CN103981363A - Device and method for extracting rare noble metals by adopting wet process - Google Patents
Device and method for extracting rare noble metals by adopting wet process Download PDFInfo
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Abstract
The invention relates to a device and a method for extracting rare noble metals by adopting a wet process. The method comprises the following steps: preprocessing rare noble metal-containing solid raw material powder by using oxygen or air to obtain materials; processing the obtained materials in the previous step by using carbon monoxide or hydrogen; putting the solid materials processed by the two steps into a glass bottle, adding an acidic solution such as potassium permanganate into the glass bottle, putting the bottle into a high-pressure kettle pre-filled with water to ensure that water outside the bottle cannot enter the bottle, filling oxygen and the like in the high-pressure kettle, sealing the high-pressure kettle, disconnecting the high-pressure kettle from an inflating line, and fixing the high-pressure kettle to a rocking bed for freely rocking; heating the water in the high-pressure kettle, and extracting the rare noble metals from the solid raw material powder in the glass bottle at high temperature under high pressure. The device and the method are especially suitable for extracting platinum, palladium and rhodium from catalysts of waste cars; the extraction rates of platinum, palladium and rhodium in optimized conditions are 99%, 99% and 99% respectively.
Description
Technical field
The present invention relates to wet method and extract the apparatus and method of rare precious metal (comprising precious metal, rare metal), relate more specifically to extract the method for for example for example vanadium of platinum metals, gold and rare metal of precious metal and rare earth metal, especially extract platinum metals and rare earth in junked-auto catalyzer, climb the apparatus and method of the blast-melted blowing gained of steel or Cheng Gangdeng Steel Plant Vanadium in Vanadium Residue.
Background technology
There is a serious shortage in the supply for China's platinum metals natural mineral resource reserves, and the Platinum metals resources reserves of finding out for 2008 are 324.13 tons, account for 0.46% of world's total reserves.Approximately 200 kilograms of China's platinum metals year outputs, can not meet national defence and industrial needs far away, 90% above dependence on import of annual requirement at present.Therefore, how from raw material such as natural mineral matter, waste material etc., to extract efficiently precious metal and have very important economic and social benefit.
In recent years, along with the high speed development of Domestic Automotive Industry, formed a large amount of inefficacy cleaning catalyst for tail gases of automobiles (abbreviation automobile catalyst), wherein very large some is external manufacturer production, and raw material sources are in abroad.In external most automobile catalysts of producing, platinum metals simple substance content summation is 0.1wt.% left and right.In automobile catalyst, Pt content is generally 300-1000ppm, and Pd content is 200-800ppm, and Rh content is 50-100ppm.China produces the spent auto-catalysts of 500 tons of left and right for 1 year at present, and approximately 600 kilograms of platiniferous, palladium, rhodiums, expected after 2014, and the spent auto-catalysts of generation will reach 5000 tons, and platiniferous, palladium, rhodium exceed 6 tons.Whole world 93%Rh, 82%Pd, 48%Pt in 2011 are used for the manufacture of cleaning catalyst for tail gases of automobiles, and abandoned car catalyzer is primary platinum metals secondary resources in many countries at present.Except platinum metals, in abandoned car catalyzer, also contain 5wt.% left and right lanthanum and cerium mischmetal oxide compound.
In addition, in the industrial production such as petrochemical complex, also can produce inefficacy platinum metal catalysts, also have a difficult problem that how to reclaim platinum metals wherein.
Overwhelming majority automobile catalyst carrier is to be made by the stupalith of good thermal shock, as trichroite, also has aluminum oxide on trichroite, and platinum metals platinum, rhodium, palladium and the catalyst aid Rare Earth Lanthanum and the cerium that play katalysis just load on such carrier.In abandoned car catalyzer, platinum metals platinum, rhodium, palladium exist with metal simple-substance or metal oxide form, and Rare Earth Lanthanum, cerium exist with oxide form.So-called extraction transferred to these elements in catalyzer in solution exactly from solid.
Routinely, with chloroazotic acid high temperature (95 DEG C) wet processing automobile catalyst, the extraction yield of platinum and rhodium is respectively less than 60% and 45%.Although the whole world has proposed the method for platinum, palladium, rhodium in many wet methods extraction abandoned car catalyzer, the extraction yield that common deficiency of these methods is rhodium is low, is generally no more than 50%.
At present mainly in the thermal-flame of 2000 DEG C of left and right, automobile catalyst is carried out to melting with plasma arc furnace in the world, to extract three kinds of platinum metals of platinum, palladium, rhodium wherein.The ferro-silicon forming in said process and platinum metals form new alloy phase Si-Fe-PGM, and this thing has extremely strong antiacid alkali ability mutually, are not easy to carry out follow-up wet processing, only have a few countries to grasp this technology.Although this process platinum metals extraction yield is high, exist energy consumption large, the weak point such as step is many, and facility investment is large, is difficult to be applied by medium-sized and small enterprises.
The present invention proposes a kind of method of platinum, palladium, rhodium and Rare Earth Lanthanum, cerium in wet high-effective extraction abandoned car catalyzer for this reason, and this method feature is that energy consumption is low, and the extraction yield of platinum, palladium, rhodium is all in 99% left and right.
Climb steel and hold steel capital use vanadium titano-magnetite, the blast-melted generation after blowing of these Steel Plant contains the vanadium slag of vanadium up to 7.3wt.%.From vanadium slag, vanadium extraction is mainly by 800 DEG C of sodium roastings and water logging at present, and the extraction yield of vanadium is in 80% left and right.Sodium roasting is mainly used rotary kiln.This extraction vanadium method existing problems energy consumption is large, facility investment and maintenance cost height and the not high difficult problem of vanadium extraction rate.The present invention proposes a kind of method of wet high-effective extraction Vanadium in Vanadium Residue for this reason, and this method feature is that energy consumption is low, and the extraction yield of vanadium can reach 99% left and right.
Metal high pressure autoclave industrial be widely used in containing pozzuolite gold mine in the oxidation of sulphur.Because autoclave is generally made as titanium or stainless steel or Hastelloy (Hastelloy) by metallic substance, under high temperature, autoclave inside is easily subject to the corrosion of the corrosion of strong acid, particularly hydrochloric acid and nitric acid.For avoiding or weaken the generation of this type of situation, the reaction unit that the present invention proposes is solid sample to be put into together with strong acid to acid corrosion-resistant, the wall good vial that conducts heat, again a vial part is immersed in water in autoclave (this water is neutral water or alkalescent water), by water in electricity or circulating water heating autoclave, the latter is also heated acid solution in vial.Although have small part acid volatilization to enter in the interior water of autoclave in reaction in vial, can not produce heavy corrosion to still inwall after water in still (particularly alkalescent water) dilution.The in-built vial of still is one of contrive equipment feature.
Metal high pressure autoclave is for keeping sealing, stir the general magnetic force driving stirring that adopts, but high temperature magnetic magnetism of material can weaken or completely dissolve, and magneticsubstance also can be corroded in high temperature strong acid steam, therefore under autoclave high temperature strong acid (particularly hydrochloric acid and nitric acid) condition, stirring is a difficult problem.For this reason, the reaction unit that the present invention proposes is that autoclave is fixed on the shaking table of a level shake, thereby plays liquid mixture in vibration vial, accelerates to leach the object of rare precious metal in solid material.Autoclave is placed on shaking table and shakes, thereby the effect of playing stirred sample is two of contrive equipment feature.
Summary of the invention
The present invention relates to wet method and extract rare precious metal method, relate more specifically to extract platinum metals in junked-auto catalyzer or petrochemical catalyst or platinum-group metal ores, and gold, copper, tin in gold mine or useless circuit card, climb Prospects of Rare Metal Vanadium in steel or Cheng Gangdeng Steel Plant vanadium slag used or Rock coal containing alum, rare-earth mineral and rare-earth tailing and neodymium iron boron and SmCo magneticsubstance waste material middle-weight rare earths.Precious metal can be ruthenium, rhodium, palladium, osmium, iridium, platinum, gold and silver etc.Rare metal can be vanadium, chromium, copper, tin, gallium, tungsten, molybdenum, tantalum, niobium, zirconium, hafnium, gallium, indium, thallium, germanium etc.
The principle one of the inventive method is first part simple substance carbon or sulphur in pressed powder raw material to be transformed into gas as CO or CO by oxygen or air roasting method
2, SO
2, SO
3deng removing, reduce simple substance carbon or sulphur or the absorption of sulfide to rare precious metal in extracting solution, and improve stock chart face pore passage structure, be easy to follow-up wet extraction rare precious metal.The 2nd, with carbon monoxide or the above-mentioned raw material of crossing through oxygen or air roasting of hydrogen treat, make the rare precious metal Reduction of Oxide in raw material become metal, be easy to follow-up wet extraction.The 3rd, pressed powder raw material after treatment above-mentioned second step is oxidized to the high volence metal ion that dissolves in diluted acid with strong oxidizers such as potassium permanganate by pressed powder raw material middle or low price rare precious metal in solution, so just rare precious metal by solid transfer in solution, thereby extract.
The present invention proposes the device of rare precious metal in a wet extraction solid material powder.Install with this, wet extraction process is carried out in an autoclave, and solid material powder and strong acid and strong oxidizer are put into an open glass bottle, then vial is immersed in autoclave in water, by water in electricity or circulating water heating autoclave, acid solution in vial is also heated.Autoclave is fixed on the shaking table of a level shake, thereby plays liquid mixture in vibration vial, accelerates to leach the object of rare precious metal in solid material.The in-built vial of still is one of contrive equipment feature.In autoclave after inflation, then disconnect being connected of autoclave and inflation line, autoclave is placed on shaking table and shakes, thereby the effect of playing stirred sample is two of contrive equipment feature.
Particularly, the present invention includes following steps:
One is extracted the apparatus and method of (comprising precious metal and rare metal) of rare precious metal in solid material simultaneously, and it comprises the following steps:
1) described solid material is packed in an open glass bottle, in vial, add hydrochloric acid or sulfuric acid and oxidant potassium permanganate; This vial is put into a titanium autoclave processed that water is housed, in still the liquid level of water lower than bottleneck, thereby the outer water of bottle can not enter in bottle;
2) by above-mentioned autoclave sealing, water in autoclave is heated to 40-250 DEG C, and keeps certain hour;
3) after having reacted, lay down autoclave internal pressure, filter respectively bottle interior and outer solution of bottle in autoclave, and wash solid residue.In solid material, rare precious metal, rare metal and rare earth metal are all enriched in the filtrate in bottle and outside bottle, thereby have reached the object of extracting above-mentioned rare precious metal in solid material.
2. further, in step 1) before can be first with oxygen or air at solid material described in 200-1000 DEG C of pre-treatment, then by hydrogen or CO (carbon monoxide converter) gas at 200-1000 DEG C of pre-treatment above-mentioned raw materials.
3. further, step 2) in before water heating, in autoclave, passed into the non-reducing gas such as oxygen or air giving in still in the past, make autoclave internal pressure reach 1 more than normal atmosphere, seal to autoclave again, then autoclave disconnects being connected of autoclave and inflation line, so that can freely shake on shaking table;
4. further, step 1) potassium permanganate also can make oxygenant and the manganese such as Manganous chloride tetrahydrate or the manganous sulfate salt that can be oxidized by oxygen such as sodium chlorate, Manganse Dioxide, hydrogen peroxide, ammonium persulphate into or not add any solid oxidizing agent in vial solution, but in autoclave, pass into oxygen or air going to in still water heating in advance.
5. further, step 1) also can add the chlorates such as sodium-chlor in vial solution.
6. further, step 1) also any two or three in interchangeable one-tenth hydrochloric acid, sulfuric acid, nitric acid of hydrochloric acid or sulfuric acid in vial solution.
7. further, wherein step 2) mesohigh still base in heat-processed can be fixed on a shaking table and shake, thus play liquid in vibration vial, accelerate to leach the object of rare precious metal in solid.
8. further, step 1) mesohigh still material titanium also can change the metallic substance of the acid corrosion-resistants such as Hastelloy (Hastelloy) into.
9. further, wherein step 1) solution also can directly be put into autoclave in vial, without vial.
10. further, junked-auto catalyzer, petrochemical catalyst, platinum-group metal ores that accessible pressed powder raw material is platinum group metal, and containing golden gold mine or containing the useless circuit card of gold, copper, tin, what contain vanadium climbs steel or Cheng Gangdeng Steel Plant vanadium slag used or Rock coal containing alum.Wherein precious metal can be ruthenium, rhodium, palladium, osmium, iridium, platinum, gold and silver etc., and rare metal can be vanadium, chromium, copper, tin, gallium, tungsten, molybdenum, tantalum, niobium, zirconium, hafnium, gallium, indium, thallium, germanium etc.
Embodiment
Method of the present invention will at length be illustrated in this part, wherein to contain such as platinum of precious metal, rhodium, the vanadium slag of the vanadium slag of palladium junked-auto catalyzer and the blast-melted blowing of Steel Plant that contains Prospects of Rare Metal Vanadium and the blast-melted blowing of Steel Plant that contains Prospects of Rare Metal Vanadium is example, but, those skilled in the art are to be understood that, method of the present invention is not limited in and is applied to junked-auto catalyzer, also can be applied to other raw material containing precious metal, for example petrochemical catalyst, petrochemical catalyst, platinum-group metal ores, and containing golden gold mine or containing gold, copper, the useless circuit card of tin etc.Precious metal can be ruthenium, rhodium, palladium, osmium, iridium, platinum, gold and silver etc.Rare metal can be vanadium, chromium, copper, tin, gallium, tungsten, molybdenum, tantalum, niobium, zirconium, hafnium, gallium, indium, thallium, germanium etc.
In filtrate, the muriatic analysis of rare precious metal can use plasma mass (ICP-MS) or ICP-AES (ICP-AES) or other analytical procedure as spectrophotometry.In filtrate, a certain rare precious metal concentration is designated as C
i(ppm).The volume of filtrate is V (mL) after measured.
Weight is the extracted amount x of certain metal i in the raw material of W (g)
ifor:
In this article, metal fall refers to that raw material powder is after above-mentioned pyrogenic process pre-treatment and wet method aftertreatment, the ratio percentage of actual this kind of metal quality containing in transferring to this kind of metal quality of solubility in the extraction filtrate of aftertreatment and dropping into the raw material powder reacting.The extraction yield η of metal i is expressed as:
μ is for to use other International Standards Method, and as the precious metal fire assaying analysis that specialty analysis personnel carry out, the weight percentage of certain metal i in the raw material drawing, can regard standard value.
Embodiment 1
10.0000g particle diameter is less than to 74 microns of spent auto-catalysts dried powders and packs in a quartz boat, quartz boat is placed in to the reaction tubes of the flat-temperature zone of upper and lower openable tube furnace.Then tube furnace is warming up to 300 DEG C under the argon gas condition of logical 8cm/min, then argon gas is switched to 16cm/min oxygen, 500 DEG C of reactions 2 hours.Again oxygen is switched to 16cm/min argon gas, ventilate half an hour, residual oxygen in pipe is removed.Again argon gas is switched to 16cm/min hydrogen, 500 DEG C of reactions 2 hours.After the pre-treatment of low temperature pyrogenic process, furnace temperature is cooled to room temperature, quartz boat is taken out from reaction tubes.
Pretreated above-mentioned process catalyst powder is all transferred in 250ml vial by quartz boat, in bottle, add 100ml mixed solution (mixed solution: hydrochloric acid 6mol/L and potassium permanganate 20g/L and sodium-chlor 20g/L), again vial is put into a titanium autoclave processed that tap water is housed in advance, vial is immersed in autoclave water, the outer liquid level of bottle is lower than bottleneck, and the outer liquid level of bottle can not enter in bottle.Titanium autoclave base processed is fixed on a horizontal shaking table.Toward the oxygen that is filled with 1.2MPa in titanium autoclave processed, then autoclave is sealed.Then heat up to tap water heating by the titanium electrically heated rod processed in insertion reaction device tap water, make water temperature in autoclave rise to 160 DEG C, at this moment autoclave internal pressure rises to 1.6MPa, make titanium autoclave processed do rotation shake back and forth at horizontal plane on shaking table simultaneously, rotation rotating speed 150r/min, then continue insulation, pressurize reaction 2h, then stop heating rotation, leave standstill cooling nearly room temperature, pressure release, opens reactor, take out vial, extract tap water in autoclave out, solution inside and outside bottle is filtered respectively, washs filter residue, measure the volume of the inside and outside filtrate of bottle.
Analyze the concentration (ppm) of platinum metals platinum, rhodium, palladium in the inside and outside filtrate of bottle with plasma mass (ICP-MS).Known by platinum metals total amount in the inside and outside filtrate of mensuration bottle, the extraction yield η of catalyst solid Pd, Pt, Rh is respectively 99%, 99%, 99%.
Embodiment 2
10.0000g particle diameter is less than to 74 microns of vanadium slag dried powders to be packed in 250ml vial, in bottle, add 100ml solution (solution: sulfuric acid 6mol/L), again vial is put into a titanium autoclave processed that tap water is housed in advance, vial is immersed in reactor water, the outer liquid level of bottle is lower than bottleneck, and the outer liquid level of bottle can not enter in bottle.Titanium autoclave base processed is fixed on a horizontal shaking table.Toward the oxygen that is filled with 1.2MPa in titanium autoclave processed, then autoclave is sealed.Then heat up to tap water heating by the titanium electrically heated rod processed in insertion reaction device tap water, make water temperature in autoclave rise to 160 DEG C, at this moment reactor pressure rises to 1.6MPa, make titanium reactor processed do rotation shake back and forth at horizontal plane on shaking table simultaneously, rotation rotating speed 150r/min, then continue insulation, pressurize reaction 2h, then stop heating rotation, leave standstill cooling nearly room temperature, pressure release, opens reactor, take out vial, tap water in extraction device, filters respectively, washs filter residue by solution inside and outside bottle, measures the volume of the inside and outside filtrate of bottle.
Analyze the concentration (ppm) of vanadium in filtrate by ICP-AES (ICP-AES).Known by vanadium total amount in the inside and outside filtrate of mensuration bottle, the extraction yield η of Vanadium in Vanadium Residue is 89%.
Embodiment 3
10.0000g particle diameter is less than to 74 microns of vanadium slag dried powders to be packed in 250ml vial, in bottle, add 100ml mixing solutions (solution: sulfuric acid 6mol/L and sodium chlorate 20g/L), again vial is put into a titanium autoclave processed that tap water is housed in advance, vial is immersed in reactor water, the outer liquid level of bottle is lower than bottleneck, and the outer liquid level of bottle can not enter in bottle.Titanium autoclave base processed is fixed on a horizontal shaking table.Toward the oxygen that is filled with 1.2MPa in titanium reactor processed, then autoclave is sealed.Then heat up to tap water heating by the titanium electrically heated rod processed inserting in autoclave tap water, make water temperature in autoclave rise to 160 DEG C, at this moment autoclave internal pressure rises to 1.6MPa, make titanium autoclave processed do rotation shake back and forth at horizontal plane on shaking table simultaneously, rotation rotating speed 150r/min, then continue insulation, pressurize reaction 2h, then stop heating rotation, leave standstill cooling nearly room temperature, pressure release, opens autoclave, take out vial, extract tap water in autoclave out, solution inside and outside bottle is filtered respectively, washs filter residue, measure the volume of the inside and outside filtrate of bottle.
Analyze the concentration (ppm) of vanadium in filtrate by ICP-AES (ICP-AES).Known by vanadium total amount in the inside and outside filtrate of mensuration bottle, the extraction yield η of Vanadium in Vanadium Residue is 99%.
Embodiment 4
10.0000g particle diameter is less than to 74 microns of vanadium slag dried powders to be packed in 250ml vial, in bottle, add 100ml mixing solutions (solution: sulfuric acid 6mol/L and sodium chlorate 20g/L), again vial is put into a titanium autoclave processed that tap water is housed in advance, vial is immersed in reactor water, the outer liquid level of bottle is lower than bottleneck, and the outer liquid level of bottle can not enter in bottle.Titanium autoclave base processed is fixed on a horizontal shaking table.Toward the oxygen that is filled with 0.1MPa in titanium autoclave processed, then autoclave is sealed.Then heat up to tap water heating by the titanium electrically heated rod processed inserting in autoclave tap water, make water temperature in autoclave rise to 95 DEG C, at this moment autoclave internal pressure is substantially constant, make titanium autoclave processed do rotation shake back and forth at horizontal plane on shaking table simultaneously, rotation rotating speed 150r/min, then continue insulation, pressurize reaction 2h, then stop heating rotation, leave standstill cooling nearly room temperature, pressure release, opens autoclave, take out vial, extract tap water in autoclave out, solution inside and outside bottle is filtered respectively, washs filter residue, measure the volume of the inside and outside filtrate of bottle.
Analyze the concentration (ppm) of vanadium in filtrate by ICP-AES (ICP-AES).Known by vanadium total amount in the inside and outside filtrate of mensuration bottle, the extraction yield η of Vanadium in Vanadium Residue is 96%.
Claims (10)
1. extract the apparatus and method of (comprising precious metal, rare metal) of rare precious metal in solid material powder, it comprises the following steps simultaneously:
1) described pressed powder raw material is packed in an open glass bottle, in vial, add hydrochloric acid or sulfuric acid and oxidant potassium permanganate; This vial is put into a titanium autoclave processed that water is housed, in still the liquid level of water lower than bottleneck, thereby the outer water of bottle can not enter in bottle;
2) above-mentioned autoclave is sealed, then water in still is heated to 40-250 DEG C, and keep certain hour;
3), after having reacted, lay down autoclave internal pressure, bottle interior and outer solution of bottle in filtration reactor respectively, and wash solid residue.In solid material, rare precious metal, rare metal and rare earth metal are all enriched in the filtrate in bottle and outside bottle, thereby have reached the object of extracting above-mentioned rare precious metal in solid material.
2. method according to claim 1, in step 1) before can be first with oxygen or air at pressed powder raw material described in 200-1000 DEG C of pre-treatment, then by hydrogen or CO (carbon monoxide converter) gas at 200-1000 DEG C of pre-treatment above-mentioned raw materials.
3. according to the method described in claim 1 or claim 1 and 2, wherein claim 1 step 2) in before feedwater heating, in autoclave, passed into the non-reducing gas such as oxygen or air in the past, make autoclave internal pressure reach 1 more than normal atmosphere, seal to autoclave again, then autoclave disconnects being connected of autoclave and inflation line, so that can freely shake on shaking table;
4. method according to claim 1, wherein 1 step 1) potassium permanganate also can make oxygenant and the manganese such as Manganous chloride tetrahydrate or the manganous sulfate salt that can be oxidized by oxygen such as sodium chlorate, Manganse Dioxide, hydrogen peroxide, ammonium persulphate into or not add any solid oxidizing agent in vial solution.
5. method according to claim 1, wherein step 1) also can add the chlorates such as sodium-chlor in vial solution.
6. method according to claim 1, wherein step 1) also any two or three in interchangeable one-tenth hydrochloric acid, sulfuric acid, nitric acid of hydrochloric acid or sulfuric acid in vial solution.
7. method according to claim 1, wherein step 2) mesohigh still can be fixed on a shaking table and shake in heat-processed, thus play liquid in vibration vial, accelerate to leach the object of rare precious metal in solid.
8. method according to claim 1, wherein step 1) in reactor material titanium also can change the metallic substance of the acid corrosion-resistants such as Hastelloy (Hastelloy) into.
9. method according to claim 1, wherein in some abstraction reaction, step 2) mesohigh still also can be only as an open container, and not inflating pressure, just by water in electricity or circulating water heating autoclave, makes in vial acid solution also heated.
According to claim 1 or claim 1 and 2 or claim 1 and 2 and 3 described in method, junked-auto catalyzer, petrochemical catalyst, platinum-group metal ores that accessible pressed powder raw material is platinum group metal, and containing golden gold mine or containing the useless circuit card of gold, copper, tin, what contain vanadium climbs steel or Cheng Gangdeng Steel Plant vanadium slag used or Rock coal containing alum.Wherein precious metal can be ruthenium, rhodium, palladium, osmium, iridium, platinum, gold and silver etc., and rare metal can be vanadium, chromium, copper, tin, gallium, tungsten, molybdenum, tantalum, niobium, zirconium, hafnium, gallium, indium, thallium, germanium etc.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106381402A (en) * | 2016-08-31 | 2017-02-08 | 四川省新源泰环保科技有限责任公司 | Method for recovering germanium and copper from germanium-copper ore |
| CN110018155A (en) * | 2019-03-06 | 2019-07-16 | 江西瑞林稀贵金属科技有限公司 | A kind of method of tin amount in aes determination electronic waste smelting ash |
| CN110291046A (en) * | 2017-03-30 | 2019-09-27 | 栗田工业株式会社 | PH, oxidation-reduction potential adjust the manufacturing device of water |
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| CN102863399A (en) * | 2012-10-09 | 2013-01-09 | 西北大学 | Synthetic method for isatoic anhydride derivative |
| CN103205563A (en) * | 2013-05-06 | 2013-07-17 | 沈少波 | Method for extracting rare noble metals by wet method |
| CN103276215A (en) * | 2013-06-03 | 2013-09-04 | 贵研资源（易门）有限公司 | Method for recovering noble metal from waste catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102863399A (en) * | 2012-10-09 | 2013-01-09 | 西北大学 | Synthetic method for isatoic anhydride derivative |
| CN103205563A (en) * | 2013-05-06 | 2013-07-17 | 沈少波 | Method for extracting rare noble metals by wet method |
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| CN106381402A (en) * | 2016-08-31 | 2017-02-08 | 四川省新源泰环保科技有限责任公司 | Method for recovering germanium and copper from germanium-copper ore |
| CN110291046A (en) * | 2017-03-30 | 2019-09-27 | 栗田工业株式会社 | PH, oxidation-reduction potential adjust the manufacturing device of water |
| CN110018155A (en) * | 2019-03-06 | 2019-07-16 | 江西瑞林稀贵金属科技有限公司 | A kind of method of tin amount in aes determination electronic waste smelting ash |
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Application publication date: 20140813 |