CA1116537A - Recovery of phosphane and methylphosphane - Google Patents
Recovery of phosphane and methylphosphaneInfo
- Publication number
- CA1116537A CA1116537A CA000311558A CA311558A CA1116537A CA 1116537 A CA1116537 A CA 1116537A CA 000311558 A CA000311558 A CA 000311558A CA 311558 A CA311558 A CA 311558A CA 1116537 A CA1116537 A CA 1116537A
- Authority
- CA
- Canada
- Prior art keywords
- zeolite
- phosphanes
- gas mixture
- waste gas
- phosphane
- 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
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910000064 phosphane Inorganic materials 0.000 title claims abstract description 32
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000005922 Phosphane Substances 0.000 title claims abstract description 12
- 238000011084 recovery Methods 0.000 title description 2
- 239000010457 zeolite Substances 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000003002 phosphanes Chemical class 0.000 claims abstract description 20
- 239000002912 waste gas Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 abstract description 20
- 238000001179 sorption measurement Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000000110 cooling liquid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5095—Separation; Purification; Stabilisation
-
- 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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/06—Hydrogen phosphides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5004—Acyclic saturated phosphines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Of Gases By Adsorption (AREA)
- Treating Waste Gases (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the disclosure Phosphane and/or methylphosphane are recovered from a waster gas mixture containing these phosphanes in admixture with hydrogen, nitrogen and/or non-polar lower hydrocarbons.
More specifically, the waste gas mixture is contacted at -20 to +30°C with a zeolite having a pore size of 5 x 10-8 to 15 x 10-8cm. The phosphanes are separated from the remainder of the waste gas mixture by absorbing them on the zeolite until it is saturated therewith.
Next, the zeolite is heated to 180 to 230°C and the desorbing phosphanes are collected.
More specifically, the waste gas mixture is contacted at -20 to +30°C with a zeolite having a pore size of 5 x 10-8 to 15 x 10-8cm. The phosphanes are separated from the remainder of the waste gas mixture by absorbing them on the zeolite until it is saturated therewith.
Next, the zeolite is heated to 180 to 230°C and the desorbing phosphanes are collected.
Description
S~'~
This invention relates to a process for recovering phosphane, methylphosphane or a mixture o~ these two phosphanes from a waste gas mixture containing one or more phosphanes in admixture with hydrogen, nitrogen and/
B 5 or oneor more ~ ~ower hydrocarbonsO
Phosphanes are normally separated from gas mixtures, especially from those which contain phosphanes in admixture with hydrogen, by subjecting these gas mixtures to con-densation. In the case o~ PH3, it is necessary to ef~ec-t the condensation at temperatures of -120 to -130C, which is a highly expensive procedure.
This is the reason why substantially no use has been made of the condensation method just described ~or the recovery o~ phosphanes ~rom gas mixtures o~ low phosphane concentration, and i-t has indeed often been necessary for these mixtures to be disposed of.
U.S. Patent 3 982 912 discloses a process, wherein a silane/phosphane-mixture is separated into its components with the aid of a zeolite. Use is more specifically made in -this process of K-A grade zeolites that are made ~rom standard A-grade zeolites, of which the exchangeable ions are replaced to an extent o~ 33.3 to 83.3 % by potassium ions and to an extent of approximately 17.7 to 66.7 ~ by zinc ions.
Re~erence to the good adsorbing power of these K-A
grade zeolites prepared in the specific manner JUSt described has been made in German Patent 2 208 Z14.
ii3~
These prior art processes are notl however, i.ree frc.m adverse effects inasmuch as the zeolites used have to ~e prepared frcm co~mercially available zeolites which are subjected to special pre-treatment. In acldition to this, the particular zeolites employed are just suitable for use in the separation of silane/phosphane-mixtures. As is known, the separating pc~er of these zeolites is critically influenced by their composi-tion (K : Zn -ratio~ so that they are not di.rectly of assistan oe in the t.reatment of other phosphane/gas-mixtures.
The adsorption of methylphosphane in contact with a zeolite has not been described heretofore in any literature reference of which we are aware.
PH3 which is produced continuously from yellow phosphorus and sodium hydrc)xide solution is always obtained together with PH3 containing con-siderable hydrogen, the latter being formed in a post-reaction during which hypophosphite unde.rgoes disprc~portionation into PH3 and phosphite, and reac-tion with water to phosphite and hydrogen.
Heretofore it has indeed been very difficult to recover concen-trated and pure phosphane frc~ phosphane~hydrogen-mixtures which contain relatively mmior proportions of PH3.
The present invention now unexpectedly provides a process for re-covering pure phosphane and/or methylphosphane from a waste gas mixture con-taining relatively minor proportions of these phosphanes in admixture with hyclrogen, nitrogen and/or non-polar lower hydrocarbons, which comprises:
contacting the waste gas mixture at temperatures within the range -20 to +30C, preferably at room temperature, with a zeolite having a pore size of 5 x 10 8 to 15 x 10 8 cm; separating the phosphanes from the remainder of the waste gas mixture by adsorbing them on the zeolite, until-the la~ter is saturated therewith; heating the zeolite to a temperature within the range 180 to 230C and collecting the desorbing phosphanes.
Preferred features of the present process provide:
a) for the waste gas mixture to contain 1 up to at most 70 volume % of the phosphanes speci~ied;
b) for the zeolite to comprise commercially available zeolites, preferably Na-A grade zeolites, with a pore size within the range 5 x 10 8 to 10 x 10 8 cm;
c) ~or the zeolite with the adsorbed phosphanes thereon to be heated to 180 to 200C so as to desorb the phos phanes;
$ 10 d) for the~ ~ lower hydrocarbons to comprise C1 - C4 hydrocarbons.
The fact that the present process can e~fecti~ely be carried out with the use of commercially available zeolites, which need no-t be pretreated, has also been an unexpected result. The useful zeolites comprise more especially A~grade zeolites which have a pore width of 5 ~, an Al:Si-ratio of 0.9 - 1.1:1 and a Na:Ca-ratio of 0c6 - 1.1:1. A-grade zeolites with a pore width of 10 ~, an Al:Si-ratio o~
0.6 - 0.9:1 and a Na:Ca-ratio of 15 - 20:1 can also be used.
In contact with the zeolite, the starting gas mixture is freed substantially completely ~rom the phosphanes; only traces of PH3 and/or CH3PH2 were found to have been retained in the remaining gas~ The steep blowout behaviour at saturation is also an index of the good adsorptive capacity 25 ~or PH3 and CH3PH2. The load capacity is 130 g PH3/kg - æeolite or 180 g CH3PHlk~ ~liteat -20C, and 100 g PH3/kg zeolite or 155 g CH3PH2/kg zeolite at +20C~ irrespective o~ the composition of the gas mixture. In those cases in which the gas mixture to be separated contains phosphane together with methylphosphane, the two gases are adsorbed simultaneously. They are easy to separate ~rom one another by desorbing and condensing the methylphosphane at tempe-ratures within the range -30 to -80C or by adsorbing it in concentrated hydrochloric acid.
3~
Steam which is present in the gas mixture in accor-dance with the steam partial pressure prevailing is also adsorbed substantially in the absence of any signi~icant adverse effect on the load capacity for PH3 or CH3PH~
during an adsorption operation.
Immediately after the treatment of the zeolite with PH3 and/or CH3PH2, it is possible to ef~ect the desorption by heating the zeolites to temperatures within the range 180 to 230C which causes the adsorbed gas to be continuous-ly set free. At temperatures higher than 200 C, -the zeolite is substantially free from PH~ and CH3PH2, respectively.
After cooling down to room temperature, the zeolite can be used again. Phosphane or methylphosphane which is recovered in the manner described is very pure (99.0 volume ~0~, irrespective of the composition of the starting gas mixtureO
In a series of adsorption and desorption tests, the process o~ the pres~nt invention was found to be repro-ducible in respect of capacity and separating ef~icienc~.
In a further long time test 9 the adsorbed phosphane was found to remain stable over some prolonged period of time.
The following Examples illustrate the invention:
EXAMPLE 1:
390 g of a grade A zeolite (5 ~; bead~ 2mm; bulk density 760 g/l; dried at 300~) was placed in a double-jacketed glass column and cooled under nitrogen down to-20C (a methanol/dry ice-mixture was the cooling liquid which was~ kept under circulation).
Next, the column was fed with PH3 until significant proportions thereo~ were found to get into a burner down-stream o~ the col D . The adsorption heat caused thetemperature in the adsorption zone to increase to +20 to 30C. The cooling liquid was removed and the zeolite was heated to 200C by means of a circulating heating liquid.
PH3 was set free continuously. The adsorbed quantity of PH~ was weighed by determining the difference in weight of the steel bottle tank, the volume of desorbed gas was determlned by means of a gas me-ter and, after conversion, compared with the adsorbed quantity of PH3 . 90 to 95 ,~
of the adsorbed PH3 was ~ound to have been set free by desorption at 200 C.
EXAMPLE 2:
Methylphosphane was adsorbed as described in Example 1 on 440 g of a grade A zeolite which had a pore size of 10 x 10 8 cm at -16C. 74 g o~ CH3PH2 was found to have been adsorbed.
A gas mixture composed of 85 volume % H2 and ~ volume ~' PH3 was separated into its components as described in Example 1 by contacting it at room temperature with the zeoli-te. The gas co~ing from the adsorption column packed with the æeolite was composed of:
99.9 volume % H2 0.02 volume % PH3 The gas desorbed by heati.ng the zeolite was composed as follows:
99.8 volume % PH3 0.2 volume % H2 E~AMPLE 4:
A gas mixture composed of 64 volume % CH4, 32 volume PH3, and 4 volume % N2 was separated into its components at room temperature as described in Example 1. The gas coming from the adsorption column was composed of:
94.1 volume % CH4 5.8 volume ~ N2 30 0.02 volume ~o PH3 and the desorbed gas was composed of:
99.0 volume % PH3 0.04 volume % CH4.
This invention relates to a process for recovering phosphane, methylphosphane or a mixture o~ these two phosphanes from a waste gas mixture containing one or more phosphanes in admixture with hydrogen, nitrogen and/
B 5 or oneor more ~ ~ower hydrocarbonsO
Phosphanes are normally separated from gas mixtures, especially from those which contain phosphanes in admixture with hydrogen, by subjecting these gas mixtures to con-densation. In the case o~ PH3, it is necessary to ef~ec-t the condensation at temperatures of -120 to -130C, which is a highly expensive procedure.
This is the reason why substantially no use has been made of the condensation method just described ~or the recovery o~ phosphanes ~rom gas mixtures o~ low phosphane concentration, and i-t has indeed often been necessary for these mixtures to be disposed of.
U.S. Patent 3 982 912 discloses a process, wherein a silane/phosphane-mixture is separated into its components with the aid of a zeolite. Use is more specifically made in -this process of K-A grade zeolites that are made ~rom standard A-grade zeolites, of which the exchangeable ions are replaced to an extent o~ 33.3 to 83.3 % by potassium ions and to an extent of approximately 17.7 to 66.7 ~ by zinc ions.
Re~erence to the good adsorbing power of these K-A
grade zeolites prepared in the specific manner JUSt described has been made in German Patent 2 208 Z14.
ii3~
These prior art processes are notl however, i.ree frc.m adverse effects inasmuch as the zeolites used have to ~e prepared frcm co~mercially available zeolites which are subjected to special pre-treatment. In acldition to this, the particular zeolites employed are just suitable for use in the separation of silane/phosphane-mixtures. As is known, the separating pc~er of these zeolites is critically influenced by their composi-tion (K : Zn -ratio~ so that they are not di.rectly of assistan oe in the t.reatment of other phosphane/gas-mixtures.
The adsorption of methylphosphane in contact with a zeolite has not been described heretofore in any literature reference of which we are aware.
PH3 which is produced continuously from yellow phosphorus and sodium hydrc)xide solution is always obtained together with PH3 containing con-siderable hydrogen, the latter being formed in a post-reaction during which hypophosphite unde.rgoes disprc~portionation into PH3 and phosphite, and reac-tion with water to phosphite and hydrogen.
Heretofore it has indeed been very difficult to recover concen-trated and pure phosphane frc~ phosphane~hydrogen-mixtures which contain relatively mmior proportions of PH3.
The present invention now unexpectedly provides a process for re-covering pure phosphane and/or methylphosphane from a waste gas mixture con-taining relatively minor proportions of these phosphanes in admixture with hyclrogen, nitrogen and/or non-polar lower hydrocarbons, which comprises:
contacting the waste gas mixture at temperatures within the range -20 to +30C, preferably at room temperature, with a zeolite having a pore size of 5 x 10 8 to 15 x 10 8 cm; separating the phosphanes from the remainder of the waste gas mixture by adsorbing them on the zeolite, until-the la~ter is saturated therewith; heating the zeolite to a temperature within the range 180 to 230C and collecting the desorbing phosphanes.
Preferred features of the present process provide:
a) for the waste gas mixture to contain 1 up to at most 70 volume % of the phosphanes speci~ied;
b) for the zeolite to comprise commercially available zeolites, preferably Na-A grade zeolites, with a pore size within the range 5 x 10 8 to 10 x 10 8 cm;
c) ~or the zeolite with the adsorbed phosphanes thereon to be heated to 180 to 200C so as to desorb the phos phanes;
$ 10 d) for the~ ~ lower hydrocarbons to comprise C1 - C4 hydrocarbons.
The fact that the present process can e~fecti~ely be carried out with the use of commercially available zeolites, which need no-t be pretreated, has also been an unexpected result. The useful zeolites comprise more especially A~grade zeolites which have a pore width of 5 ~, an Al:Si-ratio of 0.9 - 1.1:1 and a Na:Ca-ratio of 0c6 - 1.1:1. A-grade zeolites with a pore width of 10 ~, an Al:Si-ratio o~
0.6 - 0.9:1 and a Na:Ca-ratio of 15 - 20:1 can also be used.
In contact with the zeolite, the starting gas mixture is freed substantially completely ~rom the phosphanes; only traces of PH3 and/or CH3PH2 were found to have been retained in the remaining gas~ The steep blowout behaviour at saturation is also an index of the good adsorptive capacity 25 ~or PH3 and CH3PH2. The load capacity is 130 g PH3/kg - æeolite or 180 g CH3PHlk~ ~liteat -20C, and 100 g PH3/kg zeolite or 155 g CH3PH2/kg zeolite at +20C~ irrespective o~ the composition of the gas mixture. In those cases in which the gas mixture to be separated contains phosphane together with methylphosphane, the two gases are adsorbed simultaneously. They are easy to separate ~rom one another by desorbing and condensing the methylphosphane at tempe-ratures within the range -30 to -80C or by adsorbing it in concentrated hydrochloric acid.
3~
Steam which is present in the gas mixture in accor-dance with the steam partial pressure prevailing is also adsorbed substantially in the absence of any signi~icant adverse effect on the load capacity for PH3 or CH3PH~
during an adsorption operation.
Immediately after the treatment of the zeolite with PH3 and/or CH3PH2, it is possible to ef~ect the desorption by heating the zeolites to temperatures within the range 180 to 230C which causes the adsorbed gas to be continuous-ly set free. At temperatures higher than 200 C, -the zeolite is substantially free from PH~ and CH3PH2, respectively.
After cooling down to room temperature, the zeolite can be used again. Phosphane or methylphosphane which is recovered in the manner described is very pure (99.0 volume ~0~, irrespective of the composition of the starting gas mixtureO
In a series of adsorption and desorption tests, the process o~ the pres~nt invention was found to be repro-ducible in respect of capacity and separating ef~icienc~.
In a further long time test 9 the adsorbed phosphane was found to remain stable over some prolonged period of time.
The following Examples illustrate the invention:
EXAMPLE 1:
390 g of a grade A zeolite (5 ~; bead~ 2mm; bulk density 760 g/l; dried at 300~) was placed in a double-jacketed glass column and cooled under nitrogen down to-20C (a methanol/dry ice-mixture was the cooling liquid which was~ kept under circulation).
Next, the column was fed with PH3 until significant proportions thereo~ were found to get into a burner down-stream o~ the col D . The adsorption heat caused thetemperature in the adsorption zone to increase to +20 to 30C. The cooling liquid was removed and the zeolite was heated to 200C by means of a circulating heating liquid.
PH3 was set free continuously. The adsorbed quantity of PH~ was weighed by determining the difference in weight of the steel bottle tank, the volume of desorbed gas was determlned by means of a gas me-ter and, after conversion, compared with the adsorbed quantity of PH3 . 90 to 95 ,~
of the adsorbed PH3 was ~ound to have been set free by desorption at 200 C.
EXAMPLE 2:
Methylphosphane was adsorbed as described in Example 1 on 440 g of a grade A zeolite which had a pore size of 10 x 10 8 cm at -16C. 74 g o~ CH3PH2 was found to have been adsorbed.
A gas mixture composed of 85 volume % H2 and ~ volume ~' PH3 was separated into its components as described in Example 1 by contacting it at room temperature with the zeoli-te. The gas co~ing from the adsorption column packed with the æeolite was composed of:
99.9 volume % H2 0.02 volume % PH3 The gas desorbed by heati.ng the zeolite was composed as follows:
99.8 volume % PH3 0.2 volume % H2 E~AMPLE 4:
A gas mixture composed of 64 volume % CH4, 32 volume PH3, and 4 volume % N2 was separated into its components at room temperature as described in Example 1. The gas coming from the adsorption column was composed of:
94.1 volume % CH4 5.8 volume ~ N2 30 0.02 volume ~o PH3 and the desorbed gas was composed of:
99.0 volume % PH3 0.04 volume % CH4.
Claims (7)
We claim
1) A process for recovering pure phosphane and/or methyl-phosphane from a waste gas mixture containing these phosphanes in admixture with hydrogen, nitrogen and/or non-polar lower hydrocarbons, which comprises: contacting the waste gas mixture at temperatures within the range -20 to +30° C with a zeolite having a pore size of 5 x 10-8 to 15 x 10-8 cm; separating the phosphanes from the remainder of the waste gas mixture by adsorbing them on the zeolite until the latter is saturated therewith; heating the zeolite to a temperature within the range 180 to 230°C and collecting the desorbing phosphanes.
2) The process as claimed in claim 1, wherein the waste gas mixture contains 1 up to at most 70 volume % of said phosphanes.
3) The process as claimed in claim 1, wherein the waste gas mixture is contacted with the zeolite at room temperature.
4) The process as claimed in claim 1, wherein the zeolite is a Na-A grade zeolite.
5) The process as claimed in claim 1, wherein the zeolite has a pore size of 5 x 10-8 to 10 x 10-8 cm.
6) The process as claimed in claim 1, wherein the phosphanes are desorbed by heating the zeolite to a temperature within the range 180 to 200°C.
7) The process as claimed in claim 1, wherein the waste gas mixture contains C1 - C4 hydrocarbons as the non-polar lower hydrocarbons.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772746910 DE2746910A1 (en) | 1977-10-19 | 1977-10-19 | METHOD FOR RECOVERING PHOSPHANE AND METHYLPHOSPHANE |
| DEP2746910.9 | 1977-10-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1116537A true CA1116537A (en) | 1982-01-19 |
Family
ID=6021767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000311558A Expired CA1116537A (en) | 1977-10-19 | 1978-09-19 | Recovery of phosphane and methylphosphane |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0001589B1 (en) |
| CA (1) | CA1116537A (en) |
| DD (1) | DD139246A5 (en) |
| DE (2) | DE2746910A1 (en) |
| IT (1) | IT1109218B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4744221A (en) * | 1987-06-29 | 1988-05-17 | Olin Corporation | Zeolite based arsine storage and delivery system |
| US7064149B2 (en) * | 2001-09-13 | 2006-06-20 | Lc Chem, Ltd. | Process for preparing polymer latex resin powder |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR244505A1 (en) * | 1988-05-14 | 1993-11-30 | Deutsche Ges Schaedlingsbek | A method for preventing or delaying the formation of undesired phosphine levels in an environment, and the pesticide method for carrying it out. |
| JPH10130285A (en) * | 1996-10-31 | 1998-05-19 | Furukawa Co Ltd | Purification of organometal compound |
| DE602007008272D1 (en) * | 2007-12-21 | 2010-09-16 | Borealis Tech Oy | Reduction of phosphine release in plastic articles with red phosphorus |
| JP2012167551A (en) * | 2011-02-10 | 2012-09-06 | Denso Corp | Electromagnetic switch device |
| CN110548364A (en) * | 2019-10-17 | 2019-12-10 | 清远先导材料有限公司 | method and device for recovering special gas adsorbed by molecular sieve |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3982912A (en) * | 1971-03-31 | 1976-09-28 | Yoshifumi Yatsurugi | Method for preparation of an improved K-A type zeolite and for separation by adsorption polar and non-polar molecules |
| GB1385922A (en) * | 1971-03-31 | 1975-03-05 | Yatsurugi Y Kuratomi T | Preparation and use of 4-5a zeolite |
-
1977
- 1977-10-19 DE DE19772746910 patent/DE2746910A1/en not_active Withdrawn
-
1978
- 1978-09-19 CA CA000311558A patent/CA1116537A/en not_active Expired
- 1978-10-04 DE DE7878101060T patent/DE2860846D1/en not_active Expired
- 1978-10-04 EP EP78101060A patent/EP0001589B1/en not_active Expired
- 1978-10-13 DD DD78208443A patent/DD139246A5/en unknown
- 1978-10-17 IT IT51538/78A patent/IT1109218B/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4744221A (en) * | 1987-06-29 | 1988-05-17 | Olin Corporation | Zeolite based arsine storage and delivery system |
| US7064149B2 (en) * | 2001-09-13 | 2006-06-20 | Lc Chem, Ltd. | Process for preparing polymer latex resin powder |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1109218B (en) | 1985-12-16 |
| DE2746910A1 (en) | 1979-04-26 |
| DD139246A5 (en) | 1979-12-19 |
| EP0001589A1 (en) | 1979-05-02 |
| IT7851538A0 (en) | 1978-10-17 |
| EP0001589B1 (en) | 1981-07-15 |
| DE2860846D1 (en) | 1981-10-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |