PROCESS FOR PREPARING ULTRA-FINE SODIUM BICARBONATE POWDER

FIELD OF THE INVENTION

This invention relates to a process for preparing ultra-fine sodium bicarbonate

(i.e. having an average particle size of less than about 5 microns), which exhibits a narrow particle size distribution. Ultra-fine sodium bicarbonate powder made according to the method of the present invention is particularly useful as an ingredient in foaming (blowing) agents for polymeric materials such as polyethylene and other plastic or rubber materials where its small particle size and narrow particle size distribution are conducive to the production of small and uniform foam cell size in the foamed plastic.

BACKGROUND AND PRIOR ART

Sodium bicarbonate, commonly known as baking soda, is traditionally used as a leavening agent in the food industry. It is also widely used in household, personal care and industrial applications. There are two typical industrial processes for manufacturing sodium bicarbonate; the Solvay process and Trona ore mining.

Sodium bicarbonate is an intermediate product of the Solvay process, whose targeted end product is sodium carbonate. In the Solvay process, ammonia and carbon dioxide are sparged through a saturated sodium chloride solution to form a solution containing ammonium bicarbonate. This ammonium bicarbonate is then reacted with sodium chloride to form ammonium chloride and sodium bicarbonate. Ammonium chloride is very soluble, and the much less soluble sodium bicarbonate is precipitated and crystallized, if the temperature is kept below 15°C. The precipitated sodium bicarbonate is filtered off, heat is applied to decompose it and sodium carbonate is obtained as the desired end product.

A second manufacturing process is based on Trona ore, a sodium sesquicarbonate mineral ore (Na ₂ CO ₃ NaHCO ₃ ^H ₂ O), mined mostly in Wyoming,

USA. The ore is first crushed and screened. It is then calcined to raw sodium

carbonate, carbon dioxide and water The sodium carbonate is dissolved and filtered to eliminate impurities Carbon dioxide is bubbled into the saturated pure sodium carbonate solution and the sodium bicarbonate precipitates out to be collected and dried Trona ore mining is the most dominant process for producing sodium bicarbonate in North America because it is cheaper to mine the ore than to synthesize NaHCO ₃ from other raw materials

Foaming plastics and rubbers is a known industrial application of sodium bicarbonate After NaHCO ₃ is added into melted plastics or rubber material, it decomposes releasing carbon dioxide The formation of gas bubbles results in a cellular foam structure

Among the numerous desirable attributes achieved by the foaming of plastics and rubber materials are energy absorption, low thermal conductivity, sound absorption, low thermal conductivity for insulation properties, cushioning, soft and flat surfaces, high strength/weight ratios for good strength and softness, improved thermal strength and thermal and chemical inertness

A number of patents are directed to the preparation of sodium bicarbonate powder having small particle size or other particular useful physical characteristics such as substantial sphericity of the sodium bicarbonate particles [published U S Patent Application No 2002/0172713-Eιnzιnger et al and microporosity, U S Patent No 5,482,701 (Winston)]

Very fine or ultrafine sodium bicarbonate powders have been prepared by a number of methods U S Patent 5,41 1 ,750 (Lajoie et al) describes the precipitation of sodium bicarbonate from aqueous solution by the gradual addition of a water- miscible organic solvent such as CH ₃ OH This is claimed to produce sodium bicarbonate powder having an average particle size less than about 1 micron, but with a broad particle size distribution, between about 0 1 and 1 micron

U S Patent No 6,352,653 (Hirano et al) is said to produce sodium bicarbonate having a volume-based mean particle diameter of from 1 to 9 microns

This sodium bicarbonate powder is obtained by grinding NaHCθ ₃ using an impact- type grinder equipped with an air classifier, which classifies particles discharged from the grinder and returning large particles to the grinder.

SUMMARY OF THE INVENTION

We have discovered that ultra-fine sodium bicarbonate having a relatively narrow particle size distribution and desired crystal shape can be obtained by the controlled reaction of sodium chloride and ammonium bicarbonate in aqueous solution, under selected conditions of concentration, temperature and rate of agitation.

The synthetic process of this invention is essentially variation on the Solvay process. Ammonium bicarbonate itself is used as a reactant rather than the separate introduction of ammonia and carbon dioxide as sources of ammonization and carbonation. The ammonium bicarbonate is added to a sodium chloride solution under controlled temperature and agitation. The resulting sodium bicarbonate is precipitated out of the solution as slurry. The precipitate can be dried using a vacuum oven, freeze drying or spray-drying to form ultra-fine particulate sodium bicarbonate with advantageous characteristics as a plastics foaming agent.

Sodium bicarbonate prepared by the method of the invention can be formulated into blowing agent master batch by adding other functional additives and minerals such as citric acid and surfactants. The blowing agent is used for the foaming of plastics such as LDPE, LLDPE, HDPE, EVA, GPPS (General Purpose Polystyrene) and HIPS (High impact polystyrene) to produce foams exhibiting ultra- fine cell structure and narrow size distribution.

BRIEF DESCRIPTION OF THE DRAWINGS

Figures 1A and 1 B are low and high magnifications of a photomicrograph of sodium bicarbonate prepared according to the method of Example 2(a).

Figures 2A and 2B are low and high magnifications of a photomicrograph of sodium bicarbonate prepared according to the method of Example 2(b).

Figures 3A and 3B are low and high magnifications of a photomicrograph of sodium bicarbonate prepared according to the method of Example 2(c).

Figures 4A and 4B are low and high magnifications of a photomicrograph of sodium bicarbonate prepared according to the method of Example 2(d).

Figures 5A and 5B are respectively low and high magnifications of a photograph of sodium bicarbonates prepared according to the method of the invention and dried using a vacuum oven.

DETAILED DESCRIPTION OF THE INVENTION

The sodium chloride and ammonium bicarbonate solutions which are reacted together according to the method of the invention can each be saturated or unsaturated. Different concentrations result in differences in the precipitated sodium bicarbonate particle size and particle size distribution, as well as in its crystal shape.

The solubility of sodium chloride in water at O ⁰ C is 35.9g/100ml while that of ammonium bicarbonate is 1 1.9g/100ml. The solubility of sodium bicarbonate at O ⁰ C is only 6.9g/100 ml. The reaction temperature should be kept below 3O ⁰ C, with optimal results below 15°C. Stirring speeds can vary from Speed 1 to Speed 6 on a home blender. A KitchenWorks™ Model CB5700, Byupe B12 was employed in the experimental Examples herein presented with settings from lowest (Speed 1 ) to mxaimum (Speed 6). Reaction times range from 20 to 60 seconds.

To the solution, a minor amount of calcium silicate may then be added to act as a flow enhancing and anti-caking agent for the later-precipitated NaHCθ ₃ powder. This use of calcium silicate is conventional in preparing of formulated edible salts.

According to an embodiment of the process, such as GMS (glycerol

monostearate). A crystallization controlling agent to facilitate formation of sodium bicarbonates of smaller particle size.

Other organic solvents including methanol, ethanol, acetone, N ₁ N- dimethylformamide, tetrahydrofuran etc., may optionally be added at this stage in this synthesis to control the size and size distribution of the bicarbonates.

Following precipitation, a sodium bicarbonate slurry is removed from the reaction mixture by filtration and dried. Drying methods which may be used in this invention includes vacuum drying, freeze drying and spray drying. Spray drying has been found to exhibit the highest drying efficiency. Spray drying can be conducted at temperatures from 60 ⁰ C to 12O ⁰ C.

The dry NaHCO ₃ powder obtained can be post ground by an air mill to break apart any aggregates or agglomerates of the ultra-fine particles formed in the crystallization/drying process.

Sodium Bicarbonate Particle Size and Size Distribution

The following Examples illustrate the effect of reaction conditions (reaction time, stirring intensity, reactant levels and reaction temperature) on particle size and particle size distribution.

Example Ka):

40 grams of pure sodium chloride were dissolved in 100 ml of water at 3O ⁰ C to make a saturated solution. The solution temperature was kept at about 3O ⁰ C. 10 grams of ammonium bicarbonate was weighed out and added to the saturated sodium chloride solution with intensive mixing (blender Speed 1) for 20 seconds. The precipitate was filtered off with the help of a vacuum.

A single drop of the precipitated slurry was sampled onto microscope slide and examined at 10 X 40 magnification. A digital photo was taken. The photo was analyzed using Image ProPlus™ software, an image analysis software to measure

the particle size and particle size distribution. The resulting particles exhibited an average size of 1.94 microns and a particle size distribution (one standard deviation) of 1.04 microns, i.e. 53.6% of the mean particle size.

Example Kb):

40 grams of edible sodium chloride were added to 100 ml of water to prepare a saturated solution. The solution temperature was then brought to kept at 5°C and

20 grams of ammonium bicarbonate was added to the saturated sodium chloride solution with intensive mixing (Speed 1) for 20 seconds. The precipitate was vacuum-filtered away from the liquid.

One drop of the precipitated slurry was sampled as above and examined at and made into a 10 X 40 magnification. A digital photo was taken. The photo was again analyzed by Image ProPlus. The resulting particles were found have an average size of 0.69 microns and a particle size distribution of 0.40 microns, i.e.

58.0% of the mean particle size.

Sodium Bicarbonate Particle Shape

The following Examples illustrate the effect of reaction conditions (reaction time, stirring intensity, reactant solution concentration and reaction temperature) on particle shape.

Example 2(a)

20 grams of pure sodium chloride was dissolved in 100 ml of water. The solution temperature was lowered to and kept at 5 ⁰ C. 20 grams of ammonium bicarbonate was weighed and added to the saturated sodium chloride solution with intensive mixing (blender Speed 1 ) for 20 seconds. The precipitate was filtered off with help of a vacuum.

One drop of the precipitated slurry was sampled and was micro-photographed as before. A digital photo was taken and is reproduced in Figures 1A and 1 B which

clearly show the filamentous shape of the NaHCθ ₃ crystals. The photograph was analyzed by Image ProPlus. The particles have an average size of 1.93 microns and a particle size distribution of 0.73 microns (i.e. standard deviation 37.8% of mean particle size.

Example 2(bV.

20 grams of pure sodium chloride was dissolved in 100 ml of water to make a saturated solution. The solution temperature was lowered to and kept at 5°C. 10 grams of ammonium bicarbonate was added to the saturated sodium chloride solution with intensive mixing (blender Speed 6) for 60 seconds. The precipitate was vacuum-filtered.

One drop of the precipitated slurry was sampled. A digital photo was taken, reproduced as Figure 2A and 2B, showing a generally needle-like shape of crystals.

The photo is analyzed by Image ProPlus. The resulting particles were seen to have an average size of 0.80 microns and a particle size distribution of 0.32 microns (i.e. standard deviation 40.0% of mean particle size).

Example 2(c)

A saturated solution of sodium chloride was kept at 30 ⁰ C. 10 grams of ammonium bicarbonate was added to the saturated sodium chloride solution with intensive mixing (blender Speed 6) for 60 seconds. The precipitate was vacuum- filtered.

Again one drop of the precipitated slurry was sampled, deposited on a microscope slide and a digital photograph taken, reproduced in Figures 3A and 3B, from which the cubic shape of the crystals can be seen at 10 X 40 magnification. The photo was analyzed by Image ProPlus, and these particles were found to have an average size of 1.42 microns and a particle size distribution of 1.31 microns, (i.e. standard deviation 92% at mean particle size).

Example 2(d):

40 grams of edible sodium chloride was dissolved in 100 ml of water to make a saturated solution. The solution temperature was then lowered and kept at 5°C. 10 grams of ammonium bicarbonate was added into the saturated sodium chloride solution with intensive mixing (blender Speed 1 ) for 20 seconds. The precipitate was filtered off with the help of a vacuum, as in the previous Examples.

A drop of the precipitated slurry was photographed with 10 X 40 magnification and the digital photograph was analyzed by Image ProPlus. The resulting particles were found to have an average size of 1.32 microns and a particle size distribution of 0.66 microns, (i.e. standard deviation 50% of mean particle size). As may be seen from the reproduction of Figures 4A and 4B the crystals have a generally spherical shape.

The Table below summarizes experimental results from the above Examples. The width of the particle size distribution of the sodium bicarbonate powder produced in each Example is indicated by the size of one standard deviation, expressed in microns and also as a percentage of the mean particle size.

^* contains ~ 2% sodium silicate, routinely added as a flow-aid in commercially available NaCI

Effect Selection of Drying Method

Three methods were investigated: vacuum oven drying, freeze drying and spray drying.

Vacuum oven drying

As in Example 1 (a) above, 40 grams of edible sodium chloride was dissolved in 100 ml of water to make a saturated solution. The solution temperature was kept at 5 ⁰ C. 20 grams of ammonium bicarbonate was added to the saturated sodium chloride solution with intensive mixing (blender Speed 1 ) for 20 seconds.

The filtrate was dried using a vacuum oven under a 15 inch mercury vacuum at 75 ⁰ C for 72 hours. A dry powder was obtained. The dry powder was displaced. A digital photo was taken which again was analyzed by Image ProPlus.

The resulting particles had an average size of 1.27 microns, a particle size distribution of 0.38 microns (1 standard deviation = 30% of mean particle size) and are seen in photographic reproductions 5A and 5B.

Freeze drying

A precipitate of NaHCO ₃ was prepared according to the method of Example 1 (b).

The solution was filtered using a centrifuge at 8000 rpm for 10 minutes. The precipitate was dried using a freeze dryer under a vacuum at -5O ⁰ C for 150 hours and a dry NaHCO ₃ powder was obtained. The dry powder was sampled and a 10 X 40 magnification photograph was analyzed by Image ProPlus. The resulting particles have an average size of 1.34 microns and a particle size distribution of 0.38 microns (i.e. standard deviation 28% of mean particle size).

Fluidized Bed Drying A precipitate of NaHCO ₃ was prepared according to the method of Example

1 (b).

Excess water in the synthesized slurry was filtered off by vacuum filtration.

After filtering, the powder cake residue was removed and placed into a furnace at 4O ⁰ C for approximately 16 hrs. There was an approximate 8.3% weight loss after the

furnace drying step, owing to loss of moisture. The dried cake was than broken into particles in a high sheer grinder, and introduced into a fluidized bed drier system. A small fluidized bed was used for the system. The airflow rate to the fluidized bed was approximately 1 ft ² /min. The temperature of the air at the inlet to the fluidized bed was approximately 49 ⁰ C. The powder sample was divided into about four portions, and each portion was fluidized for about 3-4 hours.

The dry powder was sampled and observed using scanning electron microscopy. The resulting particles were asymmetrical in shape and of an average size of 2.55 microns, analyzed by laser diffraction.

Spray Drying

40 grams of edible sodium chloride was dissolved in 100 ml of water to make a saturated solution. The solution temperature was brought to 5°C, and 20 grams of ammonium bicarbonate was added into the saturated sodium chloride solution with intensive mixing (blender Speed 1 ) for 20 seconds.

The sodium bicarbonate slurry produced was dried using the fluidized bed technique. Subsequent drying was carried out by a spray drying technique. A 0.5% concentration of sodium bicarbonate in water was prepared and placed in the spray drier. The inlet temperature to the spray drier was set at 12O ⁰ C and the outlet temperature measured at 73 ⁰ C. The air flowrate to the system was set at 439 L/hr.

The peristaltic pump was set at 3 mL/min, and the aspirator was set at 100% to maximize the separation rate.

The dry powder was sampled and observed using scanning electron microscopy. The resulting particles were spherical in shape. The particle size of the dry powder was analyzed via a laser diffraction mechanism, and the NaHCO ₃ particles were found to have an average size of 2.47 microns.

Spray drying was also carried out using a 0.2% concentration of synthesized sodium bicarbonate in water. The inlet temperature to the spray drier was set at

120 ⁰ C and the outlet temperature measured at 55 ⁰ C - 7O ⁰ C. The air flowrate to the

system was set at 439 L/hr. The peristaltic pump was set at ~ 5 mL/min, and the aspirator was set at 100% to maximize the separation rate of the cyclone.

The dry powder was sampled and observed using scanning electron microscopy. The resulting particles were spherical in shape. The particle size of the dry powder analyzed via a laser diffraction mechanism was an average size of 1.94 microns.

Formulation of Foaming Agents

In each of the five following Examples, a foaming agent was prepared by blending 6.5 grams of a sodium bicarbonate powder, 6.5 grams of monosodium citrate, 2.6 grams of calcium stearate (Blachford) and 49.4 grams of ethylene vinyl acetate (EVA) resin (Atevar 2030™), These components were melt-mixed using a Brabender mixer at 100 ⁰ C for 1.5 minutes. The melt was cold pressed and cut into pieces. In each test, the blowing agent masterbatch was used for foaming an LDPE resin (Nova LFY-819A, Melt Index 0.75 g/10min, Density 0.920 g/cm ³ ) at a 4% letdown ratio.

Example 4 (a) Control Test

In this example the sodium bicarbonate used was a commercial grade (Church & Dwight USP Grade 5). The foamed LDPE resin which result had a average cell size 98.1 microns and bulk density of 0.25 g/cm ³ .

Example 4(b)

Sodium bicarbonate prepared according to the method of Example 3(a) was used to produce foam with an average cell size of 26.6 microns and bulk density of 0.626 g/cm ³ .

Example 4(c)

In this Example, the sodium bicarbonate used was prepared according to Example 3(b). In the result, foamed LDPE resin was produced with an average cell size of 22.7 microns and foam bulk density of 0.604 g/cm ³ .

Example 4(d)

Sodium bicarbonate according to the procedure of Example 3(c) was used to produce the blowing. The foamed LDPE resin exhibited an average cell size of 79.6 microns and foam bulk density of 0.764 g/cm ³ .

Example 4(e)

In this case, the sodium bicarbonate was produced according to Example

3(d). Foam with an average cell size of 60.9 microns and foam bulk density of 0.747 g/cm ³ was made.