CN101100756A - Preparation method for rhodium trichloride - Google Patents
Preparation method for rhodium trichloride Download PDFInfo
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- CN101100756A CN101100756A CNA2006100911772A CN200610091177A CN101100756A CN 101100756 A CN101100756 A CN 101100756A CN A2006100911772 A CNA2006100911772 A CN A2006100911772A CN 200610091177 A CN200610091177 A CN 200610091177A CN 101100756 A CN101100756 A CN 101100756A
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Abstract
Rhodium chloride is prepared from rhodium metal powder by: adding rhodium powder and hydrochloric acid into U-shaped electrolytic tank, providing AC current onto two electrodes to dissolve in solution and obtaining aqueous solution of rhodium hydrochloride, filtering the solution of rhodium hydrochloride, distilling to obtain concentrated liquid, and crystallizing in a crystallizer to obtain aqua compound of rhodium chloride or anhydrous rhodium chloride, which can be used in fine chemistry.
Description
Technical field
The present invention relates to the preparation method of Trichlororhodium, being specifically related to the metal rhodium powder is feedstock production Trichlororhodium RhCl
3XH
2The method of O.
Background technology
Trichlororhodium (RhCl
3XH
2O, x=0～5) be a kind of modal compound of rhodium.The initial feed of synthetic other rhodium compound of Chang Zuowei and preparation rhodium-containing catalyst.Rhodium-containing compound and catalyzer are widely used in petrochemical complex and organic synthesis field.For example, low pressure oxo process system butyl octanol unit, carbonylation of methanol system acetic acid and aceticanhydride device all use the compound of rhodium as homogeneous catalyst in a large number.In addition, at fields such as shortening, fuel cell, purifying vehicle exhaust, plating, RhCl
3XH
2O also is indispensable important industrial chemicals.
Rhodium is a kind of silvery white noble metal with suitable ductility, 1960 ℃ of fusing points.Usually, the form of commodity rhodium is Powdered, i.e. the rhodium powder.Its internal price is at 30～2,000,000 yuan/kilogram at present.The committed step of preparation Trichlororhodium hydrate and other rhodium compound is that the rhodium powder is dissolved in the aqueous solution.Yet rhodium is the best metal of chemical stability in the platinum metals, can not directly be dissolved in the various customary acid solution such as hydrochloric acid, sulfuric acid, nitric acid and hot chloroazotic acid.
The method (" mineral compound synthesize handbook, second volume, Japanization association volume, Chemical Industry Press, 1986) that general dissolving rhodium prepares Trichlororhodium is to be that 1: 2 rhodium powder is with KCl or NaCl porphyrize, then at Cl with mol ratio
2In 550 ℃ of heating 60 minutes, the red product that is soaked in water, filtration contained K in the filtrate in the atmosphere
3[RhCl
6], add enough KOH solution precipitations and go out Rh (OH)
3, the repetitive scrubbing precipitation is removed K
+Behind the ion, precipitation is dissolved in few hydrochloric acid of trying one's best, is prepared into chlorine rhodium aqueous acid, further evaporating solns is closely dried, can obtain the Trichlororhodium RhCl of burgundy
3XH
2The O crystallization.In addition, also available bases metal peroxides and alkali fusion are with the rhodium oxidation.Oxidized rhodium can be dissolved in the acidic aqueous solution.The fused bisul-phate also can dissolve rhodium.After the rhodium dissolving, remove other foreign ions by repeated precipitation, dissolved way, obtain purer Trichlororhodium RhCl
3XH
2O.
The method that above-mentioned various dissolving rhodium prepares Trichlororhodium exists the rhodium yield low, complex process, and rhodium loses greatly in the water washing process, and remaining K
+Or Na
+Foreign ion makes degradation shortcoming under the preparation Trichlororhodium purity.Therefore develop a kind of simply, easily and fast, cost is low, the few dissolving rhodium powder of rhodium loss prepares Trichlororhodium method is very important.
CN03153292.6 discloses a kind of electrochemical dissolution method of precious metal, precious metal can be made electrode under the effect of alternating-current, with its dissolving.But only be confined to precious metal sheets, as the dissolving of Pt sheet.
The rhodium raw material great majority of buying on the market are spongy fine powder, can't dissolve with this method.The rhodium powder is made metal electrode film 1960 ℃ of following fusions, can increase the loss of rhodium and improve tooling cost, and dissolution rate is also very slow.
Summary of the invention
The technical problem to be solved in the present invention is:
At the deficiencies in the prior art, the present invention directly is dissolved in the rhodium powder raw material in the hydrochloric acid, and does not add any other reagent, reduces production costs, and product crystallizes into and is easy to carry about with one, rhodium concentration is stablized, make things convenient for the solid-state Trichlororhodium of weighing and use.And when adopting high purity rhodium powder raw material, can avoid impurity to disturb, make highly purified Trichlororhodium.
The present invention utilizes the alternating-current solution principle, and the rhodium powder directly is dissolved in the hydrochloric acid, obtains chlorine rhodium aqueous acid, and the electrochemical reaction of its generation is as follows:
Rh+6Cl
--3e → RhCl
6 -3(oxidizing reaction)
4H
++ 4e → 2H
2↑ (reduction reaction)
Technical scheme of the present invention is:
A kind of preparation method of Trichlororhodium, it may further comprise the steps:
The 1st step, electrodissolution:
In the U-shaped electrolyzer that acid resisting material is made, be provided with the electrode of non-metallic conducting material; In this U-shaped electrolyzer, add hydrochloric acid soln and rhodium powder raw material;
Load alternating-current at described electrode two ends, generate chloric acid rhodium solution until the dissolving of rhodium powder;
The interchange electro-dissolving that the present invention adopts is different with common electrolysis process with U type electrolyzer.General electrolysis is under the direct current effect, makes dissolving metal by anodic oxidation.If under galvanic effect, because of forming passive film on rhodium powder surface, and the rhodium powder can't be continued to be oxidized to Rh
3+Water-soluble.And under the quick checker of alternating-current anode and cathode, thereby passive film is destroyed the rhodium powder is dissolved.
Thickness, length and the shape of electrode used therein rod of the present invention and U type electrolyzer are unrestricted.
In the 2nd step, filter:
The chloric acid rhodium solution of gained is filtered, leach unreacted rhodium powder;
After the electrodissolution of most of rhodium powder becomes rhodium chloride acid solution, rhodium chloride acid solution is filtered, separate with unreacted rhodium powder still.
In the 3rd step, concentrate:
Rhodium chloride acid solution after filtering is distilled, distill out excessive hydrochloric acid and water, obtain chlorine rhodium acid concentrated solution.
The 4th step, crystallization:
The chlorine rhodium acid concentrated solution of gained is carried out crystallization in crystal growing furnace, obtain RhCl
3XH
2O, wherein 0≤x≤5.
Crystalline temperature and time difference, water-content difference in the Trichlororhodium hydrate that obtains.Tc is high more, and crystallization time is long more, Trichlororhodium hydrate RhCl
3XH
2Crystal water among the O (x=0～5) is few more, and rhodium content is high more; Finally can obtain anhydrous Trichlororhodium RhCl
3Those of ordinary skills can easily determine, the suitable Tc and the time of rhodium content or crystal water content correspondence in the Trichlororhodium hydrate.
In each step of preparation technology of the present invention, except hydrochloric acid soln and two kinds of impurity that raw material contained of rhodium powder, do not add or produce any new foreign ion.Therefore the present invention can be used for the preparation of high purity Trichlororhodium, and this method is used for low-purity rhodium powder and dissolving with hydrochloric acid prepares the low-purity Trichlororhodium but this does not limit.For example, the method for low-purity rhodium powder and dissolving with hydrochloric acid electrolytic preparation low-purity Trichlororhodium may be used for the recovery and the purification process of rhodium powder, Trichlororhodium.
When being used to prepare the high purity Trichlororhodium, also to limit raw material.
The rhodium content of described rhodium powder raw material is greater than 99%.
The rhodium content of preferred described rhodium powder raw material is greater than 99.95%.
Operational condition to technical scheme also can be further qualified, to enhance productivity:
In the 1st step, in this U-shaped electrolyzer, add hydrochloric acid soln and rhodium powder raw material, described hydrochloric acid purity is that top grade is pure, the concentration of hydrochloric acid is 5～12mol/L; The weight ratio of hydrochloric acid and rhodium powder is 2: 1～500: 1; The high more dissolution rate that helps increasing the rhodium powder more of concentration of hydrochloric acid, preferred high density concentrated hydrochloric acid.
Load alternating-current at described electrode two ends, voltage is 5～120 volts, carries out constant-potential electrolysis, and electric current is 2～50 amperes; The waveform of alternating-current is sine wave, square wave or choppy sea, uses civilian sine wave alternating current easier usually, but when through the rectifier conversion, also may produce other waveforms, all can use.
Electrolysis time is 3～15 hours; The time of rhodium powder electrodissolution in electrolyzer, the longer the better, dissolves substantially fully until the rhodium powder.Common 3～15 hours proper, and electrolysis time is too short, and the dissolving of rhodium powder is not enough; Electrolysis time is long, and production efficiency reduces.
Hydrochloric acid temperature in the control electrolyzer is at 80～110 ℃;
After the 3rd step concentrated, distill out excessive hydrochloric acid and water, obtain high-purity chlorine rhodium acid concentrated solution, the rhodium content of rhodium chloride acid solution is 0.1～1.5mol/L;
In the 4th step crystallisation process, 100～450 ℃ of Tcs, crystallization time 1～10 hour.
Because rhodium powder and hydrochloric acid have adopted high-purity raw, so the Trichlororhodium of preparation also can have high purity.
Operational condition to technical scheme can also adopt preferred parameter:
In the 1st step, in this U-shaped electrolyzer, add hydrochloric acid soln and rhodium powder raw material, described hydrochloric acid purity is that top grade is pure, the concentration of hydrochloric acid is 5～12mol/L; The weight ratio of hydrochloric acid and rhodium powder is 5: 1～100: 1; Load alternating-current at described electrode two ends, voltage is 20～100 volts, and electric current is 10～40 amperes, and the waveform of alternating-current is civilian sine wave; Electrolysis time is 3～15 hours; Hydrochloric acid temperature in the control electrolyzer is at 90～105 ℃.
In order to improve raw material availability, save cost, can further take improvement project:
In the 2nd step, leach unreacted rhodium powder, unreacted rhodium powder is returned electrolyzer;
After the 3rd step concentrated, the hydrochloric acid that distills out is returned electrolyzer;
Described rhodium powder and the hydrochloric acid that returns electrolyzer carries out the 1st step process again with initiate rhodium powder raw material and hydrochloric acid.
After the 3rd step concentrated, hydrochloric acid that distills out and fresh concentrated hydrochloric acid returned electrolyzer after by 1: 1～1: 3 mixed.
For enhancing productivity, electrolysis time can not be oversize, therefore has some rhodium powder and do not reacted; Hydrochloric acid must be excessive, must steam a large amount of hydrochloric acid when therefore concentrating.For avoiding waste, can be with rhodium powder and salt acid recovery, the 1st step process of returning is re-used as prepared using.Be not directly used in other purposes but do not get rid of rhodium powder that to filter out and the hydrochloric acid that steams, as selling, be used as the raw material of other products etc. yet.Above-mentioned recovery measure industrial be reasonably, but not necessarily, select according to the producer's particular case overall equilbrium.In addition, when producing last one batch, also can prolong electrolysis time, all rhodium powder are all dissolved.Need not consider the efficiency of production cycle this moment, also just no longer need the 2nd step filtration procedure, this technical scheme is equal to the present invention in fact.
For the ease of control hydrochloric acid temperature, described electrolyzer places the recirculated cooling water groove of controlled temperature; Control the temperature of electrolyzer by the temperature of controlled chilling water.
On two mouths of pipe of U type pipe, be separately installed with prolong.To reduce the vaporization losses of HCl.
The material of electrolyzer and electrode can adopt various well known materials, as:
The material of described electrolyzer is glass, quartz or tetrafluoroethylene (teflon) etc.; Described electrode materials is a spectroscopically pure level graphite rod.
Concrete a kind of optimized technical scheme is:
A kind of preparation method of Trichlororhodium, it may further comprise the steps:
The 1st step, electrodissolution:
In the U-shaped electrolyzer that glass material is made, be provided with the electrode of spectroscopically pure level graphite rod; Described electrolyzer places the recirculated cooling water groove of controlled temperature; On two mouths of pipe of U type pipe, be separately installed with prolong;
In this U-shaped electrolyzer, add hydrochloric acid soln and rhodium powder raw material; The rhodium content of described rhodium powder raw material is greater than 99.95%; Described hydrochloric acid purity is that top grade is pure, and the concentration of hydrochloric acid is 5～12mol/L; The weight ratio of hydrochloric acid and rhodium powder is 5: 1～100: 1; Load alternating-current at described electrode two ends, voltage is 20～100 volts, and electric current is 10～40 amperes, and the waveform of alternating-current is civilian sine wave; Electrolysis time is 3～15 hours; Hydrochloric acid temperature in the control electrolyzer is at 90～105 ℃; Generate chloric acid rhodium solution until the dissolving of rhodium powder;
In the 2nd step, filter:
The chloric acid rhodium solution of gained is filtered, leach unreacted rhodium powder; Unreacted rhodium powder is returned electrolyzer;
In the 3rd step, concentrate:
Rhodium chloride acid solution after filtering is distilled, distill out excessive hydrochloric acid and water, obtain chlorine rhodium acid concentrated solution, the rhodium content of rhodium chloride acid solution is 0.5～1.2mol/L; Hydrochloric acid that distills out and fresh concentrated hydrochloric acid return electrolyzer after by 1: 1～1: 3 mixed;
The 4th step, crystallization:
The chlorine rhodium acid concentrated solution of gained is carried out crystallization, 100～450 ℃ of Tcs, crystallization time 1～10 hour in crystal growing furnace; Obtain Trichlororhodium hydrate RhCl
3XH
2O, wherein 0＜x≤5; Or obtain anhydrous Trichlororhodium RhCl
3
The invention has the beneficial effects as follows:
Rhodium powder dissolution process is simple, Trichlororhodium product purity height.The present invention has avoided removing with alkali precipitation, again K
+Or Na
+Isoionic complex process.The original impurity in rhodium powder and hydrochloric acid, the introducing of no any other new foreign metal ion and negative ion is polluted, and the Trichlororhodium foreign matter content can be less than 0.01%.
Rhodium yield height, Rh yield 〉=99.9%.The rhodium powder finally can all dissolve, whole electrodissolution, filtration, concentrate and the loss of crystallisation process rhodium less than 0.1%.
Preparation cost is low.Need high-temperature fusion and use Cl with other
2Method compare, can reduce production costs.
Do not have any by product and generate, the hydrochloric acid that concentrates generation can return electrolyzer and utilize again.Thisly can dissolve the rhodium powder in a large number, the method for preparing Trichlororhodium has the advantage of environmental protection.
Description of drawings
Fig. 1 is the synoptic diagram of U type electrolyzer.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Embodiment 1
Preparation facilities is seen Fig. 1, wherein: 1 expression alternating-current voltate regulator, 2 expression Graphite Electrodess, 3 expression condensers, 4 expression U-shaped electrolyzers, 5 expression hydrochloric acid solns, 6 expression rhodium powder.
Taking by weighing 20.0 gram purity is the U type electrolyzer that 99.99% rhodium powder is put into quartz material, adds 400ml concentration and be 37% the pure concentrated hydrochloric acid of top grade.At the civilian alternating-current of 50 volts of electrode two ends loadings, size of current changes between 10～30 amperes.Electrolytic reaction 5 hours.Therebetween, the flow of controlled chilling water, the hydrochloric acid temperature is about 105 ℃ in the maintenance electrolyzer.After stopping electrolysis, using at a slow speed, quantitative paper filters electrolytic solution.Washing, oven dry and weighing unreacted rhodium powder weigh 4.6 grams.The transformation efficiency 77% of rhodium powder.Filtrate distills out excessive hydrochloric acid through simple distillation, obtains chlorine rhodium acid H
3RhCl
6Strong solution.With H
3RhCl
6Strong solution is put into crystal growing furnace, obtains 38.6 gram Trichlororhodium hydrates at 115 ℃ of following crystallization 5h.The weight percent content of analyzing Rh with weighting method is 39.9%, is equivalent to contain 2.7 crystal water (RhCl
32.7H
2O).Press the rhodium content analytical value and calculate, the rhodium yield is 100.0%.Through icp analysis wherein ten kinds of foreign metal total weight percent content such as K, Na, Ca, Si, Ir, Au, Ag, Mg, Pt, Cu be 0.0085%.Owing to only, do not contain other SO in the Trichlororhodium hydrate with dissolving with hydrochloric acid rhodium powder yet
4 2-, NO
3-wait negatively charged ion.
Change the electrolysis alternating current voltage and be respectively 60 volts, 70 volts, size of current changes in 20～40 peaces.Other conditions are shown in embodiment 1.Rhodium powder transformation efficiency is respectively 85%, 80%.
Adjusting the electrolysis alternating current voltage is 60 volts, and the electrolytic reaction time was respectively 8 hours, 12 hours, and other conditions are shown in embodiment 1.Rhodium powder transformation efficiency is respectively 95%, 98%.
Taking by weighing 5 grams, 10 grams, 15 grams, 30 gram purity respectively is the electrolyzer that 99.95% rhodium powder is put into four glass materials, and each adds 37% top grade pure hydrochloric acid 400ml, under 60 volts of voltage of alternating current, 105 ℃ of conditions of electrolyzer temperature, and electrolytic reaction 8 hours.Rhodium powder transformation efficiency is respectively 99%, 98%, 92%, 85%.
Embodiment 10～1
Taking by weighing four part of 20 gram purity is the U type electrolyzer that 99.95% rhodium powder is put into four teflon material, adding concentration respectively is the hydrochloric acid 400ml that reclaims among 5mol/L, 8mol/L, 10mol/L and the embodiment 1～9, and electrolytic reaction is 8 hours under 60 volts of alternating-current effects.The transformation efficiency of rhodium powder is respectively 30%, 60%, 80%, 75%.
Embodiment 14
Taking by weighing 20.0 gram purity respectively is the U type electrolyzer that 99.95% rhodium powder is put into 25 quartz materials, adds 400ml concentration and be 37% the pure concentrated hydrochloric acid of top grade.In the civilian alternating-current of 60 volts of electrode two ends loadings, electrolytic reaction 8 hours.The flow of controlled chilling water therebetween keeps in the electrolyzer hydrochloric acid temperature about 105 ℃.After stopping electrolysis, using at a slow speed, quantitative paper filters electrolytic solution.Continue in every U type electrolyzer, to add again respectively 20.0 gram purity and be 99.95% rhodium powder and 400ml concentration and be 37% the pure concentrated hydrochloric acid of top grade.Electrolytic reaction is 8 hours under similarity condition, filters electrolytic solution.With a small amount of rhodium powder on residue unreacted rhodium powder and the filter paper in 25 U type electrolyzers with the concentrated hydrochloric acid flushing, merge in two U type electrolyzers, respectively add 400ml concentration again and be 37% the pure concentrated hydrochloric acid of top grade, continue electrolysis 10 hours.Filter electrolytic solution.After having filtered, use distilled water wash filter paper.Contain heavy 0.5 gram after 450 ℃ of ashing of quantitative paper of a small amount of rhodium powder.The transformation efficiency of 1200 gram rhodium powder reaches 99.95% altogether.Filtrate distills out excessive hydrochloric acid through simple distillation, obtains H
3RhCl
6Strong solution.With H
3RhCl
6Strong solution is put into crystal growing furnace, obtains 3053 gram Trichlororhodium hydrates at 103 ℃ of following crystallization 10h.The weight percent content of analyzing Rh with weighting method is 39.3%, is equivalent to contain 2.9 crystal water (RhCl
32.9H
2O).Press the rhodium content analytical value and calculate, the rhodium yield is greater than 99.99%, and rhodium loses less than 0.01%.
Embodiment 15
Take by weighing 10.00 gram embodiment 14 preparations, Rh content is the Trichlororhodium hydrate of 39.3% (weight).Heated 1 hour down at 400 ℃, obtain the anhydrous Trichlororhodium RhCl of 8.00 grams
3
Claims (10)
- The preparation method of 1 one kinds of Trichlororhodiums, it may further comprise the steps:The 1st step, electrodissolution:In the U-shaped electrolyzer that acid resisting material is made, be provided with the electrode of non-metallic conducting material;In this U-shaped electrolyzer, add hydrochloric acid soln and rhodium powder raw material;Load alternating-current at described electrode two ends, generate chloric acid rhodium solution until the dissolving of rhodium powder;In the 2nd step, filter:The chloric acid rhodium solution of gained is filtered, leach unreacted rhodium powder;In the 3rd step, concentrate:Rhodium chloride acid solution after filtering is distilled, distill out excessive hydrochloric acid and water, obtain chlorine rhodium acid concentrated solution;The 4th step, crystallization:The chlorine rhodium acid concentrated solution of gained is carried out crystallization in crystal growing furnace, obtain RhCl 3XH 2O, wherein 0≤x≤5.
- The preparation method of 2 Trichlororhodiums according to claim 1 is characterized in that:The rhodium content of described rhodium powder raw material is greater than 99%.
- The preparation method of 3 Trichlororhodiums according to claim 2 is characterized in that:The rhodium content of described rhodium powder raw material is greater than 99.95%.
- The preparation method of 4 Trichlororhodiums according to claim 1 is characterized in that:In the 1st step, in this U-shaped electrolyzer, add hydrochloric acid soln and rhodium powder raw material, describedHydrochloric acid purity is that top grade is pure, and the concentration of hydrochloric acid is 5～12mol/L; The weight ratio of hydrochloric acid and rhodium powder is 2: 1～500: 1; Load alternating-current at described electrode two ends, voltage is 5～120 volts, and electric current is 2～50 amperes, and the waveform of alternating-current is sine wave, square wave or choppy sea; Electrolysis time is 3～15 hours; Hydrochloric acid temperature in the control electrolyzer is at 80～110 ℃;After the 3rd step concentrated, the rhodium content of rhodium chloride acid solution was 0.1～1.5mol/L;In the 4th step crystallisation process, 100～450 ℃ of Tcs, crystallization time 1～10 hour.
- The preparation method of 5 Trichlororhodiums according to claim 4 is characterized in that:In the 1st step, in this U-shaped electrolyzer, add hydrochloric acid soln and rhodium powder raw material, described hydrochloric acid purity is that top grade is pure, the concentration of hydrochloric acid is 5～12mol/L; The weight ratio of hydrochloric acid and rhodium powder is 5: 1～100: 1; Load alternating-current at described electrode two ends, voltage is 20～100 volts, and electric current is 10～40 amperes, and the waveform of alternating-current is civilian sine wave; Electrolysis time is 3～15 hours; Hydrochloric acid temperature in the control electrolyzer is at 90～105 ℃.
- 6 preparation methods according to the described Trichlororhodium of one of claim 1 to 5 is characterized in that:In the 2nd step, leach unreacted rhodium powder, unreacted rhodium powder is returned electrolyzer;After the 3rd step concentrated, the hydrochloric acid that distills out is returned electrolyzer;Described rhodium powder and the hydrochloric acid that returns electrolyzer carries out the 1st step process again with initiate rhodium powder raw material and hydrochloric acid.
- The preparation method of 7 Trichlororhodiums according to claim 6 is characterized in that:After the 3rd step concentrated, hydrochloric acid that distills out and fresh concentrated hydrochloric acid returned electrolyzer after by 1: 1～1: 3 mixed.
- 8 preparation methods according to the described Trichlororhodium of one of claim 1 to 5 is characterized in that:Described electrolyzer places the recirculated cooling water groove of controlled temperature; On two mouths of pipe of U type pipe, be separately installed with prolong.
- 9 preparation methods according to the described Trichlororhodium of one of claim 1 to 5 is characterized in that:The material of described electrolyzer is glass, quartz or tetrafluoroethylene; Described electrode materials is a spectroscopically pure level graphite rod.
- The preparation method of 10 Trichlororhodiums according to claim 1 is characterized in that, may further comprise the steps:The 1st step, electrodissolution:In the U-shaped electrolyzer that glass material is made, be provided with the electrode of spectroscopically pure level graphite rod;Described electrolyzer places the recirculated cooling water groove of controlled temperature; On two mouths of pipe of U type pipe, be separately installed with prolong;In this U-shaped electrolyzer, add hydrochloric acid soln and rhodium powder raw material; The rhodium content of described rhodium powder raw material is greater than 99.95%; Described hydrochloric acid purity is that top grade is pure, and the concentration of hydrochloric acid is 5～12mol/L; The weight ratio of hydrochloric acid and rhodium powder is 5: 1～100: 1; Load alternating-current at described electrode two ends, voltage is 20～100 volts, and electric current is 10～40 amperes, and the waveform of alternating-current is civilian sine wave; Electrolysis time is 3～15 hours; Hydrochloric acid temperature in the control electrolyzer is at 90～105 ℃; Generate chloric acid rhodium solution until the dissolving of rhodium powder;In the 2nd step, filter:The chloric acid rhodium solution of gained is filtered, leach unreacted rhodium powder; Unreacted rhodium powder is returned electrolyzer;In the 3rd step, concentrate:Rhodium chloride acid solution after filtering is distilled, distill out excessive hydrochloric acid and water, obtain chlorine rhodium acid concentrated solution, the rhodium content of rhodium chloride acid solution is 0.5～1.2mol/L; Hydrochloric acid that distills out and fresh concentrated hydrochloric acid return electrolyzer after by 1: 1～1: 3 mixed;The 4th step, crystallization:The chlorine rhodium acid concentrated solution of gained is carried out crystallization, 100～450 ℃ of Tcs, crystallization time 1～10 hour in crystal growing furnace; Obtain Trichlororhodium hydrate RhCl 3XH 2O, wherein 0＜x≤5; Or obtain anhydrous Trichlororhodium RhCl 3
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| FR2616810B1 (en) * | 1987-03-25 | 1989-08-18 | Rhone Poulenc Sante | ELECTROCHEMICAL PROCESS FOR RECOVERING METAL RHODIUM FROM AQUEOUS SOLUTIONS OF USED CATALYSTS |
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| CN102337556A (en) * | 2010-07-28 | 2012-02-01 | 中国石油化工股份有限公司 | Rhodium powder dissolving device based on alternating current arc process and application thereof |
| CN102337556B (en) * | 2010-07-28 | 2013-09-25 | 中国石油化工股份有限公司 | Rhodium powder dissolving device based on alternating current arc process and application thereof |
| CN102408135A (en) * | 2010-09-25 | 2012-04-11 | 中国石油化工股份有限公司 | Method for preparing iridous chloride hydrate |
| CN102408135B (en) * | 2010-09-25 | 2013-11-06 | 中国石油化工股份有限公司 | Method for preparing iridous chloride hydrate |
| CN102557155A (en) * | 2011-10-25 | 2012-07-11 | 中国海洋石油总公司 | Method for recovering rhodium from rhodium-containing waste liquid and preparing rhodium chloride hydrate |
| CN102557155B (en) * | 2011-10-25 | 2013-07-31 | 中国海洋石油总公司 | Method for recovering rhodium from rhodium-containing waste liquid and preparing rhodium chloride hydrate |
| CN104692469A (en) * | 2014-07-01 | 2015-06-10 | 昆明铂锐金属材料有限公司 | Method for preparing rhodium triiodide |
| CN108977830A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | A kind of electrochemical preparation method of ruthenic chloride |
| CN108977834A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | A kind of electrochemical preparation method of rhodium chloride |
| CN108977829A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | A kind of electrochemical preparation method of palladium chloride |
| CN108977838A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | A kind of electrochemical preparation method of chloroplatinic acid |
| CN108977834B (en) * | 2017-05-31 | 2020-10-20 | 中国石油化工股份有限公司 | Electrochemical preparation method of rhodium trichloride |
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