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Detergents Heavy-Duty Powder

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DETERGENTS
HEAVY-DUTY POWDER
Written by student;
AbdAl-Rhman Magdy Abdullah Youssef, ID: 20160517
Department of chemical Engineering, Higher Technological Institute-10TH of Ramadan City, Egypt

Abstract
One of important goods is detergents in it’s liquid and powder phases which has different classes but the main
and widest class is alkyl-aryl sulfonates. Powder detergents have many uses and it has two main types; light duty,
and heavy-duty powder. Several raw materials are used in manufacturing powder detergents such as; surface
actants, straight-chain alkylbenzenes, fatty acids and fatty alcohols, suds regulator, builders and additives such as
piriform. Heavy duty powder manufacturing process has two main stages sulfonation-sulfation, and neutralization.
Generally, powder has different properties such as density, solubility, cake strength and particle size which affect on
its behavior. To be on the safe side it is assumed that one-quarter of the heavy-duty powder detergents contain on
average 5% alkyl polyglycosides.

Key words: Detergents, classification of detergents, heavy duty powder, powder properties, and heavy-duty
powder manufacturing

I. Introduction
The modern concept of surface-active agents includes soaps, detergents, emulsifiers, wetting agents, and
penetrants. These all owe their activity to a modification of the properties of the surface layer between two phases
in contact with another. Most of the surface-active agents are a combination of water-attracting or hydrophilic
groups on one end of the molecule, with water-repelling or hydrophobic groups on the other. The detergents possess
these special properties to effect soil removal, [1].

II. Historical Background

The consumer-packaged powders and liquids which now account for the great majority of the synthetic
detergents produced are actually the incidental result of the search for new compounds to overcome difficulties, i.e.,
acidity and hard water encountered in textile processing. Until the 1920's Turkey-red oil, a sulfated castor oil, was
the best commercial product for textile users, but a poor one at best. At that time the Germans began to search for
a "universal soap" and in 1930 the Igepon A series, sulfonated fatty acid esters, and Gardinol, a sulfated fatty alcohol,
were marketed. In 1931 the Igepon T3 series, taurine derivatives, were introduced which overcame some of the
difficulties of Igepon A in textile processing. Since these synthetics used vegetable oils which were relatively
expensive, the search began for cheaper starting materials such as petroleum. The first cyclic derived detergent, an
alkyl naphthalene sulfonate, was Nacconol which was introduced in 1933. The alkyl-aryl sulfonates are the largest
class of synthetic detergents today, [1].

III. Classification of Detergent

Many detergents with their different trade names can be grouped into five main chemical classes. The first
three are anionic detergents which ionize in water to give a negatively charged organic ion.The fourth group
comprises the cationic detergents which ionize in' water to give a positively charged ion. The last group is the nonionic
which do not ionize. Cationic and anionic are not compatible as they combine into an insoluble··precipitate. For this
same reason cationic: are not compatible with soap. Compounds of the last group, nonionic, are naturally compatible
with the other groups and this growing field shows much promise. The five groups are;
1. Sulfated Fatty Alcohols. (Orvus, Dreft, Duponol, etc.)
These are strong competitors to soap because they are stable in acid, alkaline, or hard water. Sodium lauryl
sulfate, prepared from coconut oil, represents the bulk of the sulfated fatty alcohols. It is believed that sulfated fatty
alcohols accounted for 19 per cent of the synthetic detergents sold in 1952, [1].
2. Alkyl-aryl Sulfonates. (Oronite, Ultrawet, Santomerse, Tide, Fab, Surf, Cheer, etc.)
Because of their low price, this group is extensively used in both the home and industry. Sales in 1952
accounted for 58 per cent of the synthetic detergents. Their stability and soil-suspending power is not so good as
Group 1, but by adding sodium carboxymethyl cellulose, the suspending power can be increased, [1].

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3. Miscellaneous Sulfates and Sulfonates
(a) Alkyl sulfonates, as Merpols, MP-189.
(b) Sulfated esters and acids, as Artic Syntax, Vel, Igepon A. These detergents, although unaffected by hard water,
lack stability in strong acids or alkaline solutions.
(c) Sulfated and sulfonated amides, as Igepon T. These detergents have excellent stability and soil-removing
properties.
(d) Sulfated and sulfonated oils, fats, and waxes, as Turkey red oil, [1].
4. Cationic Agents
These are not normally classified as detergents as their uses are not comparable with soap. Their chief value
is their germicidal properties. The quaternary ammonium compounds are the most important members, [1].
5. Nonionic Agents. (Spans, Tweens, Glim, Triton, etc.)
These products possess excellent soil removal and grease emulsification accompanied by low foam. The ethers
are extremely stable, in acid and alkaline solutions. The nonionic may be further sub divided ip.to these principal
types;
(a) alkyl phenol-ethylene oxide type,
(b) aliphatic polyhydric alcohol esters,
(c) fatty-acid amides, [1].

IV. Manufacturing of Detergents

1. Raw materials
A large volume of active organic compounds, or surfactants. for both detergents and soap are manufactured
in final form by soap and detergent companies. Examples are linear alkylbenzene sulfonate (LAS) and fatty alcohol
sulfate, which these companies manufacture in hundreds of millions of pounds. The same is true for fatty acids, the
basic materials for soaps. Most of the inorganic materials, such as oleum, caustic soda, and various sodium
phosphates and a large number of additives, the last-mentioned amounting to 3% or less of the total product weight
are purchased, [2]
1.1. Surface actants
These embrace "any compound that affects (usually reduces) surface tension when dissolved in water or water
solutions, or which Similarly affects interfacial tension between two liquids. Soap is such a material, but the term is
most frequently applied to organic derivatives such as sodium salts of high molecular weight alkyl sulfates or
sulfonates.
The surfactants of both soap and synthetic detergents perform the primary cleaning and sudsing of the washing
action in the same way through the reduction of surface tension.
The cleaning process consists of;
(1) thoroughly wetting the dirt and the surface of the article being washed with the soap or detergent solution,
(2) removing the dirt from the surface, and
(3) maintaining the dirt in a stable solution or suspension (detergency).
In wash water, soaps or detergents increase the wetting ability of the water so that it can more easily penetrate
the fabrics and reach the soil. Then soil removal begins, each molecule of the cleaning solution may be considered a
long chain. One end of the chain is hydrophilic (water-loving); the other is hydrophobic (water-hating, or soil-loving).
The Soil-loving ends of some of these molecules are attracted to a soil particle and surround it. At the same time the
water-loving ends pull the molecules and the soil particles away from the fabric and into the wash water. This is the
action which, when combined with the mechanical agitation of the washing machine, enables a soap or detergent to
remove soil, suspend it, and keep it from redepositing on clothes, [2].
1.2. Straight-chain alkylbenzenes.
Biodegradable detergents are made primarily from phenyl-substituted n-alkanes of 11 to 14 carbon atoms.
The straight-chain paraffins or olefins needed are produced from petroleum. In 1981, 233 kt were produced in the
United States. n-Alkanes are separated from kerosene by adsorption using molecular sieves. Branched chain and
cyclic alkanes have larger cross-sectional diameters than do the linear molecules, thus making sieve separation
possible. The other common method of separation of the normal paraffin compounds from the branched and cyclic
ones is by reaction with urea or thiourea Urea will react with linear chain hydrocarbons having at least seven carbon

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atoms to give a crystalline adduct which is separable by' filtration. No such adduct is formed with the branched chain
or cyclic compounds the adduct can then decomposed by heating with hot water at 80 to 90◦ C.
Conversely, thiourea will react with the branched chain hydrocarbons but will not form adducts with straight-
chain or aromatic ones. The separated n-paraffins are converted to benzene alkylates or are cracked to yield n-
olefins. Linear olefins are prepared by dehydrogenation of paraffins, by polymerization of ethylene to a-olefins using
an aluminum triethyl catalyst (Ziegler-type catalyst), by cracking paraffin wax, or by dehydrohalogenation of alkyl
halides. α-Olefins or alkane halides can be used to alkylate benzene through the Friedel-Crafts reaction,
employing hydrofluoric acid or aluminum fluoride as a catalyst, [2].
1.3. Fatty acids and fatty alcohol
Economics; Fatty alcohols and fatty acids are mainly consumed in the manufacture of detergents and soaps.
Fatty acids, both saturated (e.g., stearic acid) and unsaturated (e.g., oleic), have long been employed in many
industries as both free acids, and, more frequently, as salts.
Examples are:
(a) Magnesium stearates in face powders.
(b) Calcium or aluminum soaps (insoluble) employed as water repellents in waterproofing textiles and walls.
(c) Triethanolamine oleate in dry cleaning and cosmetics.
(d) Lithium stearate as a component of greases.
(e) Rosin soap consumed as a sizing for paper.
Manufacture of Fatty Acids; Basic raw materials, such as oils and fats, which have been used for a long time, since
about 1955, been very extensively supplemented by improved chemical processing and by synthetic petrochemicals.
A selection from these processes are given here. Table 3!.4 compares three processes for splitting fats that have
been used for many years. Figure (1), illustrates the high-pressure hydrolysis, catalyzed by zinc oxide, which is used
in the soap industry. Fatty acids are drawn off from the distillate receiver for sale or for further conversion to fatty
acid salts (calcium, magnesium, zinc, etc.). Several older and less used separation methods for purifying fatty acids
are panning and pressing, fractional distillation, and solvent crystallization, [2].

Figure (1): Continuous process for the production of fatty acids and soap, [2.]

Manufacture of Fatty Alcohols; The Ziegler catalytic procedure for converting α-olefins to fatty alcohols and the
methyl ester hydrogenation process are the important methods for preparing fatty alcohols.
The Ziegler procedure is an important one for manufacturing C12 to C18 α-olefins and fatty even-numbered
straight-chain alcohols for detergents. See Fig. (2). Gaseous ethylene is converted to higher, linear aluminum trialkyls
and α-olefins by the action of aluminum triethyl which takes part in the reactions, amides, aliphatic carboxylic acid
esters containing at least 18 carbons in one or preferably both acid and alcohol chains, and N-alkylated amino
triazines.

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Figure (2); Flowchart for the hydrogenolysis of methyl esters to obtain fatty alcohols and glycerin from natural fats, [2].

1.4. Suds regulators

Suds regulation is often necessary for surfactants to do an efficient jot of cleaning in a washing machine. This
is often achieved by combining different types sud as anionic with nonionic, or anionic with soap. For soaps, foam
inhibition increases 'With the amount of saturation and the number of carbons in the fatty acid residue. Soaps of
saturated C20-24 fatty acids are good foam inhibitors. Other foam inhibitors are higher fatty acid amides, aliphatic
carboxylic acid esters containing at least 18 carbons in one or preferably both acid and alcohol chains, and N-alkylated
amino triazines, [2].
1.5. Builders
Builders boost detergent power. Complex phosphates, such as sodium tripolyphosphate, have been used most
extensively. These are more than water softeners which sequester water-hardening calcium and magnesium ions.
They prevent redeposition of soil from the wash water on fabrics. Proper formulation with complex phosphates has
been the key to good cleaning with surfactants and made possible the tremendous development of detergents.
Polyphosphates (e.g., sodium tripolyphosphate and tetrasodium pyrophosphate; have a synergistic action with the
surfactant together with an enhanced effectiveness and hence reduce the overall cost.
The rapid rise in the acceptance of detergents stemmed from the building action of the polyphosphates. During
the 1960s the growth of algae and eutrophication in lakes became linked to the presence of phosphates in
detergents. Several states restricted phosphate use so that substitutes had to be found. The first compound
suggested was nitrilotriacetic acid (NTA), but it was declared a carcinogen in 1970. But new research results have
vindicated its safety; in 1980 the EPA said it saw no reason to regulate NTA.
This has not freed NTA for use because various congressional and environmental groups have challenged the
EPA decision. There are no restrictions on its use in Canada. Other builders are citrates, carbonates, and silicates. The
newest, and seemingly most promising, substitute for phosphates is the use of zeolites." By 1982 about 136 kt/year
of zeolites were being used as detergent builders. The builder market is large and amounts to over 1000 kt annually.
In 1980 phosphates accounted for 50 percent, zeolites 12 percent, silicates 13 percent, carbonates 12 percent, and
NTA and citrates 2 percent each, [2].
1.6. Additives
A- Corrosion inhibitors, such as sodium silicate, protect metal and washer parts, utensils, and dishes from the action
of detergents and water. Carboxymethyl cellulose has been used as an anti-redeposition agent. Tarnish inhibitors
carryon the work of the corrosion inhibitor and extend protection to metals such as German silver. Benzotriazole has
been used for this purpose.
B- Fabric brighteners are fluorescent dyes which make fabrics look brighter because of their ability to convert
ultraviolet light to visible light. Two dyes thus used are;
I. 4(2H-naphtho[l,2-d] triazol-2-yl) stilbene-2-sulfonate.
II. 2-Disodium 4,4'-bis (4-anilino-6-morpholino-S-triazin-2-ylamino)-2,2'-stil bene disulfonate.
C- Bluings; improve the whiteness of fabrics by counteracting the natural yellowing tendency. The ingredients used
for this purpose can vary from the long-used ultramarine blue (bluing) to new dye materials.

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D- Antimicrobial; agents include carbanilides, salicylanilides, and cationics.
E- Peroxygen-type bleaches; are also employed in laundry products.
F-The use of enzyme-containing detergents has been common in Europe for several years and recently has been
introduced into the United States. The enzymes
decompose or alter the composition of soil and render the particles more easily removable. They are particularly
useful in removing stains, particularly those of a protein nature, [2].
2. Manufacturing Process
Table [1] compares three types of detergents. The most widely used detergent, a heavy-duty granule, is
presented in Fig. 3, with the quantities of materials required.
2.1: Reactions
linear alkylbenzene sulfonation

Figure (3): Simplified continuous flowchart for the production of heavy-duty detergent granules.

Ingredients Function Ingredient on Dry-Solids Basis, Wt. %

Light-Duty High Heavy-Duty Heavy-Duty
Controlled Sudsers high Sudsers
Sudsers

Surfactants
Organic active, with Removal of oily soil, 25-40 8-20 20-35
suds regulators cleaning

Builders
Sodium Removal of inorganic soil. 2-30 30-50 30 -50
tripolyphosphate detergent-building
and/or tetrasodium
pyrophosphate

Sodium sulfate Filler with building action 30-70 0-30 10-20

in soft water

Soda ash Filler with some building 0 0-20 0-5

action

Additives
Sodium silicate having Corrosion inhibitor with 0-4 6-9 4-8
2.0 ≤ Si02/Na20 ≤ 3.2 slight building action

Carboxymethyl Antiredeposition of soil 0-0.5 0.5-1.3 0.5-1.3

cellulose

Fluorescent dye Optical brightening 0-0.05 0.05- 0.1 0.1

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Fatty alcohol sulfation

2.2: Process descriptions

Sulfonation-sulfation; The alkylbenzene CAB) is introduced continuously into the sulfonator with the requisite
amount of oleum, using the dominant bath principle to control the heat of sulfonation conversion and maintain the
temperature at about 55°C. Into the sulfonated mixture is fed the fatty tallow alcohol and more of the oleum. All
are pumped through the sulfater, also operating on the dominant bath principles, to maintain the temperature at
50 to 55°C, thus manufacturing a mixture of surfactants.
Neutralization; The sulfonated-sulfated product is neutralized with NaOH solution under controlled
temperature to maintain fluidity of the surfactant slurry. The surfactant slurry is conducted to storage. The surfactant
slurry, the sodium tri poly phosphate, and most of the miscellaneous additives are introduced into the crutcher. A
considerable amount of the water is removed., and the paste is thickened by the tripolyphosphate hydration
reaction;

This mixture is pumped to an upper story, where it is sprayed under high pressure into the 24-m-high spray
tower, counter to hot air from the furnace. Dried granules of acceptable shape and size and suitable density are
formed. The dried granules are transferred to an upper story again by an air lift which cools them from 115°C and
stabilizes the granules. The granules are separated in a cyclone, screened, perfumed, and packed.
The sulfonation conversion is shown in Fig. 4 to be extremely fast. The reactions also need 1:0 have the high
heats of reaction kept under control, depicting the

Figure (4): Alkylbenzenes sulfonation completeness versus time at 55°C, [2]

Circulating heat exchanger, or dominant baths, for both these chemical conversions and for neutralization.
The use of oleum in both cases reduces the sodium sulfate in the finished product. However, the oleum increases
the importance of control to prevent over sulfonation-In particular, alkylbenzene sulfonation is irreversible and
results in about 96 percent conversion in less than a minute when run at 55°C with 1 to 4% excess S03 in the oleum.

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A certain minimum concentration of S03 in the oleum is necessary before the sulfonation reaction will start, which in
this case is about 78.5% S03 (equivalent to 96% sulfuric acid). As both these reactions are highly exothermic and
rapid, efficient heat removal is required to prevent over sulfonation and darkening.
Agitation is provided by a centrifugal pump, to which the oleum is admitted. The recirculation ratio (volume of
recirculating material divided by the volume of throughput) is at least 20: 1 to give a favorable system. To provide
the sulfonation time to reach the desired high conversion, more time is allowed by conducting, the mixture. through
a coil, where time is given for the sulfonation reaction to go to completion. Neutralization of the acid slurry releases
six to eight times as much heat as the sulfonation reaction, [2].

V. Powder Properties
In the majority of granular detergent formulations, the physical properties of the products are determined by
the blown powder properties. The key properties are as follows:
Density
Particle size distribution
Cake strength—flow properties
Solubility
Density; is typically 250–550 kg/m3 and determined by many variables such as the formulation, slurry air
content, and process conditions. Density is an important quality item since most consumers dose by volume, and
therefore, the bulk density is the prime variable to control. Typically, droplets tend to form a skin on the outside as
they are dried, leading to the internal water diffusion out of the drop being very slow. In certain cases, this water can
turn to steam and expand the droplet causing puffing, and hence, reduced density. The extent to which this can occur
will depend on the water content of the slurry, air temperature, and chemical composition. Generally, lower density
is caused by a higher slurry water content, higher air temperatures, and a high concentration of fi informing materials.
Incorporation of air is also used at high pressures to increase this expansion. However, care must be taken not to
overdo this effect since too rapid an expansion can lead to the fracture of the granule and result in an excess of fine
material. An additional factor in bulk density is the ease with which the particles pack. One practice is to spray
perfumes and de-dusting agents onto the powder. If these are not absorbed into the granules the liquid can stay on
the outside of the particles, leading to poor flow properties and a reduction in bulk density, which is difficult to
control, [3]
Particle size distribution; A typical volume-based median particle size is ∼400–500 μm. The spread of the
distribution is typically wide with some significant fi ne and coarse powder resulting from the agglomeration process,
which takes place within the tower as wet drops collide. Acceptable ends of the spectrum typically range from <5%
below 100 μm to <2% above 800 μm. The former is for dustiness of the powder and subsequent dispersion when
wet. The latter is to control appearance and dissolution of the powder over time during the washing process, [3].
Cake strength; The cake strength as measured by a uniaxial shear test is often used as a measure of flowability
and granule stickiness. These are important properties for both postprocessing and consumer acceptance. The cake
strength tends to be an intrinsic function of the formulation and blown powder moisture. Apart from this, the process
conditions tend to have only a minor effect, [3].
Solubility; The consumer prefers a fully soluble granule, therefore insoluble residues left by a granule are
undesirable. The key factor for solubility tends to be formulation and component interactions, although process
conditions can play a role as well. Some of the better-known interactions that can cause insoluble involve sodium
silicate—a common ingredient. Poor mixing control with acidic ingredients can result in the production of insoluble
silica, and interactions can also occur with zeolite formulations, which will also cause large insoluble. In both cases,
careful control of mixing and pH is needed to avoid these problems, [3].

VI. Environmental impact of heavy-duty powder

To be on the safe side it is assumed that one-quarter of the heavy-duty powder detergents contain on average
5% alkyl polyglycosides. The area of the German Federal Republic is used as the boundary for the derivation of the
PEClocal,aquatic because Germany is representative of western Europe and a good database exists on the consumption
of detergents and cleaning products in Germany. According to a recent survey conducted by the German Cosmetics
and Detergents Association (IKW), 27,900 tons of powder detergents (category 1a) and 25,700 tons of liquid
detergents and cleaners (categories 1b6) were used in 2000 in Germany. Assuming that 25% of the powder
detergents contain on average 5% alkyl polyglycosides and that the liquid products contain on average 5% alkyl
polyglycosides too, about 2000 ton of alkyl polyglycosides are disposed of via wastewater annually. Based on a
population of 81 million in Germany and an average daily per capita water consumption of 200 L, an average waste
water concentration of 0.34 mg/L is calculated. Recent monitoring data from Eichhorn et al., although from Spain,

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indicate that this calculation, though formally not including the personal care products, like shampoos and cosmetics,
is still conservative. Eichhorn have determined the concentration of alkyl polyglycosides in the influent of three
different sewage treatment plants in Spain and found concentrations of only 6.5–16 Ag/L. Since APG removal in
sewage treatment plants is about 90% regarding DOC removal (more than 99% regarding primary degradation), it is
expected that the APG-derived effluent DOC concentration will be less than 50 Ag/L. Based on an average
effluent/river water dilution factor of 10, a PEClocal,aquatic of 5 Ag alkyl polyglycoside/L (referring to DOC) in river waters
is calculated (assuming no adsorption onto suspended matter), [4].

VII. References
1. [1] MCGRAW-HILL BOOK COMPANY, KOGAKUSHA COMPANY, LTD., R. NORRIS SHREVE, "THE CHEMICAL PROCESS
INDUSTRIES", SECOND EDITION, 1956, PAGE 629, AND 630
2. [2] MCGRAW-HILL, GEORGE T.AUSTIN, "SHREVE’S CHEMICAL PROCESS INDUSTRIES", FIFTH EDITION, 1984, PAGE
49, 51, 52, 56, 57, 58, 59, AND 60
3. [3] CRC PRESS TAYLOR & FRANCIS GROUP, URI ZOLLER, " HANDBOOK OF DETERGENTS, PART F: PRODUCTION ",
VOLUME 142, 2009, PAGE 636 and 637.
4. [4] MARCEL DEKKER, URI ZOLLER, " HANDBOOK OF DETERGENTS, PART B: ENVIRONMENTAL IMPACT", VOLUME
121, 2004, PAGE 504.

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