CHEMICAL PROCESS INDUSTRIES ChE 140

SOAPS AND DETERGENTS

Medrano, Hilda Luzelle S. Quitasol, Remedios Monica G. March 2011

INTRODUCTION

It is hard to think of the times when soaps were not present and people used other substances such as perfumes and plants to keep them clean and good smelling. Soaps and detergents are cleansing products which include bar and liquid soaps for cleaning the body and detergents and cleansers for laundry and household purposes. The production of soaps and detergents is known as the washing or soap industry (Austin 1984). The beginning of soap making did not start as an industry but just a household routine in the farms where then considered raw materials were abundant. The first record found on manufacture of soap was by Pliny the Elder in 600 A.D. describing how the Phoenicians made liquid soap from boiling goat tallow (animal fat) and ash. The soap produced from this was described to have no pleasant fragrances. The people in the earlier times used soap for medical purposes and its use in cleaning was just later discovered. The Arabs were the first to produce hard soap, which were made from olive oil and wood ashes. This kind of soap was considered a luxury item since they added scent to it and only the wealthy people could afford buying this. It was not until the thirteenth century that soap was made in large amounts that its production can be considered an industry. In the nineteenth century, Lever became a known manufacturer of soap made from plant oils which are cheaper and more fragrant than tallow soap. Then the basic manufacturing idea of soap remained the same until the 1910s, when the first synthetic detergent, or simply detergent, was developed by the Germans when animal fat shortages arose during the World War I. Henkel was later known to first produce the washing powder.

How Soaps and Detergents Work Nowadays, soaps and detergents, which can be collectively called soaps, are used in cleaning. Water is the liquid commonly used for cleaning and has the property called surface tension. Surface tension occurs when water molecules at a surface are pulled into a body of water. This slows the wetting of the surface being cleaned and inhibits the cleaning process. Water, a polar substance, alone cannot remove the dirt or soil from the surface being cleaned since soil repels water molecules. For good cleaning results, there are three types of energy needed: chemical energy, thermal energy, and mechanical energy. Soaps provide chemical energy. The primary ingredients of soaps called the surface active agents, or surfactants, have hydrophilic (water-loving) and hydrophobic (water-hating) ends. The hydrophobic end, a nonpolar and lipophilic (oil-loving) substance, is repelled by water but is attracted to the soil while the hydrophilic end is attracted to the water molecules. The action of these two ends creates two opposing forces which loosens the soil from the surface being cleaned and suspends it in the water. As more soap molecules come in contact they eventually surround the soil particles and form structures called micelles. In a micelle, the hydrophobic ends of the soap molecules keep the soil particles inside the structure while the hydrophilic end face outward into the surrounding water molecules. This forms an emulsion of dirt in the water (Figure 1).

Figure 1. Emulsification or dispersion of water-insoluble substances.

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Figure 2. Cleaning action of soap.

Thermal energy may be provided by warm or hot water (usually employed when soils stuck on surface being washed are tough or hard to remove). Water helps dissolve the soil. Machine agitation or hand rubbing pull the soil free from the surface. These provide the mechanical energy needed.

Companies Since the first time soap production was considered an industry, many companies have introduced their own product lines which had varying advertising strategies to convince buyers to use their products. Internationally, Colgate-Palmolive, Procter & Gamble, Unilever, Johnson & Johnson and Henkel have been the pioneers in soap production and are still the leading companies to produce quality soap and detergent products of varying uses. These companies have expanded their

operations from countries where they originated and even to other continents. They even have operational plants here in the Philippines. Locally, big companies which operate with high production capacity include the International Pharmaceuticals, Inc., Lamoiyan Corporation and Green Cross, Inc. Because herbal and organic products are now increasing in popularity, companies and even small groups of people engaging in small and medium enterprises (SMEs) are now into making these products but have no definite production capacity per day since they manufacture soaps and detergents depending upon the demands of customers.

Products Soaps and detergents are already a part of the everyday lives of people. They play a significant role in the personal hygiene and public health, preventing manifestation of diseases caused by germs found in soil. Soaps and detergents are useful in attaining a cleaner environment in households and commercial industries. In households, these include toiletries such as bath soap and shampoos, and laundry products, dishwashing products, and cleaning products for housekeeping purposes. Industrial uses of these materials can be incorporated in hospitals and the cosmetic industry (Austin 1984).

SOAPS

Soaps are primarily made of surfactants. The structure of a soap molecule (Figure 3) consists of a hydrocarbon end and an ionic end. Carbons and hydrogens make up the long hydrocarbon chain and this is non-polar by nature. With this characteristic, it is soluble in non-

polar substances. In contrast, the ionic end is a result of the ionic bonding of a carboxylic acid group with a metal ion, usually sodium or potassium. Thus, it is soluble in water.

O || CH3(CH2)n CONa+
Figure 3. Molecular structure of soap.

Raw Materials Soaps are water-soluble sodium or potassium salts of fatty acids. Soaps are made from fats and oils, or the fatty acids, by chemical treatment with a strong alkali.

Fatty Acid Fatty acids are the components of fats and oils used in the production of soap. The fats usually come from animal tallow. Through the process of steam rendering, where the solid animal fat is digested with steam, the tallow forms a layer above the water and is easily removed. Oils are obtained from plant sources. Oils are used to increase solubility of the soap. Fatty acids are weak acids composing of two groups (Figure 4). The carboxylic acid group consists of one hydrogen atom, two oxygen atoms, and one carbon atom. Attached to it is the long straight chain of carbon atoms with two hydrogen atoms for each carbon atom. Fats and oils are made up of mixed glycerines. A triglyceride molecule consists of its own distinct combination of three fatty acids attached to one molecule of glycerine.

Figure 4. A fatty acid composed of the carboxylic acid group and the hydrocarbon chain. (Source: http://www.bebekgroup.com/manufacturing.html).

Alkali In chemical terms, alkali refers to a basic substance which reacts and neutralizes an acid. An alkali is a soluble salt of an alkali metal. Ashes of plants are the main sources of the alkalis used in the production of soap. However, due to technology advancement, alkalis can now be made commercially. The common alkalis used are sodium hydroxide (NaOH), also called caustic soda, and potassium hydroxide (KOH), referring to the caustic potash. When the alkali is sodium hydroxide, a sodium soap is formed. Sodium soaps are hard soaps. On the other hand, a potassium soap is formed using potassium hydroxide. Potassium soaps are softer and are found in some liquid hand soaps and shaving creams.

Soap Properties Emulsifying Property Emulsification is the process of dispersing the oils or other water-insoluble substances such as grease, soil and dirt, in water and holding them in suspension until it is rinsed away. This cleaning attribute is due to the molecular structure of soap having a hydrophilic and hydrophobic end.

Behavior in Hard Water Hard water contains calcium, magnesium and iron ions which when reacted with soap replace the sodium or potassium ions. Calcium, magnesium, and iron salts create solids referred to as soap scum, which are not soluble in water, unlike the sodium and potassium salts of fatty acids. This inhibits and decreases the effectiveness of the cleaning property of soap.

Alkalinity Soap in water undergoes hydrolysis. The reaction produces an alkaline solution, which has a positive effect in removing acidic soils in the surface being cleaned.

Ability to React with Mineral Acids The fatty acids of soaps, having a carboxyl acid group attached with a long hydrocarbon chain, are polar substances. Thus, the fatty acids are not soluble in water; whereas the soap as a whole, being a sodium or potassium salt of a fatty acid is water-soluble. To prevent the soap from dissolving in water, the soap may be converted to fatty acids. A strong mineral inorganic acid is reacted with the soap, causing the fatty acid to precipitate.

Saponification The first step in manufacturing is the selection of raw materials. Raw materials are chosen depending on the standards of the desired product. This may include human and environmental safety, cost, compatibility with other ingredients, and the performance characteristics of the finished product. Pre-treatment of raw materials may be done to remove

impurities and achieve the certain characteristics desired such as color, odor, and performance features. The essence of soap production is the saponification process (Figure 5 and 6). Saponification of fats and oils is the most widely used process in soap production. This method involves mixing and heating of fats from animal tallow and oils from plant sources. The mixture is then reacted with a liquid alkali, sodium or potassium hydroxide, to produce soap in liquid form or the neat soap (soap and water) and glycerine.

Fatty Acid

Alkali

Glycerine

Soap

Figure 5. Chemical structure of the substances in a saponification reaction. (Source: Austin G. Soap and detergents. In: Shrevess chemical industries. 5 th ed. Singapore: McGraw-Hill Company Singapore, 1987.)

Figure 6. The saponification process. (Source: http://www.bebekgroup.com/manufacturing.html).

Hydrolysis (Glycerine Removal) Glycerine is a valuable by-product in the production of soap. Most of the glycerine is removed from the mixture through the process of hydrolysis (Figure 7). Glycerine is soluble in salt water, yet soap is not. Under high-pressure steam, salt is added to the wet soap causing the splitting of crude fatty acids and glycerine. Evaporation then takes place to remove and obtain the glycerine. Refining of glycerine is needed, thus its role in the industry such as food, cosmetics, drugs, is very significant. The glycerine left in the soap contributes to its softness and smoothness.

Figure 7. Removal of the by-product glycerine from the triglyceride. (Source: http://www.bebekgroup.com/manufacturing.html).

Fatty Acid Purification (Distillation) Through the process of distillation, impurities in the fatty acids are removed such that they have different boiling points. The distillation is usually done under a vacuum to achieve a reasonable boiling point for the fatty acid. Proper selection of high temperatures is needed because some components are sensitive to thermal degradation.

Neutralization After the removal of the glycerine from the triglyceride and the purification of the fatty acid, addition of the alkali in the saponification process takes place. The alkali (base) neutralizes
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the fatty acid. The reaction of the fatty acid with the alkali would now only produce the neat soap, soap and water (Figure 8).

Figure 8. Neutralization of the fatty acid by addition of alkali. (Source: http://www.bebekgroup.com/manufacturing.html).

Vacuum Drying After neutralization, the neat soap is dried. Vacuum spray drying is used to convert the neat soap into dry soap pellets. The moisture content of the pellets will vary depending on the desired properties of the soap bar.

Soap Purification In the saponification process, not all of the alkali is consumed in the reaction. Soap The remaining sodium hydroxide or potassium hydroxide is neutralized with a weak acid such as citric acid. Soap is purified by using up all the ingredients used. In this phase, two thirds of the remaining water is removed.

Finishing In the final processing step, addition of preservatives, colorants, and perfumes for fragrance is done to attain the desirable qualities in the finished product. The dry soap pellets are

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blended together with the additives and other ingredients in a mixer called an amalgamator. The mixture is refined through rolling mills and refining plodders to attain thorough blending and a uniform texture. The homogenous mixture is extruded from the plodder, cut into bar-size units and stamped into its final shape in a soap press.

Figure 9. Flow diagram of soapmaking. (Source: http://www.bebekgroup.com/manufacturing.html).

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250 C, 4.1 MPa

Figure 10. Process diagram of production of soap. (Source: Austin G. Soap and detergents. In: Shrevess chemical industries. 5th ed. Singapore: McGraw-Hill Company Singapore, 1987. p. 537.)

DETERGENTS

In response to shortage of fat and oil sources during the World War I, the Germans developed a variation of form known as synthetic detergents, or commonly known as detergents (Austin 1984). Detergents are derived from petroleum while soaps are made from animal fats and plant oils. Detergents differ from soap in their action in hard water. Hard water is water which contains ions of magnesium and calcium. Soaps form insoluble compound with the ions present in the water which precipitate out and forms scum and reduce cleaning action. Detergents on the other hand also react with hard water but the products are soluble in water (Austin 1984).

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Basically, soaps and detergents are surface active agents which are added with additives to enhance their cleaning action and differentiate one from another in terms of their specific uses. Surface active agents have four classes and are discussed here since detergents are commonly described by these classes while soaps are not. The classes are anionic, cationic, nonionic, and amphoteric (Austin 1984). Most detergents have a negative ionic group and are referred to as anionic detergents and are usually the sodium salts of organic sulphate or sulfonate. Cationic detergents have positive ionic charges and are commonly derivatives of ammonia. They are likely to be found in shampoos or fabric conditioners and their primary purpose is to neutralize the residual negative charge from the anionic detergents. Non-ionic detergents, usually used as dishwashing liquids, do not react with hard water and foam less than ionic detergents (http://www.chemistryexplained.com/Ru-Sp/Soap.html). Amphoteric detergents either have negative or positive ionic charges in their component ingredients.

Raw materials The raw materials for synthetic detergents are alkylbenzene, oleum, caustic soda, fatty alcohol, water, additives and builders.

Reactions Detergent production is a chemical as well as a physical process. It is a physical process since it involves size reduction and mixing of raw materials. It is a chemical process because it involves reactions in the molecular level. The following reactions occur in detergent production and which will be referred to later in the discussion of the production.

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Alkylbenzene + oleum alkylbenzene sulfonate Fatty alcohol + oleum fatty alcohol sulfate Sulfonate + sulfate + NaOH sodium salts Sodium salts + builders, etc. detergents

Reaction 1 Reaction 2 Reaction 3 Reaction 4

Process Detergent production may be a batch or a continuous process but oftentimes production plants operate on a continuous assembly. There are three methods which are commonly employed in detergent production. These are spray drying, agglomeration and dry mixing or a combination of the three. In spray drying method, dry and liquid ingredients are combined and slurry is formed. The tank where these ingredients are mixed is called a crutcher. Then the slurry is heated and pumped to the top of a spray tower where nozzles release the slurry to the inside of the tower in the form of droplets. The droplets fall through a current of hot air forming hollow granules. The dried granules fall to the bottom of the tower and are passed through screens for uniform size reduction. The heat sensitive ingredients like the additives and perhaps some builders are then added. Additional screening is then employed to achieve uniform granule size. The spray drying method is shown in Figure 11 (http://www.bebekgroup.com/manufacturing.html). Traditional spray drying methods yield low density powdered detergents which poses a problem on having bigger packages for very light products. The granules have low density since more air is occupying the hollow space inside the granule. Companies have and are now addressing this problem to reduce the air volume inside the granules for more efficient packaging.

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Figure 11. Powdered detergent production through spray drying method (Source: http://www.bebekgroup.com/manufacturing.html).

Agglomeration is another method quite similar to spray drying which yield high density powdered detergents. One main difference between the two methods is that in agglomeration binders are added to the basic raw ingredients and rolling or shear mixing of the ingredients causes them to adhere and collide forming large particles

(http://www.bebekgroup.com/manufacturing.html). The adhesion and collision between the particles as they go through the assembly causes heat to be produced which also helps in drying the granules in addition to drying contributed by the ambient air. The step in agglomeration method which is primarily difference between it and spray drying is shown in Figure 12.

Figure 12. Agglomeration and dry mixing methods of detergent production (Source: http://www.bebekgroup.com/manufacturing.html).

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Dry mixing method is used to produce powdered detergents when raw materials are blended in their right proportions with water so that further drying will not be necessary (Figure 12) (http://www.bebekgroup.com/manufacturing.html). The aforementioned methods are done for production of powdered detergents. Liquid detergents, which nowadays are getting popularity, are manufactured by blending ingredients which have more liquid proportions than the solid raw materials in a bladed mixer. To ensure stability and uniformity (maintain consistency and settling of ingredients will not occur) stabilizers are added (Figure 13).

Figure 13. Blending process in liquid detergent production (Source: http://www.bebekgroup.com/manufacturing.html). Packaging if now considered an essential aspect in any production lines as well as in soap and detergent production. Powdered detergents are either wrapped in plastic or slid inside paper cardboard boxes. Liquid detergents are packaged in bottles, pouches or polyethylene pouches. The selection of packaging materials and containers involves considerations of product compatibility and stability, cost, package safety, solid waste impact, shelf appeal and ease of use (http://www.bebekgroup.com/manufacturing.html).

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The aforementioned procedures involve the physical aspect of detergent production. Figure shows the flow diagram of detergent production involving the chemical and even the physical processes in producing detergents prior to mixing in the crutcher. The raw materials which are of great importance in detergent production are alkylbenzene, oleum and caustic soda. Straight-chain alkylbenzene, or hydrocarbons in general, are produced from petroleum and separation of this from the other components of petroleum are done by adsorption using molecular sieves, and reaction with urea or thiourea. Since this separation process is done prior to main production procedure this will not be discussed further. Oleum is a solution of sulfur trioxide (SO3) in sulfuric acid (H2SO4). Caustic soda is sodium hydroxide.

Alkylbenzene + oleum alkylbenzene sulfonate Fatty alcohol + oleum fatty alcohol sulfate Sulfonate + sulfate + NaOH sodium salts Sodium salts + builders, etc. detergents

Reaction 1 Reaction 2 Reaction 3 Reaction 4

The reactions shown earlier and shown above are occurring within the production line of detergents. Referring to Figure 14, after the raw materials are prepared the alkylbenzene is introduced into the sulfonator with the necessary amount of oleum with controlled temperature level at 55C. Reaction 1 occurs in sulfonation. After the sulfonator in the assembly, a sulfator mixer (not shown in the figure) mixes the sulfonated mixture from the sulfonator and fatty tallow alcohol (derived from animal body parts) and more oleum are added at maintained temperature of 50 to 55C. Reaction 2 occurs in sulfation. The use of oleum in sulfonation and sulfation

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reduces the sodium sulfate in the final surfactant which forms after neutralization process. Maintenance of temperature in the assembly is necessary to ensure desired product is obtained and not to achieve darkening of product which could affect the aesthetics and even the cleaning action of the surfactant.

Figure 14. Process flow diagram for detergent production. (Source: Austin G. Soap and detergents. In: Shrevess chemical industries. 5th ed. Singapore: McGraw-Hill Company Singapore, 1987. p. 548.)

The sulfonated-sulfated mixture is neutralized with caustic soda in the neutralizer; also under controlled temperature to maintain consistency and fluidity. The result of sulfonationsulfation pair processes and neutralization can be considered a surfactant mixture already. In other words, the crude detergent mixture is produced from neutralizing products from sulfonation-sulfation pair processes. The physical processes after neutralization were discussed earlier when the different methods were discussed (illustration in Figure 14). Prior size reduction and packaging, addition of other ingredients are done to build up to increase efficiency of cleaning action.

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Austin discussed that in order to produce 1 ton of finished detergent product by spray drying, the following materials are required:

Table 1. Amount of raw materials needed to produce 1 ton of detergent by spray drying method. Raw Materials Amount (kg) Surfactant Materials Alkylbenzene (petrochemical) 75 Fatty Alcohol (processed animal tallow) 75 Oleum 150 NaOH solution 200 Builder Sodium tripolyphospate 125 Additives Sodium silicate (corrosion inhibitor) 500 Miscellaneous 30 Water 500 th (Source: Austin G. Soap and detergents. In: Shrevess chemical industries. 5 ed. Singapore: McGraw-Hill Company Singapore, 1987. p. 542.)

ENVIRONMENTAL IMPACTS

In view of the attention being given to the environmental impacts of any industry operating nowadays, product development scientists, especially chemist and chemical engineers, are now into devising new methods and designing new equipment which can induce minimal or no negative impact at all to the environment and to the product users and even the ones working in the production facility. For years, the developers have tried ways to minimize the negative impacts when soap and detergent products are used. They have had been changing the additives incorporated to the

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surface active agents in order to address problems of eutrophication and water, air and land pollution. One main focus on battling problems with regards to the environment is in the production facility itself, as industries are the primary sources of pollutants that come in volume. With soap and detergent production, problems with regards to air, land and water arise as a result perhaps of inefficient production mechanisms or the pollutants are just inevitable and only mitigating measures can be done. As seen in Table 1, water is a raw material for soap and detergent production. Apart from it being incorporated into the product, water is also used in the facility in washing and cleaning of the equipment, machine and apparatus used so a huge volume of waste water results. This waste water goes into the receiving streams like lakes and rivers since typically production plants or facilities are situated near bodies of water for easy disposal of waste water. One problem which could be encountered with waste water from soap and detergent plants is that its characteristics may be different from that of receiving stream. Due to other materials present in the water, its alkalinity or acidity, temperature and the type of chemicals/compounds present are surely different from the ambient characteristics. Soap production plants should have waste water treatment facilities where parameters mentioned earlier should be closely monitored and if their values are not within the standard ranges they should be treated or separation processes should be done to ensure that the ambient condition of the receiving stream will not be altered. In the plant process control measures should be improved in order to reduce wastage and use of water especially in ancillary procedures like cleaning; longer production runs could also be set so that maintenance would not be so frequent.

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Soap production plants have finished products which if not neither hard bars nor liquids, are in granulated form. This poses air pollution from transport of raw materials (some may be in powder form), production phase (transfer from one vessel or tank to another, and even transport and storage of finished products. Air pollution caused by the aforementioned reasons may be minimized by transporting materials in tightly sealed containers which are durable and are not susceptible to tear when the contents are quite heavy. Also, dry and wet cyclones may and should be employed in the facility so that particulate matters (dust, etc.) will be collected from air and will not be blown out to the atmosphere. Soap production facilities dont have serious problems with gaseous pollutants (if only main reactions and processes are considered and not the derivation of raw materials from their raw materials) and only particulate matter which is considered by experts to be the one fastest to affect. Solid waste may also be a problem in the soap industry. Waste disposal should be designed properly and recycling may be done to reduce waste. Containers of raw materials may be sold or reused for storage.

REFERENCES

Anonymous. [Online]. 2007 [cited 2011 Feb 01]; Available from: URL:http://www.chemistryexplained.com/Ru-Sp/Soap.html. Austin G. Soap and detergents. In: Shrevess chemical industries. 5 th ed. Singapore: McGrawHill Company Singapore, 1987. p. 529-548. Bebek Group. [Online]. 2011 [cited 2011 Feb 01]; Available from: URL:http://www.bebekgroup.com/manufacturing.html.

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