CN111020200B - Method for recovering rhodium from rhodium-containing waste liquid - Google Patents
Method for recovering rhodium from rhodium-containing waste liquid Download PDFInfo
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- CN111020200B CN111020200B CN201911304114.4A CN201911304114A CN111020200B CN 111020200 B CN111020200 B CN 111020200B CN 201911304114 A CN201911304114 A CN 201911304114A CN 111020200 B CN111020200 B CN 111020200B
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- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 337
- 239000010948 rhodium Substances 0.000 title claims abstract description 337
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 337
- 239000007788 liquid Substances 0.000 title claims abstract description 123
- 239000002699 waste material Substances 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000000428 dust Substances 0.000 claims abstract description 170
- 238000005406 washing Methods 0.000 claims abstract description 141
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 96
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002253 acid Substances 0.000 claims abstract description 60
- 150000003283 rhodium Chemical class 0.000 claims abstract description 37
- 239000003513 alkali Substances 0.000 claims abstract description 35
- 239000002893 slag Substances 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- 239000002023 wood Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003546 flue gas Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000001704 evaporation Methods 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 130
- 238000003756 stirring Methods 0.000 claims description 68
- 238000001914 filtration Methods 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical group [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 26
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000006228 supernatant Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 20
- 238000011084 recovery Methods 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 8
- 238000005554 pickling Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 61
- 238000010992 reflux Methods 0.000 description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000779 smoke Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 3
- 229910003450 rhodium oxide Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- -1 alkaline earth metal carbonate Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005888 cyclopropanation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent 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
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 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
- C22B7/001—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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/026—Recovery of noble metals from waste materials from spent catalysts
-
- 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
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
-
- 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
-
- 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
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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Abstract
The invention belongs to the field of rhodium recovery, and particularly discloses a method for recovering rhodium from rhodium-containing waste liquid, which comprises the steps of evaporating light components from the rhodium-containing waste liquid through concentration, mixing wood dust, carrying out primary incineration on the rhodium-containing waste liquid concentrated solution, burning into rhodium-containing carbon residue, and then carrying out acid pickling and water washing; then the carbon slag containing rhodium is incinerated for the second time to be fired into rhodium-containing ash slag, and then acid washing, water washing, alkali washing and water washing are carried out, so that acid-soluble and alkali-soluble impurities can be completely removed; in the primary incineration and the secondary incineration processes, the flue gas passes through a wet dust collector and a cyclone dust collector, so that dust in the flue gas can be collected, the direct emission of the flue gas is avoided, the environment pollution is avoided, and the rhodium loss in the incineration process is reduced; and mixing the dust and the incineration residue, reacting with alkali metal acid sulfate to generate soluble rhodium salt, and reacting the soluble rhodium salt with active metal to obtain rhodium. The process of the invention can reduce the rhodium loss in the incineration process, improve the rhodium yield, remove impurities in rhodium-containing ash to ensure higher rhodium enrichment degree and simplify the recovery process.
Description
Technical Field
The invention belongs to the field of rhodium recovery, and particularly relates to a method for recovering rhodium from rhodium-containing waste liquid.
Background
The content of the noble metal rhodium element in the earth crust is only one billion, but the noble metal rhodium element has high utilization value, is widely applied to the manufacturing fields of chemical engineering, aerospace, electronic information and the like, plays a very critical role although the amount of the noble metal rhodium element is small, and is called as industrial vitamin. Rhodium octoate is an important rhodium homogeneous catalyst, has remarkable catalytic activity on cyclopropanation reaction, olefin hydroformylation reaction, ring-closing reaction and the like, and is widely applied to the fields of basic chemical industry, pharmaceutical chemical industry and the like. Like all catalysts, the rhodium octoate catalyst also has a certain service cycle and service life, however, the rhodium resource is limited, the price is high, and the price of rhodium in the international market is increasing, so that the efficient recovery of rhodium in the deactivated catalyst is of great significance to the sustainable utilization of national resources.
At present, the process method for recovering rhodium is mainly an incineration method, for example, the method for recovering rhodium from rhodium-containing waste liquid disclosed in patent CN102247841 is as follows: sending the rhodium-containing waste liquid into an incinerator for incineration, sending the incinerated material into the incinerator for incineration again, adding a mixture of sodium peroxide and sodium hydroxide into the obtained incinerated material for melting oxidation at the temperature of 800-900 ℃, converting the material into rhodium oxide, adding a proper amount of industrial hydrochloric acid into the rhodium oxide, and slowly dropwise adding 10% of NaClO at the temperature of 80-90 DEG C3And (3) converting rhodium oxide into rhodium salt aqueous solution by using an aqueous solution, and replacing the rhodium salt aqueous solution with zinc powder to obtain recovered rhodium powder.
The method for recovering rhodium from rhodium-containing waste liquid disclosed in the German patent 2438847 is as follows: feeding the rhodium-containing waste liquid and air into an immersed combustion chamber, incinerating at 1150 ℃ for 20 hours, filling water into the immersed combustion chamber, absorbing gas generated after combustion by the water in the immersed combustion chamber, leaving rhodium in the water in the immersed combustion chamber in a suspended state, and filtering to obtain recovered rhodium powder.
The method for recovering rhodium from the rhodium-containing waste liquid disclosed in patent CN1176232 is as follows: alkali metal or alkaline earth metal carbonate is used as an additive, rhodium-containing waste liquid is incinerated and incinerated under the condition of 650-700 ℃, the residual residue is reacted with alkali metal acid sulfate in a molten state to generate soluble rhodium salt, and then rhodium is separated by adopting an electrolysis technology.
However, the incineration methods of the rhodium-containing waste liquid all have the defect of large rhodium loss in the incineration process, and because the rhodium metal is expensive, the rhodium loss caused in the incineration process needs to be minimized.
Disclosure of Invention
The invention provides a method for recovering rhodium from rhodium-containing waste liquid, which can improve the final recovery rate of rhodium.
The technical scheme of the invention is realized as follows:
a method for recovering rhodium from rhodium-containing waste liquid comprises the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), uniformly stirring, putting into an incinerator for primary incineration, wherein the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is subjected to dust collection by connecting the wet dust collector and the cyclone dust collector, and the dust and incineration residues are combined to obtain rhodium-containing carbon residues;
3) crushing the rhodium-containing carbon residue obtained in the step 2) by using a ball mill, then carrying out acid washing for 1 time, carrying out water washing for 2 times, and filtering to obtain filter residue;
4) drying the filter residue obtained in the step 3), and putting the filter residue into an incinerator for secondary incineration, wherein the incinerator is connected with a wet dust collector and a cyclone dust collector, the smoke is connected with the wet dust collector and the cyclone dust collector for dust collection, and the dust and the incineration residue are combined to obtain rhodium-containing ash residue;
5) crushing the rhodium-containing ash obtained in the step 4) by using a ball mill, then carrying out acid washing for 1 time, water washing for 2 times, alkali washing for 1 time and water washing for 2 times, filtering, and drying filter residues;
6) mixing the filter residue obtained in the step 5) with alkali metal acid sulfate, crushing, heating for reaction, and adding water to obtain soluble rhodium salt;
7) adding active metal into the soluble rhodium salt obtained in the step 6), and carrying out reaction reduction to obtain rhodium.
Further, in the step 1), the concentration condition is that the vacuum degree is 0.08-0.1MPa, the concentration temperature is 100-500 ℃, and the volume of the rhodium-containing waste liquid concentrated solution is 20% -30% of the total volume of the rhodium-containing waste liquid.
Further, in the step 2), the adding amount of the wood chips is 10-100% of the mass of the rhodium-containing waste liquid concentrated solution, the primary incineration temperature is 800-1000 ℃, and the incineration time is 8-12 h.
Further, the acid washing conditions in the steps 3) and 5) are that concentrated hydrochloric acid is added according to the mass ratio of the carbon residue containing rhodium to the concentrated hydrochloric acid of 1:2, the mixture is stirred, refluxed and washed for 2 hours, and the mass concentration of the concentrated hydrochloric acid is 35-37%;
the conditions of water washing in the step 3) and the step 5) are that water is added according to the mass ratio of the rhodium-containing carbon slag to the water of 1:2 every time, and the mixture is stirred, refluxed and washed for 1 h;
the alkaline washing condition in the step 5) is that the rhodium-containing ash and the alkaline liquor are added with the alkaline liquor according to the mass ratio of 1:2, stirred, refluxed and washed for 2 hours.
Further, the conditions of the secondary incineration in the step 4) are that the temperature of the secondary incineration is 800-.
Further, the active metal is magnesium powder, aluminum powder or zinc powder, and the mass ratio of the active metal to rhodium in the rhodium-containing waste liquid is 1.2-2 times.
Further, step 6), the reaction temperature is 500-700 ℃, and the reaction time is 2-8 h.
Further, in the step 3) and the step 5), the rhodium-containing carbon slag is crushed by a ball mill, and the particle size after crushing is 100-500 meshes; the rhodium-containing ash is pulverized by a ball mill, and the particle size after pulverization is 100-500 meshes.
Further, the alkali metal acid sulfate is sodium bisulfate, and the mass ratio of the sodium bisulfate to rhodium in the rhodium-containing waste liquid is 20-30 times.
Further, step 7), the temperature of the displacement reaction is 60-100 ℃, the time is 2-3h, after the displacement reaction is finished, the supernatant is removed, then a hydrochloric acid solution with the mass concentration of 2-10% is added for pickling for 2 times, the filter residue is obtained by filtering, and the rhodium is obtained by drying.
The invention provides a method for recovering rhodium from rhodium-containing waste liquid, which comprises the steps of concentrating the rhodium-containing waste liquid to evaporate light components, mixing with wood chips, carrying out primary incineration on the rhodium-containing waste liquid concentrated solution, burning into rhodium-containing carbon residue, and then carrying out acid pickling and water washing; then burning the carbon slag containing rhodium for the second time to obtain rhodium-containing ash, then carrying out acid washing and water washing, and carrying out alkali washing and water washing after the acid washing and the water washing, so that acid-soluble and alkali-soluble impurities can be completely removed; in the primary incineration process and the secondary incineration process, the smoke passes through the wet dust collector and the cyclone dust collector, so that dust in the smoke can be collected, the smoke is prevented from being directly discharged to pollute the environment, the rhodium loss in the incineration process can be reduced, and the incineration speed is increased; and combining the collected dust and the incineration residue, reacting with alkali metal acid sulfate to generate soluble rhodium salt, and adding active metal into the soluble rhodium salt to replace rhodium. The process of the invention can not only greatly reduce the rhodium loss in the incineration process and improve the rhodium yield, but also effectively remove impurities in rhodium-containing ash slag to ensure that the rhodium enrichment degree is higher and simplify the recovery process. The experimental result shows that the yield of rhodium reaches more than 95.50 percent.
Drawings
FIG. 1 is a process flow diagram of a method for recovering rhodium from rhodium-containing waste liquid according to the present invention.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
As shown in fig. 1, a method for recovering rhodium from rhodium-containing waste liquid comprises the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), uniformly stirring, putting into an incinerator for primary incineration, wherein the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is subjected to dust collection by connecting the wet dust collector and the cyclone dust collector, and the dust and incineration residues are combined to obtain rhodium-containing carbon residues;
3) crushing the rhodium-containing carbon residue obtained in the step 2) by using a ball mill, then carrying out acid washing for 1 time, carrying out water washing for 2 times, and filtering to obtain filter residue;
4) drying the filter residue obtained in the step 3), and putting the filter residue into an incinerator for secondary incineration, wherein the incinerator is connected with a wet dust collector and a cyclone dust collector, the smoke is connected with the wet dust collector and the cyclone dust collector for dust collection, and the dust and the incineration residue are combined to obtain rhodium-containing ash residue;
5) crushing the rhodium-containing ash obtained in the step 4) by using a ball mill, then carrying out acid washing for 1 time, water washing for 2 times, alkali washing for 1 time and water washing for 2 times, filtering, and drying filter residues;
6) mixing the filter residue obtained in the step 5) with alkali metal acid sulfate, crushing, heating for reaction, and adding water to obtain soluble rhodium salt;
7) adding active metal into the soluble rhodium salt obtained in the step 6), and carrying out reaction reduction to obtain rhodium.
According to the invention, the rhodium-containing waste liquid is poured into the concentration kettle for concentration, and the light components are evaporated, so that the amount of the incineration solvent can be reduced. It is noted that the concentration condition is that the vacuum degree is 0.08-0.1MPa, the concentration temperature is 100-500 ℃, and the volume of the rhodium-containing waste liquid concentrated solution is 20-30% of the total volume of the rhodium-containing waste liquid; preferably, the vacuum degree is 0.095-0.1MPa, and the concentration temperature is 180 ℃.
Adding wood chips into the rhodium-containing waste liquid concentrated solution, uniformly stirring, putting into an incinerator for primary incineration, connecting the incinerator with a wet dust collector and a cyclone dust collector, collecting dust by connecting flue gas with the wet dust collector and the cyclone dust collector, and combining the dust and incineration residues to obtain rhodium-containing carbon residues. Wherein the adding amount of the wood dust is 10-100% of the mass of the rhodium-containing waste liquid concentrated solution, the primary incineration temperature is 800-1000 ℃, and the incineration time is 8-12 h; preferably, the addition amount of the wood chips is 50% of the mass of the rhodium-containing waste liquid concentrated solution.
It is noted that the addition of wood chips can reduce the rhodium loss in the incineration process and improve the rhodium yield.
The wet dust collector is a gravity spray wet dust collector, a cyclone wet dust collector, a self-excitation wet dust collector, a filler wet dust collector, a foam wet dust collector, a Venturi wet dust collector, a mechanical induction dust collector, a water film dust collector or a spray tower dust collector; preferably, the wet dust collector is a spray tower dust collector; the cyclone separator is a high-efficiency cyclone dust collector, a high-flow cyclone dust collector, a general cyclone dust collector or an explosion-proof cyclone dust collector; preferably, the wet dust collector is a high efficiency cyclone.
Crushing rhodium-containing carbon slag by using a ball mill, then carrying out acid washing for 1 time, carrying out water washing for 2 times, and filtering to obtain filter residue; wherein, the rhodium-containing carbon slag is crushed by a ball mill, and the particle size after crushing is 100-500 meshes; wherein the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 35-37%, and the mass ratio of the carbon residue containing rhodium to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing carbon slag in the 2-time water washing process is 2: 1; adding concentrated hydrochloric acid into the rhodium-containing carbon residue, stirring, refluxing and washing for 2h, filtering, adding water, stirring, refluxing and washing for 1h, and filtering to obtain filter residue.
And drying the filter residues, putting the filter residues into an incinerator for secondary incineration, connecting the incinerator with a wet dust collector and a cyclone dust collector, collecting dust by connecting the flue gas with the wet dust collector and the cyclone dust collector, and combining the dust and the incineration residues to obtain rhodium-containing ash residues. Wherein, the secondary incineration can thoroughly remove the carbon in the filter residue and improve the purity of the rhodium, the temperature of the secondary incineration is 800-.
It should be noted that the wet dust collector and the cyclone dust collector used in the secondary incineration process are the same as those used in the primary incineration process, and are not described herein again.
Crushing rhodium-containing ash by using a ball mill, then carrying out acid washing for 1 time, water washing for 2 times, carrying out alkali washing for 1 time, water washing for 2 times, filtering, and drying filter residues; the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 35-37%, and the mass ratio of the rhodium-containing ash to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing ash in the 4-time water washing process is 2: 1; the alkali liquor used in the alkali washing process is a sodium hydroxide solution with the mass concentration of 25-30%, and the mass ratio of the rhodium-containing ash to the alkali liquor is 1: 2. Adding concentrated hydrochloric acid into rhodium-containing ash, stirring, refluxing and washing for 2h, filtering, adding water, stirring, refluxing and washing for 1h, filtering, adding alkali liquor, stirring, refluxing and washing for 2h, filtering, adding water, stirring, refluxing and washing for 1h, and filtering to obtain filter residue.
Mixing and crushing filter residue and alkali metal acid sulfate, heating for reaction, and adding water to obtain soluble rhodium salt; the alkali metal acid sulfate is sodium bisulfate, the mass ratio of the sodium bisulfate to rhodium in the rhodium-containing waste liquid is 20-30 times, the reaction temperature is 500-700 ℃, and the reaction time is 2-8 h; preferably, the reaction temperature is 600-650 ℃, and the reaction time is 4 h.
Adding active metal into soluble rhodium salt, and carrying out reaction reduction to obtain rhodium. Wherein the active metal is magnesium powder, aluminum powder or zinc powder, and the mass ratio of the active metal to rhodium in the rhodium-containing waste liquid is 1.2-2 times; the reaction temperature is 60-100 ℃, the reaction time is 2-3h, after the reaction is finished, the supernatant liquid is removed, then hydrochloric acid solution with the mass concentration of 2-10% is added, the mixture is stirred, refluxed and washed for 2h, the hydrochloric acid solution with the mass concentration of 2-10% is added after the reaction is finished, the mixture is filtered, acid washing is carried out for 2 times, filter residue is obtained after the acid washing, and the rhodium is obtained after drying. Preferably, the active metal is zinc powder.
According to the method, the rhodium-containing waste liquid is concentrated to evaporate light components, then wood dust is mixed into the waste liquid, the concentrated liquid of the rhodium-containing waste liquid is subjected to primary incineration to burn the waste liquid into rhodium-containing carbon residue, and then acid pickling and water washing are carried out; then burning the carbon slag containing rhodium for the second time to obtain rhodium-containing ash, then carrying out acid washing and water washing, and carrying out alkali washing and water washing after the acid washing and the water washing, so that acid-soluble and alkali-soluble impurities can be completely removed; in the primary incineration process and the secondary incineration process, the smoke passes through the wet dust collector and the cyclone dust collector, so that dust in the smoke can be collected, the smoke is prevented from being directly discharged to pollute the environment, the rhodium loss in the incineration process can be reduced, and the incineration speed is increased; and combining the collected dust and the incineration residue, reacting with alkali metal acid sulfate to generate soluble rhodium salt, and adding active metal into the soluble rhodium salt to replace rhodium. The method has the advantages of simple process, easy operation and high recovery rate, and can effectively remove impurities in the rhodium recovery process and improve the recovery rate of rhodium. The experimental result shows that the yield of rhodium reaches more than 95.5 percent.
In order to further illustrate the present invention, the following will describe in detail a method for recovering rhodium from rhodium-containing waste liquid provided by the present invention with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The method for recovering rhodium from the rhodium-containing waste liquid comprises the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components; the concentration conditions were: the vacuum degree is 0.08MPa, the concentration temperature is 100 ℃, and the concentration end point is as follows: the volume of the rhodium-containing waste liquid concentrated solution is 20 percent of the total volume of the rhodium-containing waste liquid;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), wherein the adding amount of the wood chips is 10% of the mass of the rhodium-containing waste liquid concentrated solution, uniformly stirring, putting into an incinerator for primary incineration, wherein the temperature of the primary incineration is 800 ℃, the incineration time is 8 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is connected with the wet dust collector and the cyclone dust collector for dust collection, and the dust and incineration residues are combined to obtain rhodium-containing carbon residue;
3) crushing the rhodium-containing carbon slag obtained in the step 2) by using a ball mill, wherein the particle size after crushing is 100 meshes, then adding concentrated hydrochloric acid into the rhodium-containing carbon slag, stirring, refluxing and washing for 2 hours, adding water after filtering, stirring, refluxing and washing for 1 hour, and filtering to obtain filter residue;
the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 35%, and the mass ratio of the carbon residue containing rhodium to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing carbon slag in the 2-time water washing process is 2: 1;
4) drying the filter residue obtained in the step 3), and putting the filter residue into an incinerator for secondary incineration, wherein the temperature of the secondary incineration is 800 ℃, the incineration time is 8 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is subjected to dust removal by connecting the wet dust collector and the cyclone dust collector to collect dust, and the dust and incineration residue are combined to obtain rhodium-containing ash;
5) crushing the rhodium-containing ash obtained in the step 4) by using a ball mill, wherein the particle size of the crushed ash is 100 meshes, adding concentrated hydrochloric acid into the rhodium-containing ash, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, filtering, adding alkali liquor, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, and filtering to obtain filter residue;
the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 35%, and the mass ratio of the rhodium-containing ash to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing ash in the 4-time water washing process is 2: 1; the alkali liquor used in the alkali washing process is a sodium hydroxide solution with the mass concentration of 25%, and the mass ratio of the rhodium-containing ash to the alkali liquor is 1: 2;
6) mixing and crushing the filter residue obtained in the step 5) and sodium bisulfate, heating for reaction at 500 ℃ for 2h, and adding water in an amount which is 4 times of the mass of the filter residue to obtain soluble rhodium salt; the mass ratio of the sodium bisulfate to the rhodium in the rhodium-containing waste liquid is 20 times;
7) adding active metal into the soluble rhodium salt obtained in the step 6), reacting at the temperature of 60 ℃ for 2 hours, removing supernatant, adding a hydrochloric acid solution with the mass concentration of 2%, stirring, refluxing and washing for 1 hour, filtering to obtain filter residue, and drying to obtain rhodium.
Comparative example 1
The method for recovering rhodium from the rhodium-containing waste liquid comprises the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components; the concentration conditions were: the vacuum degree is 0.08MPa, the concentration temperature is 100 ℃, and the concentration end point is as follows: the volume of the rhodium-containing waste liquid concentrated solution is 20 percent of the total volume of the rhodium-containing waste liquid;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), wherein the adding amount of the wood chips is 10% of the mass of the rhodium-containing waste liquid concentrated solution, uniformly stirring, putting into an incinerator for primary incineration and secondary incineration, wherein the primary incineration and the secondary incineration are both at 800 ℃, the incineration time is both 8 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is connected with the wet dust collector and the cyclone dust collector for dust collection, and the dust and incineration residues are combined to obtain rhodium-containing carbon residue;
3) mixing and crushing the filter residue obtained in the step 2) and sodium bisulfate, heating for reaction at 500 ℃ for 2h, and adding water in an amount which is 4 times of the mass of the filter residue to obtain soluble rhodium salt; the mass ratio of the sodium bisulfate to the rhodium in the rhodium-containing waste liquid is 20 times;
4) adding active metal into the soluble rhodium salt obtained in the step 3), reacting at the temperature of 60 ℃ for 2 hours, removing supernatant, then adding a hydrochloric acid solution with the mass concentration of 2%, stirring, refluxing and washing for 1 hour, filtering to obtain filter residue, and drying to obtain rhodium.
Example 2
The method for recovering rhodium from the rhodium-containing waste liquid comprises the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components; the concentration conditions were: the vacuum degree is 0.1MPa, the concentration temperature is 500 ℃, and the concentration end point is as follows: the volume of the rhodium-containing waste liquid concentrated solution is 30 percent of the total volume of the rhodium-containing waste liquid;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), wherein the adding amount of the wood chips is 100% of the mass of the rhodium-containing waste liquid concentrated solution, uniformly stirring, putting into an incinerator for primary incineration, wherein the temperature of the primary incineration is 1000 ℃, the incineration time is 12 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is connected with the wet dust collector and the cyclone dust collector for dust collection, and the dust and incineration residues are combined to obtain rhodium-containing carbon residue;
3) crushing the rhodium-containing carbon slag obtained in the step 2) by using a ball mill, wherein the particle size after crushing is 500 meshes, then adding concentrated hydrochloric acid into the rhodium-containing carbon slag, stirring, refluxing and washing for 2 hours, adding water after filtering, stirring, refluxing and washing for 1 hour, and filtering to obtain filter residue;
the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 37%, and the mass ratio of the carbon residue containing rhodium to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing carbon slag in the 2-time water washing process is 2: 1;
4) drying the filter residue obtained in the step 3), and putting the filter residue into an incinerator for secondary incineration, wherein the temperature of the secondary incineration is 1000 ℃, the incineration time is 12 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is subjected to dust removal by connecting the wet dust collector and the cyclone dust collector to collect dust, and the dust and incineration residue are combined to obtain rhodium-containing ash;
5) crushing the rhodium-containing ash obtained in the step 4) by using a ball mill, wherein the particle size after crushing is 500 meshes, adding concentrated hydrochloric acid into the rhodium-containing ash, stirring, refluxing and washing for 2 hours, adding water after filtering, stirring, refluxing and washing for 1 hour, adding alkali liquor after filtering, stirring, refluxing and washing for 2 hours, adding water after filtering, stirring, refluxing and washing for 1 hour, and filtering to obtain filter residue;
the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 37%, and the mass ratio of the rhodium-containing ash to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing ash in the 4-time water washing process is 2: 1; the alkali liquor used in the alkali washing process is a sodium hydroxide solution with the mass concentration of 30%, and the mass ratio of the rhodium-containing ash to the alkali liquor is 1: 2;
6) mixing and crushing the filter residue obtained in the step 5) and sodium bisulfate, heating for reaction at the reaction temperature of 700 ℃ for 8h, and adding water in an amount which is 4 times of the mass of the filter residue to obtain soluble rhodium salt; the mass ratio of the sodium bisulfate to the rhodium in the rhodium-containing waste liquid is 30 times;
7) adding active metal into the soluble rhodium salt obtained in the step 6), reacting at 100 ℃ for 3 hours, removing supernatant, adding a hydrochloric acid solution with the mass concentration of 10%, stirring, refluxing and washing for 1 hour, filtering to obtain filter residue, and drying to obtain rhodium.
Comparative example 2
The method for recovering rhodium from the rhodium-containing waste liquid comprises the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components; the concentration conditions were: the vacuum degree is 0.1MPa, the concentration temperature is 500 ℃, and the concentration end point is as follows: the volume of the rhodium-containing waste liquid concentrated solution is 30 percent of the total volume of the rhodium-containing waste liquid;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), wherein the adding amount of the wood chips is 100% of the mass of the rhodium-containing waste liquid concentrated solution, uniformly stirring, putting into an incinerator for primary incineration and secondary incineration, wherein the primary incineration and the secondary incineration are both at 1000 ℃, the incineration time is 12 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is connected with the wet dust collector and the cyclone dust collector for dust collection, and the dust and incineration residues are combined to obtain rhodium-containing carbon residue;
3) mixing and crushing the filter residue obtained in the step 2) and sodium bisulfate, heating for reaction at the reaction temperature of 700 ℃ for 8h, and adding water in an amount which is 4 times of the mass of the filter residue to obtain soluble rhodium salt; the mass ratio of the sodium bisulfate to the rhodium in the rhodium-containing waste liquid is 30 times;
4) adding active metal into the soluble rhodium salt obtained in the step 3), reacting at 100 ℃ for 3 hours, removing supernatant, adding a hydrochloric acid solution with the mass concentration of 10%, stirring, refluxing and washing for 1 hour, filtering to obtain filter residue, and drying to obtain rhodium.
Example 3
The method for recovering rhodium from the rhodium-containing waste liquid comprises the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components; the concentration conditions were: the vacuum degree is 0.1MPa, the concentration temperature is 300 ℃, and the concentration end point is as follows: the volume of the rhodium-containing waste liquid concentrated solution is 25 percent of the total volume of the rhodium-containing waste liquid;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), wherein the adding amount of the wood chips is 50% of the mass of the rhodium-containing waste liquid concentrated solution, uniformly stirring, putting into an incinerator for primary incineration, wherein the temperature of the primary incineration is 900 ℃, the incineration time is 10 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is connected with the wet dust collector and the cyclone dust collector for dust collection, and the dust and incineration residues are combined to obtain rhodium-containing carbon residue;
3) crushing the rhodium-containing carbon slag obtained in the step 2) by using a ball mill, wherein the particle size of the crushed rhodium-containing carbon slag is 200 meshes, adding concentrated hydrochloric acid into the rhodium-containing carbon slag, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, and filtering to obtain filter residue;
the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 37%, and the mass ratio of the carbon residue containing rhodium to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing carbon slag in the 2-time water washing process is 2: 1;
4) drying the filter residue obtained in the step 3), and putting the filter residue into an incinerator for secondary incineration, wherein the temperature of the secondary incineration is 900 ℃, the incineration time is 10 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is subjected to dust removal by connecting the wet dust collector and the cyclone dust collector to collect dust, and the dust and incineration residue are combined to obtain rhodium-containing ash;
5) crushing the rhodium-containing ash obtained in the step 4) by using a ball mill, wherein the particle size of the crushed ash is 200 meshes, adding concentrated hydrochloric acid into the rhodium-containing ash, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, filtering, adding alkali liquor, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, and filtering to obtain filter residue;
the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 37%, and the mass ratio of the rhodium-containing ash to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing ash in the 4-time water washing process is 2: 1; the alkali liquor used in the alkali washing process is a sodium hydroxide solution with the mass concentration of 25-30%, and the mass ratio of the rhodium-containing ash to the alkali liquor is 1: 2;
6) mixing and crushing the filter residue obtained in the step 5) and sodium bisulfate, heating for reaction at 650 ℃ for 4h, and adding water in an amount which is 4 times of the mass of the filter residue to obtain soluble rhodium salt; the mass ratio of the sodium bisulfate to the rhodium in the rhodium-containing waste liquid is 25 times;
7) adding active metal into the soluble rhodium salt obtained in the step 6), reacting at 80 ℃ for 3 hours, removing supernatant, adding a hydrochloric acid solution with the mass concentration of 6%, stirring, refluxing and washing for 1 hour, filtering, adding a hydrochloric acid solution with the mass concentration of 5%, stirring, refluxing and washing for 1 hour, filtering to obtain filter residue, and drying to obtain rhodium.
Comparative example 3
The method for recovering rhodium from the rhodium-containing waste liquid comprises the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components; the concentration conditions were: the vacuum degree is 0.1MPa, the concentration temperature is 300 ℃, and the concentration end point is as follows: the volume of the rhodium-containing waste liquid concentrated solution is 25 percent of the total volume of the rhodium-containing waste liquid;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), wherein the adding amount of the wood chips is 50% of the mass of the rhodium-containing waste liquid concentrated solution, uniformly stirring, putting into an incinerator for primary incineration and secondary incineration, wherein the primary incineration and the secondary incineration are both at 900 ℃ and the incineration time is 10 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is connected with the wet dust collector and the cyclone dust collector for dust collection, and the dust and incineration residues are combined to obtain rhodium-containing carbon residue;
3) mixing and crushing the filter residue obtained in the step 2) and sodium bisulfate, heating for reaction at the reaction temperature of 650 ℃ for 4h, and adding water in an amount which is 4 times of the mass of the filter residue to obtain soluble rhodium salt; the mass ratio of the sodium bisulfate to the rhodium in the rhodium-containing waste liquid is 25 times;
4) adding active metal into the soluble rhodium salt obtained in the step 3), reacting at the temperature of 80 ℃ for 3 hours, removing supernatant, adding a hydrochloric acid solution with the mass concentration of 6%, stirring, refluxing and washing for 1 hour, filtering, adding a hydrochloric acid solution with the mass concentration of 5%, stirring, refluxing and washing for 1 hour, filtering to obtain filter residue, and drying to obtain rhodium.
Example 4
The method for recovering rhodium from the rhodium-containing waste liquid comprises the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components; the concentration conditions were: the vacuum degree is 0.095MPa, the concentration temperature is 180 ℃, and the concentration end point is as follows: the volume of the rhodium-containing waste liquid concentrated solution is 25 percent of the total volume of the rhodium-containing waste liquid;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), wherein the adding amount of the wood chips is 50% of the mass of the rhodium-containing waste liquid concentrated solution, uniformly stirring, putting into an incinerator for primary incineration, wherein the temperature of the primary incineration is 900 ℃, the incineration time is 10 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is connected with the wet dust collector and the cyclone dust collector for dust collection, and the dust and incineration residues are combined to obtain rhodium-containing carbon residue;
3) crushing the rhodium-containing carbon slag obtained in the step 2) by using a ball mill, wherein the particle size of the crushed rhodium-containing carbon slag is 300 meshes, adding concentrated hydrochloric acid into the rhodium-containing carbon slag, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, and filtering to obtain filter residue;
the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 36%, and the mass ratio of the carbon residue containing rhodium to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing carbon slag in the 2-time water washing process is 2: 1;
4) drying the filter residue obtained in the step 3), and putting the filter residue into an incinerator for secondary incineration, wherein the temperature of the secondary incineration is 900 ℃, the incineration time is 10 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is subjected to dust removal by connecting the wet dust collector and the cyclone dust collector to collect dust, and the dust and incineration residue are combined to obtain rhodium-containing ash;
5) crushing the rhodium-containing ash obtained in the step 4) by using a ball mill, wherein the particle size of the crushed ash is 300 meshes, adding concentrated hydrochloric acid into the rhodium-containing ash, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, filtering, adding alkali liquor, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, and filtering to obtain filter residue;
the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 37%, and the mass ratio of the rhodium-containing ash to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing ash in the 4-time water washing process is 2: 1; the alkali liquor used in the alkali washing process is a sodium hydroxide solution with the mass concentration of 26%, and the mass ratio of the rhodium-containing ash to the alkali liquor is 1: 2;
6) mixing and crushing the filter residue obtained in the step 5) and sodium bisulfate, heating for reaction at the temperature of 600 ℃ for 4h, and adding water in an amount which is 4 times of the mass of the filter residue to obtain soluble rhodium salt; the mass ratio of the sodium bisulfate to the rhodium in the rhodium-containing waste liquid is 25 times;
7) adding active metal into the soluble rhodium salt obtained in the step 6), reacting at 80 ℃ for 2 hours, removing supernatant, adding a hydrochloric acid solution with the mass concentration of 5%, stirring, refluxing and washing for 1 hour, filtering to obtain filter residue, and drying to obtain rhodium.
Comparative example 4
The method for recovering rhodium from the rhodium-containing waste liquid comprises the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components; the concentration conditions were: the vacuum degree is 0.095MPa, the concentration temperature is 180 ℃, and the concentration end point is as follows: the volume of the rhodium-containing waste liquid concentrated solution is 25 percent of the total volume of the rhodium-containing waste liquid;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), wherein the adding amount of the wood chips is 50% of the mass of the rhodium-containing waste liquid concentrated solution, uniformly stirring, and then putting into an incinerator for primary incineration and secondary incineration, wherein the temperature of the primary incineration and the temperature of the secondary incineration are both 900 ℃, and the incineration time is both 10 hours; the incinerator is connected with the wet dust collector and the cyclone dust collector, the flue gas is connected with the wet dust collector and the cyclone dust collector to remove dust and collect dust, and the dust and the incineration residues are combined to obtain rhodium-containing carbon residues;
3) mixing and crushing the rhodium-containing carbon residue obtained in the step 2) and sodium bisulfate, heating for reaction at the reaction temperature of 600 ℃ for 4 hours, and adding water in an amount which is 4 times of the mass of the filter residue to obtain soluble rhodium salt; the mass ratio of the sodium bisulfate to the rhodium in the rhodium-containing waste liquid is 25 times;
4) adding active metal into the soluble rhodium salt obtained in the step 3), reacting at the temperature of 80 ℃ for 2 hours, removing supernatant, adding a hydrochloric acid solution with the mass concentration of 5%, stirring, refluxing and washing for 1 hour, filtering to obtain filter residue, and drying to obtain rhodium.
Comparative example 5
The method for recovering rhodium from the rhodium-containing waste liquid comprises the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components; the concentration conditions were: the vacuum degree is 0.095MPa, the concentration temperature is 180 ℃, and the concentration end point is as follows: the volume of the rhodium-containing waste liquid concentrated solution is 25 percent of the total volume of the rhodium-containing waste liquid;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), wherein the adding amount of the wood chips is 50% of the mass of the rhodium-containing waste liquid concentrated solution, uniformly stirring, and then putting into an incinerator for primary incineration, wherein the temperature of the primary incineration is 900 ℃, and the incineration time is 10 hours, so as to obtain rhodium-containing carbon slag;
3) crushing the rhodium-containing carbon slag obtained in the step 2) by using a ball mill, wherein the particle size of the crushed rhodium-containing carbon slag is 300 meshes, adding concentrated hydrochloric acid into the rhodium-containing carbon slag, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, and filtering to obtain filter residue;
the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 36%, and the mass ratio of the carbon residue containing rhodium to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing carbon slag in the 2-time water washing process is 2: 1;
4) drying the filter residue obtained in the step 3), and putting the filter residue into an incinerator for secondary incineration, wherein the temperature of the secondary incineration is 900 ℃, and the incineration time is 10 hours, so as to obtain rhodium-containing ash;
5) crushing the rhodium-containing ash obtained in the step 4) by using a ball mill, wherein the particle size of the crushed ash is 300 meshes, adding concentrated hydrochloric acid into the rhodium-containing ash, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, filtering, adding alkali liquor, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, and filtering to obtain filter residue;
the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 37%, and the mass ratio of the rhodium-containing ash to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing ash in the 4-time water washing process is 2: 1; the alkali liquor used in the alkali washing process is a sodium hydroxide solution with the mass concentration of 26%, and the mass ratio of the rhodium-containing ash to the alkali liquor is 1: 2;
6) mixing and crushing the filter residue obtained in the step 5) and sodium bisulfate, heating for reaction at the temperature of 600 ℃ for 4h, and adding water in an amount which is 4 times of the mass of the filter residue to obtain soluble rhodium salt; the mass ratio of the sodium bisulfate to the rhodium in the rhodium-containing waste liquid is 25 times;
7) adding active metal into the soluble rhodium salt obtained in the step 6), reacting at 80 ℃ for 2 hours, removing supernatant, adding a hydrochloric acid solution with the mass concentration of 5%, stirring, refluxing and washing for 1 hour, filtering to obtain filter residue, and drying to obtain rhodium.
Comparative example 6
The method for recovering rhodium from the rhodium-containing waste liquid comprises the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components; the concentration conditions were: the vacuum degree is 0.095MPa, the concentration temperature is 180 ℃, and the concentration end point is as follows: the volume of the rhodium-containing waste liquid concentrated solution is 25 percent of the total volume of the rhodium-containing waste liquid;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), wherein the adding amount of the wood chips is 50% of the mass of the rhodium-containing waste liquid concentrated solution, uniformly stirring, putting into an incinerator for primary incineration, wherein the temperature of the primary incineration is 900 ℃, the incineration time is 10 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is connected with the wet dust collector for dust collection, and the dust and incineration residues are combined to obtain rhodium-containing carbon residue;
3) crushing the rhodium-containing carbon slag obtained in the step 2) by using a ball mill, wherein the particle size of the crushed rhodium-containing carbon slag is 300 meshes, adding concentrated hydrochloric acid into the rhodium-containing carbon slag, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, and filtering to obtain filter residue;
the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 36%, and the mass ratio of the carbon residue containing rhodium to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing carbon slag in the 2-time water washing process is 2: 1;
4) drying the filter residue obtained in the step 3), and putting the filter residue into an incinerator for secondary incineration, wherein the temperature of the secondary incineration is 900 ℃, the incineration time is 10 hours, the incinerator is connected with a wet dust collector and a cyclone dust collector, flue gas is connected with the wet dust collector for dust collection, and the dust and the incineration residue are combined to obtain rhodium-containing ash residue;
5) crushing the rhodium-containing ash obtained in the step 4) by using a ball mill, wherein the particle size of the crushed ash is 300 meshes, adding concentrated hydrochloric acid into the rhodium-containing ash, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, filtering, adding alkali liquor, stirring, refluxing and washing for 2 hours, filtering, adding water, stirring, refluxing and washing for 1 hour, and filtering to obtain filter residue;
the acid used in the acid washing process is concentrated hydrochloric acid with the mass concentration of 37%, and the mass ratio of the rhodium-containing ash to the concentrated hydrochloric acid is 1: 2; the mass ratio of water to rhodium-containing ash in the 4-time water washing process is 2: 1; the alkali liquor used in the alkali washing process is a sodium hydroxide solution with the mass concentration of 26%, and the mass ratio of the rhodium-containing ash to the alkali liquor is 1: 2;
6) mixing and crushing the filter residue obtained in the step 5) and sodium bisulfate, heating for reaction at the temperature of 600 ℃ for 4h, and adding water in an amount which is 4 times of the mass of the filter residue to obtain soluble rhodium salt; the mass ratio of the sodium bisulfate to the rhodium in the rhodium-containing waste liquid is 25 times;
7) adding active metal into the soluble rhodium salt obtained in the step 6), reacting at 80 ℃ for 2 hours, removing supernatant, adding a hydrochloric acid solution with the mass concentration of 5%, stirring, refluxing and washing for 1 hour, filtering to obtain filter residue, and drying to obtain rhodium.
The impurity content, impurity removal rate and rhodium extraction rate in examples 1 to 4 and comparative examples 1 to 6 were measured, and the results are shown in table 1.
TABLE 1 Experimental results for examples 1 to 4 and comparative examples 1 to 6
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A method for recovering rhodium from rhodium-containing waste liquid is characterized by comprising the following steps:
1) pouring the rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating out light components;
2) adding wood chips into the rhodium-containing waste liquid concentrated solution obtained in the step 1), uniformly stirring, putting into an incinerator for primary incineration, wherein the incinerator is connected with a wet dust collector and a cyclone dust collector, dedusting and collecting dust from flue gas through the wet dust collector and the cyclone dust collector, and combining the dust with incineration residues to obtain rhodium-containing carbon residues;
in the step 2), the adding amount of the wood dust is 10-100% of the mass of the rhodium-containing waste liquid concentrated solution, the primary incineration temperature is 800-;
3) crushing the rhodium-containing carbon residue obtained in the step 2) by using a ball mill, then carrying out acid washing for 1 time, carrying out water washing for 2 times, and filtering to obtain filter residue;
4) drying the filter residue obtained in the step 3), and putting the filter residue into an incinerator for secondary incineration, wherein the incinerator is connected with a wet dust collector and a cyclone dust collector, the flue gas is subjected to dust collection by the wet dust collector and the cyclone dust collector, and the dust and the incineration residue are combined to obtain rhodium-containing ash residue;
the conditions of the secondary incineration in the step 4) are that the temperature of the secondary incineration is 800-;
5) crushing the rhodium-containing ash obtained in the step 4) by using a ball mill, then carrying out acid washing for 1 time, water washing for 2 times, alkali washing for 1 time and water washing for 2 times, filtering, and drying filter residues;
6) mixing the filter residue obtained in the step 5) with alkali metal acid sulfate, crushing, heating for reaction, and adding water to obtain soluble rhodium salt; the alkali metal acid sulfate is sodium bisulfate, and the mass ratio of the sodium bisulfate to rhodium in the rhodium-containing waste liquid is 20-30: 1; the reaction temperature is 500-700 ℃, and the reaction time is 2-8 h;
7) adding active metal into the soluble rhodium salt obtained in the step 6), and carrying out displacement reaction reduction to obtain rhodium.
2. The method as claimed in claim 1, wherein the concentration conditions in step 1) are vacuum degree of 0.08-0.1MPa, concentration temperature of 100-.
3. The method for recovering rhodium from the rhodium-containing waste liquid according to claim 1, wherein the acid washing conditions in the steps 3) and 5) are that concentrated hydrochloric acid is added according to the mass ratio of the rhodium-containing carbon residue or ash to the concentrated hydrochloric acid of 1:2, and the mixture is stirred, refluxed and washed for 2 hours, wherein the mass concentration of the concentrated hydrochloric acid is 35-37%;
the conditions of water washing in the step 3) and the step 5) are that water is added according to the mass ratio of the rhodium-containing carbon slag or ash slag to the water of 1:2 each time, and the mixture is stirred, refluxed and washed for 1 hour;
the alkaline washing condition in the step 5) is that the rhodium-containing ash and the alkaline liquor are added with the alkaline liquor according to the mass ratio of 1:2, stirred, refluxed and washed for 2 hours.
4. The method for recovering rhodium from the rhodium-containing waste liquid as claimed in claim 1, wherein the active metal is magnesium powder, aluminum powder or zinc powder, and the mass ratio of the active metal to rhodium in the rhodium-containing waste liquid is 1.2-2: 1.
5. the method as claimed in claim 1, wherein in the steps 3) and 5), the rhodium-containing carbon residue is pulverized by a ball mill, and the particle size after pulverization is 100-500 meshes; the rhodium-containing ash is pulverized by a ball mill, and the particle size after pulverization is 100-500 meshes.
6. The method for recovering rhodium from the rhodium-containing waste liquid according to claim 1, characterized in that, in step 7), the temperature of the displacement reaction is 60-100 ℃ and the time is 2-3h, the method further comprises discarding the supernatant after the displacement reaction is finished, adding 2-10% by mass hydrochloric acid solution to perform acid washing for 2 times, filtering to obtain the filter residue, and drying to obtain rhodium.
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| CN114427027A (en) * | 2020-09-30 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing rhodium trichloride by recovering rhodium from waste rhodium residues and obtained rhodium trichloride |
| CN113075200B (en) * | 2021-03-22 | 2023-03-24 | 成都光明派特贵金属有限公司 | Method for measuring platinum and rhodium content in platinum-rhodium mixed solution |
| CN113075199B (en) * | 2021-03-22 | 2023-03-24 | 成都光明派特贵金属有限公司 | Method for measuring rhodium content in high-rhodium-content solution |
| CN113278813B (en) * | 2021-04-25 | 2022-12-13 | 浙江特力再生资源股份有限公司 | Method for separating and purifying rhodium in impurity-containing rhodium solution |
| CN113462900B (en) * | 2021-07-04 | 2022-06-21 | 贵研资源（易门）有限公司 | Method for recovering rhodium from waste rhodium park catalyst |
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| CN1403604A (en) * | 2001-08-27 | 2003-03-19 | 中国石油化工股份有限公司 | Method of recovering metal rhodium from waste olefine carbonylating catalyst liquid |
| CN1176232C (en) * | 2001-10-26 | 2004-11-17 | 中国石油天然气股份有限公司 | Method for recovering rhodium from waste rhodium catalyst in oxo synthesis reaction |
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