CA1097927A - Nickel recovery - Google Patents
Nickel recoveryInfo
- Publication number
- CA1097927A CA1097927A CA297,855A CA297855A CA1097927A CA 1097927 A CA1097927 A CA 1097927A CA 297855 A CA297855 A CA 297855A CA 1097927 A CA1097927 A CA 1097927A
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- Prior art keywords
- nickel
- solution
- ammonia
- ammine
- oxygen
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0446—Leaching processes with an ammoniacal liquor or with a hydroxide of an alkali or alkaline-earth metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
TITLE OF THE INVENTION
NICKEL RECOVERY
ABSTRACT OF THE DISCLOSURE
A nickel-containing residue such as coal ash remains after a carbonaceous material is gasified in the presence of a nickel catalyst. Nickel is recovered from the residue by adding an aqueous ammonia solution or aqueous solution containing ammonia and an ammonium salt to the residue to form a nickel ammine solution. Insoluble contents are separated from the nickel ammine solution, to which ammonia is further added to precipitate the nickel ammine.
NICKEL RECOVERY
ABSTRACT OF THE DISCLOSURE
A nickel-containing residue such as coal ash remains after a carbonaceous material is gasified in the presence of a nickel catalyst. Nickel is recovered from the residue by adding an aqueous ammonia solution or aqueous solution containing ammonia and an ammonium salt to the residue to form a nickel ammine solution. Insoluble contents are separated from the nickel ammine solution, to which ammonia is further added to precipitate the nickel ammine.
Description
1~9'~9;~7 BACKGROUND OF THE INV~NTION
.
This invention relates to a method oE recoVerincJ
nickel from a nickel-containing residue such as coal ash, and more particularly/ to a method of recovering nickel selectively from a residue ob-tained after a carbonaceous material ~ such as coal is gasified in the presence of a nickel-containing catalyst.
It is well known that carbonaceous materials like coal are gasified, for example, to produce coal gas. According 10 to conventional methods, carbonaceous materials or those pretreated with heat and/or various solvents are gasified at elevated temperatures in the absence of a catalyst using a gasifying agent such as hydrogen, steam, carbon dioxide and the like.
The inventors previously proposed an improvement in such gasification, which is disclosed in Japanese Patent Application No. 50-36497. Carbonaceous materials are gasified by pretreating them with liquid ammonia at room temperature to 150C to extract the matters soluble in ammonia and treating the extraction residue with a gasifying agent at a temperature of 400 to 1,000C at atmospheric pressure or under pressure in the presence or absence of a catalyst.
Nickel-containing catalysts are useful in the above gasification. Nickel catalysts should be present in an amount which is effective for catalytically promoting the gasification of carbonaceous materia]s. Vpon gasification, the nickel used is discharged partly with the gas produced t"~ "
.
and partly with residues such as coke and ash. Loss of nickel is detrimental because nickel is so expensive. In order to carry out such catalytic gasification methods com-mercially advantageously and successfully~ it is important to recover expensive nickel efficiently in a more simple manner and to regenerate it for reuse. ~owever, no method has yet succeeded in the e~ficient separation or recovery of nickel because nickel is contained in minor amounts and relatively large amounts of impurities coexist.
The inventors have made intensive and extensive investi-gations on the recovery of nickel; and have found that nickel can be selectively extracted or separated in the form of an aqueous nickel ammine solution from a nickel-containing residue obtained after gasification and that, although the solubility of nickel ammine in water is considerably high at about room temperature, it rapidly decreases to a sub-stantially insoluble level as the concentration of liberated ammonia increases. The concentrarion of liberated ammonia can be increased simply by adding ammonia to the solution.
~0 The term "liberated ammonia" used herein designates an excess amount of ammonia which exceeds 6 molar equivalents per mole of nickel in the residue.
SUMMARY OF THE INVENTION
Therefore, an object of this invention is to provide a method of recovering nickel selectively from a nickel-contalning residue obtained after the gasification of carbonaceous materials.
z~
The above and other objects are accomplished by pro-viding a method of recovering nickel from a nickel-containiny residue such as coal ash remaining after a carbonaceous mate-rial is gasified in the presence of a nickel-containin~ cata-lyst, which comprises the steps of :
(a) adding an aqueous solution containing ammonia and an am-monium salt selected from the group consisting of ammonium chloride, ammonium carbonate and ammonium nitrate to said ni-ckel containing residue in the presence of an oxygen-containing gas to dissolve and extract the nickel in the solution in the form of a nickel ammine complex salt, (b) separating the mixture into an aqueous nickel ammine solu-tion and insoluble contents, (c) further adding ammonia to the separated aqueous nickel ammine solution to increase the concentration of free ammonia to ~rom 15 to 30~ and cooling to below 2~C thereby to preci-pitate -the nickel ammine, (d) separatlng the nickel ammine precipitate, and (e) heating the separa-ted nickel ammine to decompose it into nickel oxide or a nickel salt and ammonia.
The separated nickel ammine may be converted into nickel oxide or nickel salts or into any desired form ready for reuse in a circulating manner, for example, metallic nickel.
Such conversion is generally performed by heating.
The term "nickel ammine" designates a nickel ammine complex salt in this specification.
The present me-thod is directed to the recovery of nickel from a nickel-containing residue which remains after a carbonaceous material is gasified, and essentially comprises the steps of:
-- '1 7~;~7 (a) dissol~ing and extracting nickel from the nickel-containing residue into the form of a nickel ammine complex salt;
(b) separating the aqueous nickel ammlne solution from insoluble contents, (c~ adding ammonia to the resulting nickel ammine solution to precipitate the nickel ammine; and (d) separating the nickel ammine precipitate.
In a preferred embodiment of the invention, it is contemplated to embrace the following additional steps of:
(e) heating the separated nickel ammine to decompose it into nickel oxide or a nickel salt and ammonia; and (f~ circulating the saturated nickel ammine solution result-ing from the separation step (d) to step (a) and the ammonia resulting from the decomposition step (e) to step (c) for the reuse thereof.
Other objects and advantages of the invention will be appàrent from the description given below with reference to examples and drawings.
The carbonaceous materials used herein include brown coal, lignite, bituminous coal, tar pitch, coke and their analogues. After they are gasified with,a gasifying agent in the presence of a nickel-containing catalyst, there remains a residue which contains the catalyst as well as ash. The nickel in the residue, which may vary depending upon the type of the gasifying agent, temperature and other reaction conditions, is generally present in the form of metallic nickel or nickel sulfide because it is subject to a reducing atmosphere.
7~ 7 The nickel which is me-tallic in -the residue may he dissolved in ~he form o~ a nick~l ~ne by ~dding an aqueous ammonia solution or an aqueous solu-~ion containiny ammonia and an ammonium salt to the nickel-containiny residue in ~` 5 the presence of oxygen and/or air. Illus-trative of -the dis-solution process are the following reaction equations. When ~ ammonium chloride is used as the ammonium salt, nickel is ; dissolved in the form of nickel ammine chloride. Similarly, when ammonium carbonate, sulfate, and nitrate are used, nicke] is dissolved in the form of nickel ammine carbonate, sulfate, and nitrate, respectively.
H3 2 2 Ni(NH3)6Cl2 + ~2 Ni + ( 4)2 3 4NH3 + 2 2 = Ni(NH3)6C03 -~ H O
Ni -~ (NH4)2S04 + 4NH3 -~ 2 2 = Ni(NH3)6so4 + H20 Ni -~ 2NH4N03 + 4NH3 + 2 2 = Ni(N~3)~( 3 2 2 The ammonium salts added dissociate into anions which can form ` nickel ammine salts as complex salts. Therefore, other ammonium salts which dissociate into anions capable of forming complex salts may also be employed to gain a similar effect.
It is only required to recover nickel in the form of a nickel ammine complex salt according to the invention.
The ammonium salt may not be added when nlckel is present as nickel sulfide in the resldue. Nlckel sul1de reacts with ammonia as follows~
NiS + 6NH3 ~ 22 = Ni(NH3)6So4 n this case, an aqueous ammonia solution is added to a nickel-containing residu~.
In order that the invention may be more readily under-stood, reference will now be made to the accompanying draw-ings, in which:
Fig. 1 is a graph showing solubility curves of nickel ammine chloride at different temperatures, the concentration (% by weight) of liberated ammonia in the saturated nickel ammine chloride solution being plotted as abscissa and the solubility (g/lOO g-saturated solution) as ordinate;
~ig. 2 is a graph similar to Fig. 1, showing solubility curves of nickel ammine carbona-te;
Fig. 3 is a graph similar to Fig. 1, showing solubility curves of nickel ammine sulfate;
Fig. 4 is a graph similar to Fig. 1, showing solubility curves of nickel ammine nitrate;
Fig~ 5 is a block diagram showing an emhodiment of the invention in which nickel is recovered as nickel chloride; and FigO 6 is a block diagram showing another embodiment of the invention in which nickel is recovered as nickel carbonate.
As clearly shown in Figs. 1 to 4, the nickel ammine complex salts are highly soluble at room temperature.
When liberated ammonia has a concentration of 0 to 3 ~ by weight, both nickel ammine chloride and nitrate have solubilities of about 20 to 25 g per 100 g of the saturated solution and both nickel ~ arbonate and sulfate have ~9~7 `':
higher solubilities of about 40 to 50 g per lO0 g of the -~ saturated solution at a temperature of 55C.
Although the nickel ammine complex salts are highly soluble at comparatively lower concentrations of liberated ammonia, the solubility rapidly decreases and eventually reaches near zero as the concentration of libera-ted ammonia increases.
The present process utilizes this difference in solu-bility~ The nickel ammine can effectively be precipitated by increasing the concentration of liberated ammonia from a low level at which the solubility is high to a high level at which the solubility is low. In addition, the tempera-ture may be lowered to precipita-te nickel ammine more effectively.
The type of the ammonium salt to be added, the concen-tration of liberated ammonia, the temperature of the solu-tion, the partial pressure of oxygen and other conditions may be adjusted to any desired values, depending upon the con-tent and chemical state of nickel in the residue.
In step (a), nickel is dissolved and extracted in the form of a nickel ammine complex salt from the residue.
To this end, the concentration of liberated ammonia may generally be 0 to 18.0 % by weight, preferably 3.5 to 15 by weight to maintain the solubility of a nickel ammine high enough. Although lower concentrations oE libera-ted ammonia are advantageous in view of solubility as described above in conneckion with Figs. l - 4, it takes a compara tively long time for nickel to react with an ammonium salt at a concentration o~ liberatec~ ammonia helow 3.5 ~ by 10979;Z7 weight. Therefore, the above range is preferred from the point of view of commercial dissolu-tion and ex-trac~ion effici-ency. Further, a larger partial pressure of oxygen is advanta~eous as understood from the reaction equations set forth above. The partial pressure of oxygen may generally be 1 to S0 atm, preferably 2 to 10 atm, in consideration of design and maintenance of equipment including a reactor.
The temperature of the solution may generally be 10 to 150C, preferably 30 to 120C.
According to -the invention, after a nickel-containing residue is mixed with an aqueous ammonia solution to dissolve and extract the nickel in the solution, the result-ing aqueous nickel ammine solution and the insoluble contents consisting of ash and other impurities are separated from each other, for example, by filtration~ Thereafter the nickel ammine is precipitated from its solution by adding ammonia to the separated aqueous solution to increase the concentration of liberated ammonia. At the same time, the temperature of the separated aqueous solution may pre-ferably be lowered to facilitate precipitation.
When crystals are precipitated from the aqueous nickel arnmine solution in step (c), it is preferred to ma~ntain the temperature of the solution to below 25C, especially below 15C and the concentration of liberated amrnonia to 15 to 30 % by weight, as understood from E'igs. 1 to 4.
1~979Z7 , DESCRIPTION OF PREFERRED EMBODIMENTS
In order that those skilled in the art may better unders-talld how to practice the present invention, -the following examples are given by way of illustration and are not intended to be limiting in any manner.
Example 1 Into an autoclave were admitted 88.8 g of a residue containing 16.9 % by weigh-t of nickel which was obtained after coal was gasified in the presence of a nickel chloride catalyst to produce coal gas mainly consisting of hydrogen, and 200 ml of an ammoniacal, aqueous ammonium carbonate solution containing 1.5 moles/liter of ammonium carbonate and 8.0 moles/liter of liberated ammonia and having a specific gravity of l.01v The mixture was allowed to react for 60 minutes at a temperature of 50C, an oxygen partial pressure of 4 atm. and an agitation rate of 2,000 rap.m.
It was found that 98 ~ of nickel was dissolved in the form of nickel ammine carbonate.
The insoluble contents were then removed by filtration.
With cooling in an ice bath~ ammonia gas was bubbled into the filtrate until the concentration of liberated ammonia reached 35 % by weight. There was precipitated 75.8 g of crystals. Analysis was carried out to determine the composition. lt was found that 97.0 % of nickel was re-covered. The results are shown helow.
~10- ~
. ~
Mi (wt~) NH3 twt%) Found 18.8 32.4 Calculated for Ni(NH3)6-5H2O 18.9 32.8 Example 2 Into an autoclave were admitted 87.2 g of a residue containing 17.2 % by weight of nickel which was obtained after coal was gasified in the presence of a nickel chloride catalyst to produce coal gas mainly consisting of steam, and 200 ml of an ammoniacal, aqueous ammonium sulfate solution which contained 1.5 moles/liter of ammonium sulfate and 8.0 moles/liter of liberated ammonia and had a specific gravity of 1.04. The mixture was allowed to react or 75 mlnutes at a temperature of 50C, an oxygen partial pressure of 4 atm. and an agitation rate of 2,000 r.p.m. It was found that 96.5 % of nickel was dissolved in the form of nickel ammine sulfate.
The insoluble contents were then removed by filtration.
With cooling in an ice bath, ammonia gas was bubbled into the filtrate until the concentration of liberated ammonia reached 35 % by weight. There was precipitated 66.4 g of crystals. Analysis was carried out to determine the com-position. It was found that 98.5 % of nickel was recovered.
The results are shown below~
Ni (wt%) NH3 (wt%) Found 21.5 38.2 Calculated for NitNH3)6SO~2H2O 22-1 7~7 .
; Reference is again made to the drawings.
Fig. 5 shows a preferred embodiment, in which the starting material is a nickel-containing residue which is obtained after coal ls gasified in -the presence of a nickel chloride catalyst. In a reactor 10 for gasifying coal are supplied a carbonaceous matexial (in this example, coal), a nickel chloride catalyst, and a gasifying agent through lines 1, 2, and 3, respectively. The gasification is carried out in the reactor maintained under predetermined conditions. A useful gas mixture con-taining hydroyen, methane and the like is generated, while a nickel-containing residue including ash remains. The useful gas mixture is taken out from the reactor 10 to a washing unit 11 by way of a line 5. Into the washing unit 11 is also introduced a washing liquid, for example, water or an aqueous, diluted hydrochloric acid solution through a line 7. The washing liquid serves to remove hydrochloric acid from the gas, which is then taken out through a line 6. The removed hydrochloric acid is fed to a unit 12 for forming ammonium chloride through a line 8. Ammonia fed through a line 9a is added to hydrochloric acid in the unit 12 to form ammonium chloride, which, in turn, is fed through a line 9b to an extractor 20 for dissolving and extracting nickel in the form of nickel ammine. The washing uni-t 11 and the ammonium chloride-forming unik 12 may be combined to perform both the removal of hydrochloric acid and the formation of ammonium chloride.
- ~2 -10979~Z7 The catalyst may sometimes be activated before it is used in gasification. In this case, ammonia or hydrogen chloride gas is discharged together with an activa-ting gas.
By feeding the gas mixture to the washing unit 11, amrnonium chloride may be recovered. Alternatively, an activation apparatus may separately be installed in addition to the gasifying reactor 10 in order to carry out the ac-tivation of the catalyst.
On the other hand, the residue in the gasifying reactor 10 is introduced into the extractor 20 through a line 4. Into the extractor 20 are also introduced ammonia, ox~gen and/or air, and water through lines 21, 22, and 23, respectively~ In addition, the a~ueous ammonium chloride solution is fed to the extractor 20 through the line 9b, as described above. With temperature, oxygen partial pressure and other conditions set to predetermined levels, nickel in the residue is dissolved and extracted in the form of nickel ammine chloride. The mixture may prefera~ly be stirred to facilitate dissolution. This dissolution and extraction process may be carried out in any desired manner, for example, by a batchwise or continuous, parallel current or cQunter current operation. The operation ma~ be chosen according to the amount of the residue to be treated and the nickel content.
After the dissolution and extraction process is com-pleted, the treated mixtur~ is trans~erred to a separator 30 through a line 24. The insoluble contents including ash are separated therein and discharged through a ~ine 32, ~ 79~7 `:
while the aqueous nickel ammine chloride solution is ~ed to a precipitator 40 through a line 31. Ammonia fed through a branched line 66 is added to the solution to :increase the concentration o~ liberated ammonia in the solu-tion, precipitating nickel ammine chloride. The tempera-ture of the solution may optionally be redueed in the preeipitator 40.
The precipitate is transferred together with the solution to a separator 50 through a line ~1. In the separator 50, the precipitate is separated from the solution, which is then fed to a first recovery apparatus 51 through ~a line 54. Ammonia gas is liberated from the solution due to temperature rise or pressure reduction and then combined with another ammonia gas flow ~rom a second recovery apparatus 61 to be described hereinafter. The combined ammonia gas is circulated through lines 55 and 65 ~or reuse.
The remaining solution in the first recovery apparatus 51, which contains a small amount of nickel ammine chloride, is returned to the precipitator 40 or e~tractor 20 through the line 56 or 57 for reuse. If the amount o~ impurities aeeumulated in the solution becomes larger due to repeated use, such a contaminated solution is discharged through a line 53 and a fresh solution is supplied.
The separated precipitate of nic]cel ammine chlorlde is introduced into a heater 60 for decomposing the complex sal~ through a line 52, in which nickel ammine chloride is decomposed into nickel chloride and ammonia by heating.
The separated nie]cel ehloride is, if necessary, circulated ~r~
~ 792~
to the gasifying reactor 10 through a line ~3 ~or reuse as the catalyst, while the ammonia is ~ed to the second re-covery apparatus 61 through a line 62 and dried therein.
If desired, the dried ammonia gas is circulated -to the ammonium chloride-forming unit 12 and the precipitator ~0 through the lines 65, 66 and 9a for reuse. The waste water resulting from the above drying procedure may optionally be discharged through a line 64.
The above described system may be designed so that when any of reagents, for example, ammonium chloride or ammonia deviates from the range ensuring a suitable relative proportion, such a aeviation may immediately be compensated.
The embodiment employing nickel chloride as the cata-lyst is illustratively described above, whereas the inven-tion can be applied in a similar manner to the casesemploying nlckel salts such as nickel sulfate, nitrate and carbonate, metallic nickel and nickel oxide as the catalystO
It is to be noted that when metallic nickel or nickel oxide is used as the catalyst, the nickel salt resulting from decomposition by heating in the heater 60 may further be treated by conventional methods be~ore it is circulated.
Another pre~erred embodiment is shown in FigO 6, in which nickel in the resiclue is recovered as nickel carbonate.
Referring to Fig. 6, the residue is introduced in an ex-tractor 20 ~or dissolving nickel through an inlet line 75.To this extractor 20 is also fed water through a line 7~.
Oxygen or air, carbon dioxide, and a~lmonia fed through lines 71/ 72, and 73, respectively, are blown into the water.
With stirring, nickel:in the resi~.ue is dissolved and extracted in the form of nickel ammine carbonate. The treated mixture is fed to a separator 30 through a line 76.
The insoluble contents including ash are separated therein and discharged through à line 77, whilc the separated solution of nickel ammine carbonate is ed to a precipitator ~0 through a line 78. Ammonia fed through a branched line 87 is added to the solution to increase the concentration of liberated ammonia in the solution, precipitating nickel ammine carbonate.
The precipitate is transferred together with the solu-tion to a separator 50 through a line 79. In the separator 50, the precipitate is separated from the solution, which is then fed to a recovery apparatus 82 through a line 80.
The solution is subject to elevated temperature or reduced pressure to recover ammonia and the remaining waste liquid is discharged ~rom a line 83. The above recovered ammonia is combined with another ammonia flow from a heater 60 to be described hereinafter. The combined ammonia gas is circulated to the extractor 20 and the precipitator ~0 for reuse.
The separated precipitate of nickel ammine carbonate is introduced into the heater 60 through a line 81, in which nickel ammine carbonate i5 decomposed into nickel carbonate or nickel oxide and ammonia hy heatiny. The ~enerated ammonia is ~ed to the extractor 20 and the pre-cipitator 30 through lines 85, 87, and 73 for reuse. The resulting nickel. carbonate or nickel oxlde is taken out -7~
; through a line 86 and then may either be circulatea to the gasifying reactor or be s-tored in a suitable reservoir (not shown).
; As described above, nickel can be effectively recovered from a residue resulting from the gasification of carbo~
naceous materials using nickel-containing catalysts.
In the present invention, modification and variation may be made depending upon the type of a nickel compound used as the catalyst. For example, when nickel ammine is used as the catalyst, the nickel ammine crvstals separated after precipitation may be readily circulated for reuse without further processing.
Moreover, if nickel in the residue takes a form other than metallic nickel or nickel sulfide, it should be con-verted in-to metallic nickel or nickel sulfide before the invention is applied thereto.
Since nickel is fixed and recovered in the form of a nickel ammine salt according to the invention, useful reagents, for example, ammonia can easily be circulated for reuse. As a result, nickel is economically recovered and envirollmental pollution is minimized.
.
This invention relates to a method oE recoVerincJ
nickel from a nickel-containing residue such as coal ash, and more particularly/ to a method of recovering nickel selectively from a residue ob-tained after a carbonaceous material ~ such as coal is gasified in the presence of a nickel-containing catalyst.
It is well known that carbonaceous materials like coal are gasified, for example, to produce coal gas. According 10 to conventional methods, carbonaceous materials or those pretreated with heat and/or various solvents are gasified at elevated temperatures in the absence of a catalyst using a gasifying agent such as hydrogen, steam, carbon dioxide and the like.
The inventors previously proposed an improvement in such gasification, which is disclosed in Japanese Patent Application No. 50-36497. Carbonaceous materials are gasified by pretreating them with liquid ammonia at room temperature to 150C to extract the matters soluble in ammonia and treating the extraction residue with a gasifying agent at a temperature of 400 to 1,000C at atmospheric pressure or under pressure in the presence or absence of a catalyst.
Nickel-containing catalysts are useful in the above gasification. Nickel catalysts should be present in an amount which is effective for catalytically promoting the gasification of carbonaceous materia]s. Vpon gasification, the nickel used is discharged partly with the gas produced t"~ "
.
and partly with residues such as coke and ash. Loss of nickel is detrimental because nickel is so expensive. In order to carry out such catalytic gasification methods com-mercially advantageously and successfully~ it is important to recover expensive nickel efficiently in a more simple manner and to regenerate it for reuse. ~owever, no method has yet succeeded in the e~ficient separation or recovery of nickel because nickel is contained in minor amounts and relatively large amounts of impurities coexist.
The inventors have made intensive and extensive investi-gations on the recovery of nickel; and have found that nickel can be selectively extracted or separated in the form of an aqueous nickel ammine solution from a nickel-containing residue obtained after gasification and that, although the solubility of nickel ammine in water is considerably high at about room temperature, it rapidly decreases to a sub-stantially insoluble level as the concentration of liberated ammonia increases. The concentrarion of liberated ammonia can be increased simply by adding ammonia to the solution.
~0 The term "liberated ammonia" used herein designates an excess amount of ammonia which exceeds 6 molar equivalents per mole of nickel in the residue.
SUMMARY OF THE INVENTION
Therefore, an object of this invention is to provide a method of recovering nickel selectively from a nickel-contalning residue obtained after the gasification of carbonaceous materials.
z~
The above and other objects are accomplished by pro-viding a method of recovering nickel from a nickel-containiny residue such as coal ash remaining after a carbonaceous mate-rial is gasified in the presence of a nickel-containin~ cata-lyst, which comprises the steps of :
(a) adding an aqueous solution containing ammonia and an am-monium salt selected from the group consisting of ammonium chloride, ammonium carbonate and ammonium nitrate to said ni-ckel containing residue in the presence of an oxygen-containing gas to dissolve and extract the nickel in the solution in the form of a nickel ammine complex salt, (b) separating the mixture into an aqueous nickel ammine solu-tion and insoluble contents, (c) further adding ammonia to the separated aqueous nickel ammine solution to increase the concentration of free ammonia to ~rom 15 to 30~ and cooling to below 2~C thereby to preci-pitate -the nickel ammine, (d) separatlng the nickel ammine precipitate, and (e) heating the separa-ted nickel ammine to decompose it into nickel oxide or a nickel salt and ammonia.
The separated nickel ammine may be converted into nickel oxide or nickel salts or into any desired form ready for reuse in a circulating manner, for example, metallic nickel.
Such conversion is generally performed by heating.
The term "nickel ammine" designates a nickel ammine complex salt in this specification.
The present me-thod is directed to the recovery of nickel from a nickel-containing residue which remains after a carbonaceous material is gasified, and essentially comprises the steps of:
-- '1 7~;~7 (a) dissol~ing and extracting nickel from the nickel-containing residue into the form of a nickel ammine complex salt;
(b) separating the aqueous nickel ammlne solution from insoluble contents, (c~ adding ammonia to the resulting nickel ammine solution to precipitate the nickel ammine; and (d) separating the nickel ammine precipitate.
In a preferred embodiment of the invention, it is contemplated to embrace the following additional steps of:
(e) heating the separated nickel ammine to decompose it into nickel oxide or a nickel salt and ammonia; and (f~ circulating the saturated nickel ammine solution result-ing from the separation step (d) to step (a) and the ammonia resulting from the decomposition step (e) to step (c) for the reuse thereof.
Other objects and advantages of the invention will be appàrent from the description given below with reference to examples and drawings.
The carbonaceous materials used herein include brown coal, lignite, bituminous coal, tar pitch, coke and their analogues. After they are gasified with,a gasifying agent in the presence of a nickel-containing catalyst, there remains a residue which contains the catalyst as well as ash. The nickel in the residue, which may vary depending upon the type of the gasifying agent, temperature and other reaction conditions, is generally present in the form of metallic nickel or nickel sulfide because it is subject to a reducing atmosphere.
7~ 7 The nickel which is me-tallic in -the residue may he dissolved in ~he form o~ a nick~l ~ne by ~dding an aqueous ammonia solution or an aqueous solu-~ion containiny ammonia and an ammonium salt to the nickel-containiny residue in ~` 5 the presence of oxygen and/or air. Illus-trative of -the dis-solution process are the following reaction equations. When ~ ammonium chloride is used as the ammonium salt, nickel is ; dissolved in the form of nickel ammine chloride. Similarly, when ammonium carbonate, sulfate, and nitrate are used, nicke] is dissolved in the form of nickel ammine carbonate, sulfate, and nitrate, respectively.
H3 2 2 Ni(NH3)6Cl2 + ~2 Ni + ( 4)2 3 4NH3 + 2 2 = Ni(NH3)6C03 -~ H O
Ni -~ (NH4)2S04 + 4NH3 -~ 2 2 = Ni(NH3)6so4 + H20 Ni -~ 2NH4N03 + 4NH3 + 2 2 = Ni(N~3)~( 3 2 2 The ammonium salts added dissociate into anions which can form ` nickel ammine salts as complex salts. Therefore, other ammonium salts which dissociate into anions capable of forming complex salts may also be employed to gain a similar effect.
It is only required to recover nickel in the form of a nickel ammine complex salt according to the invention.
The ammonium salt may not be added when nlckel is present as nickel sulfide in the resldue. Nlckel sul1de reacts with ammonia as follows~
NiS + 6NH3 ~ 22 = Ni(NH3)6So4 n this case, an aqueous ammonia solution is added to a nickel-containing residu~.
In order that the invention may be more readily under-stood, reference will now be made to the accompanying draw-ings, in which:
Fig. 1 is a graph showing solubility curves of nickel ammine chloride at different temperatures, the concentration (% by weight) of liberated ammonia in the saturated nickel ammine chloride solution being plotted as abscissa and the solubility (g/lOO g-saturated solution) as ordinate;
~ig. 2 is a graph similar to Fig. 1, showing solubility curves of nickel ammine carbona-te;
Fig. 3 is a graph similar to Fig. 1, showing solubility curves of nickel ammine sulfate;
Fig. 4 is a graph similar to Fig. 1, showing solubility curves of nickel ammine nitrate;
Fig~ 5 is a block diagram showing an emhodiment of the invention in which nickel is recovered as nickel chloride; and FigO 6 is a block diagram showing another embodiment of the invention in which nickel is recovered as nickel carbonate.
As clearly shown in Figs. 1 to 4, the nickel ammine complex salts are highly soluble at room temperature.
When liberated ammonia has a concentration of 0 to 3 ~ by weight, both nickel ammine chloride and nitrate have solubilities of about 20 to 25 g per 100 g of the saturated solution and both nickel ~ arbonate and sulfate have ~9~7 `':
higher solubilities of about 40 to 50 g per lO0 g of the -~ saturated solution at a temperature of 55C.
Although the nickel ammine complex salts are highly soluble at comparatively lower concentrations of liberated ammonia, the solubility rapidly decreases and eventually reaches near zero as the concentration of libera-ted ammonia increases.
The present process utilizes this difference in solu-bility~ The nickel ammine can effectively be precipitated by increasing the concentration of liberated ammonia from a low level at which the solubility is high to a high level at which the solubility is low. In addition, the tempera-ture may be lowered to precipita-te nickel ammine more effectively.
The type of the ammonium salt to be added, the concen-tration of liberated ammonia, the temperature of the solu-tion, the partial pressure of oxygen and other conditions may be adjusted to any desired values, depending upon the con-tent and chemical state of nickel in the residue.
In step (a), nickel is dissolved and extracted in the form of a nickel ammine complex salt from the residue.
To this end, the concentration of liberated ammonia may generally be 0 to 18.0 % by weight, preferably 3.5 to 15 by weight to maintain the solubility of a nickel ammine high enough. Although lower concentrations oE libera-ted ammonia are advantageous in view of solubility as described above in conneckion with Figs. l - 4, it takes a compara tively long time for nickel to react with an ammonium salt at a concentration o~ liberatec~ ammonia helow 3.5 ~ by 10979;Z7 weight. Therefore, the above range is preferred from the point of view of commercial dissolu-tion and ex-trac~ion effici-ency. Further, a larger partial pressure of oxygen is advanta~eous as understood from the reaction equations set forth above. The partial pressure of oxygen may generally be 1 to S0 atm, preferably 2 to 10 atm, in consideration of design and maintenance of equipment including a reactor.
The temperature of the solution may generally be 10 to 150C, preferably 30 to 120C.
According to -the invention, after a nickel-containing residue is mixed with an aqueous ammonia solution to dissolve and extract the nickel in the solution, the result-ing aqueous nickel ammine solution and the insoluble contents consisting of ash and other impurities are separated from each other, for example, by filtration~ Thereafter the nickel ammine is precipitated from its solution by adding ammonia to the separated aqueous solution to increase the concentration of liberated ammonia. At the same time, the temperature of the separated aqueous solution may pre-ferably be lowered to facilitate precipitation.
When crystals are precipitated from the aqueous nickel arnmine solution in step (c), it is preferred to ma~ntain the temperature of the solution to below 25C, especially below 15C and the concentration of liberated amrnonia to 15 to 30 % by weight, as understood from E'igs. 1 to 4.
1~979Z7 , DESCRIPTION OF PREFERRED EMBODIMENTS
In order that those skilled in the art may better unders-talld how to practice the present invention, -the following examples are given by way of illustration and are not intended to be limiting in any manner.
Example 1 Into an autoclave were admitted 88.8 g of a residue containing 16.9 % by weigh-t of nickel which was obtained after coal was gasified in the presence of a nickel chloride catalyst to produce coal gas mainly consisting of hydrogen, and 200 ml of an ammoniacal, aqueous ammonium carbonate solution containing 1.5 moles/liter of ammonium carbonate and 8.0 moles/liter of liberated ammonia and having a specific gravity of l.01v The mixture was allowed to react for 60 minutes at a temperature of 50C, an oxygen partial pressure of 4 atm. and an agitation rate of 2,000 rap.m.
It was found that 98 ~ of nickel was dissolved in the form of nickel ammine carbonate.
The insoluble contents were then removed by filtration.
With cooling in an ice bath~ ammonia gas was bubbled into the filtrate until the concentration of liberated ammonia reached 35 % by weight. There was precipitated 75.8 g of crystals. Analysis was carried out to determine the composition. lt was found that 97.0 % of nickel was re-covered. The results are shown helow.
~10- ~
. ~
Mi (wt~) NH3 twt%) Found 18.8 32.4 Calculated for Ni(NH3)6-5H2O 18.9 32.8 Example 2 Into an autoclave were admitted 87.2 g of a residue containing 17.2 % by weight of nickel which was obtained after coal was gasified in the presence of a nickel chloride catalyst to produce coal gas mainly consisting of steam, and 200 ml of an ammoniacal, aqueous ammonium sulfate solution which contained 1.5 moles/liter of ammonium sulfate and 8.0 moles/liter of liberated ammonia and had a specific gravity of 1.04. The mixture was allowed to react or 75 mlnutes at a temperature of 50C, an oxygen partial pressure of 4 atm. and an agitation rate of 2,000 r.p.m. It was found that 96.5 % of nickel was dissolved in the form of nickel ammine sulfate.
The insoluble contents were then removed by filtration.
With cooling in an ice bath, ammonia gas was bubbled into the filtrate until the concentration of liberated ammonia reached 35 % by weight. There was precipitated 66.4 g of crystals. Analysis was carried out to determine the com-position. It was found that 98.5 % of nickel was recovered.
The results are shown below~
Ni (wt%) NH3 (wt%) Found 21.5 38.2 Calculated for NitNH3)6SO~2H2O 22-1 7~7 .
; Reference is again made to the drawings.
Fig. 5 shows a preferred embodiment, in which the starting material is a nickel-containing residue which is obtained after coal ls gasified in -the presence of a nickel chloride catalyst. In a reactor 10 for gasifying coal are supplied a carbonaceous matexial (in this example, coal), a nickel chloride catalyst, and a gasifying agent through lines 1, 2, and 3, respectively. The gasification is carried out in the reactor maintained under predetermined conditions. A useful gas mixture con-taining hydroyen, methane and the like is generated, while a nickel-containing residue including ash remains. The useful gas mixture is taken out from the reactor 10 to a washing unit 11 by way of a line 5. Into the washing unit 11 is also introduced a washing liquid, for example, water or an aqueous, diluted hydrochloric acid solution through a line 7. The washing liquid serves to remove hydrochloric acid from the gas, which is then taken out through a line 6. The removed hydrochloric acid is fed to a unit 12 for forming ammonium chloride through a line 8. Ammonia fed through a line 9a is added to hydrochloric acid in the unit 12 to form ammonium chloride, which, in turn, is fed through a line 9b to an extractor 20 for dissolving and extracting nickel in the form of nickel ammine. The washing uni-t 11 and the ammonium chloride-forming unik 12 may be combined to perform both the removal of hydrochloric acid and the formation of ammonium chloride.
- ~2 -10979~Z7 The catalyst may sometimes be activated before it is used in gasification. In this case, ammonia or hydrogen chloride gas is discharged together with an activa-ting gas.
By feeding the gas mixture to the washing unit 11, amrnonium chloride may be recovered. Alternatively, an activation apparatus may separately be installed in addition to the gasifying reactor 10 in order to carry out the ac-tivation of the catalyst.
On the other hand, the residue in the gasifying reactor 10 is introduced into the extractor 20 through a line 4. Into the extractor 20 are also introduced ammonia, ox~gen and/or air, and water through lines 21, 22, and 23, respectively~ In addition, the a~ueous ammonium chloride solution is fed to the extractor 20 through the line 9b, as described above. With temperature, oxygen partial pressure and other conditions set to predetermined levels, nickel in the residue is dissolved and extracted in the form of nickel ammine chloride. The mixture may prefera~ly be stirred to facilitate dissolution. This dissolution and extraction process may be carried out in any desired manner, for example, by a batchwise or continuous, parallel current or cQunter current operation. The operation ma~ be chosen according to the amount of the residue to be treated and the nickel content.
After the dissolution and extraction process is com-pleted, the treated mixtur~ is trans~erred to a separator 30 through a line 24. The insoluble contents including ash are separated therein and discharged through a ~ine 32, ~ 79~7 `:
while the aqueous nickel ammine chloride solution is ~ed to a precipitator 40 through a line 31. Ammonia fed through a branched line 66 is added to the solution to :increase the concentration o~ liberated ammonia in the solu-tion, precipitating nickel ammine chloride. The tempera-ture of the solution may optionally be redueed in the preeipitator 40.
The precipitate is transferred together with the solution to a separator 50 through a line ~1. In the separator 50, the precipitate is separated from the solution, which is then fed to a first recovery apparatus 51 through ~a line 54. Ammonia gas is liberated from the solution due to temperature rise or pressure reduction and then combined with another ammonia gas flow ~rom a second recovery apparatus 61 to be described hereinafter. The combined ammonia gas is circulated through lines 55 and 65 ~or reuse.
The remaining solution in the first recovery apparatus 51, which contains a small amount of nickel ammine chloride, is returned to the precipitator 40 or e~tractor 20 through the line 56 or 57 for reuse. If the amount o~ impurities aeeumulated in the solution becomes larger due to repeated use, such a contaminated solution is discharged through a line 53 and a fresh solution is supplied.
The separated precipitate of nic]cel ammine chlorlde is introduced into a heater 60 for decomposing the complex sal~ through a line 52, in which nickel ammine chloride is decomposed into nickel chloride and ammonia by heating.
The separated nie]cel ehloride is, if necessary, circulated ~r~
~ 792~
to the gasifying reactor 10 through a line ~3 ~or reuse as the catalyst, while the ammonia is ~ed to the second re-covery apparatus 61 through a line 62 and dried therein.
If desired, the dried ammonia gas is circulated -to the ammonium chloride-forming unit 12 and the precipitator ~0 through the lines 65, 66 and 9a for reuse. The waste water resulting from the above drying procedure may optionally be discharged through a line 64.
The above described system may be designed so that when any of reagents, for example, ammonium chloride or ammonia deviates from the range ensuring a suitable relative proportion, such a aeviation may immediately be compensated.
The embodiment employing nickel chloride as the cata-lyst is illustratively described above, whereas the inven-tion can be applied in a similar manner to the casesemploying nlckel salts such as nickel sulfate, nitrate and carbonate, metallic nickel and nickel oxide as the catalystO
It is to be noted that when metallic nickel or nickel oxide is used as the catalyst, the nickel salt resulting from decomposition by heating in the heater 60 may further be treated by conventional methods be~ore it is circulated.
Another pre~erred embodiment is shown in FigO 6, in which nickel in the resiclue is recovered as nickel carbonate.
Referring to Fig. 6, the residue is introduced in an ex-tractor 20 ~or dissolving nickel through an inlet line 75.To this extractor 20 is also fed water through a line 7~.
Oxygen or air, carbon dioxide, and a~lmonia fed through lines 71/ 72, and 73, respectively, are blown into the water.
With stirring, nickel:in the resi~.ue is dissolved and extracted in the form of nickel ammine carbonate. The treated mixture is fed to a separator 30 through a line 76.
The insoluble contents including ash are separated therein and discharged through à line 77, whilc the separated solution of nickel ammine carbonate is ed to a precipitator ~0 through a line 78. Ammonia fed through a branched line 87 is added to the solution to increase the concentration of liberated ammonia in the solution, precipitating nickel ammine carbonate.
The precipitate is transferred together with the solu-tion to a separator 50 through a line 79. In the separator 50, the precipitate is separated from the solution, which is then fed to a recovery apparatus 82 through a line 80.
The solution is subject to elevated temperature or reduced pressure to recover ammonia and the remaining waste liquid is discharged ~rom a line 83. The above recovered ammonia is combined with another ammonia flow from a heater 60 to be described hereinafter. The combined ammonia gas is circulated to the extractor 20 and the precipitator ~0 for reuse.
The separated precipitate of nickel ammine carbonate is introduced into the heater 60 through a line 81, in which nickel ammine carbonate i5 decomposed into nickel carbonate or nickel oxide and ammonia hy heatiny. The ~enerated ammonia is ~ed to the extractor 20 and the pre-cipitator 30 through lines 85, 87, and 73 for reuse. The resulting nickel. carbonate or nickel oxlde is taken out -7~
; through a line 86 and then may either be circulatea to the gasifying reactor or be s-tored in a suitable reservoir (not shown).
; As described above, nickel can be effectively recovered from a residue resulting from the gasification of carbo~
naceous materials using nickel-containing catalysts.
In the present invention, modification and variation may be made depending upon the type of a nickel compound used as the catalyst. For example, when nickel ammine is used as the catalyst, the nickel ammine crvstals separated after precipitation may be readily circulated for reuse without further processing.
Moreover, if nickel in the residue takes a form other than metallic nickel or nickel sulfide, it should be con-verted in-to metallic nickel or nickel sulfide before the invention is applied thereto.
Since nickel is fixed and recovered in the form of a nickel ammine salt according to the invention, useful reagents, for example, ammonia can easily be circulated for reuse. As a result, nickel is economically recovered and envirollmental pollution is minimized.
Claims (13)
1. A method of recovering nickel from a nickel-con-taining residue obtained after a carbonaceous material is gasi-fied in the presence of a nickel-containing catalyst, which comprises the steps of:
(a) adding an aqueous solution containing ammonia and an ammonium salt selected from the group consisting of am-monium chloride, ammonium carbonate and ammonium nitrate to said nickel containing residue in the presence of an oxygen-containing gas to dissolve and extract the nickel in the solution in the form of a nickel ammine complex salt, (b) separating the mixture into an aqueous nickel ammine solution and insoluble contents, (c) further adding ammonia to the separated aqueous nickel Amman solution to increase the concentration of free ammonia to from 15 to 30% and cooling to below 25°C thereby to.
precipitate the nickel ammine, (d) separating the nickel ammine precipitate, and (e) heating the separated nickel ammine to decompose it into nickel oxide or a nickel salt and ammonia.
(a) adding an aqueous solution containing ammonia and an ammonium salt selected from the group consisting of am-monium chloride, ammonium carbonate and ammonium nitrate to said nickel containing residue in the presence of an oxygen-containing gas to dissolve and extract the nickel in the solution in the form of a nickel ammine complex salt, (b) separating the mixture into an aqueous nickel ammine solution and insoluble contents, (c) further adding ammonia to the separated aqueous nickel Amman solution to increase the concentration of free ammonia to from 15 to 30% and cooling to below 25°C thereby to.
precipitate the nickel ammine, (d) separating the nickel ammine precipitate, and (e) heating the separated nickel ammine to decompose it into nickel oxide or a nickel salt and ammonia.
2. A method as claimed in claim 1 which further comprises a step of converting the separated nickel ammine into any desired form selected from nickel oxide, nickel salts and metallic nickel.
3. A method as claimed in claim 1 wherein said car-bonaceous material from which said nickel-containing residue is obtained is selected from brown coal, lignite, bituminous coal, tar pitch, coke and their analogues.
4. A method as claimed in claim 1 wherein said oxygen-containing gas is oxygen.
5. A method as claimed in claim 1 wherein said oxygen-containing gas is air.
6. A method as claimed in claim 1 wherein the concen-tration of liberated ammonia in the solution is in the range of 0 to 18.0% by weight in step (a).
7. A method as claimed in claim 6 wherein the concen-tration of liberated ammonia is in the range of 3.5 to 15.0%
by weight.
by weight.
8. A method as claimed in claim 1 wherein the partial pressure of oxygen is in the range of 1 to 50 atm. in step (a).
9. A method as claimed in claim 8 wherein the partial pressure of oxygen is in the range of 2 to 10 atm.
10. A method as claimed in claim 1 wherein the tempe-rature of the solution is in the range of 10 to 150°C in step (a).
11. A method as claimed in claim 10 wherein the tem-perature of the solution is in the range of 30 to 120°C.
12. A method as claimed in claim 1 wherein the tempe-rature of the solution is lowered to below 15°C.
13. A method as claimed in claim 1 which further com-prises a step (f) of circulating the saturated nickel ammine solution remaining after the separating step (d) to step (a) and the ammonia resulting from the decomposition step (e) to step (c).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52-020810 | 1977-03-01 | ||
| JP2081077A JPS53106623A (en) | 1977-03-01 | 1977-03-01 | Method of recovering nickel from coal ash residue containing nickel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1097927A true CA1097927A (en) | 1981-03-24 |
Family
ID=12037385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA297,855A Expired CA1097927A (en) | 1977-03-01 | 1978-02-28 | Nickel recovery |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS53106623A (en) |
| AU (1) | AU513480B2 (en) |
| CA (1) | CA1097927A (en) |
| DE (1) | DE2808263C2 (en) |
| FR (1) | FR2382505A1 (en) |
| GB (1) | GB1560873A (en) |
| IN (1) | IN150307B (en) |
| NL (1) | NL7802008A (en) |
Families Citing this family (42)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2130566B (en) * | 1982-09-24 | 1986-07-09 | Chevron Res | Recovering metals from spent hydroprocessing catalysts |
| US4432953A (en) * | 1982-09-24 | 1984-02-21 | Chevron Research Company | Leaching cobalt from spent hydroprocessing catalysts with sulfur dioxide |
| CU22856A1 (en) * | 1997-02-18 | 2003-05-26 | Ct De Investigaciones Para La Ind Minero Metalurgi | HYDROMETALURGICAL PROCEDURE FOR THE RECOVERY OF NICKEL AND COBALT |
| WO2009016473A2 (en) * | 2007-08-01 | 2009-02-05 | Nagarjuna Energy Private Limited | A process for preventing polymerization of cracked volatile products during pyrolysis and gasification |
| WO2009086407A2 (en) | 2007-12-28 | 2009-07-09 | Greatpoint Energy, Inc. | Steam generating slurry gasifier for the catalytic gasification of a carbonaceous feedstock |
| US20090217575A1 (en) | 2008-02-29 | 2009-09-03 | Greatpoint Energy, Inc. | Biomass Char Compositions for Catalytic Gasification |
| US8349039B2 (en) | 2008-02-29 | 2013-01-08 | Greatpoint Energy, Inc. | Carbonaceous fines recycle |
| US8297542B2 (en) | 2008-02-29 | 2012-10-30 | Greatpoint Energy, Inc. | Coal compositions for catalytic gasification |
| US8286901B2 (en) | 2008-02-29 | 2012-10-16 | Greatpoint Energy, Inc. | Coal compositions for catalytic gasification |
| US8366795B2 (en) | 2008-02-29 | 2013-02-05 | Greatpoint Energy, Inc. | Catalytic gasification particulate compositions |
| US8361428B2 (en) | 2008-02-29 | 2013-01-29 | Greatpoint Energy, Inc. | Reduced carbon footprint steam generation processes |
| KR101290477B1 (en) | 2008-09-19 | 2013-07-29 | 그레이트포인트 에너지, 인크. | Processes for gasification of a carbonaceous feedstock |
| KR101330894B1 (en) | 2008-09-19 | 2013-11-18 | 그레이트포인트 에너지, 인크. | Gasification processes using char methanation catalyst |
| AU2009293087B2 (en) | 2008-09-19 | 2012-11-15 | Sure Champion Investment Limited | Processes for gasification of a carbonaceous feedstock |
| US8734547B2 (en) | 2008-12-30 | 2014-05-27 | Greatpoint Energy, Inc. | Processes for preparing a catalyzed carbonaceous particulate |
| CN102272268B (en) | 2008-12-30 | 2014-07-23 | 格雷特波因特能源公司 | Processes for preparing a catalyzed coal particulate |
| US8728182B2 (en) | 2009-05-13 | 2014-05-20 | Greatpoint Energy, Inc. | Processes for hydromethanation of a carbonaceous feedstock |
| WO2010132549A2 (en) | 2009-05-13 | 2010-11-18 | Greatpoint Energy, Inc. | Processes for hydromethanation of a carbonaceous feedstock |
| CA2773718C (en) | 2009-10-19 | 2014-05-13 | Greatpoint Energy, Inc. | Integrated enhanced oil recovery process |
| US8479834B2 (en) | 2009-10-19 | 2013-07-09 | Greatpoint Energy, Inc. | Integrated enhanced oil recovery process |
| AU2010339952B8 (en) | 2009-12-17 | 2013-12-19 | Greatpoint Energy, Inc. | Integrated enhanced oil recovery process |
| US8669013B2 (en) | 2010-02-23 | 2014-03-11 | Greatpoint Energy, Inc. | Integrated hydromethanation fuel cell power generation |
| US8652696B2 (en) | 2010-03-08 | 2014-02-18 | Greatpoint Energy, Inc. | Integrated hydromethanation fuel cell power generation |
| KR101440710B1 (en) | 2010-04-26 | 2014-09-17 | 그레이트포인트 에너지, 인크. | Hydromethanation of a carbonaceous feedstock with vanadium recovery |
| US8653149B2 (en) | 2010-05-28 | 2014-02-18 | Greatpoint Energy, Inc. | Conversion of liquid heavy hydrocarbon feedstocks to gaseous products |
| KR101424941B1 (en) | 2010-08-18 | 2014-08-01 | 그레이트포인트 에너지, 인크. | Hydromethanation of carbonaceous feedstock |
| EP2635662A1 (en) | 2010-11-01 | 2013-09-11 | Greatpoint Energy, Inc. | Hydromethanation of a carbonaceous feedstock |
| US8648121B2 (en) | 2011-02-23 | 2014-02-11 | Greatpoint Energy, Inc. | Hydromethanation of a carbonaceous feedstock with nickel recovery |
| CN103582693A (en) | 2011-06-03 | 2014-02-12 | 格雷特波因特能源公司 | Hydromethanation of a carbonaceous feedstock |
| CN103974897A (en) | 2011-10-06 | 2014-08-06 | 格雷特波因特能源公司 | Hydromethanation of a carbonaceous feedstock |
| KR101576781B1 (en) | 2012-10-01 | 2015-12-10 | 그레이트포인트 에너지, 인크. | Agglomerated particulate low-rank coal feedstock and uses thereof |
| WO2014055365A1 (en) | 2012-10-01 | 2014-04-10 | Greatpoint Energy, Inc. | Use of contaminated low-rank coal for combustion |
| CN104685039B (en) | 2012-10-01 | 2016-09-07 | 格雷特波因特能源公司 | Graininess low rank coal raw material of agglomeration and application thereof |
| WO2014055351A1 (en) | 2012-10-01 | 2014-04-10 | Greatpoint Energy, Inc. | Agglomerated particulate low-rank coal feedstock and uses thereof |
| JP5598778B2 (en) | 2013-01-25 | 2014-10-01 | 住友金属鉱山株式会社 | Method for producing high-purity nickel sulfate and method for removing impurity element from solution containing nickel |
| US10464872B1 (en) | 2018-07-31 | 2019-11-05 | Greatpoint Energy, Inc. | Catalytic gasification to produce methanol |
| US10344231B1 (en) | 2018-10-26 | 2019-07-09 | Greatpoint Energy, Inc. | Hydromethanation of a carbonaceous feedstock with improved carbon utilization |
| US10435637B1 (en) | 2018-12-18 | 2019-10-08 | Greatpoint Energy, Inc. | Hydromethanation of a carbonaceous feedstock with improved carbon utilization and power generation |
| US10618818B1 (en) | 2019-03-22 | 2020-04-14 | Sure Champion Investment Limited | Catalytic gasification to produce ammonia and urea |
| CN114426889B (en) * | 2020-10-29 | 2023-10-10 | 中国石油化工股份有限公司 | Utilization method of hydrocracking molybdenum-containing tailings |
| CN113802001B (en) * | 2021-08-13 | 2022-11-22 | 广东邦普循环科技有限公司 | Method for recovering and purifying nickel from nickel iron |
| CN115821041B (en) * | 2022-09-01 | 2024-09-10 | 广东邦普循环科技有限公司 | Nickel recovery method |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR332596A (en) * | 1903-05-06 | 1903-10-31 | Miranda Malzac | Wet desulphurization process of nickel, copper, zinc, etc. and hydroxidation of their metals, with a view to their extraction |
| FR460322A (en) * | 1912-06-20 | 1913-11-28 | Ernst Ellenberger | Process for the treatment of cuttings from sheets coated with copper, nickel, zinc, tin, etc., or alloys of these metals by detaching the covering metals and by recovering the underlying metals |
| DE887871C (en) * | 1941-03-05 | 1953-08-27 | Kupferwerk Ilsenburg A G | Process for separating copper-nickel-zinc alloys |
| BE514331A (en) * | 1951-09-21 | 1900-01-01 | ||
| DE1583911A1 (en) * | 1967-11-11 | 1970-10-15 | Ruhrchemie Ag | Process for the recovery of nickel and / or cobalt from spent catalyst masses |
| ZA731519B (en) * | 1972-06-23 | 1973-11-28 | Anaconda Co | Recovery of nickel |
| CA970167A (en) * | 1972-07-19 | 1975-07-01 | Herman F. Bakker | Selective precipitation of cobalt and nickel ammine complexes |
| US3967957A (en) * | 1973-03-26 | 1976-07-06 | Continental Oil Company | Aqueous ammonia oxidative leach and recovery of metal values |
-
1977
- 1977-03-01 JP JP2081077A patent/JPS53106623A/en active Granted
-
1978
- 1978-02-15 GB GB6002/78A patent/GB1560873A/en not_active Expired
- 1978-02-16 AU AU33349/78A patent/AU513480B2/en not_active Expired
- 1978-02-18 IN IN186/CAL/78A patent/IN150307B/en unknown
- 1978-02-22 NL NL7802008A patent/NL7802008A/en not_active Application Discontinuation
- 1978-02-25 DE DE2808263A patent/DE2808263C2/en not_active Expired
- 1978-02-27 FR FR7805540A patent/FR2382505A1/en active Granted
- 1978-02-28 CA CA297,855A patent/CA1097927A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2808263C2 (en) | 1983-10-27 |
| AU513480B2 (en) | 1980-12-04 |
| IN150307B (en) | 1982-09-04 |
| DE2808263A1 (en) | 1978-09-07 |
| AU3334978A (en) | 1979-08-23 |
| NL7802008A (en) | 1978-09-05 |
| GB1560873A (en) | 1980-02-13 |
| FR2382505A1 (en) | 1978-09-29 |
| FR2382505B1 (en) | 1981-04-10 |
| JPS53106623A (en) | 1978-09-16 |
| JPS5536692B2 (en) | 1980-09-22 |
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