CN111088438A - Method for recovering molybdenum from molybdenum-containing waste catalyst - Google Patents
Method for recovering molybdenum from molybdenum-containing waste catalyst Download PDFInfo
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- CN111088438A CN111088438A CN202010139641.0A CN202010139641A CN111088438A CN 111088438 A CN111088438 A CN 111088438A CN 202010139641 A CN202010139641 A CN 202010139641A CN 111088438 A CN111088438 A CN 111088438A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
- C22B34/345—Obtaining molybdenum from spent catalysts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- 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
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Abstract
The invention relates to a method for recovering molybdenum from a molybdenum-containing spent catalyst, which comprises the following steps: placing a molybdenum-containing waste catalyst in an acid solution, heating to a certain temperature, wherein the temperature range is 30-80 ℃, and carrying out constant-temperature oscillation treatment to obtain a molybdenum-containing water-phase leaching solution; step two, placing the molybdenum-containing water-phase leaching solution obtained in the step one into a separating funnel, adding a certain volume of an extracting agent, oscillating according to the ratio of O/A to O/A, the extraction time, the extraction temperature and the concentration of the extracting agent, and layering the solution; and step three, taking out the organic phase in the separating funnel, adding a certain volume of stripping agent, oscillating according to the ratio of O/A to the stripping time to the stripping temperature to the stripping agent concentration, layering the solution, and evaporating the obtained water phase to dryness to obtain the regenerated molybdenum oxide catalyst. The technical scheme of the invention reduces the high-temperature roasting process and avoids the problem of high cost caused by high-temperature and high-pressure equipment; the process is simplified, the recovery period is shortened, and higher metal recovery rate is obtained.
Description
Technical Field
The invention relates to the technical field of molybdenum recovery, in particular to a method for recovering molybdenum from a molybdenum-containing waste catalyst.
Background
In the petrochemical industry, molybdenum-based catalysts are one of the most commonly used catalysts, and are widely used in petroleum hydrogenation, hydrodesulfurization, propylene and ethylbenzene oxidation to produce propylene oxide, and the like. Because the molybdenum catalyst is used in a large amount and the service life of the catalyst is short, the amount of the waste catalyst is large, and the waste catalyst is rich in a large amount of metal molybdenum. The metal molybdenum in the waste catalyst is recycled, so that the pollution of the waste catalyst to the environment can be reduced, the metal molybdenum can be recycled, and the utilization of secondary resources is realized.
The traditional method for recovering the molybdenum from the waste catalyst is an alkaline leaching method, which mainly comprises the steps of melting and roasting the waste catalyst in alkali, leaching metal elements in the waste catalyst by water, evaporating and crystallizing a leaching solution, and finally extracting the molybdenum from the waste catalyst. However, in this method, since the spent catalyst is calcined by adding an alkali, calcination and high-pressure equipment are required, resulting in high product cost.
Currently, hydrochloric acid is often used as a leaching solution to extract molybdenum metal from a spent catalyst, for example, in "discussion and practice of recovering valuable metals from a spent catalyst containing molybdenum", such as Yangwang et Al, it is disclosed that a spent catalyst containing molybdenum is immersed in a hydrochloric acid solution, then the acid leaching solution is neutralized with ammonia water to precipitate molybdenum as molybdic acid, then sodium hydroxide is used to immerse molybdic acid to obtain a sodium molybdate solution, and Al is removed by precipitation and purification at different pH values3+、Mg2+And the purified solution is evaporated to separate out sodium molybdate crystals, and the sodium molybdate crystals are dried to finally obtain a sodium molybdate product. The method solves the problem of high product cost caused by roasting and high-pressure equipment required by alkaline leaching, simplifies the production process and equipment and obtains great economic benefit. But the recovery of molybdenum is low in the above method.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect of low recovery rate of metal molybdenum from the molybdenum-containing spent catalyst when hydrochloric acid is used as an extracting solution in the prior art, thereby providing a method for recovering molybdenum from the molybdenum-containing spent catalyst.
A method for recovering molybdenum from a molybdenum-containing spent catalyst comprises the following steps:
(1) the waste catalyst containing molybdenum is placed in acid solution, and the acid solution includes hydrochloric acid, sulfuric acid, carbonic acid, phosphoric acid and nitric acid, etc
(2) Heating to a certain temperature, wherein the temperature range is 30-80 ℃, carrying out constant-temperature oscillation treatment for 1-5h, and the oscillation rate is 200-;
(3) putting the leachate into a separating funnel, adding a certain volume of an extracting agent, oscillating according to the ratio of O/A, the extraction time, the extraction temperature and the concentration of the extracting agent, and layering the solution;
(4) the extractant is a neutral phosphorus extractant, an acidic phosphorus extractor or an amine extractant;
(5) the ratio A/O is 1-5;
(6) the extraction time is 1-60 min;
(7) the concentration of the extracting agent is 5% -60%;
(8) the oscillation rate is 200-500 r/min;
(9) taking out the organic phase in the separating funnel, adding a certain volume of stripping agent, oscillating according to the ratio of O/A, stripping time, stripping temperature and stripping agent concentration, layering the solution, and evaporating the obtained water phase to dryness to obtain a regenerated molybdenum oxide catalyst;
(10) the back extractant is alkali liquor such as potassium hydroxide, sodium hydroxide, ammonia water and the like, and the concentration of the back extractant is 5-60%;
(11) the phase ratio A/O is 1-5;
(12) the back extraction time is 1-60 min;
(13) the oscillation rate is 200-500 r/min;
the invention has the beneficial effects that: the technical scheme of the invention reduces the high-temperature roasting process and avoids the problem of high cost caused by high-temperature and high-pressure equipment; the process is simplified, the recovery period is shortened, and higher metal recovery rate is obtained.
The specific implementation mode is as follows:
example 1
The embodiment provides a method for recovering molybdenum from a molybdenum-containing spent catalyst, which comprises the following specific steps:
(1) putting the waste molybdenum waste liquid into a hydrochloric acid solution;
(2) heating to 60 ℃, carrying out constant-temperature oscillation treatment for 2 hours at an oscillation rate of 300 r/min, and leaching metal molybdenum into a water phase to obtain molybdenum-containing leachate;
(3) weighing the leachate into a separating funnel, adding an extracting agent, shaking according to the proportion of A/O =1, the extraction time of 10min, the extraction temperature of 45 ℃ and the concentration of the extracting agent of 20%, and layering the solution;
(4) taking out the organic phase in the separating funnel, adding a certain volume of stripping agent, oscillating according to the ratio of A/O =1, the stripping time of 15min, the stripping temperature of 30 ℃ and the concentration of the stripping agent of 5 percent, and layering the solution;
(5) taking out the aqueous solution, and placing the aqueous solution in a rotary evaporator for evaporation to dryness to obtain white molybdenum oxide particles;
example 2
The embodiment provides a method for recovering molybdenum from a molybdenum-containing spent catalyst, which comprises the following specific steps: (ii) a
(1) Putting the waste molybdenum waste liquid into a hydrochloric acid solution; (ii) a
(2) Heating to 40 ℃, carrying out constant-temperature oscillation treatment for 5 hours, wherein the oscillation rate is 200 r/min, and leaching metal molybdenum into a water phase to obtain molybdenum-containing leachate;
(3) weighing the leachate into a separating funnel, adding an extracting agent, shaking according to the proportion of A/O =2, the extraction time of 10min, the extraction temperature of 45 ℃ and the concentration of the extracting agent of 20%, and layering the solution;
(4) taking out the organic phase in the separating funnel, adding a certain volume of stripping agent, oscillating according to the ratio of A/O =2, the stripping time of 15min, the stripping temperature of 30 ℃ and the concentration of the stripping agent of 5 percent, and layering the solution;
(5) taking out the aqueous solution, placing the aqueous solution in a rotary evaporator, and evaporating the aqueous solution to dryness to obtain white molybdenum oxide particles.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and also comprise the technical scheme formed by equivalent replacement of the technical features. The present invention is not limited to the details given herein, but is within the ordinary knowledge of those skilled in the art.
Claims (5)
1. A method for recovering molybdenum from a molybdenum-containing spent catalyst is characterized by comprising the following steps:
placing a molybdenum-containing waste catalyst in an acid solution, heating to a certain temperature, wherein the temperature range is 30-80 ℃, and carrying out constant-temperature oscillation treatment to obtain a molybdenum-containing water-phase leaching solution;
step two, placing the molybdenum-containing water-phase leaching solution obtained in the step one into a separating funnel, adding a certain volume of an extracting agent, oscillating according to the ratio of O/A to O/A, the extraction time, the extraction temperature and the concentration of the extracting agent, and layering the solution;
and step three, taking out the organic phase in the separating funnel, adding a certain volume of stripping agent, oscillating according to the ratio of O/A to the stripping time to the stripping temperature to the stripping agent concentration, layering the solution, and evaporating the obtained water phase to dryness to obtain the regenerated molybdenum oxide catalyst.
2. The method for recovering molybdenum according to claim 1, wherein in the first step, the acid solution is one or more of hydrochloric acid, sulfuric acid, carbonic acid, phosphoric acid and nitric acid.
3. The method as claimed in claim 1, wherein in the step one, the temperature is in the range of 30-80 ℃, the constant temperature shaking treatment is performed for 1-5h, and the shaking rate is 200-500 r/min.
4. The method for recovering molybdenum according to claim 1, wherein in the second step, the extractant is a neutral phosphorus extractant, an acidic phosphorus extractant, or an amine extractant; the ratio A/O is 1-5; the extraction time is 1-60 min; the concentration of the extracting agent is 5% -60%; the oscillation rate is 200-500 r/min.
5. The method for recovering molybdenum according to claim 1, wherein in the third step, the stripping agent is alkali solution such as potassium hydroxide, sodium hydroxide, ammonia water, etc., and the concentration of the stripping agent is 5% -60%; the phase ratio A/O is 1-5; the back extraction time is 1-60 min; the oscillation rate is 200-500 r/min.
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| CN202010139641.0A CN111088438A (en) | 2020-03-03 | 2020-03-03 | Method for recovering molybdenum from molybdenum-containing waste catalyst |
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| CN202010139641.0A CN111088438A (en) | 2020-03-03 | 2020-03-03 | Method for recovering molybdenum from molybdenum-containing waste catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115198118A (en) * | 2022-06-29 | 2022-10-18 | 安庆市月铜钼业有限公司 | Process for producing sodium molybdate by using vanadium-molybdenum-containing calcine |
Citations (5)
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| CN1814827A (en) * | 2005-04-30 | 2006-08-09 | 李翔 | Method for separating and recovering cobalt and molybdic from waste cobalt-molybdic catalyst |
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| CN102051483A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for reclaiming metals from molybdenum-containing waste catalyst |
| KR20120125134A (en) * | 2011-05-06 | 2012-11-14 | 홍 징 메탈 코퍼레이션 | A method for recycling metals from wast molybdic catalysts |
| CN105838908A (en) * | 2016-04-08 | 2016-08-10 | 中南大学 | Efficient and clean molybdenum smelting method |
-
2020
- 2020-03-03 CN CN202010139641.0A patent/CN111088438A/en active Pending
Patent Citations (5)
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| CN1814827A (en) * | 2005-04-30 | 2006-08-09 | 李翔 | Method for separating and recovering cobalt and molybdic from waste cobalt-molybdic catalyst |
| CN102050492A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for recovering metal from molybdenum-containing spent catalyst |
| CN102051483A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for reclaiming metals from molybdenum-containing waste catalyst |
| KR20120125134A (en) * | 2011-05-06 | 2012-11-14 | 홍 징 메탈 코퍼레이션 | A method for recycling metals from wast molybdic catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115198118A (en) * | 2022-06-29 | 2022-10-18 | 安庆市月铜钼业有限公司 | Process for producing sodium molybdate by using vanadium-molybdenum-containing calcine |
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Application publication date: 20200501 |