US 4,063,896 AGrant
Removal of Phosgene Impurity From Boron Trichloride by Laser Radiation
Issue Date:1977-12-20
•7 Claims
•6 Drawing Sheets
Abstract
Phosgene, COCl.sub.2, an impurity in BCl.sub.3 is dissociated by CO.sub.2 ser radiation that is passed through a stainless steel laser cell with NaCl windows on each end of the cell. The power level of a cw CO.sub.2 multiline laser can be varied to accomplish the irradiation to effectively dissociate the COCl.sub.2 into its dissociation products, substantially CO and Cl.sub.2. The BCl.sub.3, .nu..sub.3 (956 cm.sup.-1) fundamental is resonant with CO.sub.2 (P.sub.20) laser line and strongly absorbs this energy which is followed by an intramolecular V--V transfer of energy to the COCl.sub.2 which results in its dissociation. The gaseous compound C.sub.2 H.sub.4 having combination bands and overtones that match reasonably close to the energy levels of COCl.sub.2 can also serve as a diluent for COCl.sub.2 to effect transfer of energy for dissociation of COCl.sub.2 by cw CO.sub.2 laser radiation.
Metadata
Assignee
- The United States of America as represented by the Secretary of the Army
Inventors
- James A. Merritt
- Lawrence C. Robertson
Application Information
Application Number:US 7543042
Filing Date:1976-12-27
Priority Date:1976-12-27
Art Unit:171
Classifications
IPC:
B01J 110
Field of Search:
23204254 R157.1 R
Patent Drawings (6 sheets)
Description
Background of the Invention
Commercially available BCl.sub.3 (boron trichloride) of the highest purity still contains up to 0.1 percent COCl.sub.2 (phosgene) contaminant. This contaminant or impurity causes difficulties when BCl.sub.3 is used in the electronics industry, as a catalyst in numerous ways such as in the production of styrene, as an additive for high energy fuels, in the refining of various refractory metals, etc. Removal of the impurity from BCl.sub.3 by economical methods has to data proven unsuccessful.
Advantageous would be a method to remove phosgene from boron trichloride or to change the phosgene to dissociation products which do not interfere with boron trichloride for its particular function or whereby the dissociation products of phosgene can be easily separated by conventional methods if required for boron trichloride catalysis function.
Therefore, an object of this invention is to provide a method for the dissociation of phosgene in the presence of BCl.sub.3 without loss of BCl.sub.3 concentration.
Another object of this invention is to provide a method to purify BCl.sub.3 from the contaminant phosgene with laser radiation.
A further object of this invention is to provide a method for dissociation of phosgene in BCl.sub.3 with a cw CO.sub.2 laser radiation whereby the fundamentals of BCl.sub.3 are resonant with the laser radiation to effect energy transfer to COCl.sub.2 and results in its dissociation.
Still a further object of this invention is to provide a method of dissociation of phosgene in the presence of C.sub.2 H.sub.4 that has combination bands and overtones that match reasonably close to the fundamental energy of phosgene to effect efficient V--V transfer of laser energy responsible for the dissociation of phosgene.
Summary of the Invention
The removal of COCl.sub.2 impurity in BCl.sub.3 is accomplished by using cw CO.sub.2 laser radiation. Mixtures of BCl.sub.3 and COCl.sub.2 and mixtures of C.sub.2 H.sub.4 and COCl.sub.2 are irradiated by cw CO.sub.2 multiline laser at a power level to achieve dissociation of COCl.sub.2. BCl.sub.3 and C.sub.2 H.sub.4 are gaseous compounds which are involved in the energy transfer from laser radiation to COCl.sub.2 to cause dissociation of the COCl.sub.2.
The gases in admixture were metered into a stainless steel cell with NaCl windows on each end to achieve a predetermined pressure and subsequently exposed to cw CO.sub.2 multiline laser radiation for a predetermined period of time to effect dissociation of COCl.sub.2. The predetermined pressure is to ensure efficient irradiation by the power level of the laser employed. That is, the molecular concentration of the gas in the cell should be in consonance with the power level of the cw CO.sub.2 multiline laser to achieve an efficient transfer of energy from the gases, either C.sub.2 H.sub.4 or BCl.sub.3, to COCl.sub.2 to effect dissociation of the COCl.sub.2. The spectra of the static products are then obtained with a spectrophotometer (e.g., Beckman IR5) to evaluate the experiment to ascertain that the COCl.sub.2 has been dissociated and to ascertain any depletion of the BCl.sub.3 or C.sub.2 Hhd 4 concentration.
Brief Description of the Drawing
The figures of the drawing are infrared spectra wherein the percent transmittance is shown on the ordinate and the wave number and wavelength are shown on the abscissa.
FIG. 1 is the spectra of BCl.sub.3 at 50 and 100 torr pressure showing the .nu..sub.4 (849 cm.sup.-1) and .nu..sub.2 (1827 cm.sup.-1) bands of COCl.sub.2 impurity.
FIG. 2 is the spectra of the gases of FIG. 1 after being mixed with varying concentrations of H.sub.2 and irradiated with cw CO.sub.2 laser radiation.
FIG. 3 is the spectra of a mixture of 50 torr pressure BCl.sub.3 and 0.8 torr pressure COCl.sub.2 after being irradiated with a 100 watt cw CO.sub.2 multiline laser.
FIGS. 4 and 5 are spectra which further illustrate the destruction of COCl.sub.2 in BCl.sub.3 without loss of BCl.sub.3 concentration, using a CO.sub.2 laser and a few seconds irradiation time.
FIG. 6 is the spectra of a mixture of 6 torr pressure of COCl.sub.2 and 50 torr pressure of C.sub.2 H.sub.4. Curve b illustrates the destruction of COCl.sub.2 but not as efficiently as when BCl.sub.3 is used to transfer energy to COCl.sub.2.
Description of the Preferred Embodiments
The BCl.sub.3 was obtained from Matheson Gas Products and had a stated impurity of 0.1% COCl.sub.2 maximum. It was used without further attempts to purify it. The H.sub.2 (hydrogen) was obtained from Silox Inc., and used without further purification as were the COCl.sub.2 and C.sub.2 H.sub.4 (ethylene) which were obtained from Matheson Gas Products.
The gases were metered into a laser cell (e.g., a 10 cm by 3 cm stainless steel cell with NaCl windows on each end) to provide a pressure in the range from about 5 torr to about 100 torr. Irradiation was accomplished with a cw CO.sub.2 multiline laser at varying power levels. The unfocused beam was passed through the cell for a given period of time after which the spectra of the static products were obtained with a Beckman IR5 spectrophotometer.
The detailed description of the drawing includes the figure captions as related to the experimental procedures as follows:
Fig. 1. spectra of BCl.sub.3 (with the COCl.sub.2 contaminant).
a. 100 torr pressure.
b. 50 torr pressure.
Fig. 2. the spectrum of 25 torr pressure of BCl.sub.3 (with the COCl.sub.2 contaminant) and 25 torr pressure of H.sub.2 before and after irradiation (O) for 2 sec with a 150 watt cw CO.sub.2 laser. The term WDO ABS is window absorption.
Fig. 3. spectra of 50 torr pressure of BCl.sub.3 and 0.8 torr pressure COCl.sub.2.
a. Before irradiation.
b. After 3 sec irradiation time - 100 watts cw CO.sub.2.
c. Additional 1 sec irradiation time - 100 watts cw CO.sub.2.
Fig. 4. spectra of 6 torr pressure BCl.sub.3 and 6 torr pressure COCl.sub.2.
a. Before irradiation.
b. After irradiation with a 100 watt cw CO.sub.2 laser for 15 sec.
Fig. 5. spectra of 10 torr pressure BCl.sub.3 and 100 torr pressure COCl.sub.2.
a. Before irradiation.
b. After irradiation with a 100 watt cw CO.sub.2 laser for 15 sec.
c. After an additional 20 irradiation time.
Fig. 6. spectra of 50 torr pressure C.sub.2 H.sub.4 and 6 torr pressure COCl.sub.2.
a. Before irradiation.
b. After irradiation with a 100 watt cw CO.sub.2 laser for 50 sec.
The irradiations of mixtures of BCl.sub.3 and COCl.sub.2 were accomplished with varying power levels of a cw CO.sub.2 multiline laser; however, the data illustrated by the Figures are based on a power level of a 100 watt cw CO.sub.2 multiline laser except as in FIG. 2 where the power level was at 150 watts.
FIG. 3 is the spectra of 50 torr pressure BCl.sub.3 and 0.8 torr pressure COCl.sub.2. After 3 sec irradiation time most of the COCl.sub.2 has disappeared (as evidenced by reference curve b) and an additional 1 sec irradiation essentially removes all the COCl.sub.2 from BCl.sub.3 without an appreciable depletion of the BCl.sub.3 concentration. FIGS. 4 and 5 are spectra which further illustrate the destruction of COCl.sub.2 in BCl.sub.3 without loss of BCl.sub.3 concentration, using a cw CO.sub.2 multiline laser and a few seconds irradiation time as noted hereinabove.
FIG. 5 (b and c) shows the appearance of the CO band at 2143 cm.sup.-1. Also, the addition of H.sub.2 to the cell after the irradiation resulted in large amounts of HCl being formed which indicates that Cl.sub.2 was present. The CO band and the formation of large quantities of HCl on addition of H.sub.2 indicates quite convincingly that the dissociation products of COCl.sub.2 are CO and Cl.sub.2.
The BCl.sub.3, .nu..sub.3 (956 cm.sup.-1) fundamental is resonant with the CO.sub.2 (P.sub.20) laser line and strongly absorbs this energy. The laser induced chemistry (LIC) reaction BCl.sub.3 + H.sub.2 .fwdarw.HBCl.sub.2 + HCl (See FIG. 2) is based upon this resonant absorption by .nu..sub.3 (BCl.sub.3). COCl.sub.2 does not have a fundamental resonant with the CO.sub.2 laser, consequently when pure COCl.sub.2 was irradiated, there was no change in the COCl.sub.2 concentration. This indicates that the BCl.sub.3 is involved in the dissociation of the COCl.sub.2. Thus, it is proposed that the BCl.sub.3 absorbs energy from the CO.sub.2 laser radiation, which is followed by an intramolecular V--V transfer of energy to the COCl.sub.2 which results in its dissociation into CO and Cl.sub.2. The .nu..sub.3 (240 cm.sup.-1) fundamental of COCl.sub.2 and the .nu..sub.4 (243 cm.sup.-1) fundamental of BCl.sub.3 are sufficiently close for efficient V--V transfer of energy.
If indeed the above mechanism is responsible for the dissociation of COCl.sub.2, then one could confirm this with another molecule having a fundamental that is resonant with the CO.sub.2 laser radiation and with a fundamental whose energy is close to that of one of the COCl.sub.2 fundamentals.
FIG. 6 shows 6 torr of COCl.sub.2 mixed with 50 torr of C.sub.2 H.sub.4. The .nu..sub.10 (995 cm.sup.-1) fundamental of C.sub.2 H.sub.4 is resonant with the CO.sub.2 laser radiation and does absorb this energy. However, C.sub.2 H.sub.4 has no fundamentals very close to the energy of the COCl.sub.2 fundamentals but there are combination bands and overtones that match reasonably close. FIG. 6 (b) illustrates that the COCl.sub.2 is being removed but not as efficiently as in the case where BCl.sub.3 is used for the transfer of energy.
The experimental data from this work strongly suggests that laser radiation can be used to purify materials that have fundamentals that are resonant with the laser radiation, BCl.sub.3 being a case in point, wherein efficient V--V transfer of energy takes place between the material being purified (BCl.sub.3) and the contaminant (COCl.sub.2).
As shown by examples, the contaminant COCl.sub.2 is dissociated by laser radiation if a diluent is employed such as C.sub.2 H.sub.4 which has combination bands and overtones that match reasonably close to the energy of the COCl.sub.2 so that energy transfer takes place to effect dissociation. This technique of using a diluent could be advantageous if neat phosgene were desired to be dissociated as a means to dispose of the poisonous gas. This same technique may be applicable to other combinations of an undesirable and a diluent or a host material which contains a contaminant whereby the contaminant or undesirable compound can receive energy transfer from laser radiation via a gaseous diluent or host material to effect dissociation.
The disclosures of this invention indicate that the irradiation method could be adapted for continuous flow operation or for batch operations whereby the gaseous components in a container or cell are irradiated by laser energy to effect dissociation of the undesirable or contaminant compound.
Other diluent compounds or host compounds having fundamentals that are resonant with the laser radiation or having combination bands and overtones that match reasonably close to the energy of the COCl.sub.2 could be selected for use with the method of this invention.
The primary object of this invention is to purify BCl.sub.3 from COCl.sub.2 contamination by laser irradiation to effect a dissociation of COCl.sub.2. The invention method can be adjusted to use higher power laser irradiation for larger systems or as may be required for maximum energy utilization. If separation of the dissociation products are required for the end use of the BCl.sub.3 then a separation step selected as modified from the prior art can be used in conjunction with this method.
Claims
We claim:
1. A method for dissociation of COCl.sub.2 by laser irradiation of COCl.sub.2 in presence of a gaseous compound selected from BCl.sub.3 and C.sub.2 H.sub.4, said selected gaseous compound when BCl.sub.3 having a fundamental whose energy is close to that of one of the COCl.sub.2 fundamentals and said selected gaseous compound when C.sub.2 H.sub.4 having combination bands and overtones that match reasonably close to the energy of COCl.sub.2 so that a transfer of energy takes place between said selected gaseous compounds and said COCl.sub.2 when irradiated by laser radiation to effect dissociation of said COCl.sub.2 when irradiated by laser radiation to effect dissociation of said COCl.sub.2, said method comprising: i. metering said selected gaseous compound and said COCl.sub.2 in admixture into a laser cell to achieve a predetermined pressure of said selected gaseous compound and said COCl.sub.2 which comprise the gaseous components in said laser cell, said predetermined pressure to ensure consonance between the concentration of said gaseous components and the power level of a cw CO.sub.2 multiline laser employed to irradiate said gaseous compound and said COCl.sub.2 to effect dissociation of said COCl.sub.2 ; ii. irradiating said selected gaseous compound and said COCl.sub.2 in admixture by a cw CO.sub.2 multiline laser at a predetermined power level of said cw CO.sub.2 multiline laser for a predetermined time period to effect dissociation of said COCl.sub.2 ; and, iii. obtaining a spectra of the static products of said admixture to detect said dissociation products of said COCl.sub.2 and to determine when all the COCl.sub.2 has been dissociated into dissociation products which are substantially CO and Cl.sub.2 and said spectra to additionally detect any appreciable depletion of said selected gaseous compound.
2. The method of claim 1 wherein said selected gaseous compound is BCl.sub.3 and said COCl.sub.2 is present as a contaminant in an amount of about 0.1%, said predetermined pressure is in the range from about 50 torr to about 100 torr; said predetermined power level of said cw CO.sub.2 multiline laser is about 100 watts; said predetermined time of irradiating is from about 3 seconds to about 4 seconds; and wherein said spectra detects that essentially all of said COCl.sub.2 has been dissociated into said dissociation products and that no appreciable depletion of said BCl.sub.3 concentration has taken place.
3. The method of claim 1 wherein said selected gaseous compound is C.sub.2 H.sub.4 and said COCl.sub.2 are mixed to form said admixture wherein said predetermined pressure of said C.sub.2 H.sub.4 is about 50 torr; said predetermined pressure of said COCl.sub.2 is about 6 torr; said predetermined power level of said cw CO.sub.2 multiline laser is about 100 watts; and said predetermined time or irradiating is about 50 seconds.
4. The method of claim 1 wherein said selected gaseous compound is BCl.sub.3 and said COCl.sub.2 are mixed to form said admixture wherein said predetermined pressure of said BCl.sub.3 varies from about 6 torr to about 50 torr and said COCl.sub.2 varies from about 0.8 torr to about 100 torr; said predetermined power level of said cw CO.sub.2 multiline laser is about 100 watts; said predetermined time of irradiating is from about 4 seconds to about 35 seconds; and wherein said spectra detects that essentially all of said COCl.sub.2 has been dissociated into said dissociation products and that no appreciable depletion of said BCl.sub.3 concentration has taken place.
5. The method of claim 4 wherein said predetermined pressure of said BCl.sub.3 is about 50 torr, said predetermined pressure of said COCl.sub.2 is about 0.8 torr; and said predetermined time of irradiating is about 4 seconds.
6. The method of claim 4 wherein said predetermined pressure of said BCl.sub.3 is about 6 torr; said predetermined pressure of said COCl.sub.2 is about 6 torr; and said predetermined time of irradiating is about 15 seconds.
7. The method of claim 4 wherein said predetermined pressure of said BCl.sub.3 is about 10 torr; said predetermined pressure of said COCl.sub.2 is about 100 torr; and said predetermined time of irradiating is about 35 seconds.
Non-Patent Literature (2)
- T. A. Osial, Instruments & Control Systems, Oct. 1967, pp. 101-104.
- Chem. Abstr. 75, 56720a (1971), Okabe et al.