CN103769166A - Method for recovery and utilization of cobalt in waste and old cobalt-molybdenum sulfur-resistant shift catalysts - Google Patents
Method for recovery and utilization of cobalt in waste and old cobalt-molybdenum sulfur-resistant shift catalysts Download PDFInfo
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- CN103769166A CN103769166A CN201210405492.3A CN201210405492A CN103769166A CN 103769166 A CN103769166 A CN 103769166A CN 201210405492 A CN201210405492 A CN 201210405492A CN 103769166 A CN103769166 A CN 103769166A
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Abstract
The invention relates to a method for recovery and utilization of cobalt in waste and old cobalt-molybdenum sulfur-resistant shift catalysts. The method is characterized by comprising the following steps of crushing the waste and old cobalt-molybdenum sulfur-resistant shift catalyst, dissolving the crushed catalyst by an acid solution so that cobalt in the catalyst is dissolved, carrying out filtration, putting the filtrate into a stirrer, carrying out a precipitation reaction process by aluminum nitrate, magnesium nitrate and sodium carbonate as coprecipitators, carrying out separation by a centrifuge, and carrying out washing to obtain a cobalt-containing predecessor for preparation of a sulfur-resistant shift catalyst. The method has simple processes and a high cobalt recovery rate more than 90%, realizes recovery and utilization of a precious metal resource, and reduces a sulfur-resistant shift catalyst production cost. The sulfur-resistant shift catalyst prepared by the method has catalyst activity the same as catalyst activity of a sulfur-resistant shift catalyst prepared from a conventional cobalt raw material and has good economic benefits and a popularization 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 resistance to sulphur and antitoxin performance are strong, and intensity is high, long service life, can meet the needs with heavy charge hydrogen making, synthesis gas and town gas such as heavy oil, residual oil, coals.Along with the development of China's Coal Chemical Industry, increase rapidly in the use amount of coal gasification CO conversion field co-mo antisulphuric transforming catalyst, produce every year a large amount of waste and old co-mo antisulphuric transforming catalysts.
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 the recycling of dead catalyst 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, need to be from external import, and recycling cobalt from waste and old co-mo antisulphuric transforming catalyst, not only solves environmental problem, can also produce considerable economic benefit.
The industrial recovery method to cobalt mostly is the comprehensive useful elements such as cobalt molybdenum aluminium that reclaim from dead catalyst at present, after the useful element extractions such as cobalt are separated, through complicated removal impurity purification step, produces the cobalt compounds such as cobalt oxide.To dead catalyst utilize method be by waste and old co-mo antisulphuric transforming catalyst through pulverizing after the pretreatment such as high-temperature roasting, substitute carrier material and active component is prepared raw catelyst as raw material part, but the catalyst activity making 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 process dead catalyst, cobalt, molybdenum, part solubility Al with nitric acid or chloroazotic acid
2o
3turn in liquid phase, filtrate is neutralized to Al(OH with NaOH)
3when precipitation, adsorb molybdenum, filtrate is the weakly acidic solution containing cobalt.The document precipitates with NaOH, 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 are mediated, moulding, 400-700 ℃ roasting temperature, carry out activation processing with activating solution impregnation-calcination product and make deoxidier.This patent has all been utilized the active ingredient of old catalyst, active limited, and not to old catalyst acid leaching extraction cobalt.
Patent US6777369 relates to a kind of effective utilization of used catalyst, and this used catalyst at least contains molybdenum, at least one is selected from the A element of phosphorus and arsenic and at least one and is selected from the X element of potassium, rubidium and caesium.Used catalyst is scattered in water, add wherein a kind of alkali metal compound and/or ammonia solution, then regulate the pH value to 6.5 of gained mixture or lower to generate a kind of precipitation that at least contains molybdenum and A element, and use this precipitation that the element that forms catalyst is provided as a kind of raw material.This patent is extracted the useful element in old catalyst with alkali metal and/or ammonia solution, 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 and be worth.
The recoverying and utilizing method of cobalt in a kind of waste and old co-mo antisulphuric transforming catalyst of the present invention, after it is characterized in that waste and old sulfur-resistant transformation catalyst to pulverize, with acid solution stripping cobalt wherein, after filtering, filtrate is put into agitator, using aluminum nitrate, magnesium nitrate and sodium carbonate as coprecipitator, carry out precipitation reaction, separate and wash the forerunner's material obtaining containing cobalt with centrifuge, 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 forerunner's material of cobalt as cobalt source according to the preparation method of conventional catalyst and other components for the preparation of sulfur-resistant transformation catalyst, according to the content of cobalt in forerunner's material, in the time preparing sulfur-resistant transformation catalyst, can not need to add again other cobalt sources, also can add other cobalt source raw materials, 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 more than being crushed to 160 orders, for subsequent use.
(2) according to a certain ratio, select suitable solid-to-liquid ratio, determine the consumption of spent catalyst powder, nitric acid and deionized water, 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.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 t 1, add aluminum nitrate, magnesium nitrate, stirring and dissolving obtains solution A.Prepare certain density sodium carbonate liquor 2 times in temperature t, while stirring sodium carbonate liquor is added in solution A with certain speed, keeping solution A temperature is t1, carries out coprecipitation reaction.When pH is during to certain numerical value, stop adding sodium carbonate liquor, leave standstill aging certain hour, then putting into centrifuge separates, and wash to examining and do not measure nitrate ion by deionized water, after washing, dry roasting and obtain the forerunner's material containing cobalt, 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 be 1% ~ 35%.
The spent catalyst powder of getting in step (2) is counted 100 parts with parts by weight, described nitric acid preferably adopts 50%～90% nitric acid (other concentration also can), more preferably 65%, when calculating, be converted into pure nitric acid, pure nitric acid represents with a with spent catalyst powder quality ratio, for 1:10～1:12, preferably 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, preferably 1:2.3～1:3.0.
Selected after the mass ratio and solid-to-liquid ratio of pure nitric acid and spent catalyst powder, 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, preferably 12h ~ 16h.
In step (2), the parts by weight of filtrate are with M
srepresent, cobalt concentration represents with C: the parts by weight of magnesium nitrate are 12～28M
sc, preferably 20M
sc; The parts by weight of aluminum nitrate are 40～70M
sc, preferably 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.While stopping adding sodium carbonate liquor, pH value is 7 ~ 8, is preferably 7.2 ~ 7.5.Standing ageing time is 5h ~ 25h, preferably 10h ~ 20h.
Bake out temperature is 100～140 ℃, and preferably 120 ℃, sintering temperature is 400～600 ℃, preferably 520 ℃, and roasting time 2～5h, preferably 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 method for utilizing 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 reach more than 90%, both recycled precious metal resource, reduced again co-mo antisulphuric transforming catalyst production cost, and the activity of sulfur tolerant CO shift making is suitable with the activity of sulfur tolerant CO shift that adopts conventional cobalt raw material to make, 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 in pipe, 9. condenser, 10. separator, 11. drain pumps, 12. wet flow indicators, 13. vaporizers, 14. tanks, 15. water measuring pumps
The specific embodiment
Measuring cobalt content in waste and old co-mo antisulphuric transforming catalyst is 1.00%, more than spent catalyst is crushed to 160 orders, for subsequent use.
Selected a is 1:10, and 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, in leaching process, note keeping liquid level constant; Press filtration after leaching, the mass M of mensuration filtrate
sfor 330.6g, the concentration C of filtrate cobalt is 0.27%.
Filtrate is put into agitator, and 50 ℃ of constant temperature, take aluminum nitrate 36.0g, magnesium nitrate 10.8g, put into agitator, and stirring and dissolving, obtains solution A.At 45 ℃, 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, in the time that pH is 7.7, stop adding, leave standstill aging 17h.Slurries are taken out and are put in centrifuge and separate, and with deionized water washing to existing without nitrate ion, dry at 100 ℃, 400 ℃ of roasting 2.4h, obtain the forerunner's material containing cobalt.
Table 1
The forerunner's material that contains cobalt with gained of the present invention is prepared sulfur-resistant transformation catalyst, and prepares sulfur-resistant transformation catalyst with conventional cobalt raw material, and these two kinds of catalyst activities are contrasted:
Get by embodiment 1 gained forerunner material 27.00g, boehmite 29.56g, light magnesium oxide 8.12g, metatitanic acid 10.92g and mix, put into kneader, taking ammonium molybdate 8.02g is dissolved in 30ml water and forms ammonium molybdate solution, this solution is poured into and in kneader, mediated 10～20min, extrusion, dry, roasting 3h obtains catalyst D-1 at 520 ℃.
Taking boehmite 80.55g, light magnesium oxide 22.11, metatitanic acid 12.25g mixes, put into kneader, take ammonium molybdate 9.81g and be dissolved in 20ml water, this solution is poured into and in kneader, mediated 10min, taking cobalt nitrate 13.59g is dissolved in 10ml water, this solution is poured in kneader, taken 3g citric acid and be dissolved in 5ml water, this solution is poured in kneader, mediate 10～20min, extrusion, dries, and roasting 3h obtains catalyst D-2 at 520 ℃.
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), for simulating under industrial condition, is measured CO concentration and the variation thereof of original catalyst particle size under different condition, the properties such as evaluation of catalyst activity and stability.Adopting the front process gas of certain synthetic ammonia workshop conversion is unstripped gas, allocates appropriate H into
2s, according to the requirement of different WGRs, makes the steam of high-temperature gasification react in reaction tube with unstripped gas, tail gas chromatograph after reaction.
Pressurization appreciation condition is: unstripped gas composition, 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 ℃; 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
Can be found out by above contrast, the catalyst that adopts this patent gained to prepare containing forerunner's material of cobalt is suitable with the catalyst activity that adopts conventional cobalt raw material to prepare.
Claims (8)
1. the recoverying and utilizing method of cobalt in a waste and old co-mo antisulphuric transforming catalyst, after it is characterized in that waste and old sulfur-resistant transformation catalyst to pulverize, with acid solution stripping cobalt wherein, after filtering, filtrate is put into agitator, using aluminum nitrate, magnesium nitrate and sodium carbonate as coprecipitator, carry out precipitation reaction, separate and wash the forerunner's material obtaining containing cobalt with centrifuge, for the preparation of sulfur-resistant transformation catalyst.
2. recoverying and utilizing method according to claim 1, is characterized in that concrete steps are:
(1) first measure the cobalt content in waste and old co-mo antisulphuric transforming catalyst, and more than being crushed to 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, under fluidized state, stir leaching certain hour, note keeping liquid level constant, leach rear filtration, measure weight and the cobalt concentration of filtrate, in pure nitric acid, pure nitric acid represents with a with spent catalyst powder quality ratio, 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 t 1, add aluminum nitrate, magnesium nitrate, stirring and dissolving obtains solution A, prepare certain density sodium carbonate liquor 2 times in temperature t, while stirring sodium carbonate liquor is added in solution A with certain speed, keeping solution A temperature is t1, carry out coprecipitation reaction, in the time that pH is 7-8, stop adding sodium carbonate liquor, leave standstill aging 5h ~ 25h, then putting into centrifuge separates, and wash to examining and do not measure nitrate ion by deionized water, after washing, dry roasting and obtain the forerunner's material containing cobalt, wherein temperature t 1 is 50～80 ℃, temperature t 2 is 30～50 ℃, the parts by weight of filtrate are with M
srepresent, in filtrate, cobalt concentration represents with C: 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, adding speed is 200 ~ 500ml/min.
3. recoverying and utilizing method according to claim 2, is characterized in that in step 2, pure nitric acid is 1:10.5～1:11.5 with spent catalyst powder quality than a, and the solid-to-liquid ratio b of spent catalyst powder and pickle liquor is 1:2.3～1:3.0.
4. recoverying and utilizing method according to claim 2, is characterized in that stirring leaching for 8-20h in step 2.
5. recoverying and utilizing method according to claim 2, is characterized in that nitric acid described in step 2 adopts the nitric acid that mass concentration is 50%～90%.
6. recoverying and utilizing method according to claim 2, the concentration that it is characterized in that sodium carbonate liquor in step 3 is 0.8 ~ 1.2mol/l, adding speed is 300 ~ 400ml/min, and while stopping adding sodium carbonate liquor, pH value is 7.2 ~ 7.5, and standing ageing time is 10h ~ 20h.
7. recoverying and utilizing method according to claim 2, is characterized in that described in step 3 that bake out temperature is 100～140 ℃, and sintering temperature is 400～600 ℃, roasting time 2～5h.
8. recoverying and utilizing method according to claim 2, 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 |
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2012
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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）》 * |
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