# Patent

## Title
Articles of manufacture containing increased stability low concentration gases and methods of making and using the same

## Abstract

Articles of manufacture and methods of making and using same concern a container having an internal space and a passivated internal metal surface. The container contains a composition of an acid gas and a balance gas contained within the internal space and in contact with the passivated internal metal surface. The stability of the acid gas concentration over time is enhanced.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a division of Ser. No. 12/352,925 which was filed on Jan. 13, 2009 which is a division of Ser. No. 11/168,948 filed Jun. 28, 2005 which is a continuation in part, of Ser. No. 11/063,928, filed Feb. 22, 2005 (now U.S. Pat. No. 7,229,667) which is a division of non-provisional patent application Ser. No. 10/157,468, filed May 29, 2002, now abandoned and is a division of Ser. No. 10/157,466, filed May 29, 2002, now abandoned, which claims the benefit of provisional patent application Ser. No. 60/306,014, filed Jul. 17, 2001. Each of these applications is incorporated by reference herein.


BACKGROUND OF THE INVENTION
Moisture is known to react with so-called “acid gases”, such as hydrogen sulfide, carbonylsulfide, carbondisulfide and mercaptans (mercaptans are also referred to as thiols) to form a complex compound. (The term “acid gas” is used herein to denote either gas phase, liquid phase, or mixture of gas and liquid phases, unless the phase is specifically mentioned.)
One problem presents itself: if one is interested in producing acid gas standard compositions, in other words acid gases having a known concentration of one of these gases in a matrix or carrier fluid, then one must consider how to reduce or remove the moisture. Gas standards may have to have, and preferably do have, a long shelf life, since the standard acid gas may not be required immediately after production. A source of acid gas and/or matrix gas may contain a considerable amount of moisture. Therefore, the reduction or removal of moisture from the acid gas is important if the stability of the acid gas in the standard gas is to be maintained.
U.S. Pat. Nos. 5,255,445 and 5,480,677 describe processes for drying and passivating a metal surface to enhance the stability of gas mixtures containing one or more gaseous hydrides in low concentrations in contact therewith. The process comprises purging gas in contact with the metal surface with inert gas to remove the purged gas, exposing the metal surface to an amount of a gaseous passivating or drying agent comprising an effective amount of a gaseous hydride of silicon, germanium, tin or lead and for a time sufficient to passivate the metal surface, and purging the gaseous passivating agent using inert gas. Optionally, an oxidizing agent is applied after the third step to stabilize the adsorbed stabilizing agent. The patent also mentions prior known processes, such as saturation passivation, where the container is subjected to several cycles of evacuating and filling with a much higher concentration of the same gaseous hydride, prior to being filled with the low concentration hydride mixture of interest. The two patents do not mention or describe processes to passivate containers adapted to store sulfur-containing gases, nor do they mention passivation techniques in which a first passivating agent is applied to the surface, followed by contacting with a higher concentration of the gas to be stored.
Co-pending application Ser. No. 10/157,467, filed on May 29, 2002 describes the use of certain acid gas resistant molecular sieves to reduce or remove moisture from fluid compositions comprising a sulfur-containing compound. There is no disclosure or suggestion, however, for the passivation of containers adapted to contain the moisture-reduced compositions. Such containers may have moisture adhered to the internal surfaces, which can and does react with acid gases, reducing their stability and shelf-life.
A second, related problem involves the containers that the reactive gas standards are stored in. If metal or metal lined, reactive gases will react with and/or become adsorbed onto the metal, and will ultimately change the concentration of the reactive gas.
Grossman et al. (U.S. Pat. No. 4,082,834) describes alloys, such as alloys of nickel, titanium, and zirconium, that react with water and reactive gases (such as hydrogen, hydrogen-containing compounds such as hydrocarbons, carbon monoxide, carbon dioxide, oxygen, and nitrogen) at temperatures ranging from about 200° C. to about 650° C. While the patent does not discuss acid gases, it is apparent that hydrogen sulfide, carbonyl sulfide, and mercaptans are hydrogen-containing compounds, so that there would not be any expected benefits using these alloys to remove moisture from these acid gases. While carbondisulfide does not contain hydrogen, and therefore there could be some moisture reduction from a composition comprising carbondisulfide and moisture using these alloys, the high temperature is prohibitive for commercial use.
Tamhankar et al. (U.S. Pat. No. 4,713,224) describes a one-step process for removing minute quantities of impurities from inert gases, where the impurities are selected from the group consisting of carbon monoxide, carbon dioxide, oxygen, hydrogen, water and mixture thereof. The process comprises contacting the gas with a particulate material comprised of nickel in an amount of at least about 5% by weight as elemental nickel and having a large surface area, from about 100 to about 200 m2/g. There is no disclosure of removal of moisture from reactive gases; there is therefore no discussion or suggestion of moisture removal from reactive gases, moisture removal from matrix gases and mixing same to form a standard gas composition.
Tom et al (U.S. Pat. Nos. 4,853,148 and 4,925,646) discloses processes and compositions for drying of gaseous hydrogen halides of the formula HX, where X is selected from the group consisting of bromine, chlorine, fluorine, and iodine. The patent describes the use of, for example, an organometallic compound such as an alkylmagnesium compound, on a support. The halide is substituted for the alkyl functional group. Suitable supports are, alumina, silica, and aluminosilicates (natural or synthetic). However, there is no description or suggestion of reducing or removing moisture from sulfur-containing reactive gases, or of removal of moisture from matrix gases and mixing the reduced moisture gases to form a standard gas. Alvarez, Jr. et al. (U.S. Pat. No. 5,910,292) describes a process and apparatus for removal of water from corrosive halogen gases, using a high silica zeolite, preferably high silica mordenite. The patent describes removing moisture down to less than or equal to 100 ppb water concentration in halogen gases, particularly chlorine- or bromine-containing gases, but once again, there is lacking any teaching of suggestion of standard gas compositions. U.S. Pat. No. 6,183,539 discloses utilizing high sodium, low silica faujasite particles for the adsorption of carbon dioxide and water vapor from gas streams. The disclosed types of gas streams in which this type of high sodium, low silica faujasite crystals can be utilized includes air, nitrogen, hydrogen, natural gas, individual hydrocarbons and monomers, such as ethylene, propylene, 1,3 butadiene, isoprene and other such gas systems. There is no mention of sulfur-containing acid gas purification using the faujasites, or production of standard gas compositions.
U.S. Pat. No. 4,358,627 discloses use of “acid resistant” molecular sieves, such as that known under the trade designation “AW300”, for reducing the chloride concentration in chlorinated liquid hydrocarbons that contain an ethylenically unsaturated chlorinated hydrocarbon, water and hydrogen chloride. The method includes providing certain nitrogen-containing compounds in the system and contacting the system with the molecular sieve. There is no disclosure or suggestion, however, of removal or reduction of moisture from gas phase compositions, or production of standard gas compositions.
With respect to sulfur compounds, one impetus for measurement of low levels of these compounds has come from the hydrocarbon process industry where the requirement for lower sulfur measurements is steadily increasing. Controlling the concentration of sulfur is quite important for two major reasons. First, low sulfur content in simple olefin feed stock for high purity linear polymers such as polyethylene and polypropylene is quite important. Sulfur compounds adsorb onto the surface of the catalysts and prevent the desired reactants from reaching the catalytic surface thereby deactivating the catalyst. Given the quantity of these products produced annually, the economic impact can be quite significant. Therefore, common sulfur impurities in the feed stock, such as H2S (hydrogen sulfide) and COS (carbonyl sulfide) must be carefully monitored.
Second, sulfur in the form of sulfur dioxide (SO2), has been classified as a criteria pollutant by the EPA. This translates into strict regulation of emissions from coal burning plants, motor vehicle emissions, and paper and wood pulp processing plants to name a few. Sulfur in coal and gasoline becomes sulfur dioxide when the fuel is combusted. This SO2 is a precursor to acid rain. Reducing sulfur in gas not only lowers sulfur dioxide emissions but also reduces catalytic converter poisoning. This increases a vehicle's pollution control efficiency thus reducing other pollutants.
In order to monitor, control and regulate these compounds and other reactive gases, calibration gas mixtures containing these compounds must be used. For these mixtures to be utilized successfully, they must be reliable with respect to stability (shelf life) and concentration. Significant challenges arise as the concentrations of reactive gas mixtures required to calibrate equipment are decreased. Interactions on the cylinder and tubing surfaces, such as chemical reactions and adsorption, are often insignificant with reactive gas concentrations in the range of 10 ppm and above. These interactions become quite important with reactive gases at concentrations at or below 1 ppm. Impurities, such as moisture, which are present in the source gas can also play a major role in the stability of these mixtures.
Given the problem of moisture reacting with acid gases and reactive gases in general, it would be advantageous if passivation methods could be provided which increase the shelf-life during the storage of these compounds.
SUMMARY OF THE INVENTION
In accordance with the present invention, articles of manufacture containing increased stability low concentration gases and methods of making and using the same are provided in order to enhance the stability of low concentration acid gas compositions within the articles over time.
A first aspect of the invention relates to an article of manufacture comprising:
a) a container having an internal space and a passivated internal metal surface; and
b) a composition comprising an acid gas and a balance gas contained within the internal space and in contact with the passivated internal metal surface; wherein

    
    
        i) the acid gas has a concentration in the balance gas of less than 500 ppb;
        ii) the acid gas is selected from the group consisting of carbon disulfide, carbonylsulfide, and compounds within formula (I):

Y—S—X  (I)

         wherein S is sulfur, X and Y are the same or different and are independently selected from the group consisting of hydrogen, alkyl, aryl, oxygen, hydroxyl, amine, aminosilane, oxygen, and alcohol; and
        iii) the passivated internal metal surface comprises A) the reaction product of a silicon-containing material and an oxygen-containing material and B) the acid gas adsorbed on or in the passivated internal metal surface in an amount effective to enhance the stability of the intended concentration over time.
    
    


A second aspect of the invention is a method of making an article of manufacture containing an acid gas having an intended concentration which is stably maintained over time, the method comprising the steps of:
exposing an internal metal surface of a container to a first composition comprising one or more silicon-containing compounds for a time sufficient to allow at least some of the silicon-containing compound(s) to react with oxygen-containing compounds present to form a silicon-treated surface on at least some of the internal metal surface, the silicon-containing compound(s) selected from the group consisting of compounds within the general formula (II):

SiR1R2R3R4  (II)

wherein R1, R2, R3, and R4 are the same or different and are independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, amine, halogenated alkyl, and halogenated aryl;

evacuating the container for a time sufficient to remove substantially all of the silicon-containing compound(s) that has not reacted with the oxygen-containing compound to form the silicon-treated surface;
exposing the silicon-treated surface to a second composition comprising an acid gas having a concentration that is greater than an intended concentration of the acid gas;
evacuating the container for a time sufficient to remove an amount of the second composition to enhance the stability of the intended concentration over time; and
filling the container with a third composition comprising the acid gas at the intended concentration.
A third aspect of the invention is a method of calibrating a measurement device for measuring a concentration of an acid gas, the method comprising the steps of:
providing a manufactured product comprising:

    
    
        i) a container having an internal space and a passivated internal metal surface; and
        ii) a composition comprising an acid gas and a balance gas contained within the internal space and in contact with the passivated internal metal surface; wherein
        
            A) the acid gas has an intended concentration of less than 500 ppb;
            B) the acid gas is selected from the group consisting of carbon disulfide, carbonylsulfide, and compounds within formula (I):

Y—S—X  (I)

            wherein S is sulfur, X and Y are the same or different and are independently selected from the group consisting of hydrogen, alkyl, aryl, oxygen, hydroxyl, amine, aminosilane, oxygen, and alcohol; and
            C) the passivated internal metal surface comprises I) the reaction product of a silicon-containing material and an oxygen-containing material (preferably selected from the group consisting of moisture, molecular oxygen, metal oxides, and mixtures thereof), and II) the acid gas adsorbed on or in the passivated internal metal surface in an amount effective to enhance the stability of the intended concentration over time; and
        
        
    
    


using a portion of the acid gas contained within the manufactured product in a calibration of the measurement device; and
repeating said step of using a portion at least once, wherein a period of time commencing from a first performance of said step of using a portion and expiring on a later repetition of said step of using a portion is not less than 30 days.
Further aspects and advantages of the invention will become apparent by reviewing the description of preferred embodiments that follow.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the stability of H2S concentration in low-level H2S standards over time;
FIG. 2 shows the stability of H2S concentration in low-level H2S standards over time;
FIG. 3 shows the stability of H2S concentration in low-level H2S standards over time;
FIG. 4 shows the stability of H2S and COS concentrations in low-level H2S and COS standards over time;
FIG. 5 shows the stability of SO2 concentration in low-level SO2 standards over time;
FIG. 6 shows the stability of H2S and COS concentrations in low-level H2S and COS standards over time; and
FIG. 7 shows the stability of H2S concentration in low-level H2S standards over time.



DESCRIPTION OF PREFERRED EMBODIMENTS
While the following discussion focuses on a container which has a metal internal surface, the description is not limited thereto, and could apply to a piping or tubing system, a manifold, a gas cylinder having a cylinder valve, ton unit, and the like.
Initially, it is preferred to start with an abraded internal metal surface which has been vacuum baked prior to the reaction of the organosilane with oxygen-containing compounds.
The internal surface of the container, or the surface to be treated, may be subject to abrasion prior to reaction of the silicon-containing compound with oxygen-containing compounds in order to improve adhesion of the reaction product to the metal. Typical abrasion techniques may be found in copending non-provisional patent application Ser. No. 10/157,466, filed May 29, 2002, now published as US 2003/0017359 A1.
The preferred vacuum baking step is typically, this is performed at a temperature of from about 30° C. to about 75° C., a duration of time of no less than 1 hour (preferably no less than 4 hours, even more preferably no less than 6 hours, and still more preferably no less than 12 hours), and a vacuum of no more than 100 torr (preferably no more than 1 torr and more preferably no more than 0.01 torr).
The internal metal surface is then subjected to the reaction between the silicon-containing compound and the oxygen-containing compound.
Silicon-containing compounds within the general formula (II) are known to react with oxygen-containing compounds, such as H2O, N2O, CO2, and the like, to produce SiO2, especially when the silicon-containing compounds are in the gaseous or vapor state.

SiR1R2R3R4  (II)

This fact is taken advantage of in the practice of the various aspects of the invention. The reaction product of a silicon-containing compound and an oxygen-containing compound such as water forms an amorphous or crystalline glassy material on the surfaces on which it is deposited. The amorphous or crystalline glassy material may include aluminum silicide, if the container or surface being treated comprises aluminum. Although the deposited material is referred top herein as a “coating”, it shall be readily understood that in fact the material may deposit non-uniformly, or not at all on certain areas of the surface being treated. This coating then serves the function of deactivating a surface for the adsorption of molecules of the gas that is ultimately to be contained in the container or piping system at low concentration. In other words, the coating serves to decrease the number of reactive sites on the metal surface being treated. For simplicity, silicon-containing compounds within formula (II) shall be referred to as organosilanes, although their formal name under IUPAC convention may differ.

The reaction of an organosilane within general formula (II) with oxygen-containing materials such as water proceeds without catalyst at room temperature (25° C.); however, it is preferred to carry out the reaction at moderately elevated temperatures, such as temperature ranging from 25° C. up to 100° C., in order to produce the coatings in reasonable time. Most preferably, the temperature is maintained at not more than 74° C. The pressure of the reaction of an organosilane with water vapor will generally also proceed at atmospheric pressure, however, the pressure in the container, or near the surface being treated, may either be in vacuum or above atmospheric pressure. This will of course depend on the rates of reaction of the organosilane with the oxygen-containing compound, the desired coating deposition rate, and desired thickness of the coating. It is of course within the invention to make layered coatings of two or more organosilane/oxygen-containing compound reaction products. It is also considered within the invention to employ two or more organosilanes simultaneously to make a “mixed” coating. Indeed, it is possible that the organosilane may be employed in conjunction with a non-organosilane to form either layered or mixed coatings.
Silane and organosilanes are toxic materials, and, depending on the organosilane, pyrophoric. Special care in handling these materials is warranted, preferably well-ventilated hoods. Electronic grade silane (SiH4) is available commercially in cylinders from Air Liquide America Corporation, Houston, Tex. Trimethylsilane is available commercially from Dow Corning Corporation.
Preferred silicon-containing compounds include silane, and methyl-containing organosilanes; particularly those wherein the methyl-containing organosilane is selected from the group consisting of methylsilane, dimethylsilane, trimethylsilane and tetramethylsilane. Preferred organosilane compounds include methylsilane compounds having the structure SiHn(CH3)4-n, where n=1 to 3, i.e. methylsilane, dimethylsilane, or trimethylsilane or the structure Si2Hm(CH3)6-m, where m=1 to 5. The most preferred organosilane compound is methylsilane, CH3SiH3. The organosilane compounds are hydrolyzed by reaction with water, oxygen or water-containing gases such as humid air and/or other oxygen-containing gases, such that the carbon content of the deposited film is from 1 to 50% by atomic weight, preferably about 20%.
It is conceivable to employ adjuvants during the reaction of an organosilane with water. In the practice of the invention, “adjuvant” includes physical and chemical adjuvants, and combinations thereof. Suitable physical adjuvants include electrostatic discharge, plasma discharge, laser excitation, and the like, under temperatures and pressures suitable for each of these processes. For example, plasmas are preferably best employed in moderate vacuum. A chemical adjuvant might include an oxidant gas such as oxygen, ozone, chlorine dioxide, combinations thereof, and the like. When a combination of physical and chemical adjuvants is employed, for example ozone and plasma discharge, the reaction product may be described as similar to the films produced b the process described in U.S. Pat. No. 6,054,379, which is incorporated herein by reference for its teaching of the production of such films.
Preferably, the silicon-containing composition is 1% Silane in N2 and is maintained at 100 psig for 1 day during which it reacts with any oxygen-containing compounds present, such as moisture or air.
The container or surface to be treated may be selected from the group consisting of iron, stainless steel (for example 301, 316, 401), aluminum, aluminum alloy, steel alloys and the like.
Once the metal container inner surface, or metal surface to be treated, is cleaned, and the reaction of organosilane with oxygen-containing compounds completed (either with or with out adjuvants) to form a coating, the processes of the invention include evacuating the container for a time and vacuum sufficient to remove substantially all silicon-containing compound(s) that has not reacted with oxygen-containing compounds. This first evacuation step preferably includes evacuation down to a vacuum of about 1 torr, more preferably down to 0.01 torr. The temperature during this evacuation process is not critical, but higher temperatures may tend to increase the removal rate of organosilane. This will be balanced by safety issues, in that higher temperatures may be more hazardous. Therefore, room temperature (about 25° C.), or slightly lower or slightly higher than room temperature is preferred. After the vacuum step is performed, it is followed by a N2 fill step.
Subsequent to this first evacuation step, the next step is exposing the coating to a gas composition, the gas composition having a concentration of an acid gas that is greater than an intended acid gas concentration of a manufactured product. The acid gas is caused to contact the coating and deactivate the surface even further. The acid gas preferably has a concentration of at least 10 times the concentration of the acid gas that is to be stored in the container or exposed to the surface, more preferably has a concentration 50 times greater than the concentration of the acid gas that is to be stored in the container, still more preferably 500 times greater than the ultimate concentration, and even still more preferably 50,000 times the concentration of the acid gas to be stored in the container. When H2S is selected as the acid gas, it is preferred to perform this step using 5000 ppm H2S in N2 at 100 psig.
Typical acid gases in include carbon disulfide, carbonylsulfide, and compounds within formula (I):

Y—S—X  (I)

wherein S is sulfur, X and Y are the same or different and are independently selected from the group of hydrogen, alkyl, aryl, oxygen, hydroxyl, amine, aminosilane, oxygen, and alcohol.

Examples of preferred sulfur-containing compounds within formula (I) include hydrogen sulfide, carbonyl sulfide, sulfur dioxide, methylthiol, ethylthiol, n-propylthiol, i-propylthiol, benzylthiol, and the like. Especially preferred sulfur-containing compounds within formula (I) include hydrogen sulfide, carbonyl sulfide and sulfur dioxide.
The degree of adsorption of the acid gas onto the coating depends in a complicated way on the composition and physical properties of the coating, the temperature and pressure employed during this step, as well as on the chemical and physical properties of the particular acid gas that is being adsorbed thereon. These parameters are in turn dictated by the final concentration of acid gas that is to be stored in the container. A discussion of adsorption of gaseous species onto surfaces that is helpful in this respect is included in Daniels, F. et al., “Experimental Physical Chemistry”, Seventh Edition, McGraw-Hill, pages 369-374 (1970). While the inventors are not certain, it is believed that the attraction of the acid gas to the coating is physical in nature, involving an interaction of dipoles or induced dipoles, but may be chemical in nature involving chemical bonds, as when oxygen is adsorbed on charcoal. A combination of physical and chemical forces may be at work as well. Thus, the surface area of a coating produced by the practice of the present invention may be determined by the B.E.T. method, and preferably is at least about 1 m2/gram, more preferably at least 10 m2/gram. If the coating is somewhat porous, the pore volume may be determined by nitrogen adsorption isotherm methods, and is preferably at least 0.1 ml/gram. The B.E.T. method is described in detail in Brunauer, S. Emmet, P. H., and Teller, E., J. Am. Chem. Soc., 60, 309-16 (1938). The nitrogen adsorption isotherm method is described in detail in Barrett, E. P., Joyner, L. G. and Helenda, P. P., J. Am. Chem. Soc., 73, 373-80 (1951), incorporated by reference herein. In general, if the concentration of acid gas to be stored in the container is 100 ppb, then for the same acid gas, same temperature and pressure, and same coating, the concentration of acid gas used in this step will be higher than if the ultimate concentration of acid gas is to be only 50 ppb, assuming adsorption is the governing pathway. An increase in temperature will tend to require an increase in concentration of acid gas, an increase in pressure, or both, to achieve the same degree of adsorption. In contrast, a decrease in temperature will tend to require a decreased concentration of acid gas, a decrease in pressure, or both to achieve the same level of adsorption.
After the surface has been further deactivated by exposure to the acid gas at high concentration, a second evacuation step is carried out to remove excess acid gas. In this step, evacuation of the container is carried out for a time sufficient to remove substantially all of non-adsorbed acid gas, leaving acid gas adsorbed on the coating. Once the metal container inner surface, or metal surface to be treated, is cleaned, and the reaction of organosilane with oxygen-containing compounds completed (either with or with out adjuvants) to form a coating, the processes of the invention include evacuating the container for a time and vacuum sufficient to remove substantially all silicon-containing compound(s) that has not reacted with oxygen-containing compounds. Preferably, this step is performed down to a vacuum of about 1 torr, more preferably down to 0.01 torr. The temperature during this evacuation process is not critical, but higher temperatures may tend to increase the removal rate of organosilane. This will be balanced by safety issues, in that higher temperatures may be more hazardous. Therefore, room temperature (about 25° C.), or slightly lower or slightly higher than room temperature is preferred. After the vacuum step is performed, it is followed by a N2 fill step.
When SO2 is selected as the acid gas, steps in addition to the foregoing are preferable and include the following. After completion of the reaction between the silicon-containing and oxygen-containing compounds, but before the vacuum and N2 fill step, the cylinder is subjected to five cycles of being filled with Nitrogen at 100 psi followed by venting. Similarly, after completion of the exposure of the internal cylinder surface to SO2 (the selected acid gas), but before the vacuum and N2 fill step, the treated cylinder is again subjected to five cycles of being filled with Nitrogen at 100 psi followed by venting.
The container is then filled with a gas composition comprising the intended low concentration of acid gas in the balance gas. While preferred manufactured products of the invention comprise only a single acid gas with one balance gas, two or more acid gases and/or two or more balance gases may be used. Typical balance gases include noble gases, nitrogen, ethylene, propylene, and mixtures thereof.
As shown below in the Examples, application of the method of the invention to acid gases having concentrations below 500 ppb exhibits unexpectedly good stability. The unexpected stability is even more surprising as the concentration utilized ranges from about 50 ppb to about 100 ppb.
EXAMPLES
In the following examples, hydrogen sulfide concentrations were measured using a chemiluminescence detector.
Examples 1-3
In order to betatest the process of the invention in a production environment, a betatest was performed at a specialty gas fill plant located in Santa Fe Springs, Calif. All cylinders were kept and analyzed on site for approximately one month and then transferred to a laboratory and maintained there for further analysis.
Each of the cylinders were treated as follows:
Step 1 (Vacuum Bake): Cylinders go through a vacuum/fill bake cycle for a minimum of 4 hours
Step 2 (Silane Passivation): Cylinders attached to manifold and vacuumed. Cylinders filled with 1% Silane in N2 to 100 psig and maintained for 1 day. Manifold vented and vacuumed.
Step 3 (Silane Removal and H2S Passivation): Cylinders attached to manifold and vented. Cylinders go through a vacuum/N2 fill cycle. Vacuumed cylinders filled with 5000 ppm H2S in N2 to 100 psig and maintained for 4 days. Manifold vented through a scrubber and vacuumed.
Step 4 (H2S Removal): Cylinders attached to manifold and vented out through scrubber. Cylinders go through a vacuum/N2 fill cycle. Cylinders vacuumed for at least 2 hours.
Step 5 (Standard Filling): Cylinders filled to target concentration from a 10 ppm mother mixture in Nitrogen.







TABLE 1







Cylinder Size and Fill Concentration















H2S Fill Concentration



Example
Cylinder #
Size
(ppb)















1
42553
16
53.1



2
144244
30
48.5



3
144270
30
96.9
















TABLE 2







H2S Concentration Over Time for Examples 1-3












Example 1:

Example 2:

Example 3:



Cyl. # 42553

Cyl. # 144244

Cyl. # 144270













days
ppb H2S
days
ppb H2S
days
ppb H2S















0
53.1
0
48.5
0
96.9


1
62
1
46.1
1
99


19
39.9
20
48.1
20
90.7


77
43.5
78
46.51
78
101.57


110
43.9
132
50.8
132
100.5


188
46.2
201
55.8
201
97.3


231
45.1
230
53.6
230
102.2


277
45.3
277
49.4
277
103.6


532
39.3
329
44.8
329
92.5


691
33.2
532
44.9
532
95




691
33.9
691
81.1









As best illustrated in FIG. 1, the H2S concentration for Examples 1-3 is stable over an approximate 700 day period of time.

Examples 4-7 and Comparative Examples 1-7
Examples 4-7 were prepared as follows:
Step 1 (Vacuum Bake): Cylinders go through a vacuum/fill bake cycle for a minimum of 4 hours
Step 2 (Silane Passivation): Cylinders attached to manifold and vacuumed. Cylinders filled with 1% Silane in N2 to 100 psig and maintained for the time indicated in Table 3. Manifold vented and vacuumed.
Step 3 (Silane Removal and H2S Passivation): Cylinders attached to manifold and vented. Cylinders go through a vacuum/N2 fill cycle. Vacuumed cylinders filled with 5000 ppm H2S in N2 to 100 psig and maintained for the time indicated in Table 3. Manifold vented through a scrubber and vacuumed.
Step 4 (H2S Removal): Cylinders attached to manifold and vented out through scrubber. Cylinders go through a vacuum/N2 fill cycle. Cylinders vacuumed for at least 2 hours.
Step 5 (Standard Filling): Cylinders filled to target concentration from a 10 ppm mother mixture in Nitrogen.
Comparative Examples 1-3 and 7 were prepared as follows:
Step 1 (Vacuum Bake): Cylinders go through a vacuum/fill bake cycle for a minimum of 4 hours
Step 2 (Silane Passivation): Cylinders attached to manifold and vacuumed. Cylinders filled with 1% Silane in N2 to 100 psig and maintained for the time indicated in Table 3. Manifold vented and vacuumed.
Step 3 (Silane Removal): Cylinders attached to manifold and vented. Cylinders go through a vacuum/N2 fill cycle. Cylinders vacuumed for at least 2 hours.
Comparative Examples 4-6 were prepared as follows:
Step 1 (Vacuum Bake): Cylinders go through a vacuum/fill bake cycle for a minimum of 4 hours
Step 2 (H2S Passivation): Cylinders filled with 5000 ppm H2S in N2 to 100 psig and maintained for the time indicated in Table 3. Manifold vented through a scrubber and vacuumed.
Step 3 (H2S Removal): Cylinders attached to manifold and vented out through scrubber. Cylinders go through a vacuum/N2 fill cycle. Cylinders vacuumed for at least 2 hours.
Step 4 (Standard Filling): Cylinders filled to target concentration from a 10 ppm mother mixture in Nitrogen.







TABLE 3







Cylinder Size, Silane and H2S Passivation Periods, and Fill


Concentrations

















H2S Fill



Cylinder
Cylinder
Silane

conc.



#
Size
(days)
H2S (days)
(ppb)















Comp. Ex. 1
24271
Size 7
94
0
101.2


Comp. Ex. 2
24283
Size 7
29
0
101.2


Comp. Ex. 3
24287
Size 7
96
0
101.2


Comp. Ex. 4
24235
Size 7
0
42
101.2


Comp. Ex. 5
24305
Size 7
0
39
105.0


Comp. Ex. 6
24313
Size 7
0
39
105.0


Ex. 4
24335
Size 7
35
14
105.0


Comp. Ex. 7
15042
Size 30
61
0
76.4


Ex. 5
15031
Size 30
27
30
104.0


Ex. 6
15035
Size 30
27
30
104.0


Ex. 7
15039
Size 30
8
57
76.4
















TABLE 4







H2S Concentration Over Time for Comparative Examples 1-6












Comp. Ex.1:
Comp. Ex. 2:
Comp. Ex. 3:
Comp. Ex. 4:
Comp. Ex. 5:
Comp. Ex. 6:


Cyl. # 24271
Cyl. # 24283
Cyl. # 24287
Cyl. # 24235
Cyl. # 24305
Cyl. # 24313


















days
ppb H2S
days
ppb H2S
days
ppb H2S
days
ppb H2S
days
ppb H2S
days
ppb H2S





















0
101.2
0
101.2
0
101.2
0
101.2
0
90
0
91


8
102.6
8
91.7
8
108.8
1
86.37
2
91.7
2
97.5


15
77.34
15
82
15
73.8
5
90.7
6
87
6
97.2


23
92.1
23
58
23
81.3
6
84.9
28
81.67
28
97


43
80.6
43
47.6
43
73.1
7
92.4
45
79.1
45
97.1


49
69.9
49
42.5
49
66.1
9
87.3
49
74
49
81.8


74
81.3


74
76.3
13
84.3
57
68.2
57
94.1


101
76.7


101
67.7
14
87.1
77
60.1
77
86.6


150
75


150
69
22
93
83
58.7
83
81.2


239
72.2


163
63.4
33
83.2
108
71.2
108
100.7


296
61.8


239
64.8
36
95.4
135
67.2
135
101.8


319
65.7


296
52
40
100.8
184
66.3
184
99.1


490
36.2


319
59.1
61
89.1
197
62.2
197
100.8






490
21.7
78
84.3
273
56.9
273
101.8








81
82.4
524
13.9
330
96.3








89
84.6


524
65.5








109
76.4


665
48.4








115
74.53








140
86.9








167
83.2








216
87.3








229
80.3








362
69.7








385
66.4








447
59.6
















TABLE 5







H2S Concentration Over Time for Examples 4-7 & Comparative Example 7











24335
15031
15035
15039
15042
















days
ppb H2S
days
ppb H2S
days
ppb H2S
days
ppb H2S
days
ppb H2S



















0
87
0
104
0
104
0
76.4
0
76.4


2
97.7
9
108.8
9
108.9
1
79.4
1
74.2


6
101
15
97.2
15
96
8
65.4
8
61.4


28
105.5
23
96.8
23
100.5
9
72.8
9
59.2


45
96.4
43
91.2
43
97
29
73
29
52.1


49
99.4
44
103.6
44
112.6
30
71.6
30
55.3


57
100.2
49
86
49
89.2
35
66.6
35
50.5


77
87
50
93
50
98.8
36
73.1
36
48.3


83
90.2
52
100.7
52
102
38
76.6
38
51.5


108
103.1
67
96.1
67
100
44
70.6
53
39.5


135
105.2
74
92.2
74
95.1
53
73.5
60
39.7


184
109.1
91
90.2
91
92.9
60
73
77
38.3


197
103.9
92
94
92
95
77
65
78
41.9


273
109.9
114
91.1
114
93.7
78
71.1
100
36.3


330
108
127
95.7
127
102.6
100
72.2
113
41.9


353
131.2
150
102.4
150
102.2
113
78.4
136
40


415
123.3
183
97.8
183
94.3
136
78.1
169
35.4


518
114.1
238
97.6
238
103.9
169
73.2
224
33.8


562
112.3
287
93.8
284
93.9
224
79.5
270
25.1


660
104.4
381
99.6
381
111.8
270
70.1
451
0


867
109.3
491
84.7
429
98.3
367
76.4


1023
102
574
93.9
497
95.2
477
70.8




626
78
574
107.2
560
74.1




829
86.7
626
93.9
612
65




989
78.2
829
100.8
815
70.2






989
87.3
975
63.3









As best shown in FIG. 2, Example 4 in comparison to only Silane passivation or only H2S passivation (for the same size cylinder) exhibited excellent stability.
As best shown in FIG. 3, Examples 5-7 in comparison to only Silane passivation (for the same size cylinder) exhibited excellent stability.
Example 8
In an effort to study the effect of reducing production time to less than two weeks for low-level COS/H2S in Nitrogen mixtures, the passivation times were shortened. A cylinder used for the COS/H2S mixture underwent the following treatment:
Example 8 was prepared as follows:
Step 1 (Vacuum Bake): Size 16 cylinder goes through a vacuum/fill bake cycle for a minimum of 4 hours
Step 2 (Silane Passivation): Cylinder attached to manifold and vacuumed. Cylinder filled with 1% Silane in N2 to 100 psig and maintained for 3 days. Manifold vented and vacuumed.
Step 3 (Silane Removal and H2S Passivation): Cylinder attached to manifold and vented. Cylinder goes through a vacuum/N2 fill cycle. Vacuumed cylinders filled with 5000 ppm H2S in N2 to 100 psig and maintained for 8 days. Manifold vented through a scrubber and vacuumed.
Step 4 (H2S Removal): Cylinder attached to manifold and vented out through scrubber. Cylinder goes through a vacuum/N2 fill cycle. Cylinder vacuumed for at least 2 hours.
Step 5 (Standard Filling): Cylinder filled to a concentration 52.1 ppb COS and 49.7 ppb H2S in Nitrogen.







TABLE 6







H2S and COS Concentrations Over Time for Example 8


Example 8: Cylinder # 42589









days
ppb H2S
ppb COS












0
49.7
52.1


2
59.9
52.4


32
50
64.4


38
57.9
69.9


114
57
55.5


197
48.6
56.1


401
50.3
58.3


576
56.2
48.7









As best shown in FIG. 4, Example 8 exhibited excellent stability.
Examples 9-11
The invention was also tested for H2S and COS mixtures in balance Ethylene at approximate concentrations of about 100 ppb. Two Ethylene grades were tested as the balance gas: 99.95% (CP grade) and 99.9995% (5N5 grade).
Example 9 was prepared as follows.
Step 1 (Vacuum Bake): Size 7 cylinder goes through a vacuum/fill bake cycle for a minimum of 4 hours
Step 2 (Silane Passivation): Cylinder attached to manifold and vacuumed. Cylinder filled with 1% Silane in N2 to 100 psig and maintained for 4 days. Manifold vented and vacuumed.
Step 3 (Silane Removal and H2S Passivation): Cylinder attached to manifold and vented. Cylinder goes through a vacuum/N2 fill cycle. Vacuumed cylinders filled with 5000 ppm H2S in N2 to 100 psig and maintained for 4 days. Manifold vented through a scrubber and vacuumed.
Step 4 (H2S Removal): Cylinder attached to manifold and vented out through scrubber. Cylinder goes through a vacuum/N2 fill cycle. Cylinder vacuumed for at least 2 hours.
Step 5 (Standard Filling): Filled with 106 ppb COS in 5N5 Ethylene.
Example 10 was prepared as follows:
Step 1 (Vacuum Bake): Size 16 cylinder goes through a vacuum/fill bake cycle for a minimum of 4 hours
Step 2 (Silane Passivation): Cylinder attached to manifold and vacuumed. Cylinder filled with 1% Silane in N2 to 100 psig and maintained for 3 days. Manifold vented and vacuumed.
Step 3 (Silane Removal and H2S Passivation): Cylinder attached to manifold and vented. Cylinder goes through a vacuum/N2 fill cycle. Vacuumed cylinders filled with 5000 ppm H2S in N2 to 100 psig and maintained for 9 days. Manifold vented through a scrubber and vacuumed.
Step 4 (H2S Removal): Cylinder attached to manifold and vented out through scrubber. Cylinder goes through a vacuum/N2 fill cycle. Cylinder vacuumed for at least 2 hours.
Step 5 (Standard Filling): Filled with 89.5 ppb H2S in CP grade Ethylene.
Example 11 was prepared as follows:
Step 1 (Vacuum Bake): Size 16 cylinder goes through a vacuum/fill bake cycle for a minimum of 4 hours
Step 2 (Silane Passivation): Cylinder attached to manifold and vacuumed. Cylinder filled with 1% Silane in N2 to 100 psig and maintained for 3 days. Manifold vented and vacuumed.
Step 3 (Silane Removal and H2S Passivation): Cylinder attached to manifold and vented. Cylinder goes through a vacuum/N2 fill cycle. Vacuumed cylinders filled with 5000 ppm H2S in N2 to 100 psig and maintained for 8 days. Manifold vented through a scrubber and vacuumed.
Step 4 (H2S Removal): Cylinder attached to manifold and vented out through scrubber. Cylinder goes through a vacuum/N2 fill cycle. Cylinder vacuumed for at least 2 hours.
Step 5 (Standard Filling): Filled with 98.8 ppb COS in CP grade Ethylene.







TABLE 7







H2S and COS Concentrations Over Time for Examples 9-11












Example 9:

Example 10:

Example 11:



Cylinder # 27525

Cylinder # 42573

Cylinder # 42543













days
ppb COS
days
ppb H2S
days
ppb COS















0
106
0
89.5
0
98.8


1
131.9
2
81.4
2
80.4


7
76.4
32
111.3
38
120.6


23
94.7
38
124.9
112
119.4


55
109
112
105.7
133
109.7


142
113.4
130
95
198
98.9


216
108.6
193
95.8
401
84.3


237
82.8
366
85.9
576
100.5


302
89.7
401
88.3




680
78.6
576
76.7









As best shown in FIG. 5, Example 9-11 exhibited excellent stability.
Examples 12-13
The cylinder treatment of the invention was performed with an extra step where the cylinder was filled with Nitrogen at 100 psi and vented five times after each passivation with Silane and each passivation with SO2.
Examples 12-13 were prepared as follows:
Step 1 (Vacuum Bake): Cylinder goes through a vacuum/fill bake cycle for a minimum of 4 hours
Step 2 (Silane Passivation): Cylinder attached to manifold and vacuumed. Cylinder filled with 1% Silane in N2 to 100 psig and maintained for 43 days.
Step 3 (Silane Removal and SO2 Passivation): Manifold vented and filled with N2 at 100 psig. This was repeated 4 times. Cylinder goes through a vacuum/N2 fill cycle. Vacuumed cylinders filled with 500 ppm SO2 in N2 to 100 psig and maintained for 8 days. Manifold vented through a scrubber and vacuumed.
Step 4 (SO2 Removal): Cylinder attached to manifold vented and filled with N2 at 100 psig. This was repeated 4 times. They were vacuumed and then filled with 100 psi of pure Propylene for 7 days. Cylinder attached to manifold vented and filled with N2 at 100 psig. This was repeated 4 times. Cylinder vacuumed for at least 2 hours.
Step 5 (Standard Filling): Filled with 100 ppb SO2 in Propylene at 100 psi.







TABLE 8







SO2 Concentration Over Time for Examples 12-13












Example 12:

Example 13:




Cylinder # 6513

Cylinder # 6514













days
ppb SO2
days
ppb SO2















0
100
0
100



14
71
14
93



28
113
28
101



42
73
42
110



56
88
56
142



70
104
70
129



100
102
100
129



130
112
130
127



170
108
170
140



210
105
210
114



260
98
260
113



300
97
300
111









As best shown in FIG. 6, Example 12-13 exhibited excellent stability.
Examples 14-17 and Comparative Example 8
Examples 14-17 and Comparative Example 8 were prepared as follows:
Step 1 (Vacuum Bake): Cylinders go through a vacuum/fill bake cycle.
Step 2 (Silane Passivation): Cylinders attached to manifold and vacuumed. Cylinders filled with 1% Silane in N2 to 100 psig and maintained for the period indicated in Table 9. Manifold vented and vacuumed.
Step 3 (Silane Removal and H2S Passivation): Cylinders attached to manifold and vented. Cylinders go through a vacuum/N2 fill cycle. Vacuumed cylinders filled with 5000 ppm H2S in N2 to 100 psig and maintained for the period indicated in Table 9. Manifold vented through a scrubber and vacuumed.
Step 4 (H2S Removal): Cylinders attached to manifold and vented out through scrubber. Cylinders go through a vacuum/N2 fill cycle.







TABLE 9







Passivation Times for Ex. 14-17 and Comp. Ex. 8











Silane Passivation
H2S Passivation




(days)
(days)
H2S (ppb)













Example 14
1
1
109.3


Example 15
1
2
109.3


Example 16
1
3
110.6


Example 17
1
4
96.9


Comparative
4
0
110.6


Example 8
















TABLE 10







H2S Concentration Over Time for Ex. 14-15 and Comp. Ex. 8












Comp. Ex. 8

Ex. 14

Ex. 15













days
H2S (ppb)
days
H2S (ppb)
days
H2S (ppb)















0
110.6
0
109.3
0
109.3


1
104.3
2
116.8
1
117.5


2
89.2
10
106.8
2
118.6


10
65
23
97
10
102.7


23
46.1
29
100.8
23
93.3


29
42.2
36
111.6
29
91.1


36
45.3
42
97.6
36
104


42
30.9
57
101.9
42
85.8




65
88.5
57
84.2




79
71.6
65
74.7




205
38.9
79
58.1






115
38.5
















TABLE 11







H2S Concentration Over Time for Ex. 16-17












Ex. 16

Ex. 17













days
H2S (ppb)
days
H2S (ppb)















0
110.6
0
96.9



1
113.7
1
99



2
119.2
20
90.7



10
110.7
78
101.6



23
108.1
132
100.5



29
113.2
201
97.3



36
123.6
230
102.2



42
114
277
103.6



57
124.3
329
92.5



65
116.1





79
88.9





115
92.7





269
80.9





414
61.2









As best shown in FIG. 7, increasing the H2S passivation time improved stability.
Although the description herein is intended to be representative of the invention, it is not intended to limit the scope of the appended claims.

## Claims

1. A method of calibrating a measurement device for measuring a concentration of an acid gas, the method comprising the steps of:
A) providing an article of manufacture comprising:
a) a container having an internal space and a passivated internal metal surface; and
b) a composition comprising an acid gas and a balance gas contained within the internal space and in contact with the passivated internal metal surface; wherein
i) the acid gas has an intended concentration in the balance gas of less than 500 ppb;
ii) the acid gas is selected from the group consisting of carbon disulfide, carbonylsulfide, and compounds within the formula


Y—S—X


wherein S is sulfur, X and Y are the same or different and are independently selected from the group consisting of hydrogen, alkyl, aryl, oxygen, hydroxyl, amine, aminosilane, oxygen, and alcohol; and
iii) the passivated internal metal surface comprises I) the reaction product of a silicon-containing material and an oxygen-containing material, and II) an amount of the acid gas adsorbed on or in the passivated internal metal surface is at least 500 times greater than the intended concentration of the acid gas that is to be substantially maintained in the composition, which is effective to enhance the stability of the intended concentration over time;


B) using a portion of the acid gas contained within the article of manufacture in a calibration of the measurement device; and
C) repeating said step B) at least once, wherein a period of time commencing from a first performance of said step B) and expiring on a later repetition of said step B) is not less than 30 days.

2. The method of claim 1, wherein the period of time is not less than 90 days.

3. The method of claim 1, wherein the period of time is not less than 180 days.

4. The method of claim 1, wherein the period of time is not less than 12 months.

5. The method of claim 1, wherein the period of time is not less than 18 months.

6. The method of claim 1, wherein the acid gas is selected from the group consisting of hydrogen sulfide, carbonyl sulfide, sulfur dioxide, methylthiol, ethylthiol, n-propylthiol, i-propylthiol, and benzylthiol.

7. The method of claim 1, wherein the acid gas is selected from the group consisting of hydrogen sulfide, carbonyl sulfide, and sulfur dioxide.

8. The method of claim 1, wherein the silicon-containing material of the article of manufacture is selected from the group consisting of compounds within the general formula (II):


SiR1R2R3R4  (II)


wherein R1, R2, R3, and R4 are the same or different and are independently selected from the group consisting of hydrogen, halogen, amine, alkyl, aryl, halogenated alkyl, and halogenated aryl.

9. The method of claim 1, wherein the oxygen-containing material of the article of manufacture is selected from the group consisting of moisture, molecular oxygen, metal oxides, and mixtures thereof.

10. The method of claim 1, wherein the silicon-containing material is silane.

11. The method of claim 1, wherein the silicon-containing material is a methyl-containing silane selected from the group consisting of methylsilane, dimethylsilane, trimethylsilane and tetramethylsilane.

12. The method of claim 1, wherein the acid gas contained within the internal space has a concentration of about 50-100 ppb.

13. The method of claim 1, wherein the balance gas is selected from the group consisting of noble gases, nitrogen, ethylene, propylene, and mixtures thereof.