TW200936508A - Method of reclaiming ruthenium from waste containing ruthenium - Google Patents

Abstract

This invention provides a method of effectively separating and reclaiming ruthenium from waste containing ruthenium. In the method of reclaiming ruthenium from waste containing ruthenium, mix sodium chloride of 1-7 times amount required for soluble chloration reaction of ruthenium and carbon powder of 0.5-12 times amount required fort the soluble chloration reaction of ruthenium with the powdered waste, and then heating the mixture at a temperature of from 700 degrees Celcius to 850 degrees Celcius under a chlorine atmosphere to obtain soluble ruthenium salt. After the ruthenium salt is dissolved into water, sodium bromate taken as an oxidizing agent is utilized to convert ruthenium into ruthenium tetroxide , and oxidation distillation is carried out to refine and reclaim ruthenium in hydrochloric acid solution.

Description

200936508 IX. Description of the invention: [Technical field to which the invention pertains] 纟Inventions are related to the method of easily recovering hydrazine from waste (waste) containing it ^ $ [Prior Art] ❹ 钌 has a number of atoms The order layer is sandwiched between the recording layers of the hard disk, and the effect of the recording capacity can be increased. The formation of the enamel layer is the second mining method. When it is processed into a splash (four), it will produce a cutting genus and a grinding genus. In addition, the target for money mining usually only uses 2〇~4〇% of the total, and most of the raw materials will become waste. Therefore, in order to effectively utilize the precious metal, the establishment of a technology for recycling nails is indispensable. However, since (4) is as high as MM and is not easily dissolved by acid or alkali, it is difficult to separate from waste. 〖, in order to be used in the application of the money mine, it is necessary to make the separated nails have 99 9 Cong to: = quality, but it is difficult to recover from waste containing various impurities. Patent Literature According to Japanese Patent No. 3943564 (I hope that Jichuan, under the usual conditions, is very difficult to dissolve in 7 mineral acids. In the past, the following methods were known for the method of dissolving hydrazine, and T is used for bathing Or the presence of oxygen (4) in the presence of oxygen, and then treated with mineral acid in the autumn; combined with Zn, Sn, pb, genus, and dissolved, dissolved in hydrochloric acid or sulfuric acid, etc. The activated micropowder is dissolved by aqua regia and the yttrium is converted into a soluble salt represented by Na3RuCl6. 5 200936508 Patent Document 2: Japanese Patent Laid-Open No. 2 2() No. 5635 (Japanese Patent No. 1) -25530), the method of the following is not disclosed: the Ru or its oxides, the second compound, and the wrong salt forming agent of the vaporized product are mixed, and then: heating: while introducing the gas, thereby Let Ru or its oxides become gas and then The method of reacting the wrong salt forming agent of the vaporized product to obtain Ru is the wrong salt, and then dissolving and separating the Ru to recover the Ru. The method for purifying is known to use ruthenium tetroxide (Ru04). Oxidation of sulphur (4) - Hearts - Method. According to non-specialization: Document 1. The Japan Institute of Atomic Energy recognizes 28 volumes, pages 493 to pp. (Non-Patent Document 1), which has a species of chlorine containing oxidants. The residue is dissolved in the solution, and then the volatilized ruthenium oxide is recovered. However, if the gas is introduced, the gas absorbed into the aqueous solution will be decomposed into hypogastric acid and hydrochloric acid, if the solution In the case of the acidification, the oxidizing steaming chamber cannot be carried out. Therefore, in order to increase the productivity, it is necessary to add a test and repeat the distillation. Patent Document 3: Japanese Patent Publication No. (Japanese Patent Application No. U-375235) A method for reacting a water-soluble nail compound with an integrated organic compound to form a body and then performing solid-liquid separation to remove water-soluble impurities is described. However, since the separation is insufficient, in order to obtain In the case of the purity 钌, the purification step must be repeated, and the recovery rate of the ruthenium is low, so that it cannot be efficiently purified. [Patent Document 1] Japanese Patent No. 3943564 (Japanese Patent Application No. 2004-251721) [Patent Document Japanese Patent Laid-Open No. 2 。 〇 635 635 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 μ人1 Jujube Atomic Energy Society Vol. 28 (1986-500 pages 卞; ^ [Summary] The subject of the present invention is a method for efficiently recycling a waste material containing bismuth. In view of the above, the present invention is: (1) A method for recovering hydrazine from a waste containing waste, characterized in that sodium sulphate and carbon powder are added to the waste containing and cut, in an atmosphere of atmosphere Into the water, ... 钌 becomes a soluble salt' and then the solution is washed into water to make a solution. At the beginning, the oxidizing agent is added with sodium bromate, and the hydrazine is converted into a oxidized material. The more acid, the more liquid in the liquid, and then the osmium tetroxide is introduced into the acid-acid liquid to make the vapor of strontium. (2) As stated in (1)

For the method of recovering sputum from sputum, JL:=: Γ waste material is pulverized to a particle size of 5. . ...Bottom: Mix sodium and sodium carbonate. "(3) As stated in (1) or (2), the amount of sodium added by the servant is the amount of the sputum, and the amount of sodium added is the amount of the soluble person #^ @ 7 Xiao, carbon is required to be 12 times more than the chlorination reaction. The amount of Qin added is 0.5 to the amount required for the nail. (4) The method described in any one of (1) to (3), wherein Sun Youshu The waste recovery enthalpy is carried out at a heating temperature of 7 〇〇 to 200936508 °c in the gasification sinter treatment. The invention (1) can be produced by itself (2) and can be self-contained. The waste is effectively separated from the mash. The waste is efficiently recovered at a mass of 99.9%. [Embodiment] The present invention will be described in detail below.

In the production of ί:: the object to be treated is waste containing bismuth, which is powdery. Access: Household 9' can be processed directly due to machining chips and grinding debris generated by machining. In the case of a cake having a used dry plating or the like, it may be preliminarily used by a feeder or a crusher. The granules are pulverized at a ratio of I: 500, so that the hydrazine is efficiently reacted with the added gasification hydride. Because of the machine-made Λ τ τ ^ l machining of the cuttings and grinding debris below 5 〇〇 M m of fine particles, no need to smash.

Further, when the waste contains a large amount of water, the water vapor is released when heated in the gas stream, and the partial pressure of the gas may be temporarily lowered or the oxide may be formed. Therefore, it is preferred to sufficiently dry in advance. The drying conditions are not particularly limited, but in the case of 1 GG to UOt, it is 6 to 15 hours. Further, when a material having a very small fraction of f is used, the drying step can of course be omitted. Tian right adds gasification and carbon powder to the treatment, and when heated in a gas stream for gasification and burning, (4) will become a soluble salt. Preferably, the heating temperature is 700 to 85 (rc, particularly good) (^ to 83 〇. 〇 range. Further, the processing time is not particularly limited, but preferably & u), around, especially preferably 3~ 6200936508 The reaction of Na3RuCl6 which is treated with chlorination to make hydrazine soluble is as follows: 2Ru+ 6NaCl+ 3C12-2Na3RuCl6 Here, most of the impurities contained in the waste will react with the gas. The amount of gas used for the chlorination roasting treatment is not particularly limited, and the reaction equivalent of hydrazine shown in the above reaction formula, together with the amount of maintaining the atmosphere in the furnace, is at least minimal. It is necessary, and it is considered that the impurities in the waste will react with the chlorine gas, so it will be used excessively. The gasification will be at 55 〇. The temperature above 〇 dissociates and releases the gas, so the v must be 5 5 0 At least C, the atmosphere of chlorine is maintained. Here, most of the impurities contained in the waste react with the gas to form a vapor. The amount of sodium added is preferably the reaction equivalent of the above reaction formula. 1 to 7 times In addition, if the addition amount of the vaporized sodium is increased, the proportion of the vaporized volatile processed material will be reduced relative to the total amount that can be charged into the furnace, and the treatment efficiency is deteriorated, so that it is particularly preferably 3 to 5 times. The range of cutting, processing, grinding and scraping of the drying process, the abrasion of the tool, etc., causes the bauxite powder of the iron and the abrasive (alumina powder) to be in the scrap and the iron in the scrap. At the temperature, it does not react with the gasification sodium. Therefore, it does not affect the amount of sodium chloride added. In addition, if the gas is treated in the chlorine gas stream without adding sodium vapor, it will produce poor solubility. If there is an oxide layer formed on the surface of the crucible during gasification and burning, the reaction shown by the above reaction formula will be difficult to carry out. In the waste, most of the 200936508 will become Oxide. During the gasification roasting process, an oxide layer is formed due to the oxygen mixed in the furnace or the moisture of the treated material. Therefore, it is necessary to mix the carbon powder and smear the silicon layer. Restore it. The reaction of the reduction of η κ emulsified oxime is as follows:

The amount of Ru〇2 + 2C—Ru+ 2CO carbon powder is not sufficient for the deuteration state of 4, ', and ', but it is preferably the anti-Motordan from the above-mentioned reaction formula. 〇.5~12 times. Toner, because it can shield the oxide layer on the surface of the crucible

The reduction promotes the soluble chlorination reaction, and it is possible to suppress the formation of the vaporized layer during the temperature rise, and the gp # + layer has almost no change in effect even if it is added in an amount of more than 12 times. In some cases, the ground powder of the abrasive is mixed into the scrap due to the grinding process during the dry manufacturing. Since cerium oxide is more easily reduced than alumina, the reduction reaction of cerium oxide ends first. Unreacted toner reacts with aluminum oxide but does not affect the amount of carbon powder added. The chlorinated calcined product is subjected to water immersion to dissolve the soluble salt of cerium. The condition at this time is not particularly limited, but it is preferably 5 Torr to 9 Torr. Here, most of the impurities contained in the waste become vaporized: the solution to water 'but a part of the impurities are insoluble. The residue containing excess sodium carbonate, unreacted carbon powder, insoluble impurities, and unreacted hydrazine is filtered to obtain an immersion liquid containing impurities. The recovery of hydrazine can be improved by returning the filtered residue to the chlorination roasting treatment step. Here, the sodium chloride or the carbon powder contained in the filtration residue may be used as an additive before the chlorination roasting treatment. The immersion liquid containing the ruthenium containing impurities is recovered by oxidizing and distilling the ruthenium into 200936508. ... * The acidification of the ninth agent is left-injected into the immersion liquid containing impurities. The conversion of ruthenium to sodium ruthenium oxide and the boiling point of ruthenium is about 130 ° C, so if it is heated to 7 〇 ~. Since the gasification of tetraoxide occurs, the air is poured into the immersion liquid of the illusion, and the chemical is easily dissolved in the hydrochloric acid solution to be recovered as a vapor of hydrazine. Introduction The human solution can be recovered by a known method in the following manner without contaminating the cockroaches. 3 钌 ❹ ❹ ❹ ❹ 1 1 ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ 氯化The mixture is fired, and the salt is decomposed into a β-sentence (7) in a hydrochloric acid solution containing hydrazine, and a reducing agent such as formazan, oxalic acid or hydrazine is added and heated to obtain a slab of the reduced nail. Since the reduction nail is in the form of fine particles and contains oxygen, it is calcined in a hydrogen-reducing atmosphere. I (3) The concentrated hydrochloric acid solution containing hydrazine is heated to concentrate, and the precipitated vaporized hydrazine is filtered, and then fired in a hydrogen atmosphere to form a nail. (4) An electrode plate made of titanium was placed in a hydrochloric acid solution containing hydrazine, and 4 was recovered by an electrodeposition method. [Examples] (Example 1) Hereinafter, examples of the invention will be described. It is a mixture of 5.2 kg of sodium chloride and 240 g of carbon powder mixed with i. 〇kg for the machining of the target, and the 6-part waste of the grinding genus. Table 1 shows the composition of the mixed waste and the amount of sodium carbonate added in 200936508. Here, the amount of ruthenium contained in the waste is 5.8 times the equivalent, and the amount of carbon is 19 times the equivalent ❹ [Table 1J [ΧΊ > mass (mass%) 51.9 content (g) 519 A1

Ag 0.39 4 14 4 This mixture was placed in a quartz crystal boat furnace, and heated to 780 while flowing into a gas-made tubular milk pad. (: With the gasification roasting of 1 #. The sub-maintaining for 3 hours is maintained in 8 (TC warm water to the 嗲田 acres * ϋ. ° Hai treatment is dipped, and then reduced using a real-life transition. Hunting crickets smashed 2 矣... "To the immersion liquid containing impurities, the composition, content, and leaching rate of the rinsing liquid 。 [Table 2]

12 200936508 The 33L immersion liquid is added to the oxidizer by 3%, and it is distilled for 2 hours. The volatilized nails and the hydrochloric acid solution were evaporated to obtain a hydrochloric acid solution 27B of hydrazine. Table 3 shows the composition and content of the acid solution and the recovery rate from the waste. Hydrochloric acid: The impurity component other than hydrazine is less than 1 mg/L~ 9 % of the hydrazine contained in the waste can be recovered in the hydrochloric acid solution. [Table 3] ~~ Composition of the solution, containing Jin-- Ru A1 ^ ^ m Ag Cu * XT ; ----------L·- -ΛΛΛΙμ) 17.5 473 < 0.001 < 0.027 < 0.001 < 0.027 < 0.001 ------- < 0.027 __ IN 1 < 0.001 < 0 027 ϋ (%) 91.0 — — — V · \J ^ / The solution containing hydrazine in 9 (6 hours after heating at rc, ammonium chloride was added in a ratio of 5 〇g / L, and heated at 90 t: for 2 hours. After cooling to 'filtering' to obtain ammonium hexacarbonate. Then at 5% Hydrogen argon

1 I I /, calcination 'recovered to 470g. It can recover 9 1 〇/ of the crucible contained in the waste. . The quality of the powder was measured by the glow discharge mass spectrometry (GDMS method) to measure the a ® θ rabbit component, and the oxygen content of the gas was determined by steam distillation ion chromatography. . Table 4 shows the analysis of gentlemen: 3⁄4, 0 Wo. The recovered ruthenium has less impurities and has a quality of 99.9 mass% or more. 13 200936508 [Table 4] $4 Recovered composition of mass (mass ppm) A1 Ag Cu Ni Fe Cr -w « ^ ^ xt Mo Cl —- 〇<1 <1 <1 2 42 12 1 50 1 - --- 460 (Example 2) In the examples, the block-shaped end material waste of the formed target was used as a raw material. The block-shaped end material waste was crushed by a pulverizer, and pulverized by a crusher to make it into a powder form, and a powder sample which can pass through a sieve of mesh 5 m was obtained. Table 5 shows the composition and content of the powder sample which can pass through the sieve. Sodium chloride and 220 g of carbon powder were mixed in this powder sample of i 〇kg. Here, the amount of gasification added to the amount of the amount of waste contained in the waste is 3 times the equivalent, and the amount of carbon is 1.0 times the equivalent. [Table 5] Formation and content

The crucible boat was then washed and filtered with water/text as in Example 1, whereby the mixture was charged into a quartz method for gasification and calcination treatment, and Table 6 shows the composition of the dip solution, and the obtained composition was obtained. The content of the leaching solution of the impurities, 35L, and the immersion rate. 14 200936508 [Table 6] Rabbit soil ____ main year _ ^ first liquid | composition, content and leaching rate solution group leaching rate (%)

于此 The 35 L < immersion solution was added to the oxidized sodium bromate 3 core, and the same method as in Example 1 was used to obtain a nail hydrochloric acid solution. Table: The composition and content of salt mash, and the recovery rate from waste. Hydrochloric acid solution: impurity components other than ... below. In addition, in the hydrochloric acid solution: 96% of the amount contained in the waste was recovered. [Table 7]

Ru team ~ group force 乂 Fe solution composition (g / L) 30.2 0.001 ------ 0.03 content (g) 876 recovery rate (%) 96.0 0.04

95% of the ruthenium contained in the waste which has been recovered by the method of recovering 868 g of the hydrochloric acid solution containing ruthenium to the 实 表 表 表 表 表 表 表 表 95 95 95 95 95 95 95 95 95 95 95 95 95 95 , less impurities, 99,9 mass% or more. 15 200936508 [Table 8]

(Comparative Example) A comparative example of the present invention will be described below. Comparative example, except for the table

The amount of chloranium added to 1 Gkg of the grinding residue and the grinding mixed waste was changed to G. 8 kg, and the others were subjected to gasification roasting treatment in the same manner as in the practice. Here, the amount of sodium vaporized added is 0.9 times the equivalent amount with respect to the amount of rhodium contained in the waste. The treated material was dipped in warm water maintained at 8 CTC, and then subjected to a vacuum reactor (4). A dip tank containing the enthalpy of the impurity f was obtained. Table 9 shows the composition, content, and immersion rate of the immersion liquid. The amount of retort that can be recovered is as low as 59% of the amount of waste contained in the waste, and the nail cannot be fully recovered. This is due to the insufficient amount of sodium chloride and the fact that it has a sodium salt which cannot be a soluble nail. [Table 9]

Solution composition (g/L) Content (g) Immersion rate (%) 16 200936508 (Comparative Example 2) In Comparative Example 2, the same amount of sodium carbonate and carbon powder as in Example 1 were mixed as shown in Table 1. The mixture of shavings and grinding debris is i〇kg. This mixture was placed in a quartz crystal boat in a furnace core tube. In the tubular furnace made of quartz, there is 650 in addition to the inflow of gas. (The temperature of (: was kept for 3 hours), and the others were subjected to chlorination roasting treatment in the same manner as in Example 1. The material was dipped in a warm water of 8 (TC), and then subjected to vacuum filtration. Obtaining the immersion liquid 3 containing the impurities. Table 10 shows the composition, content, and leaching rate of the immersion liquid. The amount of the immersion liquid can be recovered as low as the amount of sputum contained in the waste. 52%, and can not fully return = 钌 This is because the temperature of the gasification and calcination treatment is low, '钌 and gasification nano is not fully reacted' can not become a soluble sodium salt. [Table 10] r-washing liquid Composition, content and immersion rate Ru A1 Αμ Cu Κί Solution composition (g/L, — _ 8.2 6.1 0.06 0.39 0.11 Content (g) ---. ~277 207 2 13 4 Dipping rate (%) 53.5 95.1 52.3 92.7 98.4 (Comparative Example 3) In Comparative Example 3, you and Dong were crushed to crush the bulk end material waste of the formed target, without using the crushing and screening of the crusher, etc. Table u indicates the broken It contains the composition and content of the block end material waste of a 1 . Try 17 200936508 to the mesh 500 # m sieve, this crushed material ~ 卞物入仃4, can pass through the sieve about 40%. 4.9kg of sodium chloride, 220g magnetic 趴, Japanese people anodic powder mixed with unfiltered crushed material 1.0 kg. Here, the amount of emulsified sodium added is 3.0 times the equivalent amount, and the amount of carbon is i 〇 times the equivalent amount with respect to the amount of sputum caused by the waste. [Table 11] ^-11 The mashed powder contains f钌^Content ❹ Ru Fe A1 Pr Quality (mass%) 94.0 3.1 0.89 ------- Ni 0.07 L Content (g) 940 31 —J__ This mixture was charged into a quartz crystal boat, and the examples 丨The same method is used for gasification roasting treatment, water immersion washing, and filtration, thereby obtaining a leaching liquid 32L containing impurities from the treated material. Table 12 shows (c immersion liquid group 2 ^ content, immersion rate) The amount of waste that can be recovered in the immersion liquid is as low as the amount of waste contained in the waste. The amount of 6 y is not enough to recover 钌. This is because the particle of the waste used in the gasification and burning treatment is large. It is not fully reacted with sodium gas, and it cannot be the sodium salt of the 7 J. 200936508 - [Table 12] .· Table 12 Composition and content of the water immersion liquid And immersion rate

Ru Fe A1 Cr Ni Solution composition (g/L) 19.0 0.91 0.15 0.02 0.02 Content (g) 609 29 5 1 1 Dipping rate (%) 64.7 93.6 54.3 41.1 91.4 [Simplified illustration] Figure 1, this section A process flow diagram of one aspect of the invention. [Main component symbol description.] None

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Claims (1)

200936508 X. Application for Patent Park: 'K A method for recycling waste materials containing strontium, which is characterized by: ^Sodium chloride and carbon powder are added to the waste containing Yin, which is gasified in gas atmosphere. In the roasting treatment, the crucible is made into a soluble salt, and then the treated material is subjected to water immersion to prepare a solution, and then the oxidizing agent is added to the oxidizing agent to convert the cerium into cerium oxide. The rod 4 and the props 1 are fed into the oxidized group, and then the osmium tetroxide is introduced into the hydrochloric acid solution to prepare a vapor of cerium. ❹ 2. If you apply for a patent scope! The waste recycling nail of the self-contained (4) is: F, 'I, the raw material of the waste containing strontium is pulverized to a particle size of 500 ’' and the gasified sodium and carbon powder are mixed. 3. If the application of the patent scope 1 or 2 from the nail t, + * contains the waste recovery method, the addition amount of gasification sodium 庑张恭" Shu's soluble gasification reaction The amount of 1 to 7 toner required is 0.5 to 12 times the addition. $System, the amount required for the sufficiency 4. If the application of the scope of the second or second 钌 method is 甘 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 , , , , , , , , , , , (: proceeding. The degree of the dish is 700~850 5. If the method of claim 3 is included in the right-hand hit ★ a method, the dragon φ y 目 3 has the nail waste recycling ,, which is in the gasification roasting treatment Heating under temperature. Also von 700~850〇C 十一, 囷: as the next page 20