Carbon Dioxide and Nitrogen

Carbon dioxide (CO2) and nitrogen (N2) are commonly used in packaging both fresh and shelf-stable foods, in order to extend their shelf lives.  Fresh foods are outside the scope of this work so attention shall be focused on those foods suitable for use in storage programs.

The most common use of these gasses is for excluding oxygen (O2) from the atmosphere contained inside of a storage container (called head gas).  When head gas oxygen levels can be dropped below 2% the amount of undesirable oxidation reactions in stored foods can be greatly decreased resulting in longer shelf lives.  Actually achieving this is not a simple matter when limited to the equipment and facilities typically available in the home.  Still, with careful technique and proper packaging materials it is possible to achieve useful results.

In order for either gas to be used most effectively it is should be contained inside of packaging with high barrier properties to prevent outward diffusion over time or allowing oxygen to infuse in.  Examples of this kind of packaging are aluminized Mylar or other high barrier property plastics, metal cans or glass jars. Buckets made of HDPE plastic are relatively poor gas barriers and will, over time, allow oxygen to infuse into the container.  In order for foods to be kept for their maximum shelf lives the containers would need to be re-purged every three to four years. Foods that are particularly oxygen sensitive, such as dry milk powders, should not be stored in HDPE without a secondary gas barrier.  It is possible to use HDPE buckets alone when gas purging if a shorter rotation period is used.  An example would be using wheat in four to five years instead of the eight to ten that would be achievable if a high barrier container were used.

Purging efficiency can be greatly improved when used with a vacuum device.  By first drawing down the head gas of the container and then flooding with the purging gas much more oxygen can be removed.  Repeating the process once more will improve removal efficiency even more.  If a true vacuum pump is not available, the suction end of a home vacuum-cleaner can be made to serve and still achieve useful results.  With careful technique, oxygen levels can be dropped to between 0.5-2%.  Finely textured materials such as grain flours and meals, dry milk powders, dry eggs, and similar textured foods will purge poorly and are better packaged with oxygen absorbers.  Instructions for vacuum usage are given in A.5.1 Using Mylar Bags.  Instructions for gas purging are given below in B.1 Dry Ice and B.2 Compressed Nitrogen.

A less common, but important use for carbon dioxide is fumigation. This is killing or retarding insect life contained in a product. Many chemical fumigants are available to do this but are not thought desirable by many who have foodstuffs they want to put into storage. CO2 is not as certain as the more toxic fumigants, but it can be made to work and will not leave potentially harmful residues behind.  It is possible for nitrogen to work in a similar manner, but it must be in a head gas concentration of 99%+ whereas carbon dioxide can be effective over time at levels as low as 3%.  The precise amount of time necessary for the gas to do its work will vary according to the specific insect species and its growth stage along with the temperature and humidity level of the product being fumigated. In general, the more active the growth stage and the warmer the temperature the more effective CO2 is in killing weevil infestations.  The gas also exhibits bacterial and fungal inhibiting properties, but for our purposes this will be of little moment since all foods should be too dry to support such growth in the first place.

The procedure for fumigating foodstuffs with carbon dioxide is precisely the same as the one used in purging oxygen from storage containers mentioned below.  The only change is that for the fastest effectiveness the sealed container should be left in a warm place for a week or so before moving it into its final storage location.  The gas is still effective at cooler temperatures, but because insect life is slowed by lower temperatures the carbon dioxide takes longer to complete its mission.

NOTE: Both Mitsubishi Gas-Chemical, maker of the Ageless line of oxygen absorbers, and Multisorb, manufacturer of the FreshPax D 750 absorbers, state the their products should not be used in a high carbon dioxide environment.  There are absorbers that will work well in high carbon dioxide atmospheres but they require an external moisture source which would make them difficult to use for our purposes.

DRY ICE

Using dry ice to displace oxygen from food storage containers is straightforward.  To get the best results it is recommended that all foodstuffs and packaging materials be put in a warm location for a few hours before beginning the purging process.  The reason for this is that the cold CO2 sublimating from the dry ice will be denser than the warmer, lighter oxygen containing air.  The cold gas will tend to stay on the bottom, gradually filling the container and pushing the warm air out the top.

When you first pick up your dry ice from the supplier, put it in a moisture proof container so that air humidity will be less able to condense and freeze on it.  The sublimating gas will prevent you from achieving a tight seal, but you can slow down the water ice accumulation.

Gather your containers and any interior packaging materials.  Break off a piece of dry ice of sufficient size for the volume to be purged. One pound of dry ice will produce about 8.3 cubic feet of carbon dioxide gas so approximately two ounces per five gallon bucket will do.  Wipe off any accumulated water frost which should look whiter than the somewhat bluish frozen gas. Wrap in a paper towel to keep foodstuffs out of direct contact.  Place in the bottom of the container that will actually contain the food, i.e. the bag.  Fill the package with the food product, shaking and vibrating while doing so to achieve the maximum packing density.

If a vacuum process is not to be used then place the lid on the container, but do not fully seal.  If a liner bag is being used then gather the top together or heat seal and cut off a small corner.  This is to allow the air being purged to escape as it is pushed upward by the expanding gas from the dry ice.  Do not move or shake the container while the ice is sublimating so as to minimize turbulence and mixing. After about two hours feel the bottom of the container immediately below where you put the ice.  If it’s not still icy cold complete the seal.  Check the container every fifteen minutes or so to be sure that a pressure build up is not occurring.  A small amount of positive pressure is OK, but do not allow the container to bulge.

If a vacuum process is used then cut off a corner of the bag and insert the probe or place the container in the vacuum chamber.  Draw a vacuum and when it has reached the desired point shut it off, but do not allow air back inside.  When the dry ice has finished sublimating seal the container.  If a slightly larger piece of dry ice is used this process may be repeated once more to improve oxygen removal.  Watch for pressure signs as above.

NOTE: It is natural for some grains and legumes to adsorb carbon dioxide when stored in an atmosphere with high levels of the gas.  This will result in a drop in head space air pressure much like using oxygen absorbers will cause as they absorb oxygen.  Precautions should be taken in thin walled containers against buckling and possible loss of seal integrity. When the food products are removed from the container they will release the adsorbed CO2 and suffer no harm.

WARNING: Dry ice is extremely cold (about –110° degrees F.) and can cause burns to the skin with prolonged contact.  Because of this you should wear gloves whenever handling it. Also, dry ice evaporates into carbon dioxide gas, which is why we want it.  CO2 is not inherently dangerous, we breath it out with every breath we exhale, but you should make sure the area where you are packing your storage containers is adequately ventilated so the escaping gas will not build to a level dangerous enough to asphyxiate you.  If you must pack your containers in a coat closet, leave the door open <grin>.

IMPORTANT NOTE: Because dry ice is very cold, if there is much moisture (humidity) in the air trapped in the container with your food, it will condense.  Try to pack your containers on a day when the relative humidity is low or in an area with low humidity, such as in an air-conditioned house.  Use of a desiccant package when using dry ice to purge storage containers may be a good idea.

DRY ICE SUPPLIERS

Dry ice may be found at ice houses, welding supply shops, some ice cream stores, meat packers or you could look in your local phone book under the headings “ice”, “dry ice” or “gasses”.  If you are still unable to locate a source, contact your local hospital and ask to speak to the laboratory manager.  Ask where the hospital gets the dry ice they use to ship biological specimens.  You may be able to use the same source.

You may also want to check out Dry Ice Info.com (http://www.dryiceinfo.com) and click on the directory link to find a dry ice retailer in your area.  While you’re there check out some of the other uses for dry ice on the site.  It’s an interesting place.

COMPRESSED ITROGEN

TYPES OF AVAILABILITY

Both nitrogen (N2) and carbon dioxide (CO2) are commonly available in the form of compressed gas in cylinders.  In food storage, CO2 is mainly used in the form of dry ice (see above) which is often easier to acquire with much less necessary equipment.  Because of this, I’ll be limiting this section to the use of compressed nitrogen.  If for some reason you prefer to use compressed CO2 the information given below will work for both, though cylinder sizes may differ.

In the U.S. there are about eight principal suppliers of compressed gasses:  Air Liquide, Airco, Linde, Air Products, Matheson, Liquid Carbonic, MG Industries, and Scott.  One or more of these producers should have compressed gasses available in virtually every area of the United States and Canada.

Locating a source of compressed nitrogen is probably as easy as looking in your local phone book under the headings “compressed gas suppliers”, “gasses”, or “welding supplies”. Other sources might be automotive supply houses, university or college research departments, vo-tech schools, and medical supply houses.

Nitrogen is generally available in a number of forms ranging from gas intended for welding, to various purity assured types, to gas mixtures where N2 would be one of the components.

Unless you are knowledgeable about compressed gasses and the equipment needed to use them it is strongly recommended that you not use any gas mixtures in your food storage, but rather to stay with pure nitrogen gas.  Use of compressed gas mixtures requires knowledge and equipment beyond the scope of this FAQ.

IMPORTANT NOTE: Welding nitrogen is essentially a pure gas, but it has one important caveat.  When a cylinder of welding gas is used there is an unknown possibility that some form of contaminant may have backfed into the cylinder from a previous user. Possibly this could happen if the tank was being used in an application where the cylinder’s internal pressure fell low enough for pressure from whatever the tank had been feeding to backflush into the cylinder. Alternatively, the tank pressure may have become depleted and was repressurized using ordinary compressed service air.  The most likely contaminants will be moisture, carbon monoxide, carbon dioxide, oxygen and hydrocarbons, but there is the remote possibility of something even more exotic or toxic getting into your tank.  Welding gas cylinders may not be checked by the gas supplier before being refilled and sent back out for use.  It is this remote, but unknown possibility of contamination that causes me to recommend against the use of welding grade nitrogen in food storage.  If your supplier is willing to certify that welding gas cylinders are checked before refilling then they would be OK for use.

The varying types of purity assured nitrogen gas are slightly more difficult to find and slightly more expensive in cost, but I believe this is more than made up for by the fact you know exactly what you’re getting.  Air Liquide, as an example, offers seven types of purity assured nitrogen ranging from 99.995% to 99.9995% pure with none having a water vapor content over 1 part per million (ppm) or an oxygen content over 3 ppm.  Any of them are eminently suited to the task so the most inexpensive form is all you need buy.

As you might expect, compressed gas cylinders come in a number of different sizes.  For the sake of simplicity I will address only the most common cylinder sizes since they will almost certainly be the most inexpensive as well.

Again using Air Liquide as an example, it is their size 44 and 49 cylinders that are the most common.  There are other cylinder sizes of smaller physical dimensions and capacities. However, the logistics of compressed gas production and transport being what they are, they frequently will cost as much or even more than the larger, more common sizes.  The actual gas inside the cylinder is cheap.  Filling and moving the heavy cylinders around is not.

Table 1.    Air Liquide most common cylinder sizes.
Cylinder
Size
Capacity
Cubic Feet
Filled
PSIG
Weight
Lbs
Height
Inches
Diameter
Inches
44HH 445 6000 339 51 10
44H 332 3500 225 51 10
49 304 2640 165 55 9.25
44 234 2265 149 51 9
16 77 2000 71 32.5 7
Legend: The “H” suffix means high pressure.

PSIG = Pounds per Square Inch on the Gauge, this does not reflect atmospheric pressure which would be Pounds per Square Inch Absolute (PSIA).  PSIA is the absolute pressure of atmospheric and internal cylinder pressure combined.

Although it is not a common size, I left the #16 cylinder in the above table in case someone really wants or needs to use a smaller cylinder.

Table 2. Cylinder Size Comparison. Abbreviated table.
Alphagaz
(Air Liquide)
Airco Air
Products
Linde Liquid
Carbonic
Matheson MG
Industries
Scott
49 300 A T J 1L 300 K
44L 200 K H 1A 200 A
44 200 B
44H BY 3K 1H 2HP
44HH 500 BX 6K 1U 3HP
16 80 C Q M 2 80 B
Legend: [1] Alphagaz (Air Liquide) [2] Airco [3] Air Products [4] Linde [5] Liquid Carbonic [6] Matheson [7] MG Industries [8] Scott
Reference: High Purity Specialty Gases and Equipment Catalog; copyright 1995, Air Liquide America Corporation, Houston TX USA; pages 6 and 7.

As you can see, the size 49 cylinder from Air Liquide has an equivalent from all eight manufacturers.  This size is the one commonly seen being used to fill helium balloons at county fairs and ball games.

OBTAINING THE GAS AND NECESSARY EQUIPMENT

Although you can purchase your own the most inexpensive way to use nitrogen is to rent a cylinder from your gas supplier.  This may require filling out an application, paying a refundable cylinder deposit, and buying the gas contained in the cylinder.  Tank rental periods can vary, but the most common is for thirty days.

Having rented or purchased the cylinder you must now get the thing home. Delivery by the supplier can often be arranged or they may assist you in getting the cylinder into your vehicle.  The preferred method of transportation is for the cylinder to be chained, clamped or otherwise solidly secured in a vertical position in the transporting vehicle with the cylinder cap in place.  Transportation requirements vary from nation to nation, state to state, and even city to city so your best bet is to inquire of your gas supplier to find a safe and legal means of moving the tank.

IMPORTANT NOTE: The major expense in using compressed gas is not the cost of the gas itself, but in the equipment needed to safely handle and control it.  Unless you can borrow the appropriate mechanisms they will have to be purchased, new or used, and even the cheapest regulator and gauge are not inexpensive.  There is a temptation to forgo the expense and not use a regulator, but I must caution strongly against this.  As Table 1 above shows, a full cylinder of compressed gas will have an internal pressure of 2000+ PSIG.  Normal atmospheric pressure is about 15 PSIA.  If the cylinder valve was opened only slightly too far a great deal of high pressure gas will flow through the delivery hose and metal wand and the potential for serious injury when it began to whip around would be high.  For your safety, get the necessary equipment.  If you purchase your own regulator/gauge cluster and/or your own cylinder, there is necessity for periodic maintenance.  Regulators and gauges need to be calibrated (using a water deadweight calibrator) and cylinders need to be hydrostatically tested, typically every ten years for both.  Your gas supplier can provide you with more detailed information.

The only equipment that will come with your cylinder is the cylinder cap.  “Don’t leave home without it” and they mean it.  All of the common cylinder sizes will use the CGA-580 (Compressed Gas Assembly) cylinder fitting.  The downstream side of this fitting can be obtained with different threads, but a 1/4″ NPT (National Pipe Thread) nipple is normally needed to mate with the regulator body.  The nipple is really nothing more than a short length of high pressure pipe.  The CGA fittings come in a variety of metal compositions such as carbon steel, stainless steel and brass.  The best choice is one which matches the composition of the regulator body.  If the CGA fitting and regulator are to be used only with dry, non-oxygen gasses, in a dry environment then galvanic corrosion can be disregarded so the most inexpensive metal composition can be used even if it is not the same as the regulator.  If it is to be used in a wet area, or with oxygen containing gasses then matching metal composition becomes important.

When the tank is to be returned there must be some residual pressure still in the cylinder or the renter may have to pay a surcharge or lose their deposit.  This is particularly true of purity assured gasses because the residual gas composition will be analyzed. This is done for the safety of all cylinder users.

The regulator/gauge cluster should be carefully removed using the same procedure that is described below to put it all together. Care should be taken not to damage the cylinder valve threads. Replace the cylinder cap and transport in the same manner as you brought it home.

PUTTING IT ALL TOGETHER

If the fitting and regulator are bought separately then some 1/2″ wide Teflon tape is recommended for assembly since it is a clean and inexpensive way of sealing pipe joints.  Looking into the open end of the nipple wrap the tape clockwise around the threaded end for 1.5 to 2 turns, working from the open end backwards.  If you want to do a neat looking job, the tape may be slit lengthways to make it 1/4″ wide, but this is not a requirement.  A brass nipple may shrink somewhat during tightening and need a bit more tape than a harder metal like stainless steel would.  The Teflon tape should only be used on the end of the nipple that attaches to the regulator body, NOT to any part of the cylinder end.

The regulator end has tapered threads and uses them directly for sealing.  The cylinder end has straight threads and depends upon the precision mating of machined metal surfaces to seal. The cylinder end threads simply apply the clamping force.

Before attaching the CGA fitting to the cylinder the user should put on safety glasses and good hearing protection.  The cylinder valve can then be cracked slightly to blow out any dust or debris.  After closing the valve, inspect the cylinder valve and nipple for any abrasions, nicks, gouges, embedded particles, etc., before attachment is made.

You will need two wrenches (not adjustable pliers) to equalize the torque, particularly on the cylinder valve where it should be minimized. Put one wrench on the fitting and the other wrench on the cylinder valve and make the join.

Once the regulator/gauge cluster has been mated to the cylinder, the delivery hose can now fitted to the regulator and the metal wand to the other end of the hose.  The wand is nothing more than a short length of metal tubing at least six inches greater in length than the depth of the buckets to be filled. Copper water line works well.

When the joins have been made, a mixture of a short squirt of dish washing detergent and water can be used to check for leaks.  Be certain the detergent does not contain ammonia which can be corrosive.  Pour some on each fitting working from the cylinder end outward, opening each valve and pressurizing as you go.  Once the leak check is finished rinse off and wipe down all surfaces to minimize the chance of accidents in the future.

If the gas is not to be used at that time then the cylinder valve should be closed and all pressure should be drained to zero in the regulator and gauge.  This should be done any time that the tank is not in actual use.  If you have purchased your own cylinder then it is a good idea to also acquire one of the plastic valve plugs, similar to those seen with propane cylinders, in order to protect the cylinder valve threads and keep dust, debris and insects out of the valve.

WARNING: Care should be taken that the cylinder is used and stored in such a way as to minimize the risk of the tank falling over. With the regulator and gauge attached there is an increased likelihood of damage occurring to the cylinder valve should the tank fall. Catastrophic failure of the cylinder valve will turn the tank into a high-energy, unguided rocket with the capability of doing great damage and/or serious injury.

PUTTING IT INTO USE

Having assembled and tested your gas system, you are now ready to begin the work of packaging your food.  You’ll need containers, and food grade plastic or Mylar bags that are a bit larger in internal volume than the container.  Next is the dry food you intend to package and a pack of matches or a cigarette. You’ll also need to wear the safety glasses and hearing protection you wore when you put the gas system together.

Take the containers you are going to use to store your food in, the bags that will line them and the food you are putting up and place them in some warm (not hot) area long enough for them all to equalize to that temperature.  This will mean that the air contained inside them will also be at a warm temperature and make it more likely that it will stay on top when the cool gas from the nitrogen cylinder begins to flow in. The warm gas being on top will be the first to purge from the container, taking a good deal of the oxygen with it.

Line the interior of the container with a plastic bag or Mylar bag. Fill the container with the food product shaking to get it as full as possible.  Don’t forget to put your desiccant package on the bottom if you’re going to use one.  You don’t want any pockets left between the plastic bag and the container.  Once you have gotten it full to just short of not being able to fully put on the lid, gather the top of the plastic bag together or heat seal the edges.  If you have sealed it, cut a small corner off of the bag just large enough to allow a probe to enter.

At this point you can either simply flush the bag as described below or draw a vacuum on it first and then flush.  If using a vacuum the suction probe should be kept at the top of the bag, just inside of the opening.  The gas wand should be inserted to the bottom of the container, taking care not to poke any holes in the liner bag.  Once both instruments are inserted, draw the vacuum.  When it has reached a satisfactory level, shut off the suction, maintain the seal and turn on the gas.

Open the cylinder valve and set the regulator to a very slow gas flow and begin to fill the bag with gas.  You want the container to fill slowly so you can minimize turbulence and mixing as much as you can. It’ll take a little while to fill each container, a minute or two per bucket.  Just as with dry ice, the idea here is for the cool gas to displace the warmer atmosphere from the container.  The bag should puff a bit.  When I think it’s full I’ll hold a lit match above the bag in the air that is escaping from it.  If it snuffs right out then I let it run for about several minutes longer to flush out more of any remaining oxygen and remove the wand.

For the most efficient oxygen removal, repeat the suction/gas flushing procedure one more time.  When satisfied, tie or heat seal the bag off and seal the bucket.  Again, you want to have the bucket as full as possible so that there’ll be only minimal air space.  You should monitor the containers for an hour or two after filling to check for any signs of bulging or other pressure build up as the cool gas inside gradually warms and expands.  A slight positive pressure is OK, but serious bulging will need some of the pressure released.

NOTE: Although the procedure for flushing a container with nitrogen is straightforward enough, actually getting a good purge of the container is not.  Nitrogen flushing works best when the food particles are fairly large in size so the gas flow around and through the food is free and unrestricted.  Foods such as the larger sized grains (corn, wheat, barley, long grain rice, etc.), legumes and non-powdered dehydrated foods are best suited to this technique.  Foods with small particle sizes such as flours, meals, and dry milks will flush with mediocre results.

Because of the difficulties in purging sufficient oxygen from a container to lengthen the shelf life of the food it contains many commercial suppliers have dropped this technique in favor of using oxygen absorbers.  There is no reason that inert gas flushing and oxygen absorbers cannot be used together and one good reason that they should. If you are using five gallon plastic buckets as your storage containers, it has been observed that absorbers used in unlined pails can cause the air pressure inside the bucket to drop enough for the walls to buckle, possibly leading to a seal breach or a stack collapsing.  For this reason, flushing with inert gas (nitrogen or CO2) might be a good idea, in order to purge as much oxygen as possible so that the pressure drop caused by the absorber removing the remaining oxygen will not cause the bucket to buckle.  Liner bags can ameliorate the vacuum problems.

A big note of thanks to Lee Knoper for his assistance in putting together the above compressed gas information.