CN1207409C - Wet process of extracting vanadium and/or molybdenum from waste catalyst - Google Patents

Wet process of extracting vanadium and/or molybdenum from waste catalyst Download PDF

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CN1207409C
CN1207409C CNB03111623XA CN03111623A CN1207409C CN 1207409 C CN1207409 C CN 1207409C CN B03111623X A CNB03111623X A CN B03111623XA CN 03111623 A CN03111623 A CN 03111623A CN 1207409 C CN1207409 C CN 1207409C
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molybdenum
vanadium
ammonium
catalyst
vanadate
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CN1453379A (en
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齐牧
刘长河
白凤仁
崔传海
赵华
王景军
王相宝
高洪军
孙海英
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锦州铁合金(集团)有限责任公司
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/212Recovering metals from waste
    • Y02P10/234Recovering metals from waste by hydro metallurgy

Abstract

The present invention discloses technology for extracting vanadium and/or molybdenum by adopting a wet method and using spent catalysts as raw material, which contain alumina supporters of vanadium, molybdenum, nickel, etc. and are discharged from petrochemical engineering industry. After spent oil containing catalysts with natural particle sizes are sent into a kiln to remove oil at high temperature, soda is added. After uniformly mixed, the mixture is roasted in the kiln at high temperature for oxidation and sodium modification, and vanadium and molybdenum are converted into water soluble sodium vanadate and sodium molybdate. Agglomerate material is statically immersed in water in counter flows to obtain solution with finite concentration of vanadium and molybdenum, and then, calcium salt or magnesium salt is added to remove phosphorus and other impurity. Ammonium salt is added into the clear solution to obtain ammonium meta-vanadate through precipitation, and the ammonium meta-vanadate is decomposed and melted to obtain products of vanadium pentoxide. Acid is added to supernatant after the precipitation of the ammonium meta-vanadate to change the supernatant into subacidity. An organic phase is adopted to extract molybdenum, ammonia water is used for back extraction to obtain solution of ammonium molybdate, and then, acid is added to obtain products of ammonium tetramolybdate or molybdic acid through precipitation. The present invention has the advantages of high recovery rate of vanadium and molybdenum, strong treating capability and favorable technical index and benefit, and the product quality reaches the national standard.

Description

Wet method is extracted the technology of vanadium and/or molybdenum from useless catalyst

Technical field

The invention belongs to metallurgical technology field, particularly from useless catalyst, extract the technology of vanadium and molybdenum with wet method.

Background technology

The general aluminium sesquioxide that adopts is that the catalyst that carrier contains molybdenum, nickel carries out de-oiling or hydrogenation operation to crude oil in petroleum refining process.Impurity element such as a large amount of vanadium of catalyst absorption, phosphorus, iron in Crude Oil Processing and cause poison deactivation.Useless catalyst is handled, reclaimed vanadium, molybdenum element, not only can reduce environmental pollution, and can obtain certain economic benefits.

Learn that by retrieval the patent of this respect has two, wherein one is CN1305537A, " reclaiming the method for molybdenum and vanadium metal by alkaline leaching from spent catalyst ".It is under normal pressure with caustic alkali or toluene or dimethylbenzene to the catalyst de-oiling, catalyst after the oil removing leaches with caustic alkali in pressurized vessel, simultaneously aerating oxygen and (or) air, making at a low price, vanadium, molybdenum are oxidized to high valence state, obtain vanadic acid sodium and Sodium orthomolybdate leach liquor, transfer pH value, remove aluminium, arsenic and phosphorus impurities, solution after the purification is used amine organic solvent extraction vanadium and molybdenum under the PH=2.5 state, obtain to contain the mixing solutions of vanadic acid sodium and Sodium orthomolybdate with the ammonia soln back extraction, add the ammonium hydroxide precipitation ammonium meta-vanadate, transfer PH=2.5 again, the precipitation ammonium molybdate.The shortcoming of this method is big with toluene or dimethylbenzene price height, toxicity to the catalyst de-oiling, and it is healthy to be harmful to operator.The slip solid-liquid separation difficulty that leaching process produces, the required equipment investment is big, and production efficiency is low, and the vanadium molybdenum extracts simultaneously, weak effect, complex operation, supplies consumption height.

Another, with the immediate patent of the present invention be CN1321782A, " technology of wet method vanadium extraction from waste catalyst ".Not mentioned catalyst de-oiling technology in this article, be with addition of the Wingdale saltcake in the catalyst after de-oiling, adding water mill in wet ball mill becomes slip to send into roasting in the rotary kiln, 100 ± 5 ℃ of temperature, time 2--3 hour, grog leaches with soda ash and ammonium carbonate solution, and gained solution gets ammonium meta-vanadate with chloride precipitation.Its shortcoming is that leaching rate is low, the slip solid-liquid separation difficulty of leaching process, and facility investment is big, and molybdenum is present in the leached mud with the form of calcium molybdate and must reclaim, and it is little etc. to handle the catalyst ability.

Summary of the invention

The objective of the invention is to utilize existing is the equipment of raw material wet method vanadium extraction with the vanadium slag, high-level efficiency, and useless catalyst is handled on less expensive ground, reclaims two kinds of elements of vanadium and/or molybdenum simultaneously.

To achieve these goals, following technical scheme is proposed:

A kind of from useless catalyst wet method extract the technology of vanadium and/or molybdenum, it is characterized in that it follows these steps to carry out successively:

1, remove the oil content of useless catalyst, utilize the oil content of the useless catalyst of high temperature removal, processing condition are temperature 600-900 ℃, and time 2-4 hour, top condition was 750-800 ℃, 3 hours time.The rotary kiln high temperature removal oil content of the oily waste water catalyst of natural particle size can being made a gift to someone adopts the interior material following current of air-flow and kiln, to make full use of the contained heat energy of catalyst; The catalyst that perhaps will give up is sent into the de-oiling of Reaktionsofen high temperature;

2, batching, the catalyst after the de-oiling is with addition of being 1 by weight by single soda ash or by soda ash and salt: 0.1-0.4 mixes the additives of forming, and presses V 2O 5The catalyst of meter and the weight ratio of additives are 1: 1-4;

3, the material for preparing is carried out the high temperature oxidation sodium roasting, 700 ℃-1000 ℃ of temperature, the time is not less than 1 hour.Low price vanadium in the catalyst, molybdenum are oxidized to high valence state, and form water-soluble vanadic acid sodium and Sodium orthomolybdate with the sodium reaction, and the transformation efficiency of vanadium molybdenum is greater than 90%, and this operation can be carried out in rotary kiln or Reaktionsofen;

4, the grog after the roasting is sent into leaching vat, takes static water logging.In order to improve leaching yield, preferably adopt the adverse current water logging, temperature is higher, and the time is longer, and top condition is 25 ℃-65 ℃ of water soaking temperatures, and time 5-10 hour, the solid-liquid weight ratio was 1: 1-3; Contain in the certain density solution of vanadium molybdenum to leaching and to add calcium salt or magnesium salts (calcium chloride, nitrocalcite, magnesium chloride, sal epsom), remove impurity such as the aluminium that contains in the solution, phosphorus;

5,, the solution after will clarifying adds ammonium salt (ammonium sulfate, ammonium chloride) after being cooled to room temperature, is settled out ammonium meta-vanadate under weak base (PH=7-10) condition, realizes separating of vanadium and molybdenum.

6, the ammonium meta-vanadate that precipitation is obtained is made a gift to someone and is founded in the smelting furnace, makes powdery or piece of Vanadium product;

In order further to reclaim molybdenum element, can continue following operation from precipitation process (the 5th step):

7, acidifying

Promptly in precipitation process, isolate in the upper solution behind the ammonium meta-vanadate and add sulfuric acid, transfer PH=1--4;

8, extraction

With organic phase to above-mentioned solution extraction molybdenum.The composition of its organic phase is three sufferings/decyl tertiary amine (N 235), tributyl phosphate (TBP) and sulfonated kerosene, it is best that to form (volume ratio) be the sulfonated kerosene of three sufferings/decyl tertiary amine 5%-20%, tributyl phosphate 5%-25% and surplus.Flow (the m of organic phase and water 3/ h) than being 1: 1-3, temperature 25-55 ℃, mixing time 3-10 branch, settling time 40-90 branch;

9, back extraction

With ammoniacal liquor to load organic oppositing back-extraction.Organic phase and ammoniacal liquor flow (m 3/ h) than being 1: 0.1-0.3, ammonia concn are 8-15mol/l, mixing time 3-10 branch, settling time 30-80 branch; Water contains molybdenum concentration greater than 80g/l after the back extraction.

In order to make the organic phase recycling, the organic phase after the back extraction is adopted dilution heat of sulfuric acid regeneration.Vitriolic concentration is 5%-15%, and organic phase and reuse water phase flow rate are than (m 3/ h) being 1: 0.5-1.5, mixing time 3-10 branch, settling time are no less than 60 fens.

10, acid is heavy

Add acid (nitric acid, hydrochloric acid or sulfuric acid) in the ammonium molybdate solution after back extraction, transfer PH=2-4, be settled out ammonium tetramolybdate or molybdic acid product.

Can adopt the first six step of the present invention to extract vanadium, perhaps adopt the step except that the 6th step (founding) to extract molybdenum, also can adopt whole technologies to extract vanadium and molybdenum simultaneously.

The present invention has following advantage:

Make full use of original equipment, significantly reduce the facility investment of handling catalyst with vanadium slag wet method extraction Vanadium Pentoxide in FLAKES product.

Since adopt the natural particle size catalyst in rotary kiln with the de-oiling of flame following current high temperature, made full use of the heat energy that catalyst contains like this, save the degreasing process energy consumption.Particularly take the lead in finishing rotary kiln de-oiling technology, realize degreasing process mechanize, reduce personnel's manipulation strength, improved production efficiency.

Catalyst through rotary kiln oxidation sodium roasting, improves kiln internal reaction atmosphere with addition of additives after the employing de-oiling, and vanadium and molybdenum transformation efficiency are all fully reclaimed two kinds of elements of vanadium and molybdenum greater than 90%.

Owing to adopt static leaching of natural particle size grog adverse current in leaching vat, reduce detrimental impurity like this and entered solution, solid-liquid separation is easy, and production process is easy to control, and processing power is big, and manipulation strength is low, and tailings contains vanadium, the molybdenum composition is low, the element recovery rate height.

Because leach liquor adds ammonium salt precipitation ammonium meta-vanadate earlier, realizes separating of vanadium and molybdenum, it is good therefore to have inclined to one side vanadium quality, and raw material consumption is low, and processing power is big, and vanadium and molybdenum loss are little, and, help extraction and put forward the molybdenum process.

Adopt N 235+ TBP+ sulfonated kerosene extraction system is compared with other amine organic phase, has the percentage extraction height, divides phase velocity fast, and processing power is big, and organic phase load height helps improving the strip liquor molybdenum concentration, and raw material consumption is low, good product quality, easy control of process conditions.

In sum, Technology of the present invention has fully shown to have that technology is reasonable, processing power is big, mechanization degree is high in actual production process, and labour intensity is low, less investment, auxiliary material consumes low, vanadium molybdenum recovery height, good product quality, environmental pollution is little, advantages such as remarkable in economical benefits.

Description of drawings:

Accompanying drawing is a process flow sheet.

Embodiment

Embodiment 1, a kind of from useless catalyst wet method extract the technology of vanadium and/or molybdenum, it carries out according to the following steps:

1, send into rotary kiln high temperature removal oil content with the oily waste water catalyst of natural particle size, adopt material following current in air-flow and the kiln, to make full use of the contained heat energy of catalyst, controlled temperature is 600 ℃, 4 hours time;

2, the catalyst after the de-oiling is with addition of the additives of soda ash composition, and catalyst (is pressed V 2O 5Meter) be 1: 1 by weight with additives;

3, the material for preparing is once more through rotary kiln oxidation sodium roasting, 700 ℃ of temperature, and the time is 5 hours, the transformation efficiency of vanadium molybdenum is greater than 90%;

4, the grog after the roasting is sent into leaching vat, takes static adverse current water logging, 25 ℃ of water soaking temperatures, and 5 hours time, the solid-liquid weight ratio is 1: 1; Contain in the certain density solution of vanadium molybdenum and to add calcium chloride, remove impurity such as the aluminium that contains in the solution, phosphorus to leaching;

5, add ammonium sulfate after the solution after will clarifying is cooled to room temperature, under weak base (PH=7) condition, be settled out ammonium meta-vanadate, realize separating of vanadium and molybdenum.

6, ammonium meta-vanadate send smelting furnace to decompose fusing behind washing and filtering, obtains powdery or piece of Vanadium product.

In order further to reclaim molybdenum element, can continue following operation from precipitation process (the 5th step):

7, acidifying

Promptly in precipitation process, isolate in the upper solution behind the ammonium meta-vanadate and add sulfuric acid, transfer PH=1;

8, extraction

To above-mentioned solution extraction molybdenum, its organic phase composition (volume ratio) is 5% N with organic phase (extraction liquid) 235+ 25% TBP+ sulfonated kerosene (surplus), the flow (m of organic phase and water 3/ h) than being 1: 1,25 ℃ of temperature, mixing time 3 minutes, settling time 40 minutes;

9, back extraction

With ammoniacal liquor to load organic oppositing back-extraction, organic phase and ammoniacal liquor flow (m 3/ h) than being 1: 0.1, ammonia concn is 8mol/l, mixing time 3 minutes, settling time 30 minutes; Water contains molybdenum concentration greater than 80g/l after the back extraction.

10, acid is heavy

Add nitric acid in the ammonium molybdate solution after back extraction, transfer PH=2, be settled out ammonium tetramolybdate or molybdic acid product.

Embodiment 2, a kind of from useless catalyst wet method extract the technology of vanadium and/or molybdenum, it carries out according to the following steps:

1, send into rotary kiln high temperature removal oil content with the oily waste water catalyst of natural particle size, adopt material following current in air-flow and the kiln, to make full use of the contained heat energy of catalyst, controlled temperature is 750 ℃, 3 hours time;

2, the catalyst after the de-oiling is with addition of the additives of being made up of soda ash and salt (its weight ratio is 1: 0.1), and catalyst (is pressed V 2O 5Meter) weight ratio with additives is 1: 2;

3, with the material for preparing once more through rotary kiln high temperature oxidation sodium roasting, 850 ℃ of temperature, the time is 3.5 hours, the transformation efficiency of vanadium molybdenum is greater than 90%;

4, the grog after the roasting is sent into leaching vat, takes static adverse current water logging, 45 ℃ of water soaking temperatures, and 8 hours time, the solid-liquid weight ratio is 1: 2; Contain in the certain density solution of vanadium molybdenum to leaching and to add nitrocalcite, remove impurity such as the aluminium that contains in the solution, phosphorus;

5, add ammonium chloride after the solution after will clarifying is cooled to room temperature, under weak base (PH=8) condition, be settled out ammonium meta-vanadate, realize separating of vanadium and molybdenum.

6, ammonium meta-vanadate send smelting furnace to decompose fusing behind washing and filtering, obtains powdery or piece of Vanadium product.

In order further to reclaim molybdenum element, continue following operation from precipitation process (the 5th step):

7, acidifying

Promptly in precipitation process, isolate in the upper solution behind the ammonium meta-vanadate and add sulfuric acid, transfer PH=2;

8, extraction

To above-mentioned solution extraction molybdenum, its organic phase composition (volume ratio) is 20% N with organic phase (extraction liquid) 235The TBP (tributyl phosphate) of (three sufferings/decyl tertiary amine)+5%+sulfonated kerosene (surplus), the flow (m of organic phase and water 3/ h) than being 1: 2,45 ℃ of temperature, mixing time 7 minutes, settling time 60 minutes;

9, back extraction

With ammoniacal liquor to load organic oppositing back-extraction, organic phase and ammoniacal liquor flow (m 3/ h) than being 1: 0.2, ammonia concn is 10mol/l, mixing time 5 minutes, settling time 50 minutes; Water contains molybdenum concentration greater than 80g/l after the back extraction.

10, acid is heavy

Add hydrochloric acid in the ammonium molybdate solution after back extraction, transfer PH=3, be settled out ammonium tetramolybdate or molybdic acid product.

Embodiment 3, a kind of from useless catalyst wet method extract the technology of vanadium and/or molybdenum, it carries out according to the following steps:

1, sends into rotary kiln high temperature removal oil content with the oily waste water catalyst of natural particle size, adopt material following current in air-flow and the kiln, to make full use of the contained heat energy of catalyst.Controlled temperature is 800 ℃, 3 hours time;

2, the catalyst after the de-oiling is with addition of the additives of being made up of soda ash and salt (its weight ratio is 1: 0.2), and catalyst (is pressed V 2O 5Meter) weight ratio with additives is 1: 3;

3, the material for preparing is once more through rotary kiln high temperature oxidation sodium roasting, 950 ℃ of temperature, 3 hours time.Low price vanadium in the catalyst, molybdenum are oxidized to high valence state, and form water-soluble vanadic acid sodium and Sodium orthomolybdate with the sodium reaction, and the transformation efficiency of vanadium molybdenum is greater than 90%;

4, the grog after the roasting is sent into leaching vat, takes static adverse current water logging, 65 ℃ of water soaking temperatures, and 9 hours time, the solid-liquid weight ratio is 1: 3; Contain in the certain density solution of vanadium molybdenum to leaching and to add sal epsom, remove impurity such as the aluminium that contains in the solution, phosphorus;

5, add ammonium sulfate after the solution after will clarifying is cooled to room temperature, under weak base (PH=9) condition, be settled out ammonium meta-vanadate, realize separating of vanadium and molybdenum.

6, ammonium meta-vanadate send smelting furnace to decompose fusing behind washing and filtering, obtains powdery or piece of Vanadium product.

In order further to reclaim molybdenum element, continue following operation from precipitation process (the 5th step):

7, acidifying

Promptly in precipitation process, isolate in the upper solution behind the ammonium meta-vanadate and add sulfuric acid, transfer PH=3;

8, extraction

To above-mentioned solution extraction molybdenum, its organic phase composition (volume ratio) is 10% N with organic phase (extraction liquid) 235The TBP (tributyl phosphate) of (three sufferings/decyl tertiary amine)+15%+sulfonated kerosene (surplus), the flow (m of organic phase and water 3/ h) than being 1: 3,55 ℃ of temperature, mixing time 10 minutes, settling time 90 minutes;

9, back extraction

With ammoniacal liquor to load organic oppositing back-extraction, organic phase and ammoniacal liquor flow (m 3/ h) than being 1: 0.3, ammonia concn is 15mol/l, mixing time 10 minutes, settling time 80 minutes; Water contains molybdenum concentration greater than 80g/l after the back extraction.

10, acid is heavy

Add sulfuric acid in the ammonium molybdate solution after back extraction, transfer PH=4, be settled out ammonium tetramolybdate or molybdic acid product.

Embodiment 4, a kind of from useless catalyst wet method extract the technology of vanadium and/or molybdenum, it carries out according to the following steps:

1, sends into Reaktionsofen high temperature removal oil content with the oily waste water catalyst of natural particle size, adopt material following current in air-flow and the stove, to make full use of the contained heat energy of catalyst.Controlled temperature is 900 ℃, 2 hours time;

2, the catalyst after the de-oiling is with addition of the additives of being made up of soda ash and salt (its weight ratio is 1: 0.4), and catalyst (is pressed V 2O 5Meter) weight ratio with additives is 1: 4.

3, the material for preparing is once more through Reaktionsofen high temperature oxidation sodium roasting, 1000 ℃ of temperature, 1 hour time.Low price vanadium in the catalyst, molybdenum are oxidized to high valence state, and form water-soluble vanadic acid sodium and Sodium orthomolybdate with the sodium reaction, and the transformation efficiency of vanadium molybdenum is greater than 90%;

4, the grog after the roasting is sent into leaching vat, takes static adverse current water logging, 65 ℃ of water soaking temperatures, and 10 hours time, the solid-liquid weight ratio is 1: 3; Contain in the certain density solution of vanadium molybdenum to leaching and to add magnesium chloride, remove impurity such as the aluminium that contains in the solution, phosphorus;

5, add ammonium sulfate after the solution after will clarifying is cooled to room temperature, under weak base (PH=10) condition, be settled out ammonium meta-vanadate, realize separating of vanadium and molybdenum.

6, ammonium meta-vanadate send smelting furnace to decompose fusing behind washing and filtering, obtains powdery or piece of Vanadium product.

In order further to reclaim molybdenum element, continue following operation from precipitation process (the 5th step):

7, acidifying

Promptly in precipitation process, isolate in the upper solution behind the ammonium meta-vanadate and add sulfuric acid, transfer PH=4;

8, extraction

To above-mentioned solution extraction molybdenum, its organic phase composition (volume ratio) is 10% N with organic phase (extraction liquid) 235The TBP (tributyl phosphate) of (three sufferings/decyl tertiary amine)+15%+sulfonated kerosene (surplus), the flow (m of organic phase and water 3/ h) than being 1: 3,55 ℃ of temperature, mixing time 10 minutes, settling time 90 minutes;

9, back extraction

With ammoniacal liquor to load organic oppositing back-extraction, organic phase and ammoniacal liquor flow (m 3/ h) than being 1: 0.3, ammonia concn is 15mol/l, mixing time 10 minutes, settling time 80 minutes; Water contains molybdenum concentration greater than 80g/l after the back extraction.

10, acid is heavy

Add sulfuric acid in the ammonium molybdate solution after back extraction, transfer PH=4, be settled out ammonium tetramolybdate or molybdic acid product.

For above-mentioned each example, can extract vanadium by the first six step, perhaps extract molybdenum by the step except that the 6th step, also can extract vanadium and molybdenum simultaneously by whole processing steps.

Claims (3)

1, a kind of from useless catalyst wet method extract the technology of vanadium and/or molybdenum, it is characterized in that it follows these steps to carry out successively:
1), remove the oil content of useless catalyst, utilize the oil content of the useless catalyst of high temperature removal, processing condition are temperature 600-900 ℃, time 2-4 hour;
2), batching, the catalyst after the de-oiling is with addition of being 1 by weight by single soda ash or by soda ash and salt: 0.1-0.4 mixes the additives of forming, and presses V 2O 5Catalyst and the weight ratio of additives be 1: 1-4;
3), the material for preparing is carried out the high temperature oxidation sodium roasting, 700 ℃-1000 ℃ of temperature, the time is not less than 1 hour;
4), the grog after the roasting sends into leaching vat, takes static water logging, 25 ℃ of water soaking temperatures--and 65 ℃, time 5-10 hour, the solid-liquid weight ratio was 1: 1-3; Contain in the certain density solution of vanadium molybdenum to leaching and to add calcium salt or magnesium salts, remove impurity such as the aluminium that contains in the solution, phosphorus;
5), the solution after will clarifying adds ammonium salt after being cooled to room temperature, is settled out ammonium meta-vanadate under the weak base condition, realizes separating of vanadium and molybdenum;
6), ammonium meta-vanadate that precipitation is obtained sends in the smelting furnace and founds, and makes powdery or piece of Vanadium product.
2, according to claim 1 said a kind of from useless catalyst wet method extract the technology of vanadium and/or molybdenum, its feature is from the above-mentioned the 5th) also carry out the following step after the step successively:
7), acidifying
Promptly add sulfuric acid in the upper solution after precipitation process is isolated ammonium meta-vanadate, transfer PH=1-4;
8), extraction
To above-mentioned solution extraction molybdenum, its organic phase consists of three sufferings/decyl tertiary amine, tributyl phosphate and sulfonated kerosene with organic phase, and the throughput ratio of organic phase and water is 1: 1-3, temperature 25-55 ℃, mixing time 3-10 branch, settling time 40-90 branch;
9), back extraction
To load organic oppositing back-extraction, organic phase and ammoniacal liquor throughput ratio are 1 with ammoniacal liquor: 0.1-0.3, ammonia concn are 8-15mol/l, mixing time 3-10 branch, settling time 30-80 branch;
10), acid is heavy
Add acid in the ammonium molybdate solution after back extraction, transfer PH=2-4, be settled out ammonium tetramolybdate.
3, according to claim 2 said a kind of from useless catalyst wet method extract the technology of vanadium and/or molybdenum, it is characterized in that: organic phase adopts dilution heat of sulfuric acid regeneration after the back extraction.
CNB03111623XA 2003-05-08 2003-05-08 Wet process of extracting vanadium and/or molybdenum from waste catalyst CN1207409C (en)

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* Cited by examiner, † Cited by third party
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US20070167321A1 (en) * 2004-02-24 2007-07-19 Mitsubishi Raycon Co., Ltd. Method for recovering molybdenum and method for preparing catalyst
CN100371479C (en) * 2005-06-13 2008-02-27 山东铝业公司 Method for recovering vanadium from aluminium-base nickel-containing offscum
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TWI511938B (en) * 2014-07-09 2015-12-11 Plummonix Industry Co Ltd Reuse of Light - Containing Molybdenum Etching Waste
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CN106978534B (en) * 2017-03-22 2018-09-25 河北欣芮再生资源利用有限公司 A kind of method that substep dynamic adjusts acid extraction molybdenum
CN107915256A (en) * 2017-11-08 2018-04-17 大连东泰资源再生有限公司 Dead catalyst prepares high-purity molybdic acid method
CN108467939A (en) * 2018-06-11 2018-08-31 江苏北矿金属循环利用科技有限公司 A method of recycling nickel, molybdenum from useless nickel molybdenum catalyst

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CN102936039A (en) * 2012-11-15 2013-02-20 攀枝花市晟天钛业有限公司 Recovery process of honeycomb type selective catalytic reduction (SCR) waste catalyst containing tungsten, vanadium and titanium
CN102936039B (en) * 2012-11-15 2014-08-13 曾瑞 Recovery process of honeycomb type selective catalytic reduction (SCR) waste catalyst containing tungsten, vanadium and titanium

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