CN101638727B - Method for recovering ruthenium in activated carbon supported ruthenium catalyst - Google Patents
Method for recovering ruthenium in activated carbon supported ruthenium catalyst Download PDFInfo
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Abstract
The invention relates to a method for recovering an activated carbon supported ruthenium catalyst, which comprises the steps of: performing high-temperature roasting on an activated carbon supported ruthenium catalyst in which an alkali metal or alkaline-earth metal compound additive is not contained or is removed; performing high-temperature alkaline fusion on a roasted product; dissolving an alkaline fusion product in hot water with a temperature of between 60 and 95 DEG C to obtain a K2RuO4 or Na2RuO4 solution, adding ethanol or an alkaline solution into the K2RuO4 or Na2RuO4 solution to obtain a Ru(OH)4 precipitate; and drying the precipitate, or dissolving the precipitate by using strong acid, or using H2 to reduce the precipitate to obtain different ruthenium products. The method has the advantages that precious metal ruthenium can be efficiently recovered, the operation process of the recovery is safe, alkali metal and alkaline-earth metal additives can be synchronously recovered, and the form of the recovered product can be selected. The method has reliable technology, simple operation, low cost and no pollution.
Description
Technical field
The present invention relates to the recovery method of ruthenium in the activated carbon supported ruthenium catalyst of a kind of noble metal catalyst.
Background technology
Activated carbon supported ruthenium catalyst is widely used on the catalytic hydrogenation in fields such as petrochemical industry, fine chemicals, especially since Britain BP company in 1992 and U.S. Kellogg company succeed in developing activated carbon supported ruthenium ammonia synthesis catalyst, because can be under conditions such as lower reaction temperature, the pressure efficient synthetic ammonia of this catalyst is considered to second generation ammonia synthesis catalyst behind iron based ammonia synthesis catalyst.But because this catalyst is an active component with noble ruthenium (Ru), it costs an arm and a leg, and output in domestic seldom, and can therefore, can the ruthenium in the ruthenium catalyst be recycled, become ruthenium-based ammonia synthetic catalyst and realize one of industrialization promotion key in application.
Chinese invention patent CN200610052073.0 discloses a kind of method that reclaims ruthenium from activated carbon supported ruthenium catalyst.This method has been taked the perruthenate that obtains from the alkali fusion step is carried out oxidation distillation, then to product RuO
4Carry out the ruthenium recovery method that acid absorbs.The product RuO of oxidation distillation wherein
4Being strong oxidizer, becoming liquid in the time of 25 ℃, is gas more than 50 ℃, and the decomposition of blasting in the time of 108 ℃ has severe toxicity, and meeting low molecule organic matter can explode, and reaction must be carried out in the environment of airtight fume hood and safety.
Summary of the invention
The purpose of this invention is to provide a kind of recovery method safe, activated carbon supported ruthenium catalyst efficiently to reclaim noble ruthenium.For the catalyst that contains alkali metal and base earth metal promoter (as active carbon loading ruthenium ammonia synthesis catalyst), the present invention not only can reclaim noble ruthenium wherein, can also reclaim wherein additive alkali metal and alkaline-earth metal.
The technical solution used in the present invention is as follows:
A kind of recovery method of activated carbon supported ruthenium catalyst may further comprise the steps:
(1) with temperature be 50～90 ℃ the described activated carbon supported ruthenium catalyst of hot-water soak 2～24 hours, washing and filtering, the filtrate that obtains is alkalescence, and adding nitric acid is 5～7 to this filtrate pH value, and evaporating water obtains KNO
3, filter residue is the activated carbon supported ruthenium catalyst of removing behind the alkali metal compound, then omits this step for the activated carbon supported ruthenium catalyst of alkali-free metal promoter;
(2) step (1) is obtained remove behind the alkali metal compound or the activated carbon supported ruthenium catalyst of alkali-free metal promoter with the salt acid soak of concentration 5～9% 8～24 hours, filter, after washing filter residue to washing lotion pH value is about 7, the filter residue that obtains is the activated carbon supported ruthenium catalyst of removing behind the alkaline earth metal compound, then omits this step for the activated carbon supported ruthenium catalyst of alkali-free earth metal auxiliary agent;
(3) step (2) is obtained remove or the activated carbon supported ruthenium catalyst of alkali-free metal and alkaline earth metal compound 550～1000 ℃ of following roastings 4～10 hours, obtain the grey black mixture;
(4) grey black mixture and KOH and the KNO that step (3) is obtained
3Mix, perhaps with NaOH and NaNO
3Mix, 550～900 ℃ of heating were carried out alkali fusion in 1～3 hour in Muffle furnace, were cooled to room temperature, obtained the alkali fusion thing;
(5) the alkali fusion thing that step (4) is obtained is with 60～95 ℃ of hot water dissolvings, and a small amount of insoluble matter adds hydrochloric acid with its dissolving fully, adds sulfuric acid, makes barium with BaSO
4Form is precipitated out, filter then, for the sample of alkali-free earth metal auxiliary agent through step (4) handle the alkali fusion thing that obtains set by step (6) or set by step (11) handle;
(6) filtrate that step (5) is obtained is adjusted to pH=3～7 with alkali lye in room temperature～100 ℃, obtains hydroxide ruthenium precipitation, and this is precipitated to the cation of washings alkali-free liquid filtration washing, dry then this precipitation;
(7) filtrate that step (6) is obtained is adjusted to pH=7～14 with alkali lye under room temperature～100 ℃, is incubated 5～15 minutes, can obtain Mg (OH)
2Precipitation is filtered this precipitation, reclaims Mg; Perhaps
(8) filtrate that step (6) is obtained adds the soluble carbon acid salt solution and regulates pH=6.5～14 of this filtrate under room temperature～100 ℃, obtains MgCO
3Precipitation is filtered this precipitation, reclaims Mg;
(9) the hydroxide ruthenium precipitation hydrochloric acid that step (6) is obtained 60～100 ℃ of dissolvings down, can obtain RuCl
3The aqueous solution; Perhaps
(10) the hydroxide ruthenium that step (6) is obtained precipitates dry thing be reduced to metal Ru with hydrogen or hydrogen nitrogen mixed gas under 450～700 ℃; Perhaps
(11) the hydroxide ruthenium precipitation repeating step (4) that step (6) is obtained carries out alkali fusion, and the alkali fusion thing that obtains obtains red K with 60～95 ℃ of hot water dissolvings
2RuO
4Solution or Na
2RuO
4Solution is at K
2RuO
4Solution or Na
2RuO
4Drip ethanol in the solution, stir, red perruthenate changes into black hydroxide ruthenium precipitation and gets final product, and with the deionized water washing of heat, Buchner funnel suction filtration, cyclic washing is closely neutral to cleaning solution, till no potassium or the sodium ion;
(12) the black hydroxide ruthenium that step (11) is obtained pack into have stir and the three-necked bottle of reflux in, add concentrated hydrochloric acid, stir and be heated to closely and boil, reacted 1～2 hour, adding hydroxylamine hydrochloride before reaction finishes makes and reacts completely, leave standstill, use the Buchner funnel suction filtration, make next raw material after the ruthenium solids is dried a small amount of unreacted containing in the funnel;
(13) filtrate that step (12) or step (9) are obtained is transferred in the cucurbit, in vacuum about 4 * 10
4Decompression distillation obtains containing the β-RuCl of ruthenium amount 37%～39% to doing under the condition of Pa
3.xH
2The O crystal is used for fresh catalyst preparation;
(14) field boundary for needs processing nitric acid ruthenium closes, and can change the hydrochloric acid in the step (12) into nitric acid, but need not to add hydroxylamine hydrochloride.
The reaction that above-mentioned alkali fusion step is taken place is:
1. when alkali metal adopts K salt:
RuO
2+2KOH+KNO
3＝K
2RuO
4+KNO
2+H
2O
Ru+2KOH+3KNO
3＝K
2RuO
4+3KNO
2+H
2O
2. when alkali metal adopts Na salt:
RuO
2+2NaOH+NaNO
3＝Na
2RuO
4+NaNO
2+H
2O
Ru+2NaOH+3NaNO
3＝Na
2RuO
4+3NaNO
2+H
2O
Above-mentioned steps 5) concentration and the consumption that are used for dissolving the hydrochloric acid of alkali fusion thing in are not important, as long as be enough to the dissolving of alkali fusion thing fully.
Above-mentioned steps 6) in, the filtrate that will obtain except that Ba is adjusted to pH=3～7 with alkali lye in room temperature～100 ℃, is at containing Mg in this filtrate with the reason that obtains hydroxide ruthenium precipitation
+, when the pH value of solution value is 3～7, ruthenium will be hydroxide ruthenium precipitation by selective hydrolysis, and Mg
+Basically can not be precipitated out, separate Mg thereby reach with the hydroxide ruthenium
+Purpose.Alkali lye described here is NaOH, KOH, NH
4OH, Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3, (NH
4)
2CO
3, NH
4HCO
3, NH
2COONH
4The aqueous solution, the concentration of this aqueous slkali is not important, as long as can play the acidity adjustment effect.In order to accelerate to precipitate the speed of generation and help follow-up filter operation, this step is preferably under 60 ℃～100 ℃ carries out, and is incubated 5～25 minutes after precipitation produces under this temperature.For not containing Mg
+With the filtrate of other alkaline-earth metal ions, its pH value can be regulated arbitrarily in 3～14 scopes.
Above-mentioned steps 11) processing to perruthenate in is the process of separation alkaline-earth metal of further purifying, and is applicable to the processing to the ruthenium catalyst alkali fusion thing of alkali-free earth metal auxiliary agent.Its reaction principle is:
Promptly under alkaline atmosphere, use ethanol reduction-hydrolysis perruthenate to be the hydroxide ruthenium.Here used concentration of ethanol is not important, as long as be enough to the Ru in the solution is precipitated out fully.
Above-mentioned steps 12) purpose is that hydroxide ruthenium and concentrated hydrochloric acid are reacted to generate ruthenium trichloride, and course of reaction is as follows:
Ru (OH)
4+ 4HCl (dense)=RuCl
4+ 4H
2O
2RuCl
4+2NH
2OH.HCl＝2RuCl
3+N
2+4HCl+2H
2O
The concentration of used here hydrochloric acid is 18%～36%, in order to guarantee that the hydroxide ruthenium is converted into ruthenium trichloride, adds the small amount of hydrochloric acid azanol.The definite concentration of hydrochloric acid and the consumption of hydroxylamine hydrochloride are not important, as long as can guarantee hydroxide ruthenium complete reaction is become ruthenium trichloride, and exceed in liquid measure when obtaining the solid ruthenium trichloride and distill this ruthenium trichloride solution and to get final product.
Step 14) is with little nitric acid stirring and dissolving hydroxide ruthenium or RuO that boils in reflux
2.2H
2O, used concentration of nitric acid are 30%～62%.
The course of reaction of step 14) is:
Ru (OH)
4+ 4HNO
3=Ru (NO) (NO
3)
3+ O
2+ 4H
2O or
RuO
2.2H
2O+4HNO
3＝Ru(NO)(NO
3)
3+O
2+4H
2O
Control used nitric acid quantity and concentration, can obtain Ru (the NO) (NO of variable concentrations
3)
3Solution.
The invention has the beneficial effects as follows: the invention enables noble ruthenium to obtain safety, high efficiente callback, alkali metal in the catalyst and base earth metal promoter also obtain reclaiming simultaneously.The product that ruthenium reclaims can be made RuO respectively according to different needs
2, Ru (OH)
4, RuCl
3.xH
2O, Ru (NO) (NO
3)
3Or metal Ru.This method and technology is safe and reliable, and is simple to operate, and cost is low, pollution-free, the product recovery rate height.
The specific embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
The ruthenium catalyst of active carbon agent load (not containing auxiliary agent) 10g places Muffle furnace in 700 ℃ of roastings 6 hours, obtains grey black mixture 0.8504g.With grey black mixture and 2g mass ratio 1: 1 NaOH and NaNO
3Solid mixture loads in mixture at crucible, places Muffle furnace in 250 ℃ of insulations 0.5 hour, 630 ℃ of alkali fusions 3 hours, cooling.Cooled alkali fusion thing (high ruthenic acid sodium) is transferred in the 500mL beaker, added the 100mL temperature and be 60 ℃～95 ℃ deionized water dissolving, solution takes on a red color.With Buchner funnel elimination water-insoluble, wash this insoluble matter with a small amount of 50 ℃～80 ℃ deionized water, with the red filtrate merging of washing lotion and gained, and drip adequate amount of ethanol, stir, red perruthenate promptly changes into black hydroxide ruthenium precipitation.With 50 ℃～80 ℃ hot deionized water washings, Buchner funnel suction filtration.Cyclic washing 7～8 times, closely neutral until cleaning solution, till the no sodium ion.The hydroxide ruthenium precipitation of oven dry gained, this is deposited in 450 ℃～700 ℃ and uses H
2Reduced 5 hours, and claimed to such an extent that metal Ru 0.6241 restrains, the Ru rate of recovery is 95.4%.
Embodiment 2
The ruthenium catalyst of active carbon agent load (containing Ba, K and Mg auxiliary agent) 15g, it with the 75mL temperature 50 ℃～90 ℃ hot-water soak 3 hours, obtain filtrate and filter residue after filtration, filter residue is 50 ℃～80 ℃ hot-water soak 3 hours again with the 75mL temperature, obtains filtrate and filter residue more after filtration.The filtrate that twice filtration obtained merges, and splashes into concentration and is about 20% HNO
3Filtrate pH value is adjusted to 6, and evaporating water obtains 3.0531gKNO
3, the K rate of recovery is 91.1%;
With the filter residue that obtains with the hydrochloric acid solution 150mL of mass percent 8% soaking at room temperature 24 hours, obtain filtrate and filter residue after filtration.In filtrate, add an amount of sulfuric acid, make BaSO
4Precipitation fully, after filtration, washing, oven dry obtain BaSO
40.6477g the primary recovery of Ba is 92.2%;
To merge except that filtrate and the washing that Ba obtains, adding NaOH (or KOH) transfers to the pH value and is about 5～6, be heated to about 90 ℃ and be incubated about 15 minutes, ruthenium salt in the filtrate is hydrolyzed into hydroxide ruthenium precipitation, filter, wash this and be precipitated to wash water pH value for neutral, and can't check till sodium (potassium) ion, dry resulting precipitation, be labeled as the ruthenium precipitate A;
The filtrate and the cleaning solution of hydroxide ruthenium precipitate A are merged, add an amount of Na
2CO
3Make MgCO
3Be precipitated out, filter MgCO
3Precipitation also spends deionised water this is precipitated to the nearly neutrality of wash water pH value, and can't check till the sodium ion, dries this precipitation and obtains 0.3562g MgCO
3, the Mg rate of recovery is 71%;
To aforementioned 8% salt acid treatment and wash to the filter residue that obtains after wash water is neutrality, it is filter residue quality twice that the oven dry back adds total amount, and mass ratio is 1: 1 KOH and KNO
3Solid mixture loads in mixture at crucible, places Muffle furnace in 630 ℃ of alkali fusions 3 hours, cooling.Cooled alkali fusion thing is transferred in the 500mL beaker, add the 100mL temperature and be 60 ℃～95 ℃ deionized water dissolving, the residual 8bbbbbbb slag of low amounts of water indissoluble is with the dissolving with hydrochloric acid of an amount of mass percent 18%, the solution that acid is molten and water-soluble merges, with NaOH (or KOH) regulator solution pH value about 3～6 and be heated to about 80 ℃～100 ℃ and be incubated 5～15 minutes, obtain black hydroxide ruthenium sediment.With 50 ℃～80 ℃ hot deionized water washings, Buchner funnel suction filtration.Cyclic washing 7～8 times, closely neutral until cleaning solution, till no sodium (or potassium) ion.Oven dry gained ruthenium sediment is labeled as the ruthenium deposit B;
The ruthenium precipitate A and the ruthenium deposit B that obtain are merged, repeat the alkali fusion step, the alkali fusion thing that obtains dissolves with 60 ℃～95 ℃ hot deionized waters, adds an amount of H
25O
4, the Ba precipitation that pre-treatment is carried secretly fully, after filtration, oven dry obtains BaSO
4Should reclaim 0.15% of Ba total amount 0.0011g account for; Gained filtrate adding NaOH (or KOH) transfers to the pH value and is about 5～6, be heated to about 90 ℃ and be incubated about 15 minutes, ruthenium salt in the filtrate is hydrolyzed into hydroxide ruthenium precipitation, filter, wash this and be precipitated to wash water pH value for neutral, and can't check till sodium (potassium) ion, dry resulting precipitation, reducing this sediment with hydrogen nitrogen mixed gas under 450 ℃～700 ℃ is metal Ru, claim to such an extent that metal Ru weight is 0.6762g, the Ru rate of recovery is 93.5%.
Embodiment 3
Repeat embodiment 2, just resulting hydroxide ruthenium is precipitated with the stirring under 80 ℃～100 ℃ of 36% hydrochloric acid, dissolving, obtain RuCl
3The aqueous solution is transferred to this solution in three mouthfuls of cucurbits, in vacuum about 4 * 10
4Decompression distillation obtains containing the β-RuCl of ruthenium amount 37.5% to doing under the condition of Pa
3.xH
2O crystal 1.7569 grams, the ruthenium rate of recovery is 91.1%.
Embodiment 4
Repeat embodiment 2, just resulting hydroxide ruthenium precipitation is packed into and have in the three-necked bottle of stirring and reflux, adding 120mL concentration is～50% nitric acid, stir and be heated to little boiling, reacted about 1 hour, reacted completely to hydroxide ruthenium precipitation, can be obtained Ru (the NO) (NO of reddish black
3)
3Salpeter solution.With the thiocarbamide spectrophotometric analysis that develops the color, in metal Ru, solution amounts to and contains ruthenium 0.6827g, and the ruthenium rate of recovery is 94.4%.
Embodiment 5
Take by weighing and reclaim the metal Ru powder 1.0002g obtain, with the 2g mass ratio be 1: 1 NaOH and NaNO
3Solid mixture loads in mixture at crucible, places Muffle furnace in 630 ℃ of alkali fusions 3 hours, cooling.Cooled alkali fusion thing (high ruthenic acid sodium) is transferred in the 500mL beaker, added the 100mL temperature and be 60 ℃～95 ℃ deionized water dissolving, solution takes on a red color.Filter, wash filter residue, filter residue oven dry back is as next raw material.Washing lotion and filtrate are merged, drip adequate amount of ethanol, stir, red perruthenate promptly changes into black hydroxide ruthenium precipitation.With 50 ℃～80 ℃ hot deionized water washings, Buchner funnel suction filtration.Cyclic washing 7～8 times, closely neutral until cleaning solution, till the no sodium ion.
With black hydroxide ruthenium pack into have stir and the three-necked bottle of reflux in, add a certain amount of concentrated hydrochloric acid, stir and be heated to closely and boil, react 1～2 hour, react and add the small amount of hydrochloric acid azanol before the end and make and react completely, leave standstill.Use the Buchner funnel suction filtration, make next raw material after a small amount of unreacted ruthenium solids oven dry in the funnel.Filtrate is transferred in the cucurbit, in vacuum about 4 * 10
4Decompression distillation obtains β-RuCl to doing under the condition of Pa
3.xH
2O crystal 2 .5909 gram is through H
2The analysis of reduction gravimetric method, this β-RuCl
3.xH
2It is 37.6% that O contains the ruthenium amount, and a conversion ratio of conversion metal Ru is 97.4%.
Claims (6)
1. the recovery method of ruthenium in the activated carbon supported ruthenium catalyst is characterized in that described recovery method may further comprise the steps:
(1) with temperature be 50～90 ℃ the described activated carbon supported ruthenium catalyst of hot-water soak 2～24 hours, washing and filtering, the filtrate that obtains is alkalescence, and adding nitric acid is 5～7 to this filtrate pH value, and evaporating water obtains KNO
3, filter residue is the activated carbon supported ruthenium catalyst of removing behind the alkali metal compound, then omits this step for the activated carbon supported ruthenium catalyst of alkali-free metal promoter;
(2) step (1) is obtained remove behind the alkali metal compound or the activated carbon supported ruthenium catalyst of alkali-free metal promoter with the salt acid soak of concentration 5～9% 8～24 hours, filter, after washing filter residue to washing lotion pH value is 7, the filter residue that obtains is the activated carbon supported ruthenium catalyst of removing behind the alkaline earth metal compound, then omits this step for the activated carbon supported ruthenium catalyst of alkali-free earth metal auxiliary agent;
(3) step (2) is obtained remove or the activated carbon supported ruthenium catalyst of alkali-free metal and alkaline earth metal compound 550～1000 ℃ of following roastings 4～10 hours, obtain the grey black mixture;
(4) grey black mixture and KOH and the KNO that step (3) is obtained
3Mix, perhaps with NaOH and NaNO
3Mix, 550～900 ℃ of heating were carried out alkali fusion in 1～3 hour in Muffle furnace, were cooled to room temperature, obtained the alkali fusion thing;
(5) the alkali fusion thing that step (4) is obtained is with 60～95 ℃ of hot water dissolvings, and a small amount of insoluble matter adds hydrochloric acid with its dissolving fully, adds sulfuric acid, makes barium with BaSO
4Form is precipitated out, filter then, for the sample of alkali-free earth metal auxiliary agent through step (4) handle the alkali fusion thing that obtains set by step (6) or set by step (11) handle;
(6) filtrate that step (5) is obtained is adjusted to pH=3～7 with alkali lye in room temperature～100 ℃, obtains hydroxide ruthenium precipitation, and this is precipitated to the cation of washings alkali-free liquid filtration washing, dry then this precipitation;
(7) filtrate that step (6) is obtained is adjusted to pH=7～14 with alkali lye under room temperature～100 ℃, is incubated 5～15 minutes, can obtain Mg (OH)
2Precipitation is filtered this precipitation, reclaims Mg; Perhaps
(8) filtrate that step (6) is obtained adds the soluble carbon acid salt solution and regulates pH=6.5～14 of this filtrate under room temperature～100 ℃, obtains MgCO
3Precipitation is filtered this precipitation, reclaims Mg;
(9) the hydroxide ruthenium precipitation hydrochloric acid that step (6) is obtained 60～100 ℃ of dissolvings down, can obtain RuCl
3The aqueous solution or
(10) the hydroxide ruthenium that step (6) is obtained precipitates dry thing be reduced to metal Ru with hydrogen or hydrogen nitrogen mixed gas under 450～700 ℃; Perhaps
(11) the hydroxide ruthenium precipitation repeating step (4) that step (6) is obtained carries out alkali fusion, and the alkali fusion thing that obtains obtains red K with 60～95 ℃ of hot water dissolvings
2RuO
4Solution or Na
2RuO
4Solution is at K
2RuO
4Solution or Na
2RuO
4Drip ethanol in the solution, stir, red perruthenate changes into black hydroxide ruthenium precipitation and gets final product, and with the deionized water washing of heat, Buchner funnel suction filtration, cyclic washing is closely neutral to cleaning solution, till no potassium or the sodium ion;
(12) the black hydroxide ruthenium that step (11) is obtained pack into have stir and the three-necked bottle of reflux in, add concentrated hydrochloric acid, stir and be heated to closely and boil, reacted 1～2 hour, adding hydroxylamine hydrochloride before reaction finishes makes and reacts completely, leave standstill, use the Buchner funnel suction filtration, make next raw material after the ruthenium solids is dried a small amount of unreacted containing in the funnel;
(13) filtrate that step (12) or step (9) are obtained is transferred in the cucurbit, in vacuum 4 * 10
4Decompression distillation obtains containing the β-RuCl of ruthenium amount 37%～39% to doing under the condition of pa
3.xH
2The O crystal is used for fresh catalyst preparation;
(14) for the occasion of needs processing nitric acid ruthenium, change the hydrochloric acid in the step (12) into nitric acid, but need not to add hydroxylamine hydrochloride.
2. the recovery method of ruthenium in a kind of activated carbon supported ruthenium catalyst according to claim 1 is characterized in that: described activated carbon supported ruthenium catalyst is the Ru/ activated-carbon catalyst that contains the ruthenium catalyst of alkali metal and alkaline earth metal compound auxiliary agent or do not contain auxiliary agent.
3. the recovery method of ruthenium in a kind of activated carbon supported ruthenium catalyst according to claim 1 is characterized in that: described alkali metal or alkaline earth metal compound are one or more the mixture of arbitrary proportion of alkali metal salt, alkali salt, alkali metal hydroxide or oxide, alkaline earth metal hydroxide or oxide.
4. the recovery method of ruthenium in a kind of activated carbon supported ruthenium catalyst according to claim 1 is characterized in that: recycling step (6), (7) described alkali lye are NaOH, KOH, NH
4OH, Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3, (NH
4)
2CO
3, NH
4HCO
3Or NH
2COONH
4The aqueous solution.
5. the recovery method of ruthenium in a kind of activated carbon supported ruthenium catalyst according to claim 1, it is characterized in that: the hydroxide ruthenium temperature that recovery is obtained is 60～100 ℃, concentration is that 18～36% dissolving with hydrochloric acid becomes ruthenium trichloride, in order to guarantee that dissolving fully, add hydroxylamine hydrochloride, the consumption of hydrochloric acid and hydroxylamine hydrochloride is for to become ruthenium trichloride with hydroxide ruthenium complete reaction, and liquid measure is exceeded and got final product when distilling this ruthenium trichloride solution obtaining the solid ruthenium trichloride.
6. the recovery method of ruthenium in a kind of activated carbon supported ruthenium catalyst according to claim 1 is characterized in that: hydroxide ruthenium or RuO that recovery is obtained
2.2H
2O, in reflux with little nitric acid stirring and dissolving of boiling, to obtain Ru (NO) (NO
3)
3Salpeter solution, used concentration of nitric acid are 30～62%.
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