CN103849786A - Method for recovering molybdenum in waste catalyst - Google Patents
Method for recovering molybdenum in waste catalyst Download PDFInfo
- Publication number
- CN103849786A CN103849786A CN201210499542.9A CN201210499542A CN103849786A CN 103849786 A CN103849786 A CN 103849786A CN 201210499542 A CN201210499542 A CN 201210499542A CN 103849786 A CN103849786 A CN 103849786A
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- destructive distillation
- raw material
- ink powder
- condition
- 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.)
- Pending
Links
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
Landscapes
- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recovering molybdenum in waste catalyst. The method comprising the following steps of integrating waste ink powder and a waste catalyst by a binder, carrying out granulation, carrying out destructive distillation to obtain destructive distillation oil for waste-catalyst precious-metal regeneration pretreatment, wherein in destructive distillation, the destructive distillation oil can be used as a regeneration fuel, the produced destructive distillation gas can be used as a fuel directly used in a destructive distillation furnace and the produced destructive distillation dregs can be used as a waste-catalyst precious-metal regeneration raw material, putting the pretreated molybdenum-containing waste material into a kettle-type treatment device, and carrying out leaching on the molybdenum-containing waste material in the presence of eco-friendly biodegradable N,N'-1,2-ethanediylbis-1-aspartic acid as a chelating agent by extraction system pH adjustment to obtain a molybdenum component in the molybdenum-containing waste material.
Description
Technical field
The invention belongs to resource and reclaim comprehensive utilization field, be specifically related to a kind of method that reclaims molybdenum in discarded catalyzer.
Background technology
Molybdenum is the huge common metal of consumption in the industrial and agricultural productions such as a kind of iron and steel, chemistry, special material, in the last few years, the comprehensive utilization of molybdenum in China industry pay attention to day by day first resource and the research and development of open pit mining, to particularly paying close attention to from the research and development of the valuable metals such as recycling molybdenum of molybdenum-contained waste catalyst.But compared with abroad, China utilizes the level of molybdenum secondary resource still to have larger gap.
But when increasing along with demand, molybdenum can expected reserves continuous decrease.Meanwhile, contain the quantity of molybdenum waste also in continuous growth, therefore these wastes are reclaimed and can alleviate the pressure that molybdenum reserves decline, also can reduce the huge Environmental costs that waste brings.It is a kind of common recovery method that chemistry drop is got, and the normal sequestrant using is ethylenediamine tetraacetic acid (EDTA) (EDTA) and sodium salt class sequestrant thereof, and this sequestrant is strong to the sequestering power of metal ion, just has good drop to get efficiency.But this sequestrant is difficult to be degraded in physical environment, therefore use for a long time, in a large number this type of sequestrant to bring Secondary Organic to pollute.
N, N'-ethylenediamine disuccinic acid be a kind of in physical environment degradable sequestrant, be applied at present the drop heavy metal ion in earth that fetches earth.
Summary of the invention
The present invention proposes a kind of method that reclaims discarded molybdenum, and technical scheme of the present invention, for using will give up ink powder, spent catalyst of tackiness agent to be integrated together granulation, is then carried out destructive distillation, obtains empyreumatic oil, provides pre-treatment for spent catalyst carries out precious metal regeneration.In retort process, produce empyreumatic oil and can be used as regenerated fuel use, generation carbonization gas can be used as fuel and acts directly in gas retort, produces the raw material of destructive distillation slag as spent catalyst recover precious metals.Utilize eco-friendly N, N'-ethylenediamine disuccinic acid sequestrant, in autoclave treater, gets containing the molybdenum composition in the discarded catalyzer of molybdenum by chemical drop.
The present invention realizes by following technique means, and its concrete steps comprise:
1. take raw material: be (5 ~ 10) according to the mass ratio of spent catalyst, useless ink powder, tackiness agent and water: (0.1 ~ 3): (0.5 ~ 3): (0.5 ~ 1.5) takes respectively raw material;
2. granulation: after give up ink powder and spent catalyst are mixed in the ratio of step 1, slowly stir 10 ~ 30 minutes, then add tackiness agent and water, after continuing to puddle evenly, by raw material granulation, carry out subsequently destructive distillation;
3. destructive distillation product drops in autoclave treater, utilizes eco-friendly N, and N'-ethylenediamine disuccinic acid sequestrant, by the pH value modulation of extraction system, is got the molybdenum composition in the useless cobalt-molybdenum catalyst that petroleum industry hydrogenating desulfurization used by chemical drop.
In technical scheme mentioned above, need the adding of water in right amount, its method adding water is, water repeatedly adds on a small quantity, until with hand hold hold raw material can moulding, but bond without raw material on hand.
In technical scheme mentioned above, described destructive distillation condition is 400 ~ 500 DEG C of pyrolysis temperatures, and 2 ~ 3 hours time, more excellent destructive distillation condition is: 450 DEG C, and time 2 h.
In technical scheme mentioned above, described useless ink powder is waste duplicator, and the granularity of useless ink powder is 5 ~ 10 microns, useless ink powder organic content 30 ~ 60%.
In the method for the discarded molybdenum catalyzer of recovery provided by the present invention, the sequestrant that uses is: according to the mass ratio of 7 ~ 10:1, in autoclave treater, add environmental friendliness, biodegradable N, N'-ethylenediamine disuccinic acid.
In the method for the discarded molybdenum catalyzer of recovery provided by the present invention, discarded catalyzer is the fischer-tropsch building-up process catalyzer of manufacturing synthol, the carbon deposit composition that contains 10-20% massfraction, the molybdenum of 20-30% massfraction, 50-55% quality aluminum oxide, 5-10% massfraction magnesium oxide or ferric oxide.
In the method for the discarded molybdenum catalyzer of recovery provided by the present invention, operational condition feature is: with 25-80 ° of C, 200-600 rotating speed/minute condition under carry out the reclaimer operation of molybdenum.
In the method for the discarded molybdenum catalyzer of recovery provided by the present invention, N in autoclave treater, the pH value condition of N'-ethylenediamine disuccinic acid sequestrant extraction molybdenum is pH7-8.
In the method for the discarded molybdenum catalyzer of recovery provided by the present invention, molybdenum-N, the pH condition that N'-ethylenediamine disuccinic acid chelating system discharges molybdenum ion is between pH3-5.
In the method for the discarded molybdenum catalyzer of recovery provided by the present invention, discarded catalyzer and N in autoclave treater, the mass ratio of N'-ethylenediamine disuccinic acid is between 1 ~ 10:1.
In the method for the discarded molybdenum catalyzer of recovery provided by the present invention, under pH3-5 condition, discharge molybdenum-N, in the process of N'-ethylenediamine disuccinic acid chelating system molybdenum ion, complete N, recovery and the circulation of N'-ethylenediamine disuccinic acid sequestrant simultaneously.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1
1. take raw material: 150kg spent catalyst (carbon distribution 10%, molybdenum 25%, 60% aluminum oxide, 5% magnesium oxide), 19kg useless ink powder, 14kg clay and 15kg water.
2. granulation: after give up ink powder and spent catalyst are mixed in the ratio of step 1, slowly stir 20 minutes, then add clay and water, after continuing to puddle evenly, enter granulator granulation, the diameter of pellet is between 5 ~ 7cm.Staff enters in stove the raw material of making is put well, ensures furnace bottom all to cover, and to prevent that local dry burning from causing body of heater to damage, destructive distillation is carried out in upper cover sealing subsequently; Start heat temperature raising, from room temperature rises to 450 DEG C, be incubated 2.5 hours, stop heating, treat that temperature is down to room temperature from 450 DEG C and comes out of the stove, forbid water directly to be lowered the temperature.
3. detecting raw material oil length after destructive distillation through laboratory is 3.46%, makes raw material after destructive distillation;
4. raw material after 50kg destructive distillation is added in 100L autoclave treater, under pH7 condition, drop into 5kgN, N'-ethylenediamine disuccinic acid, stirs with 300 revs/min of speed, and be warming up to 60 ° of C, process after 1.0 hours, filter, after filtrate is cooling, add dilute sulphuric acid to make pH value be adjusted to 4, after static 0.5 hour, will separate out N, N'-ethylenediamine disuccinic acid reclaims.
Embodiment 2
1. take raw material: 150kg spent catalyst (carbon distribution 10%, molybdenum 28%, 57% aluminum oxide, 5% magnesium oxide), 19kg useless ink powder, 14kg clay and 15kg water.
2. granulation: after give up ink powder and spent catalyst are mixed in the ratio of step 1, slowly stir 20 minutes, then add clay and water, after continuing to puddle evenly, enter granulator granulation, the diameter of pellet is between 5 ~ 7cm.Staff enters in stove the raw material of making is put well, ensures furnace bottom all to cover, and to prevent that local dry burning from causing body of heater to damage, destructive distillation is carried out in upper cover sealing subsequently; Start heat temperature raising, from room temperature rises to 450 DEG C, be incubated 2.5 hours, stop heating, treat that temperature is down to room temperature from 450 DEG C and comes out of the stove, forbid water directly to be lowered the temperature.
3. detecting raw material oil length after destructive distillation through laboratory is 3.46%, makes raw material after destructive distillation;
4. raw material after 45kg destructive distillation is added in 100L autoclave treater, under pH7 condition, drop into 5kgN, N'-ethylenediamine disuccinic acid, stirs with 300 revs/min of speed, and be warming up to 70 ° of C, process after 1.0 hours, filter, after filtrate is cooling, add dilute sulphuric acid to make pH value be adjusted to 4, after static 0.5 hour, will separate out N, N'-ethylenediamine disuccinic acid reclaims.
Embodiment 3
1. take raw material: 150kg spent catalyst (carbon distribution 10%, molybdenum 29%, 46% aluminum oxide, 5% magnesium oxide), 19kg useless ink powder, 14kg clay and 15kg water.
2. granulation: after give up ink powder and spent catalyst are mixed in the ratio of step 1, slowly stir 20 minutes, then add clay and water, after continuing to puddle evenly, enter granulator granulation, the diameter of pellet is between 5 ~ 7cm.Staff enters in stove the raw material of making is put well, ensures furnace bottom all to cover, and to prevent that local dry burning from causing body of heater to damage, destructive distillation is carried out in upper cover sealing subsequently; Start heat temperature raising, from room temperature rises to 450 DEG C, be incubated 2.5 hours, stop heating, treat that temperature is down to room temperature from 450 DEG C and comes out of the stove, forbid water directly to be lowered the temperature.
3. detecting raw material oil length after destructive distillation through laboratory is 3.46%, makes raw material after destructive distillation;
4. raw material after 45kg destructive distillation is added in 100L autoclave treater, under pH7 condition, drop into 5kgN, N'-ethylenediamine disuccinic acid, stirs with 300 revs/min of speed, and be warming up to 65 ° of C, process after 1.0 hours, filter, after filtrate is cooling, add dilute sulphuric acid to make pH value be adjusted to 4, after static 0.5 hour, will separate out N, N'-ethylenediamine disuccinic acid reclaims.
Embodiment 4
1. take raw material: 150kg spent catalyst (carbon distribution 10%, molybdenum 15%, 70% aluminum oxide, 5% magnesium oxide), 19kg useless ink powder, 14kg clay and 15kg water.
2. granulation: after give up ink powder and spent catalyst are mixed in the ratio of step 1, slowly stir 20 minutes, then add clay and water, after continuing to puddle evenly, enter granulator granulation, the diameter of pellet is between 5 ~ 7cm.Staff enters in stove the raw material of making is put well, ensures furnace bottom all to cover, and to prevent that local dry burning from causing body of heater to damage, destructive distillation is carried out in upper cover sealing subsequently; Start heat temperature raising, from room temperature rises to 450 DEG C, be incubated 2.5 hours, stop heating, treat that temperature is down to room temperature from 450 DEG C and comes out of the stove, forbid water directly to be lowered the temperature.
3. detecting raw material oil length after destructive distillation through laboratory is 3.46%, makes raw material after destructive distillation;
4. raw material after 35kg destructive distillation is added in 100L autoclave treater, under pH7 condition, drop into 5kgN, N'-ethylenediamine disuccinic acid, stirs with 500 revs/min of speed, and be warming up to 80 ° of C, process after 1.0 hours, filter, after filtrate is cooling, add dilute sulphuric acid to make pH value be adjusted to 4, after static 0.5 hour, will separate out N, N'-ethylenediamine disuccinic acid reclaims.
Embodiment 5
The discarded catalyzer using is: carbon distribution 10%, molybdenum 19%, 66% aluminum oxide, 5% magnesium oxide;
Utilize described in step 1 ~ 2 of embodiment 1 method to prepare raw material after destructive distillation;
Raw material after 50kg destructive distillation is added in 100L autoclave treater, under pH7 condition, drop into 5kgN, N'-ethylenediamine disuccinic acid, stirs with 500 revs/min of speed, and be warming up to 80 ° of C, process after 1.0 hours, filter, after filtrate is cooling, add dilute sulphuric acid to make pH value be adjusted to 4, after static 0.5 hour, will separate out N, N'-ethylenediamine disuccinic acid reclaims.
Embodiment 6
The discarded catalyzer using is: carbon distribution 10%, molybdenum 25%, 60% aluminum oxide, 5% magnesium oxide;
Utilize described in step 1 ~ 2 of embodiment 1 method to prepare raw material after destructive distillation;
Raw material after 50kg destructive distillation is added in 100L autoclave treater, under pH7 condition, drop into 5kgN, N'-ethylenediamine disuccinic acid, stirs with 300 revs/min of speed, and be warming up to 60 ° of C, process after 1.0 hours, filter, after filtrate is cooling, add dilute sulphuric acid to make pH value be adjusted to 4, after static 0.5 hour, will separate out N, N'-ethylenediamine disuccinic acid reclaims.
Embodiment 7
Molybdenum-N in above embodiment, N'-ethylenediamine disuccinic acid chelating system discharges the concentration of molybdenum ion and analyzes by icp ms after acidifying.
The discarded molybdenum catalyst drop of table 1 based on ethylenediamine disuccinic acid got efficiency
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Stir (rotating speed/minute) | 300 | 300 | 400 | 500 | 500 | 300 |
| Molybdenum entirety extraction efficiency | 55 | 73 | 77 | 88 | 85 | 73 |
Claims (5)
1. a method that reclaims discarded molybdenum catalyzer, is characterized in that: comprise following operation steps:
1. take raw material: be (5 ~ 10) according to the mass ratio of spent catalyst, useless ink powder, tackiness agent and water: (0.1 ~ 3): (0.5 ~ 3): (0.5 ~ 1.5) takes respectively raw material;
2. granulation: after give up ink powder and spent catalyst are mixed in the ratio of step 1, slowly stir 10 ~ 30 minutes, then add tackiness agent and water, after continuing to puddle evenly, by raw material granulation, carry out subsequently destructive distillation; Destructive distillation condition is 400 ~ 500 DEG C, 2 ~ 3 hours;
3. add N to destructive distillation product according to the mass ratio of 7 ~ 10:1, N'-ethylenediamine disuccinic acid; By the pH value modulation of extraction system, with 25-80 ° of C, 200-600 rotating speed/minute condition under carry out the recovery of molybdenum; The pH value condition of extraction is pH7-8.
2. a kind of method that reclaims discarded molybdenum catalyzer according to claim 1, is characterized in that: the granularity of useless ink powder is 5 ~ 10 microns, useless ink powder organic content 30 ~ 60%.
3. a kind of method that reclaims discarded molybdenum catalyzer according to claim 1, it is characterized in that: the carbon deposit composition that spent catalyst contains 10-20% massfraction, the molybdenum of 20-30% massfraction, 50-55% quality aluminum oxide, 5-10% massfraction magnesium oxide or ferric oxide.
4. a kind of method that reclaims discarded molybdenum catalyzer according to claim 1, is characterized in that: the pH condition of extraction is between pH3-5.
5. a kind of method that reclaims discarded molybdenum catalyzer according to claim 1, is characterized in that: destructive distillation condition is 450 DEG C, time 2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210499542.9A CN103849786A (en) | 2012-11-28 | 2012-11-28 | Method for recovering molybdenum in waste catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210499542.9A CN103849786A (en) | 2012-11-28 | 2012-11-28 | Method for recovering molybdenum in waste catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103849786A true CN103849786A (en) | 2014-06-11 |
Family
ID=50857907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210499542.9A Pending CN103849786A (en) | 2012-11-28 | 2012-11-28 | Method for recovering molybdenum in waste catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103849786A (en) |
-
2012
- 2012-11-28 CN CN201210499542.9A patent/CN103849786A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105038822B (en) | The cleaning method and device of a kind of sludge | |
| CN102120575A (en) | Process for preparing activated carbon from chemical sludge | |
| CN103526031A (en) | Recovery method for SCR waste flue gas denitration catalyst | |
| CN102267695A (en) | Method for preparing super activated charcoal from oily sludge | |
| CN106669847B (en) | A kind of preparation method of alumina support | |
| CN103103360A (en) | Method for recovering copper, tungsten and molybdenum by use of APT (ammonium paratungstate) waste slag | |
| CN103157479B (en) | Regeneration method of vanadium-containing waste catalytic cracking balance agent | |
| Marafi et al. | Refinery waste: the spent hydroprocessing catalyst and its recycling options | |
| CN101575257B (en) | Catalytic hydrogenation method by taking toluene as hydrogen storing agent | |
| CN106480316B (en) | A method of recycling precious metal palladium from aniline tar | |
| CN103451422B (en) | Method for preparing iron oxide for iron making by using steel acid-washing wastewater sludge | |
| CN110302756A (en) | A method of heavy metal ion is removed using industrial residue modification biological charcoal | |
| CN102965512B (en) | A kind of method of cobalt in recyclable waste catalyst | |
| CN101985693B (en) | Preparation method and application of metal chelate compound of cigarette end extract | |
| CN103849786A (en) | Method for recovering molybdenum in waste catalyst | |
| CN102965516B (en) | A kind of method of manganese in recyclable slag | |
| CN103849770A (en) | Method for recovering palladium in waste catalyst | |
| CN103882226B (en) | Economic, clean and simple method for leaching cobalt from high-valence cobalt oxide | |
| KR20070096139A (en) | Method for recovering valued metal from spent catalyst | |
| CN102965513A (en) | Method capable of recovering nickel out of spent catalysts | |
| CN103045872B (en) | New technology for recovering silicon-supported palladium | |
| CN102978404A (en) | Method capable of recovering chromium in waste catalyst | |
| CN106497607A (en) | A kind of method for inactivating the quick decarburization of oil dead catalyst microwave and preparing water-gas | |
| CN104480312B (en) | A kind of method that auto-exhaust catalyst noble metal reclaims | |
| CN102978375B (en) | Pre-treatment method before regeneration of precious metal by waste catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140611 |