Tag Archives: gas chromatography

A more accurate permeation tester

There are two ASTM-approved methods for measuring the gas permeability of a material. The equipment is very similar, and REB Research makes equipment for either. In one of these methods (described in detail here) you measure the rate of pressure rise in a small volume.This method is ideal for high permeation rate materials. It’s fast, reliable, and as a bonus, allows you to infer diffusivity and solubility as well, based on the permeation and breakthrough time.

Exploded view of the permeation cell.

For slower permeation materials, I’ve found you are better off with the other method: using a flow of sampling gas (helium typically, though argon can be used as well) and a gas-sampling gas chromatograph. We sell the cells for this, though not the gas chromatograph. For my own work, I use helium as the carrier gas and sampling gas, along with a GC with a 1 cc sampling loop (a coil of stainless steel tube), and an automatic, gas-operated valve, called a sampling valve. I use a VECO ionization detector since it provides the greatest sensitivity differentiating hydrogen from helium.

When doing an experiment, the permeate gas is put into the upper chamber. That’s typically hydrogen for my experiments. The sampling gas (helium in my setup) is made to flow past the lower chamber at a fixed, flow rate, 20 sccm or less. The sampling gas then flows to the sampling loop of the GC, and from there up the hood. Every 20 minutes or so, the sampling valve switches, sending the sampling gas directly out the hood. When the valve switches, the carrier gas (helium) now passes through the sampling loop on its way to the column. This sends the 1 cc of sample directly to the GC column as a single “injection”. The GC column separates the various gases in the sample and determines the components and the concentration of each. From the helium flow rate, and the argon concentration in it, I determine the permeation rate and, from that, the permeability of the material.

As an example, let’s assume that the sample gas flow is 20 sccm, as in the diagram above, and that the GC determines the H2 concentration to be 1 ppm. The permeation rate is thus 20 x 10-6 std cc/minute, or 3.33 x 10-7 std cc/s. The permeability is now calculated from the permeation area (12.56 cm2 for the cells I make), from the material thickness, and from the upstream pressure. Typically, one measures the thickness in cm, and the pressure in cm of Hg so that 1 atm is 76cm Hg. The result is that permeability is determined in a unit called barrer. Continuing the example above, if the upstream hydrogen is 15 psig, that’s 2 atmospheres absolute or or 152 cm Hg. Lets say that the material is a polymer of thickness is 0.3 cm; we thus conclude that the permeability is 0.524 x 10-10 scc/cm/s/cm2/cmHg = 0.524 barrer.

This method is capable of measuring permeabilities lower than the previous method, easily lower than 1 barrer, because the results are not fogged by small air leaks or degassing from the membrane material. Leaks of oxygen, and nitrogen show up on the GC output as peaks that are distinct from the permeate peak, hydrogen or whatever you’re studying as a permeate gas. Another plus of this method is that you can measure the permeability of multiple gas species simultaneously, a useful feature when evaluating gas separation polymers. If this type of approach seems attractive, you can build a cell like this yourself, or buy one from us. Send us an email to reb@rebresearch.com, or give us a call at 248-545-0155.

Robert Buxbaum, April 27, 2022.

Hydrogen Cylinders versus Hydrogen Generators for Gas Chromatography

Hydrogen is an excellent cover gas for furnace brazing and electronic manufacture; it’s used as a carrier gas for gas chromatography or as a flame-detector gas, and it’s a necessity for ammonia production and most fuel cells. If you are working in one of these fields you can buy bottled hydrogen (cylinders) or a hydrogen generator . The main difference is cost. Cylinder hydrogen is typically the choice for small demand applications. A palladium membrane hydrogen purifier is added ( we make these) if high purity is important. Hydrogen generators are more generally used for larger -demand applications. They are more expensive at the start, but provide convenience and long-term savings. The essay below goes through the benefits and drawbacks of each as applies to gas chromatography.

Point of use Cylinder Hydrogen Is Simple and Allows Easy Monitoring and Control. At the smallest laboratories, those with one or two gas chromatographs, you’ll generally find you are best served by a single hydrogen cylinder for each GC, aided by a hydrogen purifier of some sort. This is called “point of use” hydrogen. Each cylinder is typically belted to a wall and used until the cylinder is empty. At that point, the application is stopped (the purifier is often stopped too) and a new cylinder switched in. There is usually a short break- in period where GC results are unreliable, but after one or two runs, everything is as before. The biggest advantage here is simplicity including ease of pressure control and monitoring. You can always check the pressure right by the GC and adjust it as needed. Long term cost is usually higher, though, and you have to stop whenever a cylinder needs switching.

Multi-cylinder Systems or Generators Provide Fewer interruptions. Larger laboratories tend to use multiple hydrogen cylinders with complex switchover systems, or hydrogen generators. Multiple cylinders are racked together and connected to a manifold and a single, larger purifier (we make these too). Tanks are emptied in series so that there is no disruption. When each tank empties, it is switched out in a way that maintains the flow. One problem is that the pressure and flow does not typically stay constant as the cylinders switch and as additional GCs or other processes are brought on line or taken off.

Purity can suffer too, as there is more tubing and more connections in the system. There is thus more room for leaks and degassing. This can be solved by replacing the single large purifier by point-of-use purifiers, installed just prior to the GC or other application.

Cylinder packs come with a safety disadvantage: with so many cylinders, there is a potential for disastrous leaks or mistakes that empty many cylinders at once — too fast to disperse the large amount of hydrogen released. Maintenance becomes an issue too since the manifolds and automatic switches become complicated quickly. Complex systems can require a trained technician to trouble-shoot and maintain; I sometimes do that, and customers don’t seem to mind, but it’s an issue.

Hydrogen generators can be cheaper and you avoid cylinder changes; Hydrogen generators are fed by tap-water or a very large tank of methanol -water. Running out is less of a problem, and adding more water or methanol to the tank does not affect the hydrogen output.

Safety is improved by limiting the output of the generator to the amount the room will vent. A room with 100 ft3 of air and some circulation can generally host a hydrogen generator 2-3 slpm output with no fear of reaching explosive limits. It’s also worthwhile to fit the hydrogen generator with an alarm or safety that shuts down if a leak is detected (we provide these for purifiers too).

Generator Options: Methanol-based hydrogen generators or electrolysis. Both options are are available in outputs from 250 ccm to 50 slpm. For larger-yet output, you’ll probably want an electrolyzer. In general, either generator will pay for itself in the first year if you use the gas, continuously, or nearly so.

In Electrolytic Hydrogen generators Purified water, either purchased separately, or purified on-site is mixed with an electrolyte, generally KOH, and converted to hydrogen and oxygen by the electrolytic reaction H2O –> H2 + ½ O2.  As the hydrogen produced is generally “wet”, containing water vapor, the hydrogen is then purified by use of a desiccant, or by passage through a metal membrane purifier. Desiccants are cheaper, but the gas is at best 99.9% pure, good enough to feed FIDs, but not good enough to be used as a carrier gas, or for chemical production. Over time desiccants wear out; they require constant monitoring and changing as they become filled with water vapor. Often electrolytic hydrogen generators also require the addition of a caustic electrolyte solution as caustic can leak out, or leave by corrosion mechanisms.

In Reformer-based hydrogen generators a methanol-water mix is pumped to about 300 psi and heated to about 350 °C. It is then sent over a catalyst where it is converted to a hydrogen-containing gas-mix by the reaction CH3OH + H2O –> 3H2 + CO2. Pure hydrogen is extracted from the gas mix by passing it through a membrane, either within the reactor (a membrane reactor), or by use of a membrane purifier external to the reactor.

Cost comparisons. Hydrogen in cylinders is fairly expensive if you use gas continuously. In Detroit, where we are, hydrogen costs about $70 each cylinder low low-purity gas, or $200 for high purity gas. Each cylinder contains 135 scf of gas. If you use 1/10 cylinder per day, you will find you’re spending about $7,300 per year on hydrogen gas, with another $1000 spent on cylinder rental and delivery. This is about the cost of a comparable hydrogen generator plus the water or methanol and electricity run it. If you use significantly less hydrogen you save money with cylinders, if you use more there is significant savings with a generator.

Most hydrogen generators have delivery pressure limitations compared to cylinders. Cylinders have no problem supplying hydrogen at 200 psi or greater pressures. By contrast, generators are limited to only the 60-150 psig range only. This pressure limitation is not likely to be a problem, even for GCs that need higher pressure gas or when the generator must be located far from the  instruments, but you have to be aware of the issue when buying the generator. Electrolysis systems that use caustic provide the highest pressures, but they tend to be the most expensive, and least safe as the operate hot and caustic can drip out. Fuel cell generators and reformers provide lower pressure gas (90 psi maximum, typically), but they are safer. In general generators should be located close to the instruments to minimize supply line pressure drop. If necessary it can pay to use cylinders and generators or several generators to provide a range of delivery pressures and a shorter distance between the hydrogen generator and the application.

Click here for the prices of REB Research hydrogen generators. By comparison, I’ve attached prices for electrolysis-based hydrogen generators here (it’s 2007 data; please check the company yourself for current prices). Finally, the price of membrane purifiers is listed here.

Maintenance required for optimal performance. Often electrolytic hydrogen generators require the addition of a caustic electrolyte solution; desiccant purified gas will require the monitoring and changing of desiccant cartridges to remove residual moisture from the hydrogen. Palladium membrane purifiers systems, and reformer systems need replacement thermocouples and heaters every few years. Understanding the required operating and maintenance procedures is an important part of making an informed decision.

Conclusion:

Cylinder hydrogen supplies are the simplest sources for labs but present a safety, cost, and handling concerns, particularly associated with cylinder change-outs. Generators tend to be more up-front expensive than cylinders but offer safety benefits as well as benefits of continuous supply and consistent purity. They are particularly attractive alternative for larger labs where large hydrogen supply can present larger safety risks, and larger operating costs.

R. E. Buxbaum, January 30, 2013, partially updated Apr. 2022.

New hydrogen generator for gas chromatographic use

Shown below is our latest product: a lower cost hydrogen generator, designed for use to provide the carrier and flame gas for gas chromatography. It’s our highest pressure, lowest hydrogen output product, outputting hydrogen at up to 90 psi. The output is still higher than any other generator in the GC space, and the purity is greater; 99.99995%, good enough to be used as the carrier gas, not just the detector gas. Fairly low price too.http://www.rebresearch.com/
Photo: Our latest new product: a lower cost, hydrogen generator for use with gas chromatography. It's our highest pressure, lowest hydrogen output product, but the output is still higher than any other in the GC space, and the price is less at that purity. </p><br />
<p>http://www.rebresearch.com/
As always, the hydrogen is made from methanol-water reforming in a membrane reactor, but we did a couple of things differently from previous designs. We closed up the front more so you don’t stick your fingers where they don’t belong. We also have a more-transpartent tank so you have a better idea what the liquid level is. The use of the membrane reactor is why our hydrogen is purer; we go through a metal membrane and our competition, (Porter, etc) uses only a desiccant.