JPH09150065A - Method for recovering valuable metals from Ni waste catalyst - Google Patents

Method for recovering valuable metals from Ni waste catalyst

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Publication number
JPH09150065A
JPH09150065A JP33252795A JP33252795A JPH09150065A JP H09150065 A JPH09150065 A JP H09150065A JP 33252795 A JP33252795 A JP 33252795A JP 33252795 A JP33252795 A JP 33252795A JP H09150065 A JPH09150065 A JP H09150065A
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JP
Japan
Prior art keywords
water
catalyst
waste
leaching
contained
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP33252795A
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Japanese (ja)
Other versions
JP3102331B2 (en
Inventor
Akira Kimura
晧 木村
Kosuke Murai
浩介 村井
Ryuzo Wakamatsu
隆三 若松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pacific Metals Co Ltd
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Pacific Metals Co Ltd
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Priority to JP33252795A priority Critical patent/JP3102331B2/en
Publication of JPH09150065A publication Critical patent/JPH09150065A/en
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Publication of JP3102331B2 publication Critical patent/JP3102331B2/en
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Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Catalysts (AREA)

Abstract

PROBLEM TO BE SOLVED: To enable Ni, Co, Mo and V to be recovered at a high yield from a waste Ni catalyst by using a method such as wet crushing, water leaching or sulfuric acid spraying by flame. SOLUTION: Waste Ni catalyst is mixed with water and the mixture is crushed using a ball mill. The waste Ni catalyst completely undergoing this wet crushing process is subjected to a water leaching process 2 and consequently, a decoction consisting mainly of the MO and V components and a decoction residue containing Ni, Co, Mo and V are obtained. Ni and Co contained in the water decoction residue are dissolved by heating the water decoction residue at a high temperature using a mixture of sulfuric acid and water (cooking 3). After adjusting the pH value of the obtained solution (4), a sulfiding agent such as sodium sulfide or sodium hydrogen sulfide is added to Ni, Co and Mo contained in the filtrate. Thus it is possible to recover Ni, Co and Mo as a mixed sulfide at an yield of 98%. On the other hand, Mo and V are contained as main components in the liquid after the water leaching step 2, and are separated and recovered using a routine process.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、Ｎｉ廃触媒から、
Ｎｉ、Ｃｏ、Ｍｏ、Ｖを高歩留で回収する方法に関す
る。TECHNICAL FIELD The present invention relates to a Ni waste catalyst,
The present invention relates to a method for recovering Ni, Co, Mo, and V with a high yield.

【０００２】[0002]

【従来の技術】重油の水素化脱硫に用いる触媒には、Ｍ
ｏを主成分とする触媒をアルミナ担体に担持したものが
使用されている。触媒上に重油中の金属成分も付着して
含まれている。現在、使用済触媒からは、ＭｏとＶが工
業的に再資源化されている。2. Description of the Related Art The catalyst used for hydrodesulfurization of heavy oil is M
A catalyst having o as a main component supported on an alumina carrier is used. The metal component in the heavy oil is also contained on the catalyst by being attached. Currently, Mo and V are industrially recycled from used catalysts.

【０００３】使用済触媒をソーダバイ焼し、続いてモリ
ブデン酸ナトリウムＮａ2ＭｏＯ4及びバナジン酸ナトリ
ウムＮａＶＯ3として温水で浸出し、続いて塩析により
Ｖをメタバナジン酸アンモニウムＮＨ4ＶＯ3、又Ｍｏを
酸添加によりモリブデン酸Ｈ2ＭｏＯ4として回収する方
法である。The used catalyst is soda-baited and subsequently leached with hot water as sodium molybdate Na 2 MoO 4 and sodium vanadate NaVO 3 , and then V is ammonium salt metavanadate NH 4 VO 3 or Mo by salting out. This is a method of recovering molybdic acid H 2 MoO 4 by adding an acid.

【０００４】重油からの付着成分としてはＶの他にＮｉ
がある。又触媒によっては、Ｎｉ及びＣｏが活性成分と
して添加されているものもある。In addition to V, Ni is used as a component adhered from heavy oil.
There is. Some catalysts have Ni and Co added as active components.

【０００５】しかしながら、現在用いられているソーダ
バイ焼法では、Ｎｉ及びＣｏはＮｉＡｌＯ4及びＣｏＡ
ｌＯ4の様な固溶体をつくり、通常の処理方法では容易
に浸出できず回収が困難であることが知られている。However, in the currently used soda-by baking method, Ni and Co are NiAlO 4 and CoA.
It is known that a solid solution such as 10 4 is formed and cannot be easily leached out by a usual treatment method, and recovery is difficult.

【０００６】このソーダバイ焼法によりＭｏ及びＶを回
収した後の廃棄物（ここではＮｉ廃触媒と呼称する。Ｍ
ｏ及びＶも一部含まれる。）からＮｉ、Ｃｏ、Ｖ、Ｍｏ
を分離・回収することは、環境保全とともに資源の延
命、安定供給という観点からも重要な課題である。Wastes after recovering Mo and V by this soda-by burning method (herein referred to as Ni waste catalyst)
Some o and V are also included. ) To Ni, Co, V, Mo
Separation and collection of waste is an important issue from the perspective of environmental conservation, prolonging the life of resources, and providing a stable supply.

【０００７】[0007]

【発明が解決しようとする課題】本発明は、通常の処理
方法ではＮｉ、Ｃｏ等の有価金属の回収が困難であると
考えられているＮｉ廃触媒から湿式粉砕、水浸出及び硫
酸高温溶解法を用いることにより、Ｎｉ、Ｃｏ、Ｍｏ及
びＶを高歩留で回収する方法を提供するものである。DISCLOSURE OF THE INVENTION The present invention is a method of wet pulverization, water leaching and sulfuric acid high temperature dissolution method from a waste Ni catalyst which is considered to be difficult to recover valuable metals such as Ni and Co by an ordinary treatment method. Is used to provide a method for recovering Ni, Co, Mo and V with a high yield.

【０００８】[0008]

【課題を解決するための手段】本発明は、Ｎｉ廃触媒と
水を混合し、湿式粉砕後、水浸出して得られた浸出残渣
に硫酸を加えて蒸煮し、得られた溶液をＰＨ調整後、こ
れに硫化剤を添加しＮｉ、Ｃｏ、Ｍｏをミックスサルフ
ァイドとして回収することを特徴とするＮｉ廃触媒から
の有価金属回収方法である。According to the present invention, sulfuric acid is added to the leaching residue obtained by mixing Ni waste catalyst and water, wet pulverizing and leaching with water, and then steaming the solution to adjust the pH. After that, a sulfidizing agent is added to this to recover Ni, Co, and Mo as mixed sulfide, which is a valuable metal recovery method from a Ni waste catalyst.

【０００９】以下、本発明実施の好ましい態様を図１に
従い各工程毎に説明する。A preferred embodiment of the present invention will be described below for each step with reference to FIG.

【００１０】（１）湿式粉砕工程 この工程では、Ｎｉ廃触媒に水を混合し、ボールミルを
用いて１００メッシュ以下に粉砕する。好ましくは１５
０メッシュ以下（１５０メッシュよりこまかく）に粉砕
する。これにより、Ｎｉ廃触媒中にモリブデン酸ナトリ
ウムＮａ2ＭｏＯ4及びバナジン酸ナトリウムＮａ4ＶＯ3
として存在しているＭｏ及びＶが次の処理工程で水浸出
が容易になる。(1) Wet crushing process In this process, water is mixed with the Ni waste catalyst and crushed to 100 mesh or less using a ball mill. Preferably 15
Grind to 0 mesh or less (finely than 150 mesh). As a result, sodium molybdate Na 2 MoO 4 and sodium vanadate Na 4 VO 3 are contained in the Ni waste catalyst.
Mo and V, which are present as, facilitate water leaching in the next treatment step.

【００１１】（２）水浸出工程 この工程では、湿式粉砕を終了したＮｉ廃触媒をスラリ
ー濃度５０〜５００ｇ／ｌ、好ましくは１００〜２５０
ｇ／ｌとし、温度７０〜１００℃、好ましくは８０〜１
００℃、撹拌速度１００〜１０００ｒｐｍ、好ましくは
３００〜５００ｒｐｍで常圧で、０．５〜５時間、好ま
しくは１〜３時間浸出し、Ｍｏ及びＶが主成分の浸出液
と、Ｎｉ、Ｃｏ、Ｍｏ、Ｖを含む浸出残渣を得る。浸出
液はＭｏ、Ｖ回収工程へ、浸出残渣はＮｉ、Ｃｏ及びＭ
ｏをミックスサルファイドとして回収する工程へ送る。(2) Water Leaching Step In this step, the Ni waste catalyst which has been wet-milled has a slurry concentration of 50 to 500 g / l, preferably 100 to 250.
g / l, temperature 70 to 100 ° C., preferably 80 to 1
Leaching at 00 ° C., stirring speed 100 to 1000 rpm, preferably 300 to 500 rpm, and atmospheric pressure for 0.5 to 5 hours, preferably 1 to 3 hours, and a leaching solution containing Mo and V as main components, and Ni, Co, Mo. , V containing leaching residue is obtained. Leachate to Mo, V recovery process, leach residue is Ni, Co and M
sent to the process of collecting o as mixed sulfide.

【００１２】（３）硫酸高温溶解工程（蒸煮工程） 水浸出後の浸出残渣中のＮｉ及びＣｏは、前述した様に
Ａｌ担体中でＮｉＡｌＯ4及びＣｏＡｌＯ4の様に固溶化
しており通常の浸出方法では浸出が困難である。このた
め、この工程では、硫酸と水の混合割合が（１：１）〜
（１０：１）、好ましくは（１：１）〜（３：１）の溶
液を用いて水浸出残渣をスラリー濃度３００〜１５００
ｇ／ｌ、好ましくは５００〜１，０００ｇ／ｌ、温度１
１０〜１７０℃、好ましくは１２０〜１３０℃で０．２
５〜２．０時間、好ましくは０．５〜１．０時間、高温
溶解する（ここではこの操作を蒸煮工程と呼称する）。
これを水に溶解することによりＮｉ、Ｃｏ、Ｍｏ、Ｖの
溶液が得られる。このときの各金属浸出率は９１％以上
である。(3) Sulfuric acid high temperature dissolution step (steaming step) Ni and Co in the leaching residue after water leaching are solid-solved in the Al carrier like NiAlO 4 and CoAlO 4 as described above, Leaching is difficult with the leach method. Therefore, in this step, the mixing ratio of sulfuric acid and water is (1: 1) to
(10: 1), preferably using a solution of (1: 1) to (3: 1), the water leaching residue is treated to a slurry concentration of 300 to 1500.
g / l, preferably 500-1,000 g / l, temperature 1
0.2 at 10 to 170 ° C, preferably 120 to 130 ° C
It is melted at a high temperature for 5 to 2.0 hours, preferably 0.5 to 1.0 hours (this operation is referred to as a cooking step here).
By dissolving this in water, a solution of Ni, Co, Mo and V can be obtained. Each metal leaching rate at this time is 91% or more.

【００１３】（４）ＰＨ調整工程 この工程は、蒸煮工程で得られた溶液中のＮｉ、Ｃｏ及
びＭｏをミックスサルファイドして効率的に回収するた
め実施する。(4) PH adjusting step This step is carried out in order to efficiently mix Ni, Co and Mo in the solution obtained in the steaming step for mixed sulfide recovery.

【００１４】ここでは、浸出液を水酸化カルシウムを用
いてＰＨを２．５〜４．５、好ましくは２．７〜３．６
にし、温度を４０〜９０℃、好ましくは６０〜８０℃で
０．２５〜１．５時間、好ましくは０．５〜１．０時間
保持した後、濾過分離を行う。これにより濾過後のケー
キには、Ｆｅ（ＩＩＩ）とＡｌの一部が分離される。一
方、濾液は硫化工程へ送る。The pH of the leachate is 2.5 to 4.5, preferably 2.7 to 3.6, using calcium hydroxide.
The temperature is maintained at 40 to 90 ° C., preferably 60 to 80 ° C. for 0.25 to 1.5 hours, preferably 0.5 to 1.0 hour, and then filtered and separated. As a result, Fe (III) and a part of Al are separated from the filtered cake. On the other hand, the filtrate is sent to the sulfurization step.

【００１５】（５）硫化工程 この工程は、ＰＨ調整後の濾液からＮｉ、Ｃｏ及びＭｏ
をミックスサルファイドとして回収するために実施す
る。(5) Sulfidation step In this step, Ni, Co and Mo are removed from the filtrate after pH adjustment.
To collect as mixed sulfide.

【００１６】この工程は、ＰＨ調整後、濾液中に含まれ
るＮｉ、Ｃｏ及びＭｏに対して硫化ナトリウム、硫化水
素ナトリウムの様な硫化剤を１．０〜２．０当量、好ま
しくは１．１〜１．３当量添加し、温度２０〜９０℃、
好ましくは６０〜８０℃で０．２５〜２．０時間、好ま
しくは０．５〜１．０時間反応させる。これによりＮ
ｉ、Ｃｏ及びＭｏは９８％以上の歩留でミックスサルフ
ァイドとして回収される。In this step, after adjusting the pH, a sulfidizing agent such as sodium sulfide or sodium hydrogen sulfide is 1.0 to 2.0 equivalents, preferably 1.1 with respect to Ni, Co and Mo contained in the filtrate. ~ 1.3 equivalents added, temperature 20-90 ° C,
The reaction is preferably carried out at 60 to 80 ° C. for 0.25 to 2.0 hours, preferably 0.5 to 1.0 hour. This gives N
i, Co and Mo are recovered as mixed sulfide with a yield of 98% or more.

【００１７】（６）不純物除去工程―（Ａ） ミックスサルファイドを分離後の濾液中には、Ａｌとそ
の他の微量の成分が含まれており、水酸化カルシウムを
用いてＰＨ８〜９．５、好ましくは８．３〜８．７に中
和し濾過分離し、ケーキと濾液を得る。(6) Impurity removing step- (A) The filtrate after separation of mixed sulfide contains Al and other trace amounts of components, and calcium hydroxide is used to obtain PH of 8 to 9.5, preferably. Is neutralized to 8.3 to 8.7 and separated by filtration to obtain a cake and a filtrate.

【００１８】一方、水浸出工程後の液中には主としてＭ
ｏ及びＶが含まれており、従来から実施されている方法
（常法）で分離回収する。On the other hand, mainly M is contained in the liquid after the water leaching step.
O and V are contained, and they are separated and recovered by a conventionally practiced method (normal method).

【００１９】（７）脱Ｐ工程 水浸出液中には、約２０〜５０ｐｐｍのＰが含まれてい
る。Ｐは混入を防ぐためＶ回収工程及びＭｏ回収工程へ
入る前に除く。このＰを分離するため塩化マグネシウム
ＭｇＣｌ2をＰに対し、１．３〜３．０当量添加し温度
４０〜５０℃で、１〜２時間反応させる。続いて２０℃
以下の温度で２〜３時間保持することによりＰをリン酸
マグネシウムＭｇ3（ＰＯ4）として晶析分離する。(7) Step of removing P The water leachate contains about 20 to 50 ppm of P. P is removed before entering the V recovery step and the Mo recovery step to prevent contamination. In order to separate this P, magnesium chloride MgCl 2 is added in an amount of 1.3 to 3.0 equivalents to P, and the reaction is carried out at a temperature of 40 to 50 ° C. for 1 to 2 hours. Then 20 ℃
By holding at the following temperature for 2 to 3 hours, P is crystallized and separated as magnesium phosphate Mg 3 (PO 4 ).

【００２０】（８）Ｖ回収工程 脱Ｐ後の濾液にＶをメタバナジン酸アンモニウムＮＨ4
ＶＯ3として回収するに必要な化学当量の１．１〜１．
３倍の塩化アンモニウムＮＨ4Ｃｌを添加し、２０〜３
０℃で０．５〜１時間反応させバナジン酸アンモニウム
結晶を得る。これを４００〜５００℃で０．５〜１時間
反応させメタバナジン酸アンモニウム結晶を得る。これ
を４００〜５００℃でさらに０．５〜１時間仮焼するこ
とにより五酸化バナジウムＶ2Ｏ5を得る。(8) V recovery step V is added to the filtrate after dephosphorization with ammonium metavanadate NH 4
The chemical equivalent of 1.1 to 1. of the chemical equivalent required for recovery as VO 3 .
Add 3 times ammonium chloride NH 4 Cl and add 20 to 3
Reaction is carried out at 0 ° C. for 0.5 to 1 hour to obtain ammonium vanadate crystals. This is reacted at 400 to 500 ° C. for 0.5 to 1 hour to obtain ammonium metavanadate crystals. This is further calcined at 400 to 500 ° C. for 0.5 to 1 hour to obtain vanadium pentoxide V 2 O 5 .

【００２１】（９）Ｍｏ回収工程 Ｖ回収後の濾液にＭｏをモリブデン酸Ｈ2Ｍｏ4として回
収するのに必要な化学当量の１．１〜１．３倍の塩酸を
加え、３０〜６０℃で２〜３時間反応させることにより
モリブデン酸を得る。(9) Mo recovery step V To the filtrate after the recovery, 1.1 to 1.3 times the chemical equivalent of hydrochloric acid necessary to recover Mo as molybdic acid H 2 Mo 4 is added, and the temperature is 30 to 60 ° C. Molybdic acid is obtained by reacting for 2 to 3 hours.

【００２２】（１０）不純物除去工程―（Ｂ） Ｍｏ回収後の液中には、微量の成分が含まれており、水
酸化カルシウムを用いてＰＨ８．５に中和後濾過分離し
ケーキと濾液を得る。(10) Impurity removing step- (B) A small amount of component is contained in the liquid after Mo recovery, which is neutralized to pH 8.5 with calcium hydroxide and then separated by filtration to obtain a cake and a filtrate. To get

【００２３】本発明は、以上に示したプロセスにより、
Ｎｉ廃触媒からＮｉ、Ｃｏ、Ｍｏ及びＶの有価金属を高
歩留で回収する方法を提供するものである。以下に実施
例を示し上述の内容を例証する。The present invention is based on the process described above.
The present invention provides a method for recovering valuable metals of Ni, Co, Mo and V from a Ni waste catalyst with high yield. Examples will be shown below to exemplify the above contents.

【００２４】[0024]

【実施例１】第１表に示す成分のＮｉ廃触媒２５０ｇを
水１，０００ｍｌと混合し、ボールミルで１５０メッシ
ュ以下に粉砕した後、温度１００℃で３時間水浸出した
結果、第２表に示す様な浸出液、浸出残渣及び浸出率が
得られた。Example 1 250 g of Ni waste catalyst having the components shown in Table 1 was mixed with 1,000 ml of water, ground in a ball mill to 150 mesh or less, and then leached with water at a temperature of 100 ° C. for 3 hours. The leachate, leach residue and leach rate as shown were obtained.

【００２５】[0025]

【表１】 [Table 1]

【００２６】[0026]

【表２】 [Table 2]

【００２７】Ｍｏ及びＶは各６２．１％及び３０．４％
浸出されている。Mo and V are 62.1% and 30.4%, respectively.
It is leached.

【００２８】[0028]

【実施例２】実施例１で得られた水浸出残渣２２５ｇ
を、Ｈ2ＳＯ4：水―１：１の硫酸５７２ｍｌで温度１２
０℃で１時間蒸煮処理後、２，２５０ｍｌの水に溶解し
た結果第３表の様な浸出液、浸出残渣及び浸出率が得ら
れた。Ｎｉ、Ｃｏ、Ｍｏ及びＶの浸出率は各９１．６
％、９４．６％、１００．０％及び９１．７％であっ
た。Example 2 225 g of water leaching residue obtained in Example 1
Was heated at a temperature of 12 with 572 ml of H 2 SO 4 : water-1: 1 sulfuric acid.
After steaming for 1 hour at 0 ° C., it was dissolved in 2,250 ml of water. As a result, a leachate, a leach residue and a leach rate as shown in Table 3 were obtained. The leaching rate of Ni, Co, Mo and V is 91.6 each.
%, 94.6%, 100.0% and 91.7%.

【００２９】[0029]

【表３】 [Table 3]

【００３０】[0030]

【実施例３】実施例２で得られた濾液２，２５０ｍｌを
Ｃａ（ＯＨ）2でＰＨ３．６にＰＨ調整し、濾過分離し
て回収した濾液に、ＮａＨＳをＮｉ、ＣＯ、Ｍｏに対し
１．１当量添加し、６０℃で１時間反応させ第４表に示
すミックスサルファイド、濾液及び回収率を得た。ミッ
クスサルファイド中のＮｉ、Ｃｏ及びＭｏ成分は、各３
０．６％、５．７％及び１．２％であった。又、この時
のＮｉ、Ｃｏ及びＭｏの回収率は、９９．９％、９９．
３％及び９８．８％であった。Example 3 The pH of 2,250 ml of the filtrate obtained in Example 2 was adjusted to pH 3.6 with Ca (OH) 2 , and the filtrate recovered by filtration separation had NaHS of 1 for Ni, CO and Mo. 1 equivalent was added, and the mixture was reacted at 60 ° C. for 1 hour to obtain mixed sulfide, filtrate and recovery rate shown in Table 4. Ni, Co and Mo components in mixed sulfide are 3 each
It was 0.6%, 5.7% and 1.2%. The recovery rates of Ni, Co and Mo at this time are 99.9% and 99.
3% and 98.8%.

【００３１】[0031]

【表４】 [Table 4]

【００３２】[0032]

【実施例４】実施例１の水浸出液１，０００ｍｌに塩化
マグネシウムを０．４ｇ添加し、温度４０℃で２時間反
応させた後、１５℃で２時間冷却し第５表に示す結果を
得た。Ｐは、ｔｒ状態まで分離された。Example 4 0.4 g of magnesium chloride was added to 1,000 ml of the water leachate of Example 1, reacted at a temperature of 40 ° C. for 2 hours and then cooled at 15 ° C. for 2 hours to obtain the results shown in Table 5. It was P was separated to the tr state.

【００３３】[0033]

【表５】 [Table 5]

【００３４】[0034]

【実施例５】実施例４で得られたＰ分離後液９９９ｍｌ
に塩化アンモニウムＮＨ4Ｃｌを１．３ｇ添加し２５℃
で１時間反応させ、メタバナジン酸アンモニウム２．８
ｇを回収した。第６表にＶの回収状況を示す。メタバナ
ジン酸アンモニウムを５００℃で仮焼し、２．２ｇの五
酸化バナジウムを回収した。Example 5 999 ml of the liquid after P separation obtained in Example 4
Add 1.3 g of ammonium chloride NH 4 Cl to 25 ° C
After reacting for 1 hour, ammonium metavanadate 2.8
g was collected. Table 6 shows the recovery status of V. Ammonium metavanadate was calcined at 500 ° C. to recover 2.2 g of vanadium pentoxide.

【００３５】[0035]

【表６】 [Table 6]

【００３６】[0036]

【実施例６】実施例５に示したＶ分離後液９９９ｍｌに
ＣｏｎｃＨＣｌ １．１ｍｌ添加し、４０℃で２時間反
応させ０．４ｇのモリブデン酸を回収した。第７表にＭ
ｏの回収状況を示す。Ｍｏはほぼ全量モリブデン酸とし
て回収された。Example 6 1.1 ml of ConcHCl was added to 999 ml of the solution after V separation shown in Example 5 and reacted at 40 ° C. for 2 hours to recover 0.4 g of molybdic acid. M in Table 7
The recovery status of o is shown. Mo was almost totally recovered as molybdic acid.

【００３７】[0037]

【表７】 [Table 7]

【００３８】[0038]

【発明の効果】本発明によりＮｉ廃触媒から湿式粉砕・
水浸出及び蒸煮法を用いることによりＮｉ、Ｃｏ、Ｍｏ
をミックスサルファイドとして、又Ｍｏ及びＶを各モリ
ブデン酸及び五酸化バナジウムとして、高歩留で回収で
きる。EFFECTS OF THE INVENTION According to the present invention, wet pulverization from a waste Ni catalyst is carried out.
Ni, Co, Mo by leaching and steaming methods
As mixed sulfide, and Mo and V as molybdic acid and vanadium pentoxide, respectively, with high yield.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明回収方法の説明図である。FIG. 1 is an explanatory view of a recovery method of the present invention.

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】 Ｎｉ廃触媒と水を混合し、湿式粉砕後、
水浸出して得られた浸出残渣に硫酸を加えて蒸煮し、得
られた溶液をＰＨ調整後、これに硫化剤を添加しＮｉ、
Ｃｏ、Ｍｏをミックスサルファイドとして回収すること
を特徴とするＮｉ廃触媒からの有価金属回収方法。1. A Ni waste catalyst and water are mixed and wet-milled,
Sulfuric acid was added to the leaching residue obtained by leaching with water, and the solution was boiled. After adjusting the pH of the resulting solution, a sulfidizing agent was added to this,
A method for recovering valuable metals from a Ni waste catalyst, which comprises recovering Co and Mo as mixed sulfides.
JP33252795A 1995-11-29 1995-11-29 Method for recovering valuable metals from waste Ni catalyst Expired - Fee Related JP3102331B2 (en)

Priority Applications (1)

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JP33252795A JP3102331B2 (en) 1995-11-29 1995-11-29 Method for recovering valuable metals from waste Ni catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP33252795A JP3102331B2 (en) 1995-11-29 1995-11-29 Method for recovering valuable metals from waste Ni catalyst

Publications (2)

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JPH09150065A true JPH09150065A (en) 1997-06-10
JP3102331B2 JP3102331B2 (en) 2000-10-23

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Publication number Priority date Publication date Assignee Title
JP2011510806A (en) * 2008-01-30 2011-04-07 ヴァリアブル・ダニエル Method for recovering noble metals from used and / or voided catalyst supports
US20120087849A1 (en) * 2010-10-06 2012-04-12 Ferro Duo Gmbh Method for recovering lanthanum from zeolites containing lanthanum
JP2012206867A (en) * 2011-03-29 2012-10-25 Sumitomo Metal Mining Co Ltd Method for producing molybdenum trioxide
WO2013187367A1 (en) * 2012-06-12 2013-12-19 住友金属鉱山株式会社 Neutralization method
JP2013256691A (en) * 2012-06-12 2013-12-26 Sumitomo Metal Mining Co Ltd Neutralization method
CN104321449A (en) * 2012-06-12 2015-01-28 住友金属矿山株式会社 Neutralization method
CN111100987A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Recovery method of waste catalyst metal components in tail oil

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