CA1041026A - Process for the recovery of carbonyls and carbon monoxide from carbonyl process gases - Google Patents
Process for the recovery of carbonyls and carbon monoxide from carbonyl process gasesInfo
- Publication number
- CA1041026A CA1041026A CA222,418A CA222418A CA1041026A CA 1041026 A CA1041026 A CA 1041026A CA 222418 A CA222418 A CA 222418A CA 1041026 A CA1041026 A CA 1041026A
- Authority
- CA
- Canada
- Prior art keywords
- kpa
- carbon monoxide
- activated alumina
- gas mixture
- carbonyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
- C22B23/06—Refining
- C22B23/065—Refining carbonyl methods
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0009—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/20—Dry methods smelting of sulfides or formation of mattes from metal carbonyls
-
- 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
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
- Treating Waste Gases (AREA)
Abstract
Abstract of the Disclosure Nickel and iron carbonyls are separated and recovered from an impure gas mixture by adsorption on activated alumina at pressures between 34 and 10,340 kPa and temperatures between -12 and +25°C. Thereafter, the carbonyls are desorbed from the activated alumina at pressures between 7 and 100 kPa and temperatures between 55°C and 105°C and subsequently converted to elemental form in a decomposer.
Description
`
` 1(~410~f~
This invention is directed to a process for separating nickel and iron carbonyls from an impure gas mixture.
The decompo3ition of nickel carbonyl gas to form pellet or powdered nickel is an important industrial process.
In this highly selective process, carbon monoxide is used to extract nickel from an impure feed material by the formation of nickel carbonyl at temperatures between 35C and 175C.
Subsequently, the pure nickel carbonyl is decomposed to solid nic~el and carbon monoxide at temperatures between 150C and 315C. Impurity gases may be introduced or even generated at various points in this process. An inert gas, generally nitrogen, is used to purge the carbonylation vessel free from air during start-up and prior to shut-down for ~olids removal.
Gas mixtures containing carbonyls and nitrogen also result from the purging of carbonyl decomposition e~uipment prior to the discharge of solid nickel or iron and from maintenance pro-cedures. Carbon dioxide may be present as a decomposition product of carbon monoxide.
Since the presence of nitrogen and carbon dioxide even in small quantities will retard the carbonylation process by lowering the partial pressure of the reacting carbon monoxide, it is necessary to remove these gases from the circuit.
Carbonyls and carbon monoxide are highly toxic gases and as a consequence they cannot be vented to the atmosphere. Also, they have considerable intrinsic value. Furthermore, carbonyls may plate out on metallic surfaces, such as those of com-pressors and piping systems, thereby clogging or interfering with the overall operation of a system. For these reasons, it is important to completely separate and recover the carbonyls and carbon monoxide from the other gases in mixtures occurring from routine purging operations involved in the production of nickel and iron by the carbonyl process.
. :.
.
" lO~Q~6 It i5 the principal object of the present invention to provide a process for removing and recovering nickel and iron carbonyls from a process gas str~am containing, in addition, carbon monoxide, nitrogen and other impurities.
It is another object of the invention to improve the efficiency of the carbonyl process for refining nickel.
Further objects and advantages will become more ' apparent when taken in conjunction with the following descrip-tion and the accompanying figure. -Figure 1 depicts a diagrammatic cross-sectional view of a reaction vessel containing activated alumina.
Generally speaking, the present invention contemplates a process for removing a metal carbonyl from a gas mixture comprising passing said gas mixture at pressures between 34 and 10,340 kPa (5 and 1500 psig) through activated alumina held at temperatures between -12C and +24C to remove said metal carbonyl from said gas mixture by adsorption into said activated alumina; and thereafter desorbing said metal carbonyl from said activated alumina by passing carbon monoxide at pressures between 7 kPa and 100 kPa (1 psig and 15 psig) through said activated alumina maintained at temperatures between 55C and 105C to release said metal carbonyls to said carbon mono~ide. ~-In practice, it has been found advantageous to maintain pressures between 1380 kPa and 8270 kPa (200 and 1200 psig) `~
and temperatures between -5C and 15C during the step in which a metal carbonyl is transferred from the gas mixture to the activated alumina by adsorption. Similarly, it has been found advantageous to maintain pres~ures between 14 and 55 kPa (2 and 8 psig) and temperatures between 55C and 85C during the step in which a metal carbonyl i5 transferred from the activated alumina to the carbon monoxide by desorption.
.
` 1(~410~f~
This invention is directed to a process for separating nickel and iron carbonyls from an impure gas mixture.
The decompo3ition of nickel carbonyl gas to form pellet or powdered nickel is an important industrial process.
In this highly selective process, carbon monoxide is used to extract nickel from an impure feed material by the formation of nickel carbonyl at temperatures between 35C and 175C.
Subsequently, the pure nickel carbonyl is decomposed to solid nic~el and carbon monoxide at temperatures between 150C and 315C. Impurity gases may be introduced or even generated at various points in this process. An inert gas, generally nitrogen, is used to purge the carbonylation vessel free from air during start-up and prior to shut-down for ~olids removal.
Gas mixtures containing carbonyls and nitrogen also result from the purging of carbonyl decomposition e~uipment prior to the discharge of solid nickel or iron and from maintenance pro-cedures. Carbon dioxide may be present as a decomposition product of carbon monoxide.
Since the presence of nitrogen and carbon dioxide even in small quantities will retard the carbonylation process by lowering the partial pressure of the reacting carbon monoxide, it is necessary to remove these gases from the circuit.
Carbonyls and carbon monoxide are highly toxic gases and as a consequence they cannot be vented to the atmosphere. Also, they have considerable intrinsic value. Furthermore, carbonyls may plate out on metallic surfaces, such as those of com-pressors and piping systems, thereby clogging or interfering with the overall operation of a system. For these reasons, it is important to completely separate and recover the carbonyls and carbon monoxide from the other gases in mixtures occurring from routine purging operations involved in the production of nickel and iron by the carbonyl process.
. :.
.
" lO~Q~6 It i5 the principal object of the present invention to provide a process for removing and recovering nickel and iron carbonyls from a process gas str~am containing, in addition, carbon monoxide, nitrogen and other impurities.
It is another object of the invention to improve the efficiency of the carbonyl process for refining nickel.
Further objects and advantages will become more ' apparent when taken in conjunction with the following descrip-tion and the accompanying figure. -Figure 1 depicts a diagrammatic cross-sectional view of a reaction vessel containing activated alumina.
Generally speaking, the present invention contemplates a process for removing a metal carbonyl from a gas mixture comprising passing said gas mixture at pressures between 34 and 10,340 kPa (5 and 1500 psig) through activated alumina held at temperatures between -12C and +24C to remove said metal carbonyl from said gas mixture by adsorption into said activated alumina; and thereafter desorbing said metal carbonyl from said activated alumina by passing carbon monoxide at pressures between 7 kPa and 100 kPa (1 psig and 15 psig) through said activated alumina maintained at temperatures between 55C and 105C to release said metal carbonyls to said carbon mono~ide. ~-In practice, it has been found advantageous to maintain pressures between 1380 kPa and 8270 kPa (200 and 1200 psig) `~
and temperatures between -5C and 15C during the step in which a metal carbonyl is transferred from the gas mixture to the activated alumina by adsorption. Similarly, it has been found advantageous to maintain pres~ures between 14 and 55 kPa (2 and 8 psig) and temperatures between 55C and 85C during the step in which a metal carbonyl i5 transferred from the activated alumina to the carbon monoxide by desorption.
.
-2-. . . ~ . .
1041Q;~
Reference to Figure 1 will serve to make clear the operation of the process of this invention. The apparatus consists of a container, reference character 11, charged with a bed of activated alumina 12. The container is surrounded by a jacket 13. Although only one container is shown in Figure 1, a plurality of containers may be present. The space between the jacket and the container holds a medium for heating and cooling 14 which may consist of circulating aqueous ethylene glycol. The medium is heated or cooled as required by a heat exchanger, not shown.
During adsorption, temperatures between -12 and +24C are maintained. Impure carbonvlation gas, at pressures o~ 34 kPa to 10,340 kPa (5 to 1500 psig), enters the container through valve 15 and conduit means 16, interacts with the activated alumina, and exits at the opposite end through the conduit means 17 and valve 18. Valves 19 and 20 are closed during this part of the process.
During passage through the activated alumina, nickel carbonyl, iron carbonyl and carbon dioxide are adsorbed and removed from the gas stream. The purified gas that exits through the valve 18 is treated for carbon monoxide recovery by an established process. The carbon dioxide and nitrogen composing the balance of the gas stream are vented.
Once the alumina in the container has been charged with adsorbed nickel carbonyl, iron carbonyl and carbon dioxide, valves 15 and 18 are closed and the desorption portion of the cycle started. This is accomplished by increasing the tempera-ture of the container to 55C to 105C. Relatively pure carbon monoxide is admitted to the container through valve 19 and conduit means 17 at pressures ranging from 7 to 100 kPa ` ~Q~O;~
(1 to 15 psig). Valve 20 is concurrently opened to allow passage through conduit means 16, of the carbon monoxide now loaded with desorbed nickel carbonyl, iron carbonyl and carbon dioxide -The carbon monoxide containing the desorbed nickel and iron carbonyls is passed through a conventional thermal decomposer, not shown, where the carbonyls are decomposed to nickel and iron powder. The carbonyl-free gases exiting from the decomposer and consisting of carbon monoxide and carbon dioxide are subsequently processed for carbon dioxide removal and carbon monoxide recovery.
In order to give those skilled in the art a better understanding of the invention, the following examples are given which illustrate the adsorption and the desorption steps.
EXA~LE I
The concentration of nickel and iron carbonyls within the gas mixture to be treated affects the adsorptive capacity of the alumina. Tests were performed in apparatus such as that illustrated in Figure 1, which used a 14.6 cm.I.D., 4.6 meter high container pressurized to 6,895 kPa (1000 psiq) held at a temperature of 4C and with a flow rate of 0.6 cubic meters per minute. Run 1 showed that with a concentration of 4.8 grams per cubic meter of nickel plus iron in the impure gas mixture, 2.8 Kg of nickel and iron as carbonyls were adsorbed per 100 Kg of activated alumina with a breakthrough time of 10.2 hours (i.e., the time period before which the exit gas begins to show the presence of carbonyls). ~n run 2, with an enriched gas mixture containing 19.9 grams per cubic meter of nickel and iron, a total of 5.4 Kg of nickel and iron as carbonyls were adsorbed per 100 Xg of activated alumina with a breakthrough time of S.0 hours.
~, ..... . . ..
V~6 EXAMPLE II
The ability of activated alumina to adsorb nickel and iron carbonyls (loading capacity) is substantially increased by operation at lower temperatures. Tests conducted in the same container as that of Example I at a pressure of 6,895 kPa (1000 psig) and inlet gas concentration of about 20 grams cf nickel plus iron per cubic meter showed that when the tempera-ture of the reaction vessel was 22C, the loading capacity was 4.3 Kg of nickel and iron as carbonyls per 100 Kg of activated alumina (run 3). Under the same conditions, but at a temperature of 16C (run 4), the loading capacity was 5.2 Kg of nickel and iron as carbonyls per 100 Kg of activated alumina.
At 4C (run 2), the loading capacity was 5.4 K~ of nickel and iron as carbonyls per 100 Kg of activated alumina. At -3C (run 5), the loading capacity was 6.0 ~g of nickel and iron as carbonyls per 100 Kg of activated alumina.
EXAMPLE III
~igh inlet gas pressure also increases loading capacity during adsorption. At an operating temperature of 4C
using ~he container described in Example I, and with an inlet gas concentration of 19.9 grams of nickel and iron per cubic meter, a loading capacity of 5.4 Kg of nickel and iron as carbonyls per 100 Kg of activated alumina was obtained (run 2) at a pressure of 6,895 kPa (1000 psig). The loading capacity was reduced to 4.2 Kg of nickel and iron as carbonyls per 100 Kg of activated alumina at a pressure of 2,068 kPa (300 psig) with an inlet gas concentration of 18.3 grams of nickel and iron per cubic meter (run 6).
EXAMPLE IV
The desorption operation is illustrated for a variety of preferred conditions. This portion of the operation is shown for runs 1 through 6 described previously in Examples I through .: ..
' :
10~10~6 III and for run 7 in which high purity carbon monoxide was used for desorption. All tests were conducted at the same low pressure 34 kPa (5 psig).
The amount of nickel plu~ iron as carbonyls, prior to desorption, is expressed in the top line of Table I in Kilograms per 100 Kilograms of activated alumina. Pure and impure lots of carbon monoxide, as well as combinations of the two, were used to desorb the activated alumina.
During desorption, the temperature of the container was increased to the desired level. This was accomplished by heating and circulating the ethylene glycol surrounding the container~
Although a somewhat impure carbon monoxide containing 19.7 g/m3 of nickel and 1.08 g/m3 of iron as carbonyl could be used to desorb the metal carbonyls from the activated alumina (run 3), it was found advantageous to use a combination of impure carbon monoxide, containing as much as about 20 g/m3 and even 30 g/m3 of metal as carbonyl, followed by essentially pure carbon monoxide, containing about 0.01 and even as much as 1.5 g/m3 of metal as carbonyl for flow times of 5 and 1 hours, respectively, (runs 1 and 3 through 6). This more economical combination of gases was as effective as high purity carbon monoxide containing 0.02 g/m30fnickelas carbonyl and 0.01 g/m3 of iron as carbonyl used continuously (run 7).
In practice, a container temperature during desorption of about 75C is preferred since it is compatible with the pressurized carbonyl process. Lower temperatures, e.g., 65C, lead t~ incomplete desorption, especially of iron carbonyl.
Higher temperatures, e.g., 85C and even 100C, may cause decomposition of the metal carbonyls within the activated alumina, especially decomposition of the iron carbonyl.
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Althou~h the present invention has been described in conjunction with preferred e~bodiments, it is to be understoo~ that modifications and variations may be res0rted to without departing from the spirit and sco~e of the invention, as those skilled in the art will readily un~er-stand. Such modifications and variations are considere~l to be within the purview an~ scope of the invention and a~pended claims.
.' . .
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., ~ 8 ~
.
1041Q;~
Reference to Figure 1 will serve to make clear the operation of the process of this invention. The apparatus consists of a container, reference character 11, charged with a bed of activated alumina 12. The container is surrounded by a jacket 13. Although only one container is shown in Figure 1, a plurality of containers may be present. The space between the jacket and the container holds a medium for heating and cooling 14 which may consist of circulating aqueous ethylene glycol. The medium is heated or cooled as required by a heat exchanger, not shown.
During adsorption, temperatures between -12 and +24C are maintained. Impure carbonvlation gas, at pressures o~ 34 kPa to 10,340 kPa (5 to 1500 psig), enters the container through valve 15 and conduit means 16, interacts with the activated alumina, and exits at the opposite end through the conduit means 17 and valve 18. Valves 19 and 20 are closed during this part of the process.
During passage through the activated alumina, nickel carbonyl, iron carbonyl and carbon dioxide are adsorbed and removed from the gas stream. The purified gas that exits through the valve 18 is treated for carbon monoxide recovery by an established process. The carbon dioxide and nitrogen composing the balance of the gas stream are vented.
Once the alumina in the container has been charged with adsorbed nickel carbonyl, iron carbonyl and carbon dioxide, valves 15 and 18 are closed and the desorption portion of the cycle started. This is accomplished by increasing the tempera-ture of the container to 55C to 105C. Relatively pure carbon monoxide is admitted to the container through valve 19 and conduit means 17 at pressures ranging from 7 to 100 kPa ` ~Q~O;~
(1 to 15 psig). Valve 20 is concurrently opened to allow passage through conduit means 16, of the carbon monoxide now loaded with desorbed nickel carbonyl, iron carbonyl and carbon dioxide -The carbon monoxide containing the desorbed nickel and iron carbonyls is passed through a conventional thermal decomposer, not shown, where the carbonyls are decomposed to nickel and iron powder. The carbonyl-free gases exiting from the decomposer and consisting of carbon monoxide and carbon dioxide are subsequently processed for carbon dioxide removal and carbon monoxide recovery.
In order to give those skilled in the art a better understanding of the invention, the following examples are given which illustrate the adsorption and the desorption steps.
EXA~LE I
The concentration of nickel and iron carbonyls within the gas mixture to be treated affects the adsorptive capacity of the alumina. Tests were performed in apparatus such as that illustrated in Figure 1, which used a 14.6 cm.I.D., 4.6 meter high container pressurized to 6,895 kPa (1000 psiq) held at a temperature of 4C and with a flow rate of 0.6 cubic meters per minute. Run 1 showed that with a concentration of 4.8 grams per cubic meter of nickel plus iron in the impure gas mixture, 2.8 Kg of nickel and iron as carbonyls were adsorbed per 100 Kg of activated alumina with a breakthrough time of 10.2 hours (i.e., the time period before which the exit gas begins to show the presence of carbonyls). ~n run 2, with an enriched gas mixture containing 19.9 grams per cubic meter of nickel and iron, a total of 5.4 Kg of nickel and iron as carbonyls were adsorbed per 100 Xg of activated alumina with a breakthrough time of S.0 hours.
~, ..... . . ..
V~6 EXAMPLE II
The ability of activated alumina to adsorb nickel and iron carbonyls (loading capacity) is substantially increased by operation at lower temperatures. Tests conducted in the same container as that of Example I at a pressure of 6,895 kPa (1000 psig) and inlet gas concentration of about 20 grams cf nickel plus iron per cubic meter showed that when the tempera-ture of the reaction vessel was 22C, the loading capacity was 4.3 Kg of nickel and iron as carbonyls per 100 Kg of activated alumina (run 3). Under the same conditions, but at a temperature of 16C (run 4), the loading capacity was 5.2 Kg of nickel and iron as carbonyls per 100 Kg of activated alumina.
At 4C (run 2), the loading capacity was 5.4 K~ of nickel and iron as carbonyls per 100 Kg of activated alumina. At -3C (run 5), the loading capacity was 6.0 ~g of nickel and iron as carbonyls per 100 Kg of activated alumina.
EXAMPLE III
~igh inlet gas pressure also increases loading capacity during adsorption. At an operating temperature of 4C
using ~he container described in Example I, and with an inlet gas concentration of 19.9 grams of nickel and iron per cubic meter, a loading capacity of 5.4 Kg of nickel and iron as carbonyls per 100 Kg of activated alumina was obtained (run 2) at a pressure of 6,895 kPa (1000 psig). The loading capacity was reduced to 4.2 Kg of nickel and iron as carbonyls per 100 Kg of activated alumina at a pressure of 2,068 kPa (300 psig) with an inlet gas concentration of 18.3 grams of nickel and iron per cubic meter (run 6).
EXAMPLE IV
The desorption operation is illustrated for a variety of preferred conditions. This portion of the operation is shown for runs 1 through 6 described previously in Examples I through .: ..
' :
10~10~6 III and for run 7 in which high purity carbon monoxide was used for desorption. All tests were conducted at the same low pressure 34 kPa (5 psig).
The amount of nickel plu~ iron as carbonyls, prior to desorption, is expressed in the top line of Table I in Kilograms per 100 Kilograms of activated alumina. Pure and impure lots of carbon monoxide, as well as combinations of the two, were used to desorb the activated alumina.
During desorption, the temperature of the container was increased to the desired level. This was accomplished by heating and circulating the ethylene glycol surrounding the container~
Although a somewhat impure carbon monoxide containing 19.7 g/m3 of nickel and 1.08 g/m3 of iron as carbonyl could be used to desorb the metal carbonyls from the activated alumina (run 3), it was found advantageous to use a combination of impure carbon monoxide, containing as much as about 20 g/m3 and even 30 g/m3 of metal as carbonyl, followed by essentially pure carbon monoxide, containing about 0.01 and even as much as 1.5 g/m3 of metal as carbonyl for flow times of 5 and 1 hours, respectively, (runs 1 and 3 through 6). This more economical combination of gases was as effective as high purity carbon monoxide containing 0.02 g/m30fnickelas carbonyl and 0.01 g/m3 of iron as carbonyl used continuously (run 7).
In practice, a container temperature during desorption of about 75C is preferred since it is compatible with the pressurized carbonyl process. Lower temperatures, e.g., 65C, lead t~ incomplete desorption, especially of iron carbonyl.
Higher temperatures, e.g., 85C and even 100C, may cause decomposition of the metal carbonyls within the activated alumina, especially decomposition of the iron carbonyl.
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Z ~ Z
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Althou~h the present invention has been described in conjunction with preferred e~bodiments, it is to be understoo~ that modifications and variations may be res0rted to without departing from the spirit and sco~e of the invention, as those skilled in the art will readily un~er-stand. Such modifications and variations are considere~l to be within the purview an~ scope of the invention and a~pended claims.
.' . .
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Claims (8)
1. A process for removing a metal carbonyl from a gas mixture comprising: passing said gas mixture at pressures between 34 kPa and 10,340 kPa through activated alumina held at temperatures between minus 12°C and 24°C to remove said metal carbonyl from said gas mixture by adsorption into said activated alumina; and thereafter desorbing said metal carbonyl from said activated alumina by passing carbon monoxide at pressures between 7 kPa and 100 kPa through said activated alumina maintained at temperatures between 55°C and 105°C to release said metal carbonyls to said carbon monoxide.
2. A process as defined in claim 1 wherein said gas mixture passes through said activated alumina at pressures between 1380 kPa and 8,270 kPa and at temperatures between minus 5°C and 15°C.
3. A process as defined in claim 1 wherein said carbon monoxide passes through said activated alumina at pressures between 14 kPa and 55 kPa and at temperatures between 55°C
and 105°C.
and 105°C.
4. A process as defined in claim 1 wherein said steps are accomplished within a single container.
5. A process as defined in claim 1 wherein said gas mixture flow direction is opposite to said carbon monoxide flow direction.
6. A process as defined in claim 1 wherein said gas mixture contains at least about 0.1 and up to about 30 grams per cubic meter of nickel as carbonyl and at least about 0.1 and up to about 10 grams per cubic meter of iron as carbonyl as measured at standard temperature and pressure.
7. An apparatus for removing a metal carbonyl from a gas mixture comprising: a container for holding activated alumina having a conduit means at each end, a source of a high pressure gas mixture containing said metal carbonyl connected to said conduit means; a source of carbon monoxide connected to said conduit means; a means to convey a depleted process gas away from said container; a means to convey a loaded carbon monoxide away from said container; and a means to controllably maintain said container within a temperature range of minus 12°C and 105°C.
8. An apparatus as defined in claim 7 wherein a plurality of said containers are included within said means to control-lably maintain temperature.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA222,418A CA1041026A (en) | 1975-03-18 | 1975-03-18 | Process for the recovery of carbonyls and carbon monoxide from carbonyl process gases |
| GB10211/76A GB1535802A (en) | 1975-03-18 | 1976-03-15 | Production of metal carbonyls |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA222,418A CA1041026A (en) | 1975-03-18 | 1975-03-18 | Process for the recovery of carbonyls and carbon monoxide from carbonyl process gases |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1041026A true CA1041026A (en) | 1978-10-24 |
Family
ID=4102570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA222,418A Expired CA1041026A (en) | 1975-03-18 | 1975-03-18 | Process for the recovery of carbonyls and carbon monoxide from carbonyl process gases |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1041026A (en) |
| GB (1) | GB1535802A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740361A (en) * | 1986-03-27 | 1988-04-26 | Union Carbide Corporation | Process for removing metal carbonyls from gaseous streams |
| US5451384A (en) * | 1993-04-23 | 1995-09-19 | Den Norske Stats Oljeselskap A.S. | Process for reducing the content of metal carbonyls in gas streams |
-
1975
- 1975-03-18 CA CA222,418A patent/CA1041026A/en not_active Expired
-
1976
- 1976-03-15 GB GB10211/76A patent/GB1535802A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740361A (en) * | 1986-03-27 | 1988-04-26 | Union Carbide Corporation | Process for removing metal carbonyls from gaseous streams |
| US5451384A (en) * | 1993-04-23 | 1995-09-19 | Den Norske Stats Oljeselskap A.S. | Process for reducing the content of metal carbonyls in gas streams |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1535802A (en) | 1978-12-13 |
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