CHAPTER ONE 1.

0 INTRODUCTION Detergents and their ingredients have recently been the subject of public environmental interest. Individual chemicals have attracted various levels of attention because of their high level of environmental pollution. This has led to the industry making efforts towards ecological optimization of detergents. Several research projects have been undertaken with this in mind, and have produced reliable basic information. Linear alkylbenzene sulfonate is the worlds largest-volume synthetic surfactant and is widely used in household detergents as well as in numerous industrial applications. It was developed as a biodegradable replacement for nonlinear alkylbenzene sulfonate and has largely replaced branched alkyl benzene sulfonate in household detergents throughout the developed countries.

1.1 WHAT IS SODIUM ALKYLBENZENE SULFONATE? Sodium dodecylbenzenesulfonate is a series of organic compounds with the formula C12H25C6H4SO3Na. It is a colourless salt with useful properties as a surfactant. It is usually produced as a mixture of related sulfonates. It is a major component of laundry detergent

Fig 1.0 Structural formula of sodium dodecylbenzene sulfonate

Table 1.0 Table showing formula and various names of sodium dodecylbenzene sulfonate

1.1.1 PROPERTIES OF SODIUM DODECYLBENZENE SULFONATE. The following are properties of sodium dodecylbenzene sulfonate include the following: 1) It has the physical appearance of a white or light yellow flake 2) It is soluble in water with a solubility of 5-10mg/ml at 66 o F 3) It has a molecular weight of 348.49g/mol and melting point of 572 o F 4) It has a flash point of over 200 o F

1.2 USES OF SODIUM DODECYLBENZENE SULFONATE Sodium dodecylbenzene sulfonate can be used as raw material to produce kinds of detergent, emulsion. Such as laundry powder, dish wash cleaner in daily chemical industrial; cleaner, dyeing assistant in textile industrial; degrease agent in electroplate, leather; de-inking agent in papering.

1.3 METHODS FOR PRODUCING SODIUM DODECYL BENZENE SULFONATE Sodium dodecylbenzene sulfonate is prepared commercially by sulfonating dodecylbenzene with either oleum (10-25% sulfur trioxide [SO3] in sulfuric acid) or an SO3- air mixture and then neutralizing with sodium hydroxide solution. In both processes, sulfur trioxide is the sulfonating agent and the major product is the sodium dodecylbenzene sulfonic acid. Both batch and continuous processes are used.

1.3.1 Sulfonation of dodecylbenzene with oleum In a typical batch oleum sulfonation process, oleum is added to the dodecylbenzene reaction mixture. Under normal conditions, 1.0-1.2 pounds of oleum are required per pound of dodecylbenzene. The reaction temperature is carefully controlled while the acid is added, and the reaction goes on to completion during a 30 to 45 minute digestion period. Excessive time or temperature produces undesirable dark-colored products. In a typical continuous oleum sulfonation process, oleum and dodecylbenzene are proportioned to a reactor mixing head exchanger. The reaction is generally completed in eight to fifteen minutes. Whether batch or continuous, the reaction is carried out until sulfonation is 98-99% complete. Sulfonation with oleum produces dodecylbenzene sulfonic acid containing considerable excess sulfuric acid. If this material is neutralized with aqueous sodium hydroxide, the resulting lowactive detergent slurry contains about four parts of sodium sulfate for every six parts of the active dodecylbenzene. These low-active detergent slurries are somewhat restricted in their application because of the high sodium sulfate content. This shortcoming of the oleum-derived products may be partially overcome by adding enough water to the final sulfonation reaction mixture to dilute the sulfuric acid present from about 98% to 71-72%. At this concentration, the sulfuric acid is insoluble in the dodecylbenzene sulfonic acid and seperates as a second layer. Decanting of this sulfuric acid layer leaves an upper phase containing 87-90% dodecyl sulfonic acid and also 7-9% sulfuric acid. When this product is neutralized with caustic soda, a high-active detergent slurry results.

1.3.2 Sulfonation of dodecylbenzene with oleum In a typical batch SO3- air process, liquid sulfur trioxide is vaporized in a stream of dry air and the resulting 5-15% SO3 stream is then reacted with the dodecylbenzene. As in the oleum processes, good mixing and heat removal are necessary to avoid oxidation and charring, which result in dark-colored products. The reaction mixture is digested to complete the reaction. Air and the small remaining excess of sulfur trioxide (only a 3-5% molar excess is used) are removed. The reaction mixture is then hydrated with a small amount of water to hydrolyze and dodecylbenzene sulfonic acid anhydrides present in the reaction mixture. In continuous SO3- air processes, the color of the sulfonic acid products is improved by careful control and maintenance of reaction temperatures. Variations in the method of temperature control include recycling the reaction mixture through heat exchangers and the use of two or more reactors connected in series. When the mixture is neutralized with sodium hydroxide, a 96-97% sulfonate product is obtained.

1.4 PROCESS ROUTE CHOSEN AND JUSTIFICATION The process route which will be used for the purpose of this design is the method of sulfonation of dodecylbenzene with oleum and the oleum used in the sulfonation process is produced from the raw material sulfur.

Justification of Selected Process This process of manufacturing sodium dodecyl benzene sulfonate (C12H25C6H4SO3Na) is from the available raw material of benzene, dodecene and sulfur. This process allows the maximazation of the available raw material through the presence of distillation columns which allows for the recycle of benzene and dodecene. Also the process also gives room for purity which enhances the quality of product. The presence of seperators to remove impurities such as spent acid (H2S04) from the Deodecylbenzenesulfonic acid generated from the sulfornator and this in turn can be used in the contact process to produce oleum. The method involving sulfur trioxide has not been selected for the following reasons: 1. It is highly exothermic thus requiring extra expense on cooling equipment.

2. It cannot be added directly to the alkyl hydrocarbon because extensive charring and dealkylation of the alkylaromatic will take place. 3. It is a very difficult process to control. The Oleum method is the more acceptable method of production when the the desired end product is expected in powder form. Its principal disadvantage is the formation of sodium sulphate but this can be remedied by the addition of water which reduces the concentration of the acid produced. The inability of the acid produced to dissolve in LAS acid results in a separate layer formation. Decanting of this layer gives a highly concentrated alkyl sulphonic acid whose neutralization will give highly-active detergent slurry. But it must be noted that a benefit of the above mentioned method is that it requires lower-cost reagents and the product formed has lower sodium sulphate content. Also this method is suitable for the production of liquid- based detergents. This method gives quality product at a very good overall economic analysis.

1.5 PROCESS DESCRIPTION 1.5.1 ALKYLATION The alkylation process chosen is the FriedelCrafts alkylation which involves the alkylation of an aromatic ring with an alkyl halide using a strong Lewis acid catalyst. With anhydrous ferric chloride as the catalyst, the alkyl group attaches at the former site of the chloride ion. For the purpose of this design, the alkylation process is the reaction of dodecene with benzene in the presence of ferric chloride catalyst (AlCl3). C6H6 + C12H24 AlCl3 C6H5C12H25

The alkylation process is in a reaction vessel (alkylator) and the reaction maintained at 450C maximum. The intermediate product at this stage is dodecylbenzene. An excess of benzene is used to suppress the formation of by-products. Aluminum chloride requirement is 10 wt% of dodecene.

After removal of aluminum chloride sludge, the reaction mixture is fractionated to recover excess benzene (which is recycled to the reaction vessel), a light alkyl aryl hydrocarbon, dodecylbenzene, and a heavy alkyl aryl hydrocarbon. 1.5.2 SULFONATION. A continuous sulfonation of the dodecylbenzene is chosen using 20 percent oleum as opposed to sulfuric acid and anhydrous sulfur trioxide and a batch process. The process is very exothermic but to be maintained (cooled) at a temperature of 38-600C with 550C chosen. C6H5C12H25 + H2SO4 C12H25C6H4SO3H + H2O

Removal of the spent sulfuric acid from the sulfonic acid is facilitated by adding water to reduce the sulfuric acidstrength to about 78 percent. This dilution prior to neutralization results in a finalneutralized slurry having approximately 85 percent active agent based on the solids. Due to the fact that the available material is sulfur and not oleum , a by-process of producing oleum(25% SO3) from sulfur is designed as well. Oleum is gotten as a by-product from the contact process. Sulfur is burnt in excess air allowing for the oxidation of sulfur to SO2 and subsequently to SO3. Purification of air and SO2 is necessary before conversion to SO3 as a process condition. Hydrochloric acid is used to absorb SO3 to give the needed oleum. 1.5.3 NEUTRALIZATION The sulfonic acid is neutralized with 40 percent caustic soda solution to a pH of 8 and at a temperature of about 500C. Chemical builders are added to enhance the detersive, wetting, and other desired properties in the finished product.

C12H25C6H4SO3H

NaOH

C12H25C6H4SO3Na

H2 O

A bead product is obtained by spray drying.

The Block Flow Diagram of the process showing the manufacture of sodium dodecylbenzene sulfonate with the key points is shown below:

1.6 PROPERTIES OF RAW MATERIALS 1.6.1 DODECENE

Physical properties

Dodecene is a clear water-white, mobile liquid with a molecular formula of C12H24 and molecular weight of 168.319, a boiling point of 2130C, freezing point of -350C and a flash point temperature of 770C(explosive vapor/air mixtures are formed at this temperature). It is insoluble in water but soluble in hydrocarbon solvents. Chemical properties

Dodecene reacts with strong oxidants, halogens (such as chlorates and nitrates) and inorganic acids. Attacks rubber, paints and lining materials. Storage

Dodecene is stored under a nitrogen blanket. It is not corrosive to steel or aluminum. Contact with air, water or oxygen should be avoided because alpha olefins are sensitive to moisture and auto-oxidation which form impurities that can interface with subsequent reactions.

1.6.2 BENZENE Physical properties

Benzene is a clear, colorless to light yellow aromatic hydrocarbon with a sweet odour but highly inflammable, has a molecular formula of C6H6 and a molecular weight of 78.11. Benzene's solubility in water is 1750 mg/L at 25 degrees C. It readily mixes with ethanol, ethyl ether, acetone and chloroform. Its melting point is 5.50C and the boiling point is 80.10C. It has a flash point of -110C. Chemical properties

Benzene is incompatible with strong oxidizing agents, many fluorides, many perchlorates and nitric acid. Benzene is an excellent ligand in the organometallic chemistry of low-valent metals

1.6.3 ALUMINIUM CHLORIDE Physical Properties

Aluminium chloride (AlCl3) is the main compound of aluminium and chlorine. It is white, but samples are often contaminated with iron trichloride, giving it a yellow colour. The solid has a low melting and boiling point. Chemical properties

The compound is often cited as a Lewis acid. It is an example of an inorganic compound that "cracks" at mild temperature, reversibly changing from a polymer to a molecule. Anhydrous aluminium chloride is a powerful Lewis acid, capable of forming Lewis acid-base adducts with even weak Lewis bases such as benzophenone and mesitylen Aluminium chloride is hygroscopic, having a very high affinity for water. It fumes in moist air and hisses when mixed with liquid water as the Cl- ions are displaced with H2O molecules in the lattice to form the hexahydrate AlCl36H2O (also white to yellowish in color). The anhydrous

phase cannot be regained on heating as HCl is lost leaving aluminum hydroxide or alumina (aluminum oxide): Al(H2O)6Cl3 Al(OH)3 + 3 HCl + 3 H2O On strong heating (~400C), the aluminum oxide is formed from the aluminum hydroxide via: Al(OH)3 Al2O3 + 3 H2O

1.6.4 SULFUR Physical properties

In nature, sulfur can be found as the pure element and as sulfide and sulfate minerals. Elemental sulfur is a bright yellow crystalline solid. Sulfur forms polyatomic molecules with different chemical formulae, with the best-known allotrope being octasulfur, cyclo-S8.Octasulfur is a soft, bright-yellow solid with only a faint odor, similar to that of matches It melts at 115.21 C, boils at 444.6 C and sublimes easily. Chemical properties

Sulfur burns with a blue flame concomitant with formation of sulfur dioxide, notable for its peculiar suffocating odor. Sulfur is insoluble in water but soluble in carbon disulfide and, to a lesser extent, in other nonpolar organic solvents, such as benzene and toluene. sulfur can react as either an oxidant or reducing agent. It oxidizes most metals and several nonmetals, including carbon, which leads to its negatives charge in most organosulfur compounds, but it reduces several strong oxidants, such as oxygen and fluorine.

1.7 PLANT LOCATION

The geographical location of the plant can have strong influence on the success of an industrial venture,therefore considerable care has been exercised in selecting the plant site, and many different factors have been considered. Primarily, the plant should be located where the minimum cost of production and distribution can be obtained, but other factors, such as room for expansion and safe living conditions for plant operation as well as the surrounding community, are also important. The choice of the final site is based on a complete survey of the advantages and disadvantages of various geographical areas and, ultimately, on the advantages and disadvantages of available real estate. After several considerations of the major factors which may affect production as well as profitability, Atan in Ogun State has been chosen as the suitable site. The principal factors which led to this decision include:

Suitable large expanse of land Sufficient suitable land must be available for the proposed plant and for future expansion. Wide expanse of land for various production facilities and utilities required for plant which cannot be easily obtained in densely populated Lagos or other industrialized cities like Port-Harcourt, can be obtained in Atan located in Ogun state which even though its not an industrial city in itself, is gradually developing and at the same time still close enough to places like Lagos to enjoy fringe benefits of industrial concentration. Labor Supply The type and supply of labor available in the vicinity of a proposed plant site was examined and consideration was given to prevailing pay scales, restrictions on number of hours worked per week, and variations in the skill and productivity of the workers. The type of labor that will be required to run the plant varies from skilled labor to unskilled labor. Both of these kinds of labor are available in Atan. The skilled labors available are provided by the unemployed university graduates that are present in Atan. While the unskilled labor available is provided by the locals that live in Atan.

1.8 ENVIRONMENTAL ISSUES Linear alkyl benzene sulfonate has been safely consumed in large volumes throughout the developed world for over 20yrs. Although its use was once questioned in Western Europe because of its lack of biodegradability under anaerobic conditions, it is disposed under aerobic conditions (i.e. sewage treatment plants), where it does fully biodegrade. In any case, no legislation adversely affecting the use of LAS is expected and it is expected to remain the worlds largest surfactant used in detergents for many years. According to a recent comprehensive risk assessment study carried out by the Netherlands government, the use of LAS in laundry detergent powders does not involve any significant environmental risk. LAS, as well as other large-volume surfactants are efficiently removed in the sewage treatment systems. A report recently submitted by Britains Department of the environment states that LAS is readily biodegradable and its use in consumer products poses no hazard to human health or the environment."

1.9 STORAGE Keep container dry. Keep in a cool place. Ground all equipment containing material. Keep container tightly closed. Keep in a cool, well-ventilated place. Combustible materials should be stored away from extreme heat and away from strong oxidizing Sodium dodecyl benzene sulphonate is produced in the most common route of alkylation, sulfonation and neutralization. However there are different conditions and routes for each of these three processes.