F A C T O R S T H A T A F F E C T T H E C H E M IC A L G A S S IN G O F E M U L S IO N E X P L O S IV E S

Jo h n S . M a n k a , P h .D . T h e L u b riz o l C o rp o ra tio n 29400 L a k e la n d B o u le v a rd W ickliffe , O h io 4 4 0 9 2

ABSTRACT Of the various methods used to reduce the density of emulsion explosives prior to detonation; ammonium nitrate prill addition, glass micro-balloon addition and chemical gassing, chemical gassing is the method most often selected by emulsion explosive end users. Chemically gassing emulsions costs less than adding micro-balloons and chemically gassed emulsions have better water resistance than emulsions that add ammonium nitrate prills to reduce the bulk density. Unfortunately, the chemical gassing of emulsion explosives can be intricate and is often more art than a science. To gain a better understanding of chemical gassing, we investigated the factors that may affect the chemical gassing of emulsion explosives. Variables investigated as having an effect on gassing were the pH of the oxidizer phase, the amount and type of nitrogen in the emulsifier, the composition of the oxidizer phase, the use of pH buffers in the oxidizer phase, and how the gassing reagents are added to the emulsion. BACKGROUND A typical ammonium nitrate emulsion explosive, such as an emulsion with a 90%wt:10%wt oxidizer to fuel ratio, has an initial density of 1.30-1.40g/ml. The bulk emulsion density can vary due to the fuel to oxidizer ratio employed, which nitrate salts are used in the oxidizer phase, the oxidizer to water ratio, and which fuel is used. For an ammonium nitrate emulsion to be detonated, the density must be reduced from 1.30-1.40g/ml to about 0.90 - 1.10 g/ml (While many emulsions used in the field can have a .9 to 1.1 density, many emulsions have a higher final density from 1.15 to close to 1.25g/ml.. This is often achieved by the addition of AN prills. The original AN bulk emulsions used in the US had a bulk density of 1.2 using microballoons) with the targeted density determined by the specific blasting application. Density reduction lowers the density of the emulsion to a point where the emulsion will maintain a steady state velocity of detonation (VOD) at the required level, usually 5000 meters/second. Density Reduction - There are three common methods of emulsion density reduction. Two methods involve adding low-density solids; porous ammonium nitrate prills or low density, hollow glass microballoons, to the emulsion. The third method uses the chemical or in-situ generation of gas bubbles. Combinations of these three methods can also be used together to achieve the desired cost/performance targets.

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Each of the three methods has advantages and disadvantages. The addition of porous ammonium nitrate prill is inexpensive. However prills reduce the water resistance of the emulsion-prill mixture and can decrease the emulsion stability by absorbing the fuel phase from the emulsion causing the emulsion to break. The addition of micro-balloons maintains the water resistance of the emulsion and does usually not hurt emulsion stability. Using micro-balloons also ensures a uniform void size, void volume and distribution of the voids through out the emulsion. Unfortunately, micro-balloons are expensive. Chemical gassing is less expensive than adding micro-balloons, maintains the water resistance as compared to ammonium nitrate prill, and if done properly, does not hurt emulsion stability. Compressible Voids Emulsion density reduction is a misnomer. Although the emulsion density is reduced by the addition of prills, micro-balloons or nitrogen bubbles, it is not the actual aggregate density of the emulsion that is important. It is the voids that are put into the emulsion by adding the prills, micro-balloons and gas bubbles that are critical for detonation. Voids are added to provide room for the compression and super heating of the emulsion during detonation. The compression of the voids generates hot spots so that the detonation can progress properly throughout the explosive column. When the propagating shock wave started by the high explosive used to detonate the emulsion moves through the explosive, the shock wave hits a void or gas bubble, and compresses it. The pressure compressing the voids or gas bubble during detonation is on the order of 7,000 to 200,000 atmospheres. When the void compresses, it generates heat between 3,0007,000C. This instantaneous heat generation propagates shock energy in front of the denotation, which starts the procedure over again with the next void. A loss of voids, or a change in size of the gas bubbles, can cause the emulsion to misfire, burn, or fail to detonate. When this happens it is referred to as "dead pressing." If this condition is brought about by the action of the shock wave from an explosion hitting emulsion in adjacent holes causing the density of the emulsion to increase or changes the gas bubble size or density, it is called "pre-compression. C H E M IC A L G A S S IN G There are two methods to chemically gas emulsion explosives. The choice of which method to use depends on the temperature of the emulsion when gassing. Both methods use a sodium nitrite-gassing agent but for low temperature gassing applications, a catalyst is added to increase the gassing rate. Hot Gassing - For emulsion gassing at temperatures of 40-100C, an aqueous solution of 15%wt sodium nitrite is used in conjunction with acid to produce nitrogen gas. The sodium nitrite solution is added to the emulsion stream at a range of 0.6% to 2.0%wt but is typically used at 0.9%wt. Equations 1 and 2 show the proposed chemical reactions, which lead to nitrogen gas bubbles being formed within the emulsion. The nitroso ion (also represented as +N==O or NO+) generated by the reaction of nitrite and acid, Equation 1, reacts with ammonia as shown in Equation 2 to yield nitrogen gas. Equations 1 and 2 also show that protons (H+) are necessary for nitrogen gas evolution so the appropriate acidity of the oxidizer phase is critical. If the oxidizer phase is too acidic, there will not be enough ammonia (NH3) for the gassing reaction to go to completion since the ammonia will exist as the

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protonated ammonium ion. If the oxidizer phase is too basic there will not be enough protons available to complete the gassing reaction.

E q u a tio n 1: P ro d u ctio n o f N O
H O N

H H O N

H2O H O H N O N O

E q u a tio n 2: R e a ctio n o f A m m o n ia with N O

H N NH3 O H N H N O

H exchange H N N O H H

loss of H H2O N2 + H+

Importance of Oxidizer pH - Instead of saying acidity or basicity, we usually talk about the pH of the oxidizer phase. pH is a convention used to discuss how acidic or basic an aqueous solution is. pH ranges from 0 to 14. Acidic solutions have low pHs (less than pH= 7). Basic solutions have high pHs (greater than pH= 7). pH= 7 is considered neutral. pH is the negative logarithm of the proton (H+) concentration of an aqueous solution. The smaller a negative logarithm the larger a quantity it represents. A solution with a pH= 3 has a larger proton concentration than a solution with a pH= 8. Another fact to keep in mind is that pH represents an exponential scale. This means that an increase of one unit in pH represents an increase in the proton concentration or acidity of the solution of 10 units. For example, the proton concentration of a solution with a pH= 1 is ten times larger or more acidic than the proton concentration of a solution with a pH= 2. A solution with a pH= 3 has 100,000 times more protons than a solution with a pH= 8. This exponential effect is why pH control is so important to chemical gassing. If the pH of the system varies only a small amount it can greatly affect the rate of gassing. Cold Gassing - For gassing below 40C, a sodium thiocyanate catalyst is needed to facilitate the generation of nitrogen gas. The thiocyanate ion is a stronger nucleophile than the nitrite ion and allows the reaction to take place at lower temperatures than with the nitrite ion. A typical cold gassing solution consists of 15-20%wt sodium nitrite, 15%-30%wt sodium thiocyanate and 70-50%wt water. This solution is also added at about 0.9%wt to the emulsion stream. Equation 3 shows the chemical reaction for cold gassing. The nitroso ion (also known as +N==O or NO+) generated by the reaction of sodium nitrite and acid previously shown in Equation 1, reacts with thiocyanate to yield nitrogen gas (N2).

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It is crucial for the emulsion system to be at the proper pH when using a sodium thiocyanate catalyst. If the pH is too high, there is insufficient acid present and the thiocyanate may react with the amine based emulsifier, instead of the acid, as shown in Equation 4. If the emulsifier reacts with the thiocyanate the emulsifier can no longer act as it should and emulsion stability may be decreased. Equation 3: Reaction of Thiocyanate with NO+

NO S C N

+ S C N N O NH 3 H 2N

S C N H S N O NH 3

NH 2

NH 2

N H

+H H exchange

H 2O

N2 + H +

E q u a tio n 4 : R e a ctio n o f T h io c y a n a te with A m in e B a s e d E m u lsifie r

S + H+ -S C N + H2 N Emulsifier H 2N S C H 2N N H Emulsifier -NH3 S C N Emulsifier C N H Emulsifier

Emulsifier

H2 N

Emulsifier

Emulsifier

N H

N H

Emulsifier

E X P E R IME N T A L Emulsions - Laboratory emulsions were prepared using a Black & Decker Model HP3000 food processor. The fuel and oxidizer phases were emulsified using our standard lab procedure so that emulsion-to-emulsion variability was minimized. All of the emulsions were made to the same viscosity within experimental error of the Brookfield viscometer. The oxidizer phase buffers were made by adding a conjugate base (for example sodium acetate) to the oxidizer phase and then titrating the oxidizer phase with the conjugate acid (acetic acid in this example) until the oxidizer phase reached the desired pH as measured by a pH meter. The exact experimental details can be obtained by writing the author. The general emulsion formula was:

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75.44%wt Agricultural grade ammonium nitrate prills 16.56%wt Water 1.7%wt Emulsifier 6.3%wt Fuel phase Raw Materials - The emulsifiers were commercial products supplied by the Lubrizol Corporation. The fuel phase was commercial #2 diesel fuel oil. The ammonium nitrate (AN), sodium nitrate (SN) and calcium nitrate (CN) were all reagent grade. Laboratory Emulsion Gassing and Density Measurement The exact procedure for the emulsion gassing and density determination can be obtained by writing the author. An abbreviated description of the cold gassing procedure is listed here. The hot gassing procedure is very similar. A sample of emulsion was heated or cooled to the desired gassing temperature. For cold gassing, 1.0%wt of an aqueous 15% sodium nitrite solution / 30% sodium thiocyanate gassing solution was added to the emulsion sample. Acetic acid is typically added at the same time as the gassing solution unless the oxidizer phase already has its pH adjusted to the appropriate pH. The gassing solution was quickly mixed into the emulsion by hand, and the resulting emulsion was used to completely fill a preweighed plastic cup that has a known volume. As the gassing proceeds, the emulsion increases in volume and foams out of the plastic cup. At regular time periods, the excess gassed emulsion was removed flush from the surface of the plastic cup. The emulsion and cup were weighed at various times with the density calculated from the weight of the emulsion remaining in the cup and the known volume of the cup. R E S U L T S A N D D IS C U S S IO N Effect of pH on Chemical Gassing - Equation 1 showed that gassing requires protons for nitrogen gas formation and that proper pH is important for successful gassing. Graph 1 shows the effect of the oxidizers pH on the emulsion-gassing rate. Even slight changes in pH have a large effect on gassing rates. In general, at high pH there is not enough acid to form nitrogen gas at a reasonable rate. A high pH may cause the cold gassing sodium thiocyanate catalyst to react with the emulsifier instead of any free acid. The reaction of the sodium thiocyanate with the emulsifier depletes the amount of emulsifier and thus destabilizes the emulsion. At low pH, the acid may react with the emulsifier instead of reacting to form nitrogen gas. The reaction of the acid with the emulsifier can destabilize the emulsion by changing the hydrophilic lipophilic balance (HLB) of the emulsifier, see Equation 5. E q u a tio n 5 : R e a ctio n o f A cid with A m in e B a s e d E m u lsifie r
Acid + H2N Emulsifier H3+N Emulsifier

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It is recommended that when lab or field chemical gassing, the pH of the oxidizer phase be checked with pH paper, or better still a pH meter. An oxidizer phase pH less than 3.0 will gas very quickly but may cause the emulsion to crystallize if using amine-based emulsifiers. A pH between 3.0 and 4.0 is desired for efficient gassing rates and emulsion stability. At pH greater than there may not be enough acid to form the nitrogen gas at a reasonable rate. G ra p h 1 : T h e E ffe c t o f O xid iz e r P h a s e p H o n E m u lsio n C o ld G assin g R a te .
pH=2 pH=2.5 pH=3 pH=4 pH=4.5

1.4 1.3 Density in g/ml 1.2 1.1 1 0.9 0 5 10 15 Time in Minutes 20 25 30

Graph 1 also shows that over time the rate of gassing decreases as shown by the change in slope or the flattening out of the density curves. This likely due to the exhaustion of the gassing reagents but it may also be due in part to an increase in the pH as the acid is used up. To promote a constant gassing rate over changing pH, some emulsion manufactures use buffers to maintain the pH through out the gassing. Use of Buffer in the Oxidizer Phases - A buffer is a solution that resists changes in pH. Buffers maintain a given pH even when the solution is diluted or when small amounts of either acid or base are added or removed from the solution. The best buffers contain equal concentrations of a conjugate acidbase pair. For example, in emulsion explosives, an effective buffer solution can be made of acetic acid and sodium acetate. The acetic acid is the acid and sodium acetate is the conjugate base. Together they make up a conjugate acid-base pair. We have found that an acetic acid / sodium acetate buffer at a pH= 3.5 or a zinc nitrate / sodium carbonate buffer at pH= 3.5 were especially effective buffer systems for use with amine based emulsifiers. Other buffer systems are also effective in these systems. Method of pH Adjustment of the Oxidizer Phase - A typical 80:20 ammonium nitrate / water oxidizer phase has a pH around 4.5. It is easy to adjust the pH of the oxidizer phase before the emulsion is made. However, when you add acid to the oxidizer phase, there is a chance that the emulsion may be less stable due to the reaction of the acid with the emulsifier before the emulsion is gassed. An alternative method adjusts the pH of the finished emulsion just prior to gassing. Production equipment is available that can add acid to the emulsion at the same time that the gassing solution is

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mixed into the emulsion as the emulsion is pumped down hole. We investigated these two methods of pH adjustment to see if there was a difference in their gassing rates. Table 1 shows the formulas for two emulsions made using the two different pH adjustment methods. The buffered oxidizer emulsion has the oxidizer phase buffered with acetic acid and sodium acetate adjusted to the appropriate pH prior to making the emulsion. The Post Added Acid emulsion is treated with acetic acid just prior to gassing. T a b le 1 : E m u lsio n s U s e d to Investig a te th e D iffe re n ce b e twe e n B u ffe re d O xid iz e r a n d P o st A d d e d A cid E m u lsio n s . Buffered Oxidizer Emulsion Emulsifier Diesel Fuel Oil Water Ammonium Nitrate Glacial Acetic Acid Sodium Acetate Total Gassing Solution Water Glacial Acetic Acid Sodium Nitrite Sodium Thiocyanate Total 1.8 %wt 3.8 %wt 17.0 %wt 77.3 %wt 0.07 %wt 0.04 %wt 100.0 %wt 55.00%wt 15.00%wt 30.00%wt 100.0 %wt Post Added Acid 1.8 %wt 3.8 %wt 17.1 %wt 77.3 %wt 100.00 %wt 35.00%wt 50.00%wt 7.00%wt 8.00%wt 100.00 %wt

Graph 2 shows that the Post Added Acid emulsion gasses faster than the buffered oxidizer phase emulsion. The slower gassing rate of the buffered oxidizer phase emulsion may be due to the amine emulsifier consuming some of the acid during storage prior to gassing. G ra p h 2 : T h e G assin g R a te s fo r th e p H A d justm e n t S yste m s in T a b le 1

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Buffered Oxidizer

Post Added Acid

1.35 1.25 Density in g/ml 1.15 1.05 0.95 0.85 0 5 10 15 Time in Minutes 20 25 30

The Effect Of Sodium Nitrate And Calcium Nitrate On Gassing Rate Emulsion manufactures will occasionally substitute calcium or sodium nitrate in place of ammonium nitrate. Adding calcium nitrate lowers the fudge point of the oxidizer phase reducing the emulsifier requirement. Adding sodium nitrate increases the energy and sensitivity of the emulsion and requires less water in the oxidizer phase. Sodium nitrate also increases emulsion stability especially in wax package products. We wanted to investigate the effect of change the oxidizer phase on the rate of emulsion gassing. Graph 3 shows that both sodium and calcium nitrate have a detrimental effect on gassing. This makes sense since ammonium nitrate can donate or accept protons and act like a buffer during the gassing reaction. Sodium and calcium nitrate cannot provide nor accept protons so they have no beneficial buffering effect on pH and thus retards gassing relative to an all ammonium nitrate oxidizer.

G ra p h 3 : E ffect o f S o d iu m a n d C a lciu m N itra te o n G assin g R a te a t p H = 3.5

All AN

AN SN

AN CN

Density g/ml

1.30 1.10 0.90 0.70 0 5 minutes 10 15

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Effect of % Nitrogen in the Emulsifiers on Gassing Since the nitrogen of the amine based emulsifiers has the potential to react with acid or with the thiocyanate catalyst during gassing, we investigated if there was a relationship between the % nitrogen in the emulsifier and the emulsion gassing rate. Graph 4 shows a plot of emulsion density after an arbitrarily chosen 13 minutes (effectively a measure of the gassing rate) versus the % nitrogen present in the various amines based emulsifiers tested. The correlation of % nitrogen with gassing rate was R2 = 0.26. This poor correlation implies that the rate of gassing is only very weakly dependant on the amount of nitrogen in the emulsifier. Effect of Emulsifier Total Base Number on Gassing The data showed that % nitrogen does not correlate well with gassing rate. This may mean that not every nitrogen containing species present in the emulsifiers is detrimental to chemical gassing. Since we were concerned with the consumption of acid and the thiocyanate, we proposed that only basic amine structures within the emulsifiers may be detrimental to gassing. Therefore we investigated the correlation of total base number (TBN) of the emulsifier on the emulsion-gassing rate. Graph 4: The Effect of Emulsifier % Nitrogen on Emulsion Gassing Rate
Density in g/ml after 13 minutes

1.25 R2 = 0.26 1.15 1.05 0.95 0.85 1.00

1.50

2.00 % Nitrogen

2.50

3.00

Graph 5 shows that there is very little or no correlation (R2 = 0.086) between the density after 13 minutes (gassing rate) of the emulsion and the TBN of the emulsifier. This implies that gassing is not dependant on the amount of basic amine present in the emulsifier. Since neither the % nitrogen nor the amount of basic nitrogen (TBN) present in an emulsifier has any effect on the rate of emulsion gassing, other properties of the emulsifier must play a significant role. We plan to investigate this area further and report those results at a future conference. Graph 5: The Effect of Emulsifier Total Base Number on Emulsion Gassing Rate

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1.25
Density in g/ml after 13 minutes

1.20 1.15 1.10 1.05 1.00 0.95 0.90 0.85 20.0 30.0 40.0 50.0 60.0 70.0 80.0
R2 = 0.086

Total Base Number

CONCLUSIONS 1) Proper pH control is very important for efficient gassing rates and for the stability of amine based emulsifier emulsions. 2) pH buffers can be used to stabilize the rate of gassing and increase the stability of the emulsion. 3) Adjusting the emulsion pH immediately before gassing gave a faster gassing rate than adjusting the pH of the oxidizer phase prior to emulsion making. 4) There is a weak correlation between gassing rate and emulsifier %nitrogen. 5) There is very little or no correlation between the gassing rate of the emulsion and the TBN of the emulsifier. 6) Using calcium or sodium nitrate in place of ammonium nitrate reduces the rate of chemical gassing.

A C K N O W LE D G E ME N T The author would like to thank Dr. Brian B. Filippini and Dr. Jim H. Bush for their contributions to this paper.

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