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USOO5378439A United States Patent (19) 11 Patent Number: 5,378,439 Delobel et al. 45) Date of Patent: Jan. 3, 1995

54 PROCESS FOR REMOVING GASEOUS 4,605,812 8/1986 Nowack et al...... 423/20 HYDRDES FROMA SOLID SUPPORT 4,910,001 3/1990 Kitahara et al...... 423/210 COMPRISING METALLC OXDES 4,996,030 2/1991 Kitahara et al...... 423/210 75 Inventors: Olivier Delobel, Paris; Jean Louise, FOREIGN PATENT DOCUMENTS Villejuif, Philippe Cornut, Echirolles, 0060742 9/1982 European Pat. Off. . all of France 0194366 9/1986 European Pat. Off. . 280585 8/1988 European Pat. Off...... 423/210 73) Assignee: L'Air Liquide, Societe Anonyme Pour 2063216 7/1971 France . Etude et l'Exploitation des Procedes 62-95119 5/1987 Japan ...... 423/20 Georges Claude, Paris, France 62-286520 12/1987 Japan...... 423/20 21) Appi. No.: 914,215 2114911 9/1983 United Kingdom . 22 Fied: Jul. 16, 1992 Primary Examiner-Gary P. Straub Assistant Examiner-Peter DiMauro Related U.S. Application Data Attorney, Agent, or Firm-Young & Thompson 63 Continuation of Ser. No. 583,432, Sep. 17, 1990, aban 57 ABSTRACT doned. The invention concerns a process for removing gaseous 30 Foreign Application Priority Data from a solid support of metallic oxides, which Sep. 22, 1989 FR) France ...... 89 2448 consists in causing a gas flow to circulate, at room tem perature, on a solid support comprising at least copper 51) Int. Cl'...... B01D 53/34 and chromium and having a specific area lower than or 52 U.S. Cl...... 423/210; 423/230 equal to 100 m2/g. This process may be used for the 58 Field of Search ...... 423/210, 230; 55/68, destruction of gaseous hydrides from the industry of 55/72; 95/116, 136 semi-conductors, for example silanes, arsine, phosphine, 56) References Cited diborane, germane, stannane, gallane, stibine, and hy U.S. PATENT DOCUMENTS drogen , selenide and sulfide. 4,048,387 9/1977 Lahme et al...... 423/20 4,532,115 7/1985 Nishino et al...... 423A210 21 Claims, 1 Drawing Sheet

U.S. Patent Jan. 3, 1995 5,378,439

5,378,439 1. 2 This solid support has the great advantage that it can PROCESS FORREMOVING GASEOUSHYDRDES be regenerated after saturation. This regeneration, FROMA SOLID SUPPORT COMPRISING which may also be carried out before complete satura METALLIC OXDES tion, is carried out by passing a gas flow containing a 5 perfectly controlled oxygen content in nitrogen This application is a continuation of application Ser. through the apparatus, this oxygen content being of the No. 07/583,432, filed Sep. 17, 1990, now abandoned. order of 1 to 5% by volume and preferably from 1 to 2% by volume. BACKGROUND OF INVENTION The regeneration gas flow ensures the reoxidation of (a) Field of the Invention 10 the metallic elements which have been previously re The present invention concerns a process for remov duced by the passage and the destruction of the hy ing gaseous hydrides from a solid support of metallic drides. oxides. Since the oxidation is also highly exothermic, it is (b) Description of Prior Art recommended to control the change of temperature Gaseous hydrides such as silanes, arsine, phosphine, 15 with accuracy. diborane, germane, stannane, gallane, stibine, The regeneration cycle may be renewed many times. telluride, selenide or sulfide are compounds which are According to a preferred embodiment of the process largely used in the industry of semi-conductors and of the invention, in addition to copper and chromium, industries related to optic fibers, new materials, etc. In the solid support also contains manganese. this type of industry, the chemical reactions within 20 According to a particularly preferred embodiment of manufacturing reactors are never complete and some the process according to the invention, the solid support times substantial quantities of these gases are found at used for the removal of the gaseous hydrides also con the outlet of pumping systems as well as during flushing tains barium which consolidates the support, increases of the lines used. its lifespan and promotes the diffusion of the gases Because of the highly toxic and inflammable charac 25 ter of these gases, it appears essential to provide highly towards the active sites of the solid support. efficient treating devices which enable to obtain reject The solid support used in the process according to gases in which the hydrides do not exceed admissible the invention preferably has the following composition: minimum concentrations which for example are in the Cu 25 to 70 weight % order of 0.05 ppm for arsine, 0.3 ppm for phosphine, 5 30 Cr 15 to 40% weight % ppm for silane and 0.1 ppm for diborane. Ba 0 to 15% weight % Among the existing industrial technologies, the de Mn 0 to 5% weight % struction of gaseous on solid reactive materials The inert gas used for the dilution of the gaseous has already produced interesting results. However, it hydrides is preferably nitrogen. appears necessary to find solid phases which are more 35 The volume concentration of the hydrides in the gas reliable and more performing with respect to lifespan. flow hydride-dilution inert gas is 0.1 to 10 volume %, and preferably 1 to 5 volume %. SUMMARY OF INVENTION The process according to the invention is used with Thus the applicant has discovered that certain solids gas flows that one skilled in the art will be able to adapt supports, which are available in the industry, could 40 as a function of the time of residence of the gas flow on enable to treat hydride gases rejected by the industry of the solid support, and in order to obtain turbulent condi semi-conductors and related industries with a very high tions. efficiency. BRIEF DESCRIPTION OF OR AWING These solid supports are compounds of metallic ox ides containing at least one of the elements comprising 45 The invention will be better understood from a study copper and chromium and having a specific area lower of the detailed description of a preferred embodiment of than or equal to 100 m2/g. the invention given by way of example but without It is therefore an object of the present invention to limitation and in which the single figure represents an provide a process for removing gaseous hydrides con apparatus which can be used to carry out the process of sisting in causing the gas flow containing these hydrides SO the invention. diluted in an inert gas, to circulate, at room tempera ture, on a solid support comprising at least copper and DESCRIPTION OF PREFERRED chromium and having a specific area lower than or EMBODIMENTS equal to 100 m2/g. The gaseous hydride flow is introduced into the appa The process according to the invention may be used 55 ratus from a container under pressure 1, while dilution for the destruction of gaseous hydrides such as silanes nitrogen is introduced through valve 2. This gas mix and more particularly silane SiH4, arsine AsH3, phos ture is sent to a pressure reducer 3, then in mass flow phine PH3, diborane B2H6, germane, stannane Snha, regulators 4 and/or 5, in homogenisers 8 and/or 9, to gallane Gahs, stibine SbH3, hydrogen telluride TeH2, reach cartridges 10 and/or 11, which are here made of SeH2 and H2S. 60 glass and which contain the solid support of metallic The reaction is carried out at room temperature but oxides. Hydride detectors (DHAL) 12 and 13 are since it is highly exothermic, the temperature of the mounted at the outlet of the cartridges containing the apparatus must be controlled, either by outside cooling solid support and pick up a sample of a portion of the or by increasing the inert gas used for dilution. A pres gas flow treated in order to monitor the destruction of sure close to atmospheric pressure is used. 65 the hydrides which are present therein. The gas flow(s) The solid support is in the form of granular materials are thereafter sent at 14 towards a container containing ready for use. A simple treatment with nitrogen is suffi a catalyst of the type Hopcalite before being sent back cient to make it inert before use. to free air. 5,378,439 3 4. Mass flow regulators 6 and 7 are also provided to control the flow of regeneration gas introduced at 15. EXAMPLE 2 Nitrogen which is used as flushing gas may also be The operation is the same, as in example 1, exept that introduced at 16 in order to flush the apparatus at the there is used a solid support consisting of 33 weight % end of the cycle. 5 copper, 27.5 weight % chromium and 11.5 weight % The mass regulators 4 and 5 on the one hand and 6 barium, the remainder consisting of oxygen, having a and 7 on the other hand, homogenisers 8 and 9 as well specific area of 30 m2/g and an apparent density of 1.8. as the solid support cartridges 10 and 11 and the hydride The amount of destruction of phosphine is 79 1/1 of detectors 12 and 13 can operate in parallel or alter solid support after two cycles of destruction and two nately, the solid supports found at 10 and 11 being iden- 10 cycles of regeneration. tical or different. The process of regeneration on solid support is identi The process of the invention will be better illustrated cal to that of example 1. by means of the examples which follow which are given The operating parameters and the results are given in only as illustrations and are not intended to limit the the following table 2. scope of the invention. 15 TABLE 2 EXAMPLE 1. Catalyst 2 A gas flow containing 5 volume 26 phosphine in Mass 104.5 g Volume 650 cm nitrogen, with a total flow of 50 l/h is sent over a solid 1st Des- 1st Re- 2nd Des- 2nd Re support or catalyst containing- 42 weight % copper and 20 truction generation truction generation 26.5 weight % chromium, the balance consisting of 3. flow 50 50 50 50 SO 50 oxygen, having a specific area of 40 m2/g and an appar- Concentration 5% 5% ent density of 1.8. The maximum temperature measured in PH3 is 120° C. Concentration 2%. 5% 2%. 5% The amount of destruction of phosphine is 75 liters of 25 TE... maxi. 108 25 22 65 26 26 phosphine per liter of solid support after two cycles of ited destruction and two cycles of regeneration. Temp. maxi. 58 47 In order to prevent that the container containing the Wall'C. solid support warms up too rapidly, the following oper- Yelts 44 7.5 ating conditions are used for the regeneration of the 30 WE O2 in 1 15 9.8 solid support: Yield 1 PH3/1 67 79 total flow: 50 l/hr catalyst O2 content: 2 volume % Vol. total O2 24 39 maximum temperature measured: 120°O C. 1/1 catalyst The various operating parameters and the results 35 obtained are given in the following table 1. EXAMPLE 3 TABLE I The operation is the same as in the previous examples Catalyst 1 except that there is used a catalyst containing 35 weight Mass 1031 g Volume 560 cm- 40 % copper, 31 weight % chromium, 2 weight % barium 1st Des- 1st Re- 2nd Des- 2nd Re- and 2.5 weight % manganese, the balance consisting of truction generation truction generation oxygen, having a specific area of 30 m2/g and an appar Total flow 50 50 50 50 50 50 ent density of 1.8. &ncentation 5% 5% The amount of destruction of phosphine is 95 1/1 of in PH3 45 solid support after three cycles of destruction and three Concentration 2%. 5% 2%. 5% cycles of regeneration. i O2 92 48 25 37 48 39 The process of regeneration of the solid support is the E". same as the one of example 1. Temp. maxi. 51 The operating parameters and the results obtained are wall C. given in the following table 3. Volume PH3 39 2.5 destroyed 1 Volume O2 in 1 15 9.8 Yield 1 PH3/1 70 75 catalyst Vol. total O2 1/1 catalyst 27 45

TABLE 3 Catalyst 3 Mass 1014 g Volume 530 cm 1st 1st 2nd 2nd 3rd 3rd Destruction Regeneration Destruction Regeneration Destruction Regeneration Total flow 50 50 50 50 50 50 1/hr Concentration 5% 5% 5% in PH3 Concentration 2% 2% 4% in O2 5,378,439 5 TABLE 3-continued Catalyst 3 Mass 1014 g Volume 530 cm 1st 1st 2nd 2nd 3rd 3rd Destruction Regeneration Destruction Regeneration Destruction Regeneration Temp. maxi. 09 OO 67 43 36 98 internal C. Volume PH3 39.2 8.7 2.3 destroyed 1 Volume O2 in 1 20 25 19 Yield 1 PH3/1 74 90.5 94.8 catalyst Vol. total O2 38 83 120 1A1 catalyst

15 9. Process according to claim 7, wherein the inert gas is nitrogen. 10. Process according to claim 7, wherein the gaseous hydrides are selected from the group consisting of si EXAMPLE 4 lanes,y arsine, phosphine, diborane,group germane, stannane,9. A gas flow containing 2.5 volume 2% of arsine Ash: 20 gallane, stibine, hydrogen telluride, hydrogen selenide in nitrogen is allowed to pass with a flow of 120 l/hr on and hydrogen sulfide. a solid support containing 35 weight % copper, 31 11. Process according to claim 7, wherein the gaseous weight % chromium, 3.2 weight 2% barium and 2.5% hydrides are selected from the group consisting of si weight % managanese, the balance consisting of oxy lanes, phosphine, diborane, germane, stannane, gallane, gen, having a specific area of 30 m/g and an apparent 25 hydrogen telluride and hydrogen selenide. density of 1.8. 12. Process according to claim 11, wherein the gase A cartridge having a diameter of 80 mm containing ous hydride is SiH4. 1252 g of solid support having a volume of 700 cm3, is 13. Process according to claim 7, wherein the concen used. tration of the hydrides in the gas flow is comprised The rate of destruction of arsine is 70 1/1 of solid 30 between 5 and 10 volume 2%. Support. 14. Process according to claim 7, and subjecting the The process of regeneration of the solid support is the solid support to at least one regeneration cycle. same as previously. 15. Process according to claim 14, wherein the regen We claim: eration is carried out by exposing the solid support to a 1. Process for removing gaseous inorganic hydrides 35 gas flow containing 1 to 5 volume % oxygen. from a gas stream, comprising circulating a gas flow 16. Process for removing gaseous inorganic hydrides containing the hydrides diluted in an inert gas, on a solid from a gas stream, comprising circulating a gas flow support consisting essentially of metallic oxides of man containing from 1 to 10 volume % of the hydrides di ganese, copper and chromium, and having a specific luted in an inert gas, on a solid support consisting essen area lower than or equal to 100 m2/g, said solid support tially of metallic oxides of copper, chromium, barium having from 2.5 to 5 weight % Mn, 25 to 70 weight % and manganese said manganese being present in an Cu, and 15 to 40 weight % Cr, and wherein said hy amount from 2.5 to 5 weight %, and having a specific drides are selected from the group consisting of silanes, area lower than or equal to 100 m2/g, said hydrides phosphine, diborane, germane, stannane, gallane, hy being selected from the group consisting of silanes, drogen telluride and hydrogen selenide. 45 phosphine, diborane, germane, stannane, gallane, hy 2. Process according to claim 1, wherein the inert gas drogen telluride and hydrogen selenide. is nitrogen. 17. Process according to claim 16, wherein the inert 3. Process according to claim 1, wherein the volume gas is nitrogen. concentration of the hydrides in the gas flow is com 18. Process according to claim 16, wherein the vol prised between 1 and 10 volume 2. 50 ume concentration of the hydrides in the gas flow is 4. Process according to claim 1, wherein the volume comprised between 5 and 10 volume 9%. concentration of the hydrides in the gas flow is com 19. Process according to claim 16, and subjecting the prised between 5 and 10 volume %. Solid support to at least one regeneration cycle. 5. Process according to claim 1, and subjecting the 20. Process according to claim 19, wherein the regen solid support to at least one regeneration cycle. 55 eration is carried out by exposing the solid support to a 6. Process according to claim 5, wherein the regener gas flow containing 1 to 5 volume % oxygen. ation is carried out by exposing the solid support to a 21. Process for removing gaseous inorganic hydrides gas flow containing 1 to 5 volume % oxygen. from a gas stream, comprising circulating a gas flow 7. Process for removing gaseous inorganic hydrides containing the hydrides diluted in an inert gas, on a solid from a gas stream, comprising circulating a gas flow support consisting essentially of metallic oxides of man containing from 2.5 to 10 volume % of the hydrides ganese, copper, chromium, and barium, and having a diluted in an inert gas, on a solid support consisting specific area lower than or equal to 100 m2/g, said solid essentially of metallic oxides of copper, chromium, support having from 2.5 to 5 weight % Mn, 25 to 70 barium and manganese said manganese being present in weight %, Cu, and 14 to 40 weight % Cr, and wherein an amount from 2.5 to 5 weight%, and having aspecific 65 said hydrides are selected from the group consisting of area lower than or equal to 100 m2/g. silanes, phosphine, diborane, germane, stannane, gal 8. Process according to claim 7, wherein the solid lane, hydrogen telluride and hydrogen selenide. support comprises at most 15 weight % barium. k . . . .