CN103769166B - The recoverying and utilizing method of cobalt in waste and old co-mo antisulphuric transforming catalyst - Google Patents
The recoverying and utilizing method of cobalt in waste and old co-mo antisulphuric transforming catalyst Download PDFInfo
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- CN103769166B CN103769166B CN201210405492.3A CN201210405492A CN103769166B CN 103769166 B CN103769166 B CN 103769166B CN 201210405492 A CN201210405492 A CN 201210405492A CN 103769166 B CN103769166 B CN 103769166B
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Abstract
The recoverying and utilizing method of cobalt in a kind of waste and old co-mo antisulphuric transforming catalyst of the present invention, it is characterized in that after waste and old sulfur-resistant transformation catalyst pulverizing, with acid solution stripping cobalt wherein, after filtering, filtrate puts into agitator, using aluminum nitrate, magnesium nitrate and sodium carbonate as coprecipitator, carry out precipitation reaction, be separated with centrifuge and wash the forerunner's material obtained containing cobalt, for the preparation of sulfur-resistant transformation catalyst.This technique is simple, the rate of recovery of cobalt is high, reach more than 90%, both precious metal resource had been recycled, again reduce co-mo antisulphuric transforming catalyst production cost, and obtained activity of sulfur tolerant CO shift is suitable with the activity of sulfur tolerant CO shift adopting conventional cobalt raw material to obtain, and has good economic benefit and promotional value.
Description
Technical field
The invention belongs to waste and old co-mo antisulphuric transforming catalyst recovery and utilization technology field, products obtained therefrom is for the preparation of co-mo antisulphuric transforming catalyst.
Background technology
Co-Mo sulfur-tolerant shift catalyst has wider active warm area, and by force, intensity is high, long service life, can meet with the needs of heavy charge hydrogen making, synthesis gas and the town gas such as heavy oil, residual oil, coal for resistant to sulfur and antitoxin performance.Along with the development of China's Coal Chemical Industry, the use amount converting field co-mo antisulphuric transforming catalyst at coal gasification CO increases rapidly, the waste and old co-mo antisulphuric transforming catalyst that annual generation is a large amount of.
Along with becoming increasingly conspicuous of mineral resources and environmental problem, many countries pay much attention to the comprehensive utilization to secondary resource, as Japan lacks various metals resources, just note spent catalyst recovery and utilizing as far back as the 1950's, within 1970, enact a law and confirm that dead catalyst is environmental contaminants; The turnover of U.S. domestic dead catalyst in 1996 has reached 500,000,000 dollars.China's cobalt resource lacks, and need from external import, from waste and old co-mo antisulphuric transforming catalyst, recycling cobalt, not only solves environmental problem, can also produce considerable economic benefit.
The industrial recovery method to cobalt mostly to be from dead catalyst the useful elements such as synthetical recovery cobalt molybdenum aluminium at present, by the useful element extraction and isolation such as cobalt out after, through the removal impurity purification step of complexity, produce the cobalt compounds such as cobalt oxide.To the Application way of dead catalyst be by waste and old co-mo antisulphuric transforming catalyst after pulverizing the pretreatment such as high-temperature roasting, substitute carrier material as feedstock portions and active component prepares raw catelyst, but obtained catalyst activity is limited.
Document " cobalt in hydrometallurgic recovery dead catalyst and molybdenum " relates to a kind of method of cobalt and molybdenum in hydrometallurgic recovery dead catalyst.First with nitric acid or chloroazotic acid process dead catalyst, cobalt, molybdenum, part solubility Al
2o
3turn in liquid phase, filtrate is neutralized with NaOH, Al(OH)
3absorption molybdenum while precipitation, filtrate is the weakly acidic solution containing cobalt.Document NaOH precipitates, and adopts document gained cobalt production co-mo antisulphuric transforming catalyst cost higher.
Patent CN02135207 relates to a kind of preparation of low cost sulfur transformation resistant deoxidizing agent, waste and old CoMo series catalysts is crushed to 80-400 order, add that pore creating material and peptizing agent carry out mediating, shaping, 400-700 DEG C roasting temperature, carry out activation process with activating solution impregnation-calcination product and obtain deoxidier.This patent all make use of the active ingredient of old catalyst, limited activity, and not to old catalyst acid leaching extraction cobalt.
Patent US6777369 relates to a kind of effective utilization of used catalyst, and the element A that this used catalyst at least contains molybdenum, at least one is selected from phosphorus and arsenic and at least one are selected from the X element of potassium, rubidium and caesium.Used catalyst is scattered in water, add a kind of alkali metal compound and/or ammonia solution wherein, then regulate the pH value to 6.5 of gained mixture or lower to generate a kind of precipitation at least containing molybdenum and element A, and use this precipitation to provide the element forming catalyst as a kind of raw material.This patent alkali metal and/or ammonia solution extract the useful element in old catalyst, but not to old catalyst acid leaching extraction cobalt.
Summary of the invention
Technical problem to be solved by this invention is to provide the recoverying and utilizing method of cobalt in a kind of waste and old co-mo antisulphuric transforming catalyst, for the preparation of co-mo antisulphuric transforming catalyst, reduce sulfur-resistant transformation catalyst production cost, there is good economic environmental benefit and society generalization value.
The recoverying and utilizing method of cobalt in a kind of waste and old co-mo antisulphuric transforming catalyst of the present invention, it is characterized in that after waste and old sulfur-resistant transformation catalyst pulverizing, with acid solution stripping cobalt wherein, after filtering, filtrate puts into agitator, using aluminum nitrate, magnesium nitrate and sodium carbonate as coprecipitator, carry out precipitation reaction, be separated with centrifuge and wash the forerunner's material obtained containing cobalt, for the preparation of sulfur-resistant transformation catalyst.
The present invention is applicable to the co-mo antisulphuric transforming catalyst of all industrial utilizations.Obtain containing cobalt forerunner's material as cobalt source conveniently the preparation method of catalyst and other components for the preparation of sulfur-resistant transformation catalyst, according to the content of cobalt in forerunner's material, can not need when preparing sulfur-resistant transformation catalyst to add other cobalt sources again, also other cobalt source raw materials can be added, to reach the content requirement of cobalt in catalyst.
Concrete steps are as follows:
(1) first measure the cobalt content in waste and old co-mo antisulphuric transforming catalyst, and be crushed to more than 160 orders, for subsequent use.
(2) according to a certain ratio, selected suitable solid-to-liquid ratio, determines the consumption of spent catalyst powder, nitric acid and deionized water, nitric acid and deionized water is made into pickle liquor, be placed in acid corrosion-resistant container, get spent catalyst powder and put into pickle liquor, sealing.Under fluidized state, stir leaching certain hour, note keeping liquid level constant, leached rear press filtration, measure weight and the cobalt concentration of filtrate.
(3) filtrate is put into agitator, keep temperature t1, add aluminum nitrate, magnesium nitrate, stirring and dissolving obtains solution A.Under temperature t2, prepare certain density sodium carbonate liquor, while stirring sodium carbonate liquor is added in solution A with certain speed, keep solution A temperature to be t1, carry out coprecipitation reaction.When solution ph is to certain numerical value, stop adding sodium carbonate liquor, leave standstill aging certain hour, then put into centrifuge to be separated, and spend deionized water to inspection do not measure nitrate ion, dry forerunner's material that roasting obtains containing cobalt after washing, can be used for preparing sulfur-resistant transformation catalyst.
Wherein, the cobalt mass content in the waste and old co-mo antisulphuric transforming catalyst in step (1) can 1% ~ 35%.
The spent catalyst powder got in step (2) counts 100 parts with parts by weight, described nitric acid preferably adopts the nitric acid (other concentration also can) of 50% ~ 90%, be more preferably 65%, pure nitric acid is converted into during calculating, pure nitric acid represents than with a with spent catalyst powder quality, for 1:10 ~ 1:12, preferred 1:10.5 ~ 1:11.5.The solid-to-liquid ratio of spent catalyst powder and pickle liquor represents with b, is 1:2 ~ 1:3.5, preferred 1:2.3 ~ 1:3.0.
After the mass ratio that have selected pure nitric acid and spent catalyst powder and solid-to-liquid ratio, just can determine the consumption of deionized water, the quality representation of deionized water is:
M
water=(1/b-20a/13) M
powder
It is 8h ~ 20h that spent catalyst described in step (2) stirs leaching time, best 12h ~ 16h.
Temperature t1 described in step (3) is 50 ~ 80 DEG C, preferably 70 DEG C; Temperature t2 is 30 ~ 50 DEG C, preferably 40 DEG C.
In step (2), the parts by weight of filtrate are with M
srepresent, cobalt concentration represents with C, then: the parts by weight of magnesium nitrate are 12 ~ 28M
sc, preferred 20M
sc; The parts by weight of aluminum nitrate are 40 ~ 70M
sc, preferred 54.8M
sc.
The concentration of sodium carbonate liquor is 0.2 ~ 2mol/l, best 0.8 ~ 1.2mol/l.Adding speed is 200 ~ 500ml/min, best 300 ~ 400ml/min.When stopping adding sodium carbonate liquor, pH value is 7 ~ 8, is preferably 7.2 ~ 7.5.Standing ageing time is 5h ~ 25h, best 10h ~ 20h.
Bake out temperature is 100 ~ 140 DEG C, preferably 120 DEG C, and sintering temperature is 400 ~ 600 DEG C, preferably 520 DEG C, roasting time 2 ~ 5h, preferred 3h.
The rate of recovery computational methods of cobalt are:
The rate of recovery=100%*M
sc/M
powders, wherein M
sfor the quality of filtrate, C is cobalt concentration, M
powderfor spent catalyst powder quality, S is spent catalyst cobalt content.
The invention provides the Application way of cobalt in a kind of waste and old co-mo antisulphuric transforming catalyst, this technique is simple, the rate of recovery of cobalt is high, can more than 90% be reached, both precious metal resource had been recycled, again reduce co-mo antisulphuric transforming catalyst production cost, and obtained activity of sulfur tolerant CO shift is suitable with the activity of sulfur tolerant CO shift adopting conventional cobalt raw material to obtain, and has good economic benefit and promotional value.
Accompanying drawing explanation
Fig. 1 is catalyst pressurization activity rating device schematic flow sheet;
In figure: 1. raw material gas purifying device, 2. pressure reducer, 3. blender, 4. Pressure gauge, 5. lockout valve, 6. heating furnace, 7. reaction tube, 8. thermocouples tube, 9. condenser, 10. separator in pipe, 11. drain pumps, 12. wet flow indicators, 13. vaporizers, 14. tanks, 15. water measuring pumps
Detailed description of the invention
Measuring cobalt content in waste and old co-mo antisulphuric transforming catalyst is 1.00%, spent catalyst is crushed to more than 160 orders, for subsequent use.
Selected a is 1:10, b is 1:3.5, takes 329.4g deionized water and is placed in acid corrosion-resistant container, (conversion is the quality of pure nitric acid to take 10g nitric acid, lower same), slowly pour in deionized water, stir, take 100g spent catalyst powder and put into this container, add a cover, the moisture of evaporation is refluxed, be heated to boiling, stir leaching 8h, note in leaching process keeping liquid level constant; Press filtration after leaching, measures the mass M of filtrate
sfor 330.6g, the concentration C of filtrate cobalt is 0.27%.
Filtrate is put into agitator, constant temperature 50 DEG C, take aluminum nitrate 36.0g, magnesium nitrate 10.8g, put into agitator, stirring and dissolving, obtain solution A.At 45 DEG C, prepare the sodium carbonate liquor of 1.4mol/l, while stirring sodium carbonate liquor is added in solution A with the speed of 380ml/min, stop when solution ph is 7.7 adding, leave standstill aging 17h.Slurries are taken out to be put in centrifuge and is separated, and spend deionized water to without nitrate ion existence, dry at 100 DEG C, 400 DEG C of roasting 2.4h, obtain the forerunner's material containing cobalt.
Embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6, embodiment 7, embodiment 8, embodiment 9, embodiment 10, embodiment 11 technical process are identical, and its data are in table 1.
Table 1
Prepare sulfur-resistant transformation catalyst with gained of the present invention containing forerunner's material of cobalt, and prepare sulfur-resistant transformation catalyst with conventional cobalt raw material, these two kinds of catalyst activities are contrasted:
Get and mix by embodiment 1 gained forerunner material 27.00g, boehmite 29.56g, light magnesium oxide 8.12g, metatitanic acid 10.92g, put into kneader, take ammonium molybdate 8.02g to be dissolved in 30ml water and to form ammonium molybdate solution, this solution is poured in kneader and mediate 10 ~ 20min, extrusion, dry, at 520 DEG C, roasting 3h obtains catalyst D-1.
Take boehmite 80.55g, light magnesium oxide 22.11, metatitanic acid 12.25g mix, put into kneader, take ammonium molybdate 9.81g and be dissolved in 20ml water, this solution is poured in kneader and mediates 10min, taking cobalt nitrate 13.59g is dissolved in 10ml water, this solution is poured in kneader, takes 3g citric acid and be dissolved in 5ml water, this solution is poured in kneader, mediate 10 ~ 20min, extrusion, dries, and at 520 DEG C, roasting 3h obtains catalyst D-2.
Detect two kinds of catalyst activity constituent contents as table 2.
Table 2
Two kinds of catalyst normal pressure eigentransformation activity are as shown in table 3.
Table 3
Two kinds of catalyst pressurized shift activity are as shown in table 4.
Pressurization activity rating device (flow process as shown in Figure 1), under simulating industrial condition, measures original catalyst particle size CO concentration at different conditions and change thereof, the properties such as evaluation of catalyst activity and stability.Before adopting certain synthetic ammonia workshop to convert, process gas is unstripped gas, allocates appropriate H into
2s, according to the requirement of different WGR, makes the steam of high-temperature gasification and unstripped gas react in reaction tube, tail gas chromatograph after reaction.
Pressurization appreciation condition is: unstripped gas forms, CO 47 ~ 49%(V/V), CO
25 ~ 10%(V/V), H
2s>0.05%(V/V), remaining is hydrogen; Dry gas air speed: 3000h
-1; Pressure: 4.0MPa; Evaluate inlet temperature: 250 DEG C; Catalyst loading amount: 100mL.
CO interconversion rate computing formula is: X
cO=(Y
cO– Y
cO ')/[Y
cO(1+Y
cO ')] × 100%
Y
cOthe molar fraction (butt) of-Reactor inlet gas CO
Y
cO 'the molar fraction (butt) of-reactor outlet gas CO
Table 4
As can be seen from above contrast, catalyst prepared by the forerunner's material adopting this patent gained to contain cobalt is suitable with the catalyst activity adopting conventional cobalt raw material to prepare.
Claims (7)
1. the recoverying and utilizing method of cobalt in waste and old co-mo antisulphuric transforming catalyst, is characterized in that concrete steps are:
(1) first measure the cobalt content in waste and old co-mo antisulphuric transforming catalyst, and be crushed to more than 160 orders, for subsequent use;
(2) nitric acid and deionized water are made into pickle liquor, be placed in acid corrosion-resistant container, get spent catalyst powder and put into pickle liquor, sealing, leaching certain hour is stirred under fluidized state, note keeping liquid level constant, leach rear filtration, measure weight and the cobalt concentration of filtrate, in pure nitric acid, pure nitric acid represents than with a with spent catalyst powder quality, for 1:10 ~ 1:12, the solid-to-liquid ratio of spent catalyst powder and pickle liquor represents with b, is 1:2 ~ 1:3.5, and the quality representation of deionized water is: M
water=(1/b-20a/13) M
powder;
(3) filtrate is put into agitator, keep temperature t1, add aluminum nitrate, magnesium nitrate, stirring and dissolving obtains solution A, certain density sodium carbonate liquor is prepared under temperature t2, while stirring sodium carbonate liquor is added in solution A with certain speed, solution A temperature is kept to be t1, carry out coprecipitation reaction, when solution ph is 7-8, stop adding sodium carbonate liquor, leave standstill aging 5h ~ 25h, then put into centrifuge to be separated, and spend deionized water to inspection do not measure nitrate ion, forerunner's material that roasting obtains containing cobalt is dried after washing, wherein temperature t1 is 50 ~ 80 DEG C, temperature t2 is 30 ~ 50 DEG C, the parts by weight of filtrate are with M
srepresent, in filtrate, cobalt concentration represents with C, then: the parts by weight of magnesium nitrate are 12 ~ 28M
sc, the parts by weight of aluminum nitrate are 40 ~ 70M
sc, the concentration of sodium carbonate liquor is 0.2 ~ 2mol/l, and adding speed is 200 ~ 500ml/min.
2. recoverying and utilizing method according to claim 1, it is characterized in that in step 2, pure nitric acid and spent catalyst powder quality are 1:10.5 ~ 1:11.5 than a, the solid-to-liquid ratio b of spent catalyst powder and pickle liquor is 1:2.3 ~ 1:3.0.
3. recoverying and utilizing method according to claim 1, is characterized in that stirring leaching in step 2 for 8-20h.
4. recoverying and utilizing method according to claim 1, is characterized in that nitric acid described in step 2 adopts mass concentration to be the nitric acid of 50% ~ 90%.
5. recoverying and utilizing method according to claim 1, it is characterized in that the concentration of sodium carbonate liquor in step 3 is 0.8 ~ 1.2mol/l, adding speed is 300 ~ 400ml/min, and when stopping adding sodium carbonate liquor, pH value is 7.2 ~ 7.5, and standing ageing time is 10h ~ 20h.
6. recoverying and utilizing method according to claim 1, it is characterized in that bake out temperature described in step 3 is 100 ~ 140 DEG C, sintering temperature is 400 ~ 600 DEG C, roasting time 2 ~ 5h.
7. recoverying and utilizing method according to claim 1, is characterized in that cobalt mass content in described waste and old co-mo antisulphuric transforming catalyst is 1% ~ 35%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3170760A (en) * | 1961-11-09 | 1965-02-23 | Snia Viscosa | Process for recovering cobalt base catalysts |
| CN1692981A (en) * | 2005-04-13 | 2005-11-09 | 潍坊联信化学有限公司 | Cobalt-molybdenum type carbon-monoxide sulfur-resistance transformation catalyst and its prepn. method |
-
2012
- 2012-10-22 CN CN201210405492.3A patent/CN103769166B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3170760A (en) * | 1961-11-09 | 1965-02-23 | Snia Viscosa | Process for recovering cobalt base catalysts |
| CN1692981A (en) * | 2005-04-13 | 2005-11-09 | 潍坊联信化学有限公司 | Cobalt-molybdenum type carbon-monoxide sulfur-resistance transformation catalyst and its prepn. method |
Non-Patent Citations (1)
| Title |
|---|
| 潘志信.湿法回收废催化剂中的钴和钼.《烟台师范学院学报(自然科学版)》.1994,第10卷(第3期), * |
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