℃ and the reaction was continued with stirring for 24 h.
6. The method of claim 1, wherein: the iron-based ionic liquid is obtained by adopting the following steps of standing and liquid separation in the step 1-2): mixing the 1-butyl-3-methyl imidazole chloride solution obtained in the step 1-1) with FeCl3·6H2And O is uniformly mixed according to the molar ratio of 1:2 and fully reacted, then the mixture is put into a separating funnel and stands until the solution is separated into two phases, and after the liquid at the lower layer is drained from the lower port of the separating funnel, the dark green liquid at the upper layer, namely the iron-based ionic liquid, is collected from the upper port.
7. The method of claim 1, wherein: and 2) washing the waste platinum-rhodium thermocouple with ethanol and deionized water before crushing.
8. The method of claim 1, wherein: the structural formula of the iron-based ionic liquid is as follows:
9. the method of claim 1, wherein: the concentration of the hydrochloric acid in the step 2-1) is 4-14 mol/L.
10. The method of claim 1, wherein: the concentration of the iron-based ionic liquid in the step 2-1) is 2-8 mol/L.
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| CN101476044A (en) * | 2009-01-21 | 2009-07-08 | 中国化工供销太原贵金属有限公司 | Method for recycling platinum and rhodium from binary aqua regia insoluble slag |
| JP2009256744A (en) * | 2008-04-18 | 2009-11-05 | Foundation For The Promotion Of Industrial Science | Method for recovering noble metal |
| CN108265180A (en) * | 2017-12-28 | 2018-07-10 | 核工业北京化工冶金研究院 | The leaching method of platinum, palladium, rhodium in useless three-way catalyst |
| CN111054933A (en) * | 2019-12-09 | 2020-04-24 | 重庆材料研究院有限公司 | Method for preparing high-purity rhodium powder from platinum-rhodium waste |
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| JP2009256744A (en) * | 2008-04-18 | 2009-11-05 | Foundation For The Promotion Of Industrial Science | Method for recovering noble metal |
| CN101476044A (en) * | 2009-01-21 | 2009-07-08 | 中国化工供销太原贵金属有限公司 | Method for recycling platinum and rhodium from binary aqua regia insoluble slag |
| CN108265180A (en) * | 2017-12-28 | 2018-07-10 | 核工业北京化工冶金研究院 | The leaching method of platinum, palladium, rhodium in useless three-way catalyst |
| CN111054933A (en) * | 2019-12-09 | 2020-04-24 | 重庆材料研究院有限公司 | Method for preparing high-purity rhodium powder from platinum-rhodium waste |
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