CN116607018A - Method for preparing ruthenium trichloride from complex waste material containing ruthenium, rhodium and iridium - Google Patents
Method for preparing ruthenium trichloride from complex waste material containing ruthenium, rhodium and iridium Download PDFInfo
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- CN116607018A CN116607018A CN202310669021.1A CN202310669021A CN116607018A CN 116607018 A CN116607018 A CN 116607018A CN 202310669021 A CN202310669021 A CN 202310669021A CN 116607018 A CN116607018 A CN 116607018A
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- ruthenium
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- iridium
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 78
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000010948 rhodium Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 31
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 title claims abstract description 29
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 23
- 239000002699 waste material Substances 0.000 title claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000004821 distillation Methods 0.000 claims abstract description 37
- 239000000956 alloy Substances 0.000 claims abstract description 34
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- -1 platinum group metals Chemical class 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 4
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000007800 oxidant agent Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002893 slag Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical class [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 239000010953 base metal Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000006188 syrup Substances 0.000 claims description 4
- 235000020357 syrup Nutrition 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000001698 pyrogenic effect Effects 0.000 claims description 2
- 238000009853 pyrometallurgy Methods 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- 238000011084 recovery Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000001556 precipitation Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 abstract description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000007133 aluminothermic reaction Methods 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- 239000012535 impurity Substances 0.000 description 10
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000012047 saturated solution Substances 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 5
- 229910001018 Cast iron Inorganic materials 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical class [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C22B11/06—Chloridising
-
- 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
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
-
- 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
-
- 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
- C22B7/001—Dry processes
-
- 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
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing ruthenium trichloride from complex waste materials of ruthenium, rhodium and iridium. The material is subjected to aluminothermic reaction with aluminum and iron at 800-1400 ℃ under the protection of inert gas to form an alloy, and then the alloy is crushed and dissolved to obtain high-activity noble metal enrichment. Washing the enriched matter, chloridizing leaching, regulating acidity, 2-stage oxidizing distillation, ruO 4 Absorbing the gas with hydrochloric acid, concentrating and crystallizing to obtain ruthenium trichloride product; and (3) hydrolyzing the ruthenium distillation residual liquid, washing sodium salt, performing acid-soluble ion exchange, and separating by adopting an ammonium sulfide precipitation method and a DETA precipitation method to obtain qualified rhodium powder and iridium powder. The invention has wide applicability and can directly treat saltRuthenium in the acid medium has the advantages of high recovery rate of platinum group metals, simple and easy operation, safety, low production cost, environment friendliness, energy conservation, environmental protection and the like, and has remarkable economic benefit and wide market popularization value.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of platinum group metal secondary resources, and particularly relates to a method for preparing ruthenium trichloride from complex waste materials containing ruthenium, rhodium and iridium.
Background
Platinum group metals are widely used in many high and new technology fields due to their unique properties. Is praised as an industrial vitamin. Ruthenium is the least element in platinum group metals, and is finally found in platinum group elements, and the ruthenium extracted from primary ores in China is less than 100 kg each year. The special chemical nature of ruthenium, and its inexpensive price relative to other platinum group metals, makes it very promising for catalyst applications. In recent years, with the increasing number of ruthenium catalysts used in the chemical industry, studies on recovery of ruthenium from ruthenium catalysts have been also increased. At present, two main methods for recovering ruthenium at home are adopted, one is that alkaline oxidation roasting is adopted, then ruthenium as an oxidant is added, and RuO is adopted for the ruthenium under the high temperature condition 4 Is volatilized and then is absorbed and distilled by hydrochloric acid solution. The other is to add sodium chlorate into sulfuric acid medium to volatilize the ruthenium into gas after oxidation. The corrosion resistance requirement on equipment in the alkaline oxidation roasting process is high, the equipment is easy to damage, a large amount of sodium salt is introduced, and in the distillation process of complex alloy waste, other metals in the material form hydroxide to wrap ruthenium due to the reduction of the alkalinity, so that the ruthenium distillation efficiency is low. The problem can be solved by dropwise adding sodium chlorate under the condition of sulfuric acid, but the distillation and volatilization efficiency of ruthenium is too low, the ruthenium distillation time is long, and the sodium sulfate generated by the reaction of sodium chlorate and sulfuric acid is easy to form crystallization to cause pipeline blockage.
Disclosure of Invention
In order to solve the problems, it is important to develop a rapid, green and clean process for preparing ruthenium trichloride from complex alloy scraps. Based on the above consideration, the invention provides a method for preparing ruthenium trichloride from complex waste materials containing ruthenium, rhodium and iridium, which uses the synergistic effect of potassium permanganate and sodium chlorate to directly recover ruthenium from hydrochloric acid medium to prepare ruthenium trichloride, solves the problems of low ruthenium recovery rate, long production period, high production cost, large wastewater amount and the like of the materials in the traditional recovery process, and has the characteristics of simple operation, simple equipment, environmental protection, high recovery rate and the like. The production verification proves that the ruthenium direct yield reaches more than 95%. The invention is realized by the following technical scheme:
a method for preparing ruthenium trichloride from complex waste materials containing ruthenium, rhodium and iridium, comprising the steps of:
(1) Activating, namely melting complex waste materials containing ruthenium, rhodium and iridium, aluminum powder and iron powder into alloy at high temperature under the protection of inert gas, and dissolving the aluminum and the iron in the alloy by using acid to obtain high-activity and high-dispersion noble metal powder;
(2) Chloridizing leaching: chloridizing leaching the obtained noble metal powder, and transferring the leached slag into a pyrogenic process for enrichment;
(3) Ruthenium steaming: regulating acidity of the solution subjected to chloridizing leaching, adding an oxidant in sections, and carrying out reduced pressure ruthenium distillation in a distillation kettle with stirring and heating, wherein the temperature in the reaction kettle is controlled to be 90-110 ℃, the pressure is controlled to be minus 0.02Mpa to minus 0.1Mpa, and ruthenium is oxidized into RuO 4 The gas is absorbed by hydrochloric acid solution containing ethanol; concentrating the absorption liquid to syrup by a rotary evaporator, pouring out, and baking by an infrared lamp to obtain a qualified ruthenium trichloride finished product;
(4) And (3) hydrolysis refining: the acidity of the solution is regulated by the residual liquid of the distilled ruthenium, rhodium and iridium are separated out in the form of hydrolysis slag, and after sodium salt is washed, acid solution is subjected to ion exchange to remove base metals, and then extraction, separation and purification are carried out.
The specific operation of the step (1) is as follows: complex waste material containing ruthenium, rhodium and iridium, iron powder and aluminum powder according to the proportion of 1:0.2 to 0.5: mixing evenly in a weight ratio of 2-4; then placing the materials in a high-temperature furnace, preserving heat for 2-4 hours at 800-1400 ℃ under the protection of inert gas, and melting into alloy; pouring the melted alloy into a preheated iron pan, cooling, transferring into a plastic kettle, adding water with the weight 5-8 times of the weight of the alloy, slowly adding hydrochloric acid or sulfuric acid to dissolve iron and aluminum in the alloy, extracting upper waste liquid after the reaction is finished, and adding water with the volume 1-3 times of the material volume into the obtained slag for 2-4 times to obtain noble metal powder.
The specific operation of the step (2) is as follows: mixing the noble metal powder obtained in the step (1) with hydrochloric acid and water according to the following ratio of 1: 3-6: adding the mixture into a reaction kettle according to the mass ratio of 1-3, heating to 70-100 ℃, and dropwise adding an oxidant for dissolution, wherein the consumption of the oxidant is 1-2 times of the ruthenium content in the noble metal powder; after chloridizing leaching, solid-liquid separation is carried out, slag is transferred into a pyrometallurgy system for enrichment, and leaching liquid is combined to obtain solution after chloridizing leaching.
The specific operation of the step (3) is as follows: adjusting the concentration of hydrogen ions in the solution after chloridizing leaching to 0.5-2 mol/L by using water or sodium hydroxide, and then placing the solution in a distillation kettle with stirring and heating for ruthenium distillation under reduced pressure; the first segment adopts saturated KMnO 4 Oxidizing the solution as an oxidizing agent to saturate KMnO 4 The dosage of the solution is 0.1-0.5 times of the ruthenium content, and the second stage adopts saturated NaClO 3 、NaClO、NaBrO 3 One or more of the above are used as an oxidant for oxidation, and the dosage of the oxidant adopted in the second section is 2-5 times of the content of ruthenium; ruthenium is used as RuO in the process of dropwise adding the oxidant in the first stage and the oxidant in the second stage 4 Form(s) of (a) volatilizing from solution, ruO 4 The residual liquid after volatilization is ruthenium distillation residual liquid; washing RuO with ultrapure water 4 Then HCl with the concentration of 6mol/L is used for RuO 4 Performing 4-level absorption; concentrating the absorption liquid to syrup by a rotary evaporator, pouring out, and baking by an infrared lamp to obtain a qualified ruthenium trichloride finished product; chlorine gas generated in the absorption process is neutralized with alkali.
The specific operation of the step (4) is as follows: adjusting acidity of the ruthenium distillation raffinate to 8-9 by sodium hydroxide, and carrying out solid-liquid separation on the distillation raffinate to obtain hydrolysis slag; washing sodium ions with water, dissolving with HCl, diluting and filtering the obtained solution, performing ion exchange to remove base metals, and extracting, separating, purifying and recovering rhodium and iridium.
Preferably, the oxidant used in step (2) is NaClO 3 、H 2 O 2 、Cl 2 And HNO 3 One or more of them.
Compared with the prior art, the invention has the following beneficial effects:
1. the method solves the problems that the distillation efficiency of ruthenium is lower and the use of chlorine is relatively unsafe because base metal and other platinum group metals or ions generate precipitates in alkali liquor to wrap the surface of distilled materials in the traditional alkali oxidation distillation process;
2. the problems of slower ruthenium distillation efficiency and easy crystallization of solution in the traditional sulfuric acid and chlorate process are overcome;
3. the method of the invention is proved by production, and the ruthenium direct yield can reach more than 95%, so the method has the advantages of high ruthenium recovery rate, simple and easy method, small reagent dosage, low production cost, environment protection, strong practicability and the like, and has remarkable economic benefit and wide market popularization value.
Drawings
FIG. 1 is a schematic illustration of the process flow of the present invention.
Detailed Description
The present invention will be further described with reference to the drawings and examples, but the scope of the present invention is not limited by the examples.
Example 1
The material is derived from high-grade alloy powder obtained by extracting platinum, palladium and rhodium from a certain domestic refinery, then capturing the platinum, palladium and rhodium by lead, and then grinding the noble metal obtained by ash blowing and sampling, wherein the chemical analysis result is (%) Ru:77.53%, pt:0.51%, rh:2.31%, ir:9.69%. From the analysis results, it can be seen that the material contains mainly ruthenium. Mixing 1kg of the material with 0.5kg of iron powder, uniformly mixing 3kg of aluminum powder, introducing inert gas into a high-temperature furnace to protect the material, smelting the material into an alloy, maintaining the temperature at 1100 ℃, pouring the alloy into a preheated cast iron plate after 4 hours of heat preservation, and cooling to obtain 4.4kg of alloy. Adding water 30L into the plastic kettle, adding alloy material, slowly adding hydrochloric acid 35L, clarifying, and discardingThe clear liquid and the slag are repeatedly washed for 3 times by adding water. The residue was transferred to a reactor, and 15L of 37% hydrochloric acid and 5L of water were added. 2kg saturated solution containing sodium chlorate is added dropwise after the temperature is raised to about 80 ℃, and the solution is filtered after the temperature is raised. The filtrate is sampled to measure the acidity of the solution to be 1.2mol/L, and sodium hydroxide is added to adjust the acidity of the solution to be 0.8mol/L, and the volume is as follows: 30L, sampling to measure the ruthenium content of 24.89g/L, pumping into a distillation kettle, heating to 90 ℃ and controlling the pressure in the distillation kettle to be-0.02 Mpa. Dripping 100g KMnO into the mixture 4 The solution was saturated and then 2000g of a saturated sodium chlorate solution containing sodium chlorate was added dropwise. After the distillation was completed, the ruthenium content was analyzed as 28.1mg/L and the volume was 27.8L by taking a ruthenium distilled raffinate. The primary absorption liquid is concentrated to be sticky by rotary evaporation, and is baked to obtain 2009.67g of ruthenium trichloride with the content of 37.12%. The detected impurity content in ruthenium trichloride is 50ppm, which is far beyond the requirement of impurity elements in HG/T3679-2011, and the direct yield is as follows: 96.22%.
Adding solid sodium hydroxide into the ruthenium distillation raffinate to adjust the acidity of the solution to 8-9, adding water to wash after centrifugal dehydration, dissolving hydrochloric acid, exchanging ions, and separating rhodium and iridium by adopting an ammonium sulfide precipitation method and a DETA precipitation method to finally obtain rhodium powder and iridium powder with the purity of more than 99.95%, wherein the comprehensive recovery rate is Rh:95%, ir:93%
Example 2
The material is derived from high-grade alloy powder obtained by extracting platinum, palladium and rhodium from a certain domestic refinery, then capturing the platinum, palladium and rhodium by lead, and then grinding the noble metal obtained by ash blowing and sampling, wherein the chemical analysis result is (%) Ru:70.58%, rh:7.25%, ir:6.99%. From the analysis results, it can be seen that the material contains mainly ruthenium. Mixing 1kg of the material with 0.5kg of iron powder, uniformly mixing 3kg of aluminum powder, introducing inert gas into a high-temperature furnace to protect the material, smelting the material into an alloy, maintaining the temperature at 1100 ℃, pouring the alloy into a preheated cast iron plate after 4 hours of heat preservation, cooling, and knocking into small blocks to obtain 4.34kg of alloy. Adding water into a plastic kettle for 30L, slowly adding hydrochloric acid for 35L, clarifying, discarding supernatant, and repeatedly washing residues with water for 3 times. The residue was transferred to a reactor, and 15L of 37% hydrochloric acid and 5L of water were added. 2kg saturated solution containing sodium chlorate is added dropwise after the temperature is raised to about 80 ℃, and the solution is filtered after the temperature is raised. Sampling the filtrate to obtain solution with acidity of 1.3mol/L, adding sodium hydroxide to adjust solution acidity to 0.8mol/L and volume to 30L, and samplingThe ruthenium content of the solution was measured to be 22.92g/L, which was pumped into a still, heated to 90℃and the pressure in the still was controlled to be-0.1 MPa. Dripping KMnO into the mixture 4 100g of saturated solution, and then a saturated sodium chlorate solution was added dropwise. After distillation, the ruthenium content of the distilled ruthenium raffinate is analyzed to be 22.13mg/L, and the volume is as follows: 26.94L, the primary absorption liquid is concentrated to be sticky by rotary evaporation, and then baked to dryness, thus obtaining 1838.86g of ruthenium trichloride with the content of 37.36%. The detected impurity content in ruthenium trichloride is 50ppm, which is far beyond the requirement of impurity elements in HG/T3679-2011, and the direct yield is as follows: 97.34%.
Adding solid sodium hydroxide into the ruthenium distillation raffinate to adjust the acidity of the solution to 8-9, adding water to wash after centrifugal dehydration, dissolving hydrochloric acid, exchanging ions, and separating rhodium and iridium by adopting an ammonium sulfide precipitation method and a DETA precipitation method to finally obtain rhodium powder and iridium powder with the purity of more than 99.95%, wherein the comprehensive recovery rate is Rh:96%, ir:95% of
Example 3
The material is derived from crude ruthenium powder which is replaced by zinc powder from electroplating tail liquid in a certain refinery at home, and the chemical analysis result is (%) and contains Ru:65.91%. Mixing 1kg of the material with 0.5kg of iron powder, uniformly mixing 3kg of aluminum powder, smelting the material into an alloy in a high-temperature furnace under the protection of inert gas, preserving the temperature of 1100 ℃ for 4 hours, pouring the alloy into a preheated cast iron plate, cooling, and knocking into small blocks to obtain 4.4kg of alloy. Adding water into a plastic kettle for 30L, slowly adding hydrochloric acid for 35L, clarifying, discarding supernatant, and repeatedly washing residues with water for 3 times. The residue was transferred to a reactor, and 10L of 37% hydrochloric acid and 5L of water were added. 2kg saturated solution containing sodium chlorate is added dropwise after the temperature is raised to about 80 ℃, and the solution is filtered after the temperature is raised. Sampling the filtrate to obtain solution with acidity of 1.7mol/L, adding sodium hydroxide to adjust solution with acidity of 0.8mol/L and volume of 30L, sampling to obtain solution with ruthenium content of 21.56g/L, pumping into a distillation kettle, heating to 110deg.C, and controlling pressure in the distillation kettle to-0.6 Mpa. Dripping KMnO into the mixture 4 80g of saturated solution, and then a saturated sodium chlorate solution was added dropwise. After the distillation was completed, the ruthenium content was 19.65mg/L and the volume was 27.87L as analyzed by taking a ruthenium distilled raffinate. The primary absorption liquid is concentrated to be sticky by rotary evaporation, and is baked to obtain 1738.79g of ruthenium trichloride with the content of 37.17%. The content of impurities in the detected ruthenium trichloride is 50ppm, which is far awayFar exceeds the requirements of impurity elements in HG/T3679-2011, and the direct yield is as follows: 98.06%.
Comparative example 4
The material is derived from high-grade alloy powder obtained by extracting platinum, palladium and rhodium from a certain domestic refinery, then capturing the platinum, palladium and rhodium by lead, and then grinding the noble metal obtained by ash blowing and sampling, wherein the chemical analysis result is (%) Ru:70.58%, rh:7.25%, ir:6.99%. From the analysis results, it can be seen that the material contains mainly ruthenium. Taking 1kg of the material, mixing 2kg of sodium peroxide, 1kg of sodium hydroxide, maintaining the temperature at 700 ℃, cooling, knocking into small blocks, adding 20L of water into a plastic kettle, and stirring for dissolution. Pumping into a distillation kettle, heating to 100 ℃ and controlling the pressure in the distillation kettle to be minus 0.08Mpa. Introducing Cl 2 Oxidative distillation was performed. The absorption liquid is washed by 1-grade water and absorbed by 4-grade hydrochloric acid. After the distillation is completed, the primary absorption liquid is taken for rotary evaporation and concentration to be sticky, and is baked to obtain 845.29g of ruthenium trichloride, the content is 37.29%, and the recovery rate is as follows: the impurity content in 44.66% of detected ruthenium trichloride meets the requirement of impurity elements in HG/T3679-2011.
Comparative example 5
The material is derived from high-grade alloy powder obtained by extracting platinum, palladium and rhodium from a certain domestic refinery, then capturing the platinum, palladium and rhodium by lead, and then grinding the noble metal obtained by ash blowing and sampling, wherein the chemical analysis result is (%) Ru:70.58%, rh:7.25%, ir:6.99%. From the analysis results, it can be seen that the material contains mainly ruthenium. Mixing 1kg of the material with 0.5kg of iron powder, uniformly mixing 3kg of aluminum powder, introducing inert gas into a high-temperature furnace to protect the material, smelting the material into an alloy, maintaining the temperature at 1100 ℃, pouring the alloy into a preheated cast iron plate after 4 hours of heat preservation, cooling, and knocking the alloy into small blocks to obtain 4.33kg of alloy. Adding water into a plastic kettle for 30L, slowly adding hydrochloric acid for 35L, clarifying, discarding supernatant, and repeatedly washing residues with water for 3 times. Transferring the slag into a kettle, adding 9mol/L sulfuric acid for 30L, and beginning to drop 4kg saturated solution containing sodium chlorate at the temperature of about 80 ℃. After distillation, the ruthenium content of the distilled ruthenium raffinate is analyzed to be 25.72mg/L, and the volume is: 23.8L. The primary absorption liquid is concentrated into a viscous state by rotary evaporation, and is transferred into a quartz disc for baking by an infrared lamp, thus obtaining 1723.41g of ruthenium trichloride with the content of 37.03%. The detected impurity content in ruthenium trichloride is 50ppm, which is far beyond the requirement of impurity elements in HG/T3679-2011, and the direct yield is as follows: 90.42%.
Washing ruthenium residue, dissolving aqua regia, concentrating the solution, removing nitrate and acid, performing ion exchange, and separating rhodium and iridium by adopting an ammonium sulfide precipitation method to finally obtain rhodium powder and iridium powder with purity of more than 99.95%, wherein the comprehensive recovery rate is Rh:90%, ir:89%.
While there has been shown and described what is at present considered to be the fundamental principles and the main features of the invention and the advantages thereof, it will be understood by those skilled in the art that the present invention is not limited to the foregoing embodiments, but is described in the foregoing description merely illustrates the principles of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as hereinafter claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A process for the preparation of ruthenium trichloride from complex wastes containing ruthenium, rhodium, iridium, characterized in that it comprises the following steps:
(1) Activating, namely melting complex waste materials containing ruthenium, rhodium and iridium, aluminum powder and iron powder into alloy at high temperature under the protection of inert gas, and dissolving the aluminum and the iron in the alloy by using acid to obtain high-activity and high-dispersion noble metal powder;
(2) Chloridizing leaching: chloridizing leaching the obtained noble metal powder, and transferring the leached slag into a pyrogenic process for enrichment;
(3) Ruthenium steaming: regulating acidity of the solution subjected to chloridizing leaching, adding an oxidant in sections, and carrying out reduced pressure ruthenium distillation in a distillation kettle with stirring and heating, wherein the temperature in the reaction kettle is controlled to be 90-110 ℃, the pressure is controlled to be minus 0.02Mpa to minus 0.1Mpa, and ruthenium is oxidized into RuO 4 The gas is absorbed by hydrochloric acid solution containing ethanol; concentrating the absorption liquid to syrup by a rotary evaporator, pouring out, and baking by an infrared lamp to obtain a qualified ruthenium trichloride finished product;
(4) And (3) hydrolysis refining: the acidity of the solution is regulated by the residual liquid of the distilled ruthenium, rhodium and iridium are separated out in the form of hydrolysis slag, and after sodium salt is washed, acid solution is subjected to ion exchange to remove base metals, and then extraction, separation and purification are carried out.
2. The method for preparing ruthenium trichloride from complex waste materials containing ruthenium, rhodium, and iridium according to claim 1, wherein the specific operation of step (1) is as follows: complex waste material containing ruthenium, rhodium and iridium, iron powder and aluminum powder according to the proportion of 1:0.2 to 0.5: mixing evenly in a weight ratio of 2-4; then placing the materials in a high-temperature furnace, preserving heat for 2-4 hours at 800-1400 ℃ under the protection of inert gas, and melting into alloy; pouring the melted alloy into a preheated iron pan, cooling, transferring into a plastic kettle, adding water with the weight 5-8 times of the weight of the alloy, slowly adding hydrochloric acid or sulfuric acid to dissolve iron and aluminum in the alloy, extracting upper waste liquid after the reaction is finished, and adding water with the volume 1-3 times of the material volume into the obtained slag for 2-4 times to obtain noble metal powder.
3. The method for preparing ruthenium trichloride from complex waste materials containing ruthenium, rhodium, and iridium according to claim 2, wherein the specific operation of step (2) is as follows: mixing the noble metal powder obtained in the step (1) with hydrochloric acid and water according to the following ratio of 1: 3-6: adding the mixture into a reaction kettle according to the mass ratio of 1-3, heating to 70-100 ℃, and dropwise adding an oxidant for dissolution, wherein the consumption of the oxidant is 1-2 times of the ruthenium content in the noble metal powder; after chloridizing leaching, solid-liquid separation is carried out, slag is transferred into a pyrometallurgy system for enrichment, and leaching liquid is combined to obtain solution after chloridizing leaching.
4. A process for the preparation of ruthenium trichloride from complex waste materials containing ruthenium, rhodium, iridium according to claim 3, wherein step (3) is carried out as follows: adjusting the concentration of hydrogen ions in the solution after chloridizing leaching to 0.5-2 mol/L by using water or sodium hydroxide, and then placing the solution in a distillation kettle with stirring and heating for ruthenium distillation under reduced pressure; the first segment adopts saturated KMnO 4 Oxidizing the solution as an oxidizing agent to saturate KMnO 4 The dosage of the solution is 0.1-0.5 times of the ruthenium content, and the second stage adopts saturated NaClO 3 、NaClO、NaBrO 3 One or more of the above-mentioned materials are used as oxidant for oxidation, and the oxidant used in second stage is 2 of ruthenium content5 times; ruthenium is used as RuO in the process of dropwise adding the oxidant in the first stage and the oxidant in the second stage 4 Form(s) of (a) volatilizing from solution, ruO 4 The residual liquid after volatilization is ruthenium distillation residual liquid; washing RuO with ultrapure water 4 Then HCl with the concentration of 6mol/L is used for RuO 4 Performing 4-level absorption; concentrating the absorption liquid to syrup by a rotary evaporator, pouring out, and baking by an infrared lamp to obtain a qualified ruthenium trichloride finished product; chlorine gas generated in the absorption process is neutralized with alkali.
5. The method for preparing ruthenium trichloride from complex waste materials containing ruthenium, rhodium, and iridium according to claim 4, wherein the specific operation of step (4) is as follows: adjusting acidity of the ruthenium distillation raffinate to 8-9 by sodium hydroxide, and carrying out solid-liquid separation on the distillation raffinate to obtain hydrolysis slag; washing sodium ions with water, dissolving with HCl, diluting and filtering the obtained solution, performing ion exchange to remove base metals, and extracting, separating, purifying and recovering rhodium and iridium.
6. A process for preparing ruthenium trichloride from complex wastes containing ruthenium, rhodium and iridium according to claim 3, wherein the oxidizing agent used in step (2) is NaClO 3 、H 2 O 2 、Cl 2 And HNO 3 One or more of them.
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