Table 2 Quality factα5 VS
performance indices
Table 3
Table 4 Heuristics (pr∞uct
form selecli。이
Table 6 Vis∞sity behavior
vs. structu re
Input information
Identification of quality factors
Oesired product quality factors
Product formulation
Product form, microstructure, and
ingredients
Design of manufacturing process
Flowsheet and operating conditions
Table 1 Quality factors for
detergents
F빙ure 4 Generic process
f10wsheet
Figurc R. Systcmatic procedure for proccss synthesis and development of detergents.
Table 2. Exarnples ofrelationships between quality factors and perforrnance indices
Perforrnance Indices
工gf E1 「∞‘
Quality Factors
)(nηz
Primary qllality fa ctors
Faster dissolution , fastcr effect • •
Higher convenience for use 에
More powerful c leaning
Higher formulation compatibili ty
Higher product stabi lity
Bctter performance in cold temperatures and • hard water
Srnaller weightlvolurne and less packaging
8roader spectrum of targeted 50ils 닝
Secondary quality factors
Higher biodegradability
More desirable foam amount and duration 에
Color retaining
UV protcction/sun fade protection of fabrics
(for laundry detergents only)
Human skin protcction
Fewer spots/fiI rns afìer wash
• = can be achieved by increasing the perforrnance index • = can be ach ieved by decreasing the perforrnance index
I~ 약CBi g:Ei
흐울 정그 정그
O aP ~。그õ 응그gs 1‘ g“。;;1경ng’r그ii ε그ι§그;:, gz그ggC그;p。:i
‘ g<
‘) 。a-〈
• • •
•
• • •
•
..J = can be achieved by adj usting (increasing or decreasing) thc pcκbnnance index
。ggζa。그 죠t@∞i
gg 읍
aftg1 g『:。-zs-「-9-~‘,
n [5: 흩n
•
i
•
에
•
4
‘ J 에
4
닝
4
dispersion
갇=펴仁느각양=> dispersion (opaque)
수=펴 W/O emulsions
Clear solution
Hazy
‘훈=각C
@ Q I
m」m mw a a m
= 。; 그 -。m
OIW emulsions i 품=二피 ! Solubilization
파 석싹 빼
E
。; mQ --a a m
iQ
그 1。」α
Detergency!
20 15 10
HLBop
5 0
Figure 1. Dependence of surfactant solution appearance and product app1ication on HLBop'
Tablc 3. Relationship bctween selected perfonnance indices and material or structural attributes
Peφrmance
index Optimum
hydrophilicIipophilic balance, HLBop
Critical micelle concentratlOn’ CMC
Soil solubilization capacity, S
Related material or structural a IIributes
Weight percentage of hydrophilic group in surfactant moleωle, W↓lθm
Weight 띠ction , Wj (for mixtures)
Polymeric additive concentra‘:ton
뾰띤쁘뀐쁘 Branching of surfactant, br Valency of counter-ions, z* Prod띠ct solution ionic
딴많딴L pH
Mole fraction'Yi (for mixtures)
Soil polarity
Critical micelle concentratJo띠‘ αIC
Relationship
HLB=쁘'dro 5
w.HLB. +w.HLB. HLB=~ AI lS- - -- t1
WA +wB
In general decreases upon addition of polymeric additives
lncreases with increasing HLBon lncreases with increasing br Decreases with increasing z‘ Decreases with increasing J (smaller effect
fÌ>r nonionic surfactants) System specific (for weak acids and
멜쁘쁘뜨~
CMC = ~.'---c'--_ 2:(y;f CMC,)
(for ideal mixed micelles of nonionic
암쁘띤쁘l In general, S is higher for polar soils than
fÌ>r non-polar ones Decreases with increasing CMC
니pophilic group volume of Decreases with increasing v surfactant molecule, v
Cross-sectional area of Decreases with increasing a。hydrophilic group, a。
Length oflipophilic group, l, Increases with increasing ι
Product solution ionic strenl낀h.l
Kraffi point, T"ια Surfactant chain length, l
Product solution ionic E쁘많딱」
Branι:hing of surfactant, br Valency of counter-ions, z*
Cloud point, Tcioud Surfactant chain length, 1
Degree of ethoxylation, Õ".", Product solution ionic 판떤웰,l,
Inιreases with increasing J (for ionic
원따띤쁘l lnιreases with increasing 1
Increases with increasing J
Decreases with increasing br Increases with increasing z* Decreases with inα'easing 1
lncreases with increasing 0".", Decreases with increasing J
Table 3. Relationship between selected perfonnance indices and material or structural attributes ( continued).
Peηormance
index Viscosity, η
Calcium binding capaclty
Surface tension reduction at CMC, I1ακ
Dissolution time, tdi (for powder)
Díssolution time, t씨 (for tablet)
Re/ated materia/ or structural attributes
Polymeric additíve concentratlon
Branchíng of surfactant, br Continuous phase viscosity, η。
Dispersed phase viscosity, ηi Díspersed phase volume
fraction, Øv
Builder’s hard ions complexation constant, K
Builder’s complexing mechanism
Branching of surfactant, br Product solution ionic
판댄윌뜨l Partíc1e mass, m Mass transfer coefficíent, k Solubílity, S Particle radius, r 쁘쁘파Z.P.. Tablet mass, m Diffu‘ sivity, D Grain particle síze, d" Tablet size, H
쁘므꽉뇨 ê
Relationshψ
ln general, increases with addítion of polymeric additives
Decreases with increasíngbr
」L = η,../ = 1 + 2 .5따 for ø, < 0.05 η”
'7; + 2/5'7 Inη,“ = 2.5('; r ... , '''1" )(øl' + ø,513 + ø,~ 11 3 )
η; +η。
for 0.05 < ø, . < 0.4
Increases with increasing K
System specific
M
·m
-·m
빠
-”띠 여
r -‘Il 、,
AU-Il
d”
.때-매
m
잃-잃 t q
p: e ‘,-u
、---、)
m -m
민μ m
-%
-3
「”
lf -/
’
‘--‘
t
c3-ι” ”” -r、」
.민씨 m-m
4-“
않 -않 α-C L -
%
-웠 때一 m
=
야 -야 u-s
이
‘‘ -‘‘
CJ-v
”
tl
h -h
-H
Order-of-magnitude model derived from Fick’s and Darcy’s laws [6]
2m 2
td; = π2d~H4D&(l -ê)2
Table 4. Heuristics for product fonn selection.
P'roduct form
Spray
Advantages Disadvantages
• does not require dilution • suitable for unifonn application
over a small area (spot cIeaning)
Unstructured Iiquid • dissolve rapidly in cold water
Structured liquid
• does not generate dust • lenient phase stability and
VISCOSlty reqUlrements
• dissolve rapidly in cold water • does not generate dust • can accommodate insoluble
solids
• increased dwell time and less runoff compared to liquid fonn
• dissolve faster than solid fonn • allow suspension of insoluble
solids
• very precise dosage • convenient storage and usage
Gel
Sachet
Powder • light and small packaging • lenient solubility requirement for
mgredients
• very precise dosage • convenient storage and usage
Tablet
VJ 따
」u
w“ 없
l r‘ 3 rl e ” 빼 빼
M
째
•
• tend to be heavy and bulky
• can only incorporate soluble ingredients (no insoluble solids)
• tend to be heavy and bulky • strict phase stability and viscosity
reqUl rements
• reqUlre extra processmg steps
• stricter processingand packaging requirements compared to liquidlgel
• no cIeaning action without dissolution
• caking problem during storage • requlre extra processmg steps • prone to breaking and
disintegration during processing
Table 5. Heuristics for surfactant selection.
Tar-get properP’ Good cleaning power
Low environmental tmpact
Low cost
Long-Iasting foam
Mildness to human skin
High solubility
Resistance to water hardness
Fabric softening
S'election guidelines
• Use a mixture of surfactants to better match the required HLBop
• Choose surfactants with high detergency, usually in the CIOC 16 range
• Choose surfactants with linear hydrocarbon chains over those with branched chains, since the earlier is more biodegradable
• Choose from the fo l1owing most widely used ones: soaps, linear alkylbenzene sulphonates (LABS), alcohol ethoxysulphates (AES), aJcohol sulphates (AS), alkane or paraffin sulphonate (SAS), and a1cohol ethoxylates (AE)
• Use anionic or amphoteric surfactants, or a mixture ofthe two &r high foaming
• Use nonionic surfactants, zwitterionic surfactants, or a combination ofboth with additives that are antiirritants, such as modified proteins or p이ymers
• Use surfactants with shorter carbon chains
• Choose potassium salt surfactants over their sodium cation counterparts
• Use nonionic surfactants, which are less sensitive to hard water ions than anionics, especially when solubility limitation imposed by the product restricts the use ofhigh builder level
• Use cationic surfactants for their high substantivity on surfaces, especially negative!y charged ones and the subsequent surface modification
Table 6. Dependence ofviscosity behavior on packing factor.
P'ackingfactor
。<v/aol,‘ <0.33
0.33<v/aol,‘<0.5
0.5<v/aolc<1
v/aol,‘>1
P'hase slructure spherical micelles with p이ar ends in the outer shell
cylindrical micelle in hexagρnal structure
Lamellar
reversed micelle in non-polar medium
Viscosiη
0-1 ,000 cP (Newtonian)
1,000-100,000 cP (Rheopecti c/th i xotropi c)
l ,000-50,000 cP (Thixotropic)
0-1 ,000 cP (Newtonian)
Table 7. Typical additives 야ed in detergents
Additive Desired function Selection criteria Examples Typical amount
Abrasives Provide smoothing, Hardness Calcite 0-55% (DW, HC) scrubbing, or Feldspar 60-9()')‘ polishing action Quartz
Sand 0-15% Acids (HC) NaeluktamUlnlZitey o orf a odtjhuesrt pHEn taarlg perto fdburc tthe Acetic acid 0.5-10%
Citric acid 0.5-20% ingredients Hydrochloric acid 0 ‘ 5-20%
Phosphoric acid 0.5-20% Sulfuric acid
Alkalis (LD, NeutrallZr oef oort ahdejlust pH t1aaIlg Iet fbr the Ammonium DW, HC, acidity of other final product hydroxide 0-10% ADW) ingredients, make Ethanolamine 0-10%
surfactants and Sodium carbonate 0-10% builders more
Sodium hydroxide 0-10% efficient Sodium silicate 3-15%
Antimocrobial Ki l\ or inhibit Efficacy on targeted Pine oil 0-5% agents (LD, growth of mlcroorganlsms Q@alu뻐j찌mat%memonarIyum c때S DW, HC) mlcκIC r:αro∞orgaOlsms Potential for human 0-5%
that cause skin sensitization Sodium diseases or odor Effect on surfaces hypochlorite 0-1%
to be c\eaned HpyedrrOoXgledne
A(SnLittlDlroe,nd De apgWoe-)nts Prevent soi 1 from
Efsdffaulisbcsppareic히cryIs sS1 ouiOofrnfnsa omc onerl
Carboxymethyl
rreesmeottvllanlg d auRrlenrg cel\ulose < 1% Polycarbonates < 1%
washing Pogllyyecothlylene lnteraction with < 1%
surfactant system Sodium silicate 3-15% Dissolution rate
Binder(LD, Increase Hamaker constant Pogl!yyectohlylene ADW) cohesiveness of Young’ s modulus 3-6%
pthoewmde torg aentdh hoId Surface fracture Pollldyovnlneylpyrm-er to energy 3-6% form granules Polyacrylates 3-6%
Acrylate cop이ymers 3-6%
Bleaches (LD, Rcmove stains, Bleaching power Sodium DW, ADW, chlorine bleaches Biocidal efficacy hypochlorite 0-1% HC) also disinfect Potcntial of color Sodium perborate 0-13%
dfaadmlnagge or fabrlC Sodium percarbonate
Ease of mtoc fobmr11o1urala-tion in
LD ~ laundry detergents, DW ~ dishwashing liquids, ADW ~ automatic dishwasher dctergcnts, HC ~ household cleaners, FC ~ fabric conditioners
Table 7. Typical additives used in detergents (continued)
Additive Desired function Selection criteria Examples Typical amount
Builders (LD, Enhance c1eaning Calcium binding Zeolite 20-30% ADW, HC) efficiency of capaclty Citrate 0-4%
surfactant by Soil dispersibil ity Polycarboxylate 0-5% reducing water Alkalinity Carbonate 5-30% hardness
Bleach stabilization Sodium silicates 1-20% and anticorrosion capability
Colorants (LD, PrpblOdrhVeouInddntuelgtcy st ap,c teo ptclrOOlanVllde
pH and thermal Pigments/dyes < 0.1% DW, ADW, stability HC) Lightfastness
Risk of staining cleaned 。이ects
Corrosion Protect metallic AcboIlrlrtoys tioon lnhlblt Sodium silicate 3-15% inhibitors
mcanluadcnh mal pneaaen plea umntessn,, slls (LD, DW, ADW)
DlSLlDrit,eg ArDanWt Facilitate the break- Dissolution rate Sodium 5-15% (LD, ADW) up oftablet bicarbonate-
citric acid
Dlyneh tlrbalntosrfser Prevent dye transfer Complexing power Polyvinylpyπolid 0.05-0.5% and preseπe color onep이ymers
(LD) ofn ganrgm wenastsh during washing
EnDzWym, e AsD (LWD,, Break down and Efficacy Amylase 0.2- 1.0% removc 5Oil, also Need for Lipase 0.2-0.6%
HC) c1arifies colors by stabilization Prot않se 0.1- 1.5% removing fu깅
Cellulase 1-3% Fabric ImrepdauI1ce % smta1ess and Asbtuatll1yC to reduce Qauna1ten1ronnar,uyn1 10-15%
softcners static electricity (FC) electricity in compounds
fabrics F1uorescent Create a Substantivity on Bistriazinyl 0.1-0.5%
wtuteril(nLgD) brightening effect fabrics derivatives of agents
Coollmmkeper batl ,lenbaglcIrlheηde Wlth 4,4’-diamino-
Icnts stilbene-2,2’-e Dleacnes disul“oic acid
H(yLdDro,tr DoWpe,s Maintain product Asmulrlftayc ttoan ltncrease Cumene sulfonate 0-10% homogeneity Ethyl alcohol
HC) S이ubility Toluene Color and odor sulfonates 0-10%
Xylene sulfonates 0-10%
O(ApLaDDclW,fi De, rW HsC,) Moaapk sapeqe pucreloa,d| pu ercofftvelcdtes Ability to block UV Polymers 0-3%
rays Titanium dioxide 0-3%
LD = laundry detergents, DW = dishwashing liquids, ADW = automatic dishwasher detergents, HC = household c1eaners, FC = fabric conditioners
Table 7. Typical additives used in detergents (αmtinued).
Additive Desired function Selection criteria Examples Typical amount
Perfumes (LD, Mask base Ability to deliver a Perfume blends 0-1% DW, ADW, malodors of specific smell HC, FC) S inOgl!rse‘d plents and Tafirngaelt pH of the
rovide nal product pleasant odors to clothes or room
Preservatives Guards against Ability to decrease 8utylated (LD, DW, product aging by water availability hydroxytoluene 0.05-0.2% ADW, HC, delsccaoy!, Ethylene diamine 0.05-0.2% FC) discoloration, Glutaraldehyde
oxidation, and bacterial attack
Rhmeoodlolfgielcrasl Improve flow Rheological Clays 0.5-2% properties of behavior Polymers 0.5-2%
(LD, DW , product, enhance Sodium silicate 3-15% ADW‘ HC, consumer appeal ,
Sodium sulfate FC) asslst ma때nu“f얘àcαtunng Solvents 0-5%
Solvents (LD, Prevent separation Ab. , gllrteyd tIoe dlssolve Ethanol 0-50% DW, ADW, or deterioration of mgre(lIents Isopropanol 0-50% HC, FC) ingredients in Cost Propylene glycol 0-5%
liquid products, dissolve soils, clean without leaving residues
Suds Give more suds Abi 1 ity to lower the Alkanolamides 0-5% stabilizers when suds level is CMCofthe
AOlkXyldlaemslne 0-5% (DW, HC) an IInportant surfactant system
indicator of cieaning power
Suds Limit suds amount Sensitivity to wash Alky 1 phosphates 0-5% suppressors when suds will temperature, Silicones 0-5% (LD, DW, interfere with water hardness, Soap ADW, HC) cleaning and builder
system Efficiency on the
surfactant system
LD = laundry detergents, DW = dishwashing Iiquids, ADW = automatic dishwasher detergents, HC = household cieaners, FC = fabric conditioners
Table 8. Heuristics for additive selection
Selection of abrasives
• Choose abrasives that are ha며 enough to assist c1eaning but not too hard to scratch the surface, preferably with a hardness ofabout 3 in the Mohs scale [10]
Selection of acids/alkalis
• Choose acids or alkalis to render the optimum pH for best performance of surfactants and enzymes (typically 6-8 for dishwashing liquids, 9.5-11 for laundry detergents, and 8-12 for allpurpose household cleaners)
• Choose acidic formulations for products designed to dissolve soap scum, hard water spots, stains, rust, or encrustations that are mainly calcium or magnesium salts [10]
• Choose alkaline ~이mulations for products designed to remove 이Is and organic soils or to treat acid-sensitive surfaces such as marble
Selection of antimicrobial agents
• Choose hypochlorite, which is the most inexpensive and effective disinfectant, for application on clean surfaces, as disinfecting capability ofhypochlorite decreases dramatically with presence ofproteins and soils
• Consider adding metasilicate to reduce the corrosive effect of hypochlorite, or use a less active agent such as hydrogen peroxide, for application on metallic surfaces
• Consider using quaκmaryammo끼ium compounds ifthe product is intended to be used at pH = 8-9 and in the absence ofanionics, pro‘eins, and milk residues. Their germicidal activity increases in the order of mono매er = dimer < trimer < tetramer < polymer, with a peak of efficacy for C J2 - C'6 compounds [17].
• Do not use quatemary ammonium compounds in products designed to c1ean cement, synthetic rubber, and aluminum because ofpossible surface damage
• Consider using anionic and amphoteric surfactants to enhance the performance of antimicrobial agents, since they make the cell wall of microorganisms more permeable to disinfectants
• Consider using organic compleχes like iodophors and povidone-iodine that get trapped in surfactant micelles and release iodine as a disinfectant upon dilution, for products that contact human skin
Selectio깨 of antiredeposition agents
• Consider using methylcelluloses with high degrees of substitution (DS - 2.6) and low molecular weights (- 5000) for soil removal applications, since they were found to have good antiredeposition activity while minimizing the interference with soil removal [19]
• Use carboxymethylcell비ose only in small amount in unstructured liquid products, since it has lowa에ueous solub내 lity
• Do not use ester-ba
Table 8. Heuristics for add’tive selection (continued)
Selcction of bleaches
• Choose peroxygen bleaches over hypochlorite to minimize color fading or fabric damage
• Choose oxygen bleach 。이얀 마lorine bleach ifthe product contains enzymes or perfumes
• Choose peroxycarboxylic acids or peracids 。이er peroxygen “r applκations at low or ambient temperatures and ncutral pH
• Scparate peroxygen bleaches, hydrogen peroxide, or 따 sources like sodium perboratc Or sodium percarbonate from water to prevent premature reaction, such as by suspending the solids between surfactant lamellae in the structured Iiquid
• Use transition mctal sequestrants 5uch as phosphonates or nitrilotriacetic acid in the fonnulation containing peroxygen bleacheι since transition metals can catalyze the decomposition of pero에de
Selection of builders
• Choose a builder and its amount depending on the aqueous solubility ofthe builder in the product besides 따 chelating power. For instance, do oot use ìnsoluble zeolitcs in unstructured Iiquid detergen이S
• Consider using phosphates where they are still pennitted, because they are emcient buildcrs with unsurpassed cost effcctiveness and cleaning ability
• Do not use precipitation builders for laundry detergcnts, since they can leave behind insoluble deposits on c1othes, causing damage on fabric and washing machine pa l1s
• Use bιlilders with pK.α ~ 5 with minimurn molccular weight for liquid automatic dishwasher detergents. In general, the order ofpreference is ’ substitute쇠 malonate > malonate > succinale > acetate > propionate [20]
Selection of colorants
• Consider using acid dyes and polymeric colorants only for use in dctergents
• Choose a colorant with high aqueρus solubility to give an attractive 、Nell-dispcrsed color to the product
• Ch。‘)se a suitable colorant by also considering degradation by light and s‘aining of fabrics or surfaccs
Selection of corrosion inhibitors
• Choose builders Iìke sodium silicates as corrosion inhibitors, since they can fonn barrier on mctal or poπ리ain enamel surface
• Avoid using builders likc sodium nitrilotriacetate or sodium tripolyphosphate as they will corrode metals.
Selection of disintegrants
• Choose a disintegrant that has high water amnity and solubil ity, to facilitate tablet breakup.
Selection of dye transfer inhibitors
• Consider using polyvinyl pyrr,이 idone (PVP), which is widcly used becausc ofits biologκal compatibility, low toxicity, high complexing power, an
Table 8. Heuristics for additivc selection (continued).
Selection of enzymes
• Choose enzymes which have alkaline optimum pH, are most effective at low wash temperatures of 20-400 C and stable for temperatures up to 60 oC.
• Do not use e깨zymes in formulations containing cationic surfactants, anionic surfactants like alkylbenzene sulfonates, and blea이les Iike hypochlorite and percarboxylic acids, since they can degrade enzymes.
• Use just enou뱅 amount of enzyme in the product, since the cleaning perfonnance of enzymatic stains increases with concentration but saturates at high 삐zyme concentratton
Selection of fabric softeners
• Choose fabric softeners based on their softening power, which decreases in the order of DHTDMAC > imidazoline quaternary > amidoamine quaternary ~ TEA ester quaternary.
• Choose esterquats over DHTDMAC for environmentally friendly products, since theγ biodegrade more rapidly and are less toxic to aquatκ life.
• Consider incorporating additives Iike monoalkyl quats, ethoxylated alcohols, ethoxylat떼 amines, or solvents for ultras (concentrated fabric softeners), since they usually solve dispersibility problem stemm혀 from high concentration.
Selection of tluorescent whitening agents (FW A)
• Use distyrylbiphenyl type and triazolylstilbene type, but not derivatives of 4,4 ’-diamino-stilbenzene-2,2’ -disulfonic acid, for products containing chlorine bleach, due to compatibility
• Avoid using FW As with anionic sιlrfactants, since they will enhance deposition of FW A on fabrics [22]
• Adjust the desired solubility, substantivity, and other perfonnance factors ofthe tluorescent whitening molecules, mainly CCIDAS or DASC-bis-triazinyl d에ivatives of 4,4 ’-diaminostilbenzene-2,2’-disulfonic acid, by adding different substituent groups like alkoxy, hydroxyl, or amino groups.
Selection of hydrotropes
• Choose colorless and odorless hydrotropes Iike sodium xylene sulfonate, sodium cumene sulfonate, or ethanol with products for which color and odor are und녕sirable.
• Consider using urea in formulations with alkaline pH and for which ammo깨a smell is not a problem, since it is a cheap and effective hydrotrope.
• Choose alkylnaphthalene sulfonates and s비fosuccinate esteπ as hydrotroψes in formulations where foaming needs to be controlled, as they enhance solubility of anionic surfactants Without increasing foam amount [20].
Selection of opaαfiers
• Choose the type and amount of opacifier depending on
T'able 8 , Heuristics for additive selection (continued)
Selection of perfumes
• Choose a perfume blend that is comp와ible with other ingredients like hypo야llorite bleach, peroxygen salts, and 태zymes, and does not have p이ential of increasing product viscosity or causing phase separation (야pecial1y for structured liquids) ,
• Choose specific pe얘1mes to mask malodors by identifying their 5Ource, such as ethoxylated alcoh이 nonionic surfactants (fatty malodors) and PVP dye transfer inhibitors (mouse.like od아).
• Consider using antimicrobial essential oils or perfumes extracted from plants in place of p.roprietary preservatives to make prod따ts with natural protection c1aims
Selection of preservatives
• Consider using preseπatives in detergent products containing biodegradable raw materials with a neutral pH, especia l1y low concentration liquid detergents
• Use preservatives for products containing anionic suñaιtants as they are 양od nutrients for bacteria, but not for those containing cationic suñactants with nonionics as they can act as preservatJves
• 00 not use formaldehyde and formaldehyde donors as preseπatives, as their safety is doubtful
• 00 not use brominated nitropropanes/dioxanes for applications at pH ab야e 8 or temperature ab。이 e 60.C because of decomposition, or with secondary or tertiary amines or amides because offormation ofhealth hazards [17]
• Consider using dimethylhydantoin to have protcction against bacteria, and iodopropylbutyl. carbamate (IPBC) against molds and yeast. Use their mixture for lower usa양 and CQsteff농cttveness.
Selection of rheological modifiers
• Ch∞se nonionic polymers for products containing electrolytes, but not for th야e c.이,tammg acid, base, peroxide, persulfate, or hypochlorite as they may be unstable with these substances [15]
• Use anionic polymers such as polyacrylic acids cross.linked with a l1yl ethers ofpentaerythritol or sucrose as thickeners, ifa gel structure and pseudoplastic (shear.thinning) properties are desirable‘ Consid삐r adding co l1oidal alumina to further increase the viscosity at pH - 13 [15]
• Do oot use cationic p이ymers for produιt5 containing anionic surfactants, strong oxidizing agents, or electrolytes.
• Consider usi앤 organic thickeners such as carboxymethyl ce l1ulose and hydro얘yethyl ce l1ulose with different substitution level per ring to obtain the desircd thixotropy and water 50lubility behavior
Selection of solvents
• Choose a solvent that can dissolve a l1 aιttve mg
Table 8. Heuristics for additive selection (continued).
Selection of suds stabilizers
• Choose nonionics as suds stabilizers for use with foaming surfactants that are ionic. Prefer those with higher ability to lower the critical micelle concentration (CMC) ofthe foaming surfactant.
• Do not use electrolytic suds stabilizers for products with nonionic surfactants, since it has no effect.
• Choose macromolecular compounds like water-soluble polymers and proteins over surfactants and electrolytes as foam stabilizers for products with enhanced skin feel and skin mildness.
Selection of suds suppressors
• Consider using long chain soaps for applications at temperatures > 60oC, and shorter chains (C 12-C 14) for application at low temperatures. Use in a mixture with ethoxylated fatty alcohols to enhance efficiency.
• Do not use soap as antifoam for products with nonionic surfactants, since it has only Iimited effect.
Sachet
Tablet
}←쉬
싸내
Raw materials
REACTIONI SEPARATION
THERMOFORMING, BULK SOLlDS | • FILLlNG, AND
SEALlNG PROCESSING r:
TABLETINGI DISPERSION COATING PROCESSING
----------- __ --c:2'l. ~
짧f7Spray 치 Liquid
Figure 3. Unit operations in detergent manufacturing.
Powder
Unstructured liquid
,--Structured
liquid ‘
~굶ueous liquid
Ingredients Ingredients
Final Product
Figure 4. General flowsheet for a detergent manufacturing process.
Tablc 9. Examples of eq비pment for manufacturing different product forms of detergents
P'roduct Fnrm / Feαf Powder
Aqucous sol비lons
Powder and flakcs Liquid and solids
Spray, Liquid and Gel Solublc liquids Liquid and insolublc
‘olids Immisciblc liquids
Tablet Powdcr
Sachet Liquid
Powder and Tablet I’owdcr
Powdcr or flakcs
Powdcr LIq뼈 and solids
Spray, Liquid, Gel, and Sachet
L iquid and/or solids
Unit operations
Spray drying Dry blending Sizc enlargement
Mixing Dispersion
Emulsitication
Examψles o[ equÎpment
Spray drying tower V -shaped mixer, ribbon b’ender High shear mixer granulator, fluidized granulator (bubbling bed.
월쁘브뺑l
Agitated vessel, in-line mixer Agitated vessel, planetary mixer, Mixer-kneader Turboemulsitier (agitated vessel)
Tableting Tableting machine
Thermoforming, tilling, and TFS machine
프반모묘뜨l
Mixing
Sizc rcduction
Scrccning Coating
Droplct/solid size distribution control
High shear mixer granulator, fluidized granulator (bubbling bed, spouted bed) Jaw crusher, roller crusher, fluid jet mill Vibrating screen Spray drier, tluidized bed coater
Colloid mill , tandcm shear pipeline mlxer
Tablc 10. Hcuristics for equipment sclection for dctergents manufacturc.
Granulator
• Usc fluidized granulator to obtain granulcs of highcr rclativc dcnsity (0.6 - O.X)‘ and high shcar mixer granulator lowcr rclative density (0.3 - 0.5) and thus faster solubilily or casicr dispcrsion.
• U、c fluidizcd granulator for high lempcralure feed .
• Prcfcr high shear mixcr granulator over tluidizcd granulator for handling cohcsivc matcrial~’; or for hi상hcr throughput (up to 50 tonneslhr comparcd 10 <500 kg for batch typc fluidizcd granulator)
• Prcfcr fluidized granulator ovcr high shcar mixcr granulator if better tcmpcraturc control for proccssing heat-scnsitivc matcrials is desircd.
Solid blender
• Usc ωntinuous V -shapcd mixer only for handling powdcr of diameter >0.0 I mm. For smallcr powdcrs ‘ usc ribbon blendcr.
• Usc V -shapcd Illixer for abrasivc powdcrs.
Liquid mixer
• Usc static mixcr or agitatcd vesscl to mix scparatc phases to fonn a pre-emulsion.
• U、c planctaη mixer for mixing suspcnsions with high solid volulllc fraction .
• l샤c an agitatcd vcssel cq비pped with a scrapcr for proccssing clllulsions that arc scnsitivc 10
llcating or cooling‘ to minimizcd s띠gnanl zoncs in thc mixcr.
Cruslter
• Usc fluidjct mill for producing particles ofmicron sizc rangc, roller crushcr for mm to cm sizc rangc, and jaw crushcr for cm size rangc.
Table 1 1. Design equations and operating conditions for selected equipment units
탁뾰뜨낀 Spray drying
tower
Turboemulsifier
Des껴"n eqνations and operating conditions Required drying air rate
L = _ .[Ev(.< +0.46T. - η) 0.245(T. - T. )
+ PCp(Tp-η) + QL + (L.~ x 0.24 x (T. - T ... )]
Residence time • 10 - 20 s for particles of few μm • 20 - 35 s for particleS :5 180 μm • 35s or more for particles of200 - 275 μm Typical diameter of droplets -100 um Typical pressure of atomizer 얘o bar Hot air temperature: 250 - 400 .C Shear rate,
4찌V r=-~:-;
I-(~r Mixing time, O. = f(N. , N" ,S,)
N. _ = D' Np(8N)' -' (~) R, K l3n+ rJ
Impeller configurations:
Nr=~ “ gD
• Open impellers or anchors for '1 = 5,000-50,000 cP • Helicals for 1/ = 50,000-500,000 cP
Rotary tablet Typical number of stations per press = 20 - 40 press Typical throughput = 9,000 - 300,000 tablets/hr
Tablet diameter = 10 - 30 mm Typical maximum compression force -80 kN
TFS machine Typical web width -up to 650 mm Typical throughput -up to 1 ,α)() pieceνmm
Fluid jet mill Minimum f1 uid velocity
I N: O". u., = .1----•
P. sin ' 0 RolI crusher Typical roll speed = 50 - 100 φm
Typical capacity -10 - 25 tonlhr (6 mm particles) Jaw crusher Typical rotor speed -300 rpm
Typical capacity = 1- 30 tonlhr V-shaped mixer Rotational speed, Nc = 50 - 80% of Nc.c,
Ncü = 0.498 -". =펴=
Powders fill때 to 30 - 50 % of vessel volume Ribbon blender Powders filled to >70 % ofvessel volume High shear mixer Typical rotational speed -3,000 rpm
g:ranulator Product Rranule size = O. 1 - 2 mm Fluidized bed u싹二&二뜨프L 뿔쁘먼or Produ디 Jl;ran비e size = 0.1 - 2 mm
Ref [24]
[25] [26]
[27]
[23]
[28]
[29]
[30]
[31]
[32]
[33]
묘죄 [34]
딩2 」옆L
Table 12. Examples of dependence of structural attributes on operating variables.
S'Iruclural atlributes Operal;ng variables
Powder (;n spray dlηI;ng lower) Mean particle size,
0"’r “”
Particle density, 까,
Air / liquid mass flow ratio, MR
Air density, Pa Liquid viscosity, μI Relative air liquid velocity at
띤깊붙~ Atomizer wheel design
Feed rate,f Outlet air temperature, π
Inlet air temperature, κ Nature offeed
Direction of air flow
Tablel (in rolary lablel press) Porosity ‘ c Applied pressure, P
Relationshψ
Kim-Marsha l1 equation [26] trO.4μ0 . 3Z 1
D",ro. = 535아 ‘ 0 <7 “ “ ‘II‘ ] (v”lPa)” AG” pl’ ,。 ‘
u.2
“ 07.1 •• 1 I二Lr-" x[τy-]x[-:-:--]’ x3436 Plg V써 M R
Wheels with curved vanes produce powders with higher density [24)
Increases with increasingf
Decreases with increasing T"
Decreases with increasing T;
Suspensions give higher particle density than solutions
Counter-current air flow gives higher partic1e density than co-current flow
Empirical equation [36]
lnL= klP+k2 E
where k) and k2 are constants affected by material properties and deforrnation
Tab’c 13 ‘ Summary of product fonnulation ωr Example 1.
Propcnics ofTablct Outcr-ponion
Mas‘ 20 g
Dissolution timc 0 .33 g/min
Constitucnt panicJe size 5 μm
Fonnulation
Buildcrs
Enzymcs
Sodium tripolyphosphate
Carbonatc
Silicate (a1 5O as cOTTosion inhibitor)
Proteasc
Amylasc
52.8 wt.%
15.4 wt.%
12.6 wt.%
I ‘o wt.%
0.75 wt.%
Blcach: Anhydrous ‘αJium pcrborate monohydrate 12.6 wt.%
Surfactant Primary alcohol cthoxylatc 1.65 wt.%
( ~"f>II~1 = OllC‘ HLBop = 14)
Pcrfumc: pcrfumc blcnd 0.05 wt.%
Watcr Balancc
Propcnics of Gelatinous Inncr-ponion
Mass 3.5 g
Viscosity 75.000 cP at 250 C
Fonnulation
Rhcological modificr: Polycthylcnc glycol (MW = l!OOO) 4.0 wt.%
Organic so lvcnt : Glyιcrol triacctatc 34.0 wt.%
Enzymcs Protcasc pri 11 12.8 wt.%
Amylase prill 7.2 wt.%
Disintcgrant Anhydrous sodium bicarb이latc 24.0 wt.%
Citric acid 18.0 wt.%
Ingredients PEG in gel body (gelling agent)
Liquid ingredients tor
tablet body
Solid ingredients tor
tablet body
Finished product
Figure 5. Flowsheet for manufacturing an ADW tablet with gelatinous inner-portion (Examplc 1).
Table 14. Summary of product fonnulation for Example 2.
Properties of Extemal Film
Material
Thickness
Dissolution time
Properties of Intemal Liquid
Viscosity
Phase
Formulation
Surfactant:
Builder:
Solvents:
Suds stabilizer:
Polyvinyl alcohol
5 mil
20 sec
40cP
Spherical micelle
Sodium lauryl sulfate
(HLB = 9.4, T knfl‘ = 380C)
Hexylene glycol
(HLB = 16.7, Tcloud = 950C)
Dimethyl glyoxime
2-butoxyethanol
Monoethanolamine
D-Iimonene (also as perfume)
Ethanol
Alkanolarnide
4.0 wt.%
15.0 wt.%
0.5 w t.%
13 .5 wt.%
2.0wt.%
15.0 wt.%
47.5 wt.%
2.5 wt.%
Ingredients
Agitated vessel
Thennofonning, filling, and
sealing machine
Packaging
Finished product
Figure 6. Flowsheet for manufacturing a household cleaning sachet (Example 2).
T.blc 15. Summ.ry of product formul.tion for Example 3
Propcrtics of thc final pr,“Juct
Viscosity 3000 cP‘ rheoφccttc
Phasc Cylindrical micclle
Fonnu’ation of final product
Surfactant‘ Sodium linc.r .Ikylbcnzcne sulfon.π (N.LAS) powdcr (HL8 ~ 7. 1. r..삐 ~ 3 ’ 50 C) 20.26 wt. %
Solvcnt
Buildcr
Blcach
Hlcach acti\'ator
Alcohol cthoxyl.tes (C" .Icohol. EO ~ 7)
(HL8 ~ 12.5‘ r.“‘I ~ 620C)
Butoxy-propoxy-propanol (BPP)
SαJjum citratc dihydratc
Sodium carbonatc (particlc sizc: 10-40μm)
Dicthylcnc triaminc pcntaacctic acid (DTPA) (chclating agent to protect pcroxygen blcach)
S이Jium pcrboratc
Citratc.co3tcd nonanoyloxybcn7.cnc
‘ulfo‘Jnatc (NOBS)
Rhcolog’‘;al modificr: Maleic-acrylic copolymcr
Enzymc‘
Sud“ upprcssor
Pcrfumc
Whitcning agcnt
Propcrtics of NaLAS powdcr
Fonnulation
Titanium dioxidc (cnhances clasticity)
Proteasc prills (200-8애 μm)
Amylasc prills (2α)-800I1m )
Alkyl phosphatc
Pcrfumc blcnd
Disodium 4‘4 ‘ -bis-(2-morpholin04-anilinos-triazin-6-ylamino) stilbcnc disulphonate
Surfactant : Sod ium lincar alkylbcnzcnc sulfonatc
Dilucnt : Sod ium ‘ulfatc
Hydrotropc: Sodium sulfosuccinatc
18 .82 wt. %
18.82 wt. %
4.32wt. %
II .5X wt. %
O.77wt. %
2.86 wt. %
8.49 w t. %
11 .58 w t. %
0.54 wt. %
0.77 wt. %
039wl. %
0.03 wt. %
0.46 wt. %
(1.3 1 wt. %
85 wt. %
Ilwt.%
2wl.%
Watcr Balance
Numbcr of phascs: 2 (insoluble and solublc in non-.queous organic liquids)
Amount of in‘olublc phasc ”‘,vt%
Particlc si 7.C 0.4 - 2flln
Ingredients for NaLAS powder
Non-millable ingredients for the structured liquid
Millable ingredients for the structured
liquid
Finished product
Figurc 7. Flowshcct for manufacturing non-aqueous structurcd laundry dctcrgcnt with surfactant α)wdcr (Exall1plc 3)
Detergent Requirements6
In this file we estimate the amount of detergent required for a single wash in a washing machine. Starting point is the structure oftextile in Figure 4-7. The solid paπ ‘4 ’ ofthe textile consists of fibres with a diameter of ten micrometres:
The mass of texti le for a ft니 1 wash is:
and the density of the fibres:
The fibres have a volume
Ifwe consider than to be cylinders, they have a sUlface area
The diameter of the surfactant ‘5 ’ is (F igure 1-5 in ‘ Colloids ’).
The molar mass is (roughly)
The surface occupied by one molecule of surfactant is
So the number of molecules required to cover the surface is
With the Avogadro number
the amount (number of moles) becomes
and the mass required is
d4 := 10. 10- 6 . m
m 4 := 5. kg
P4 := 1400 . kg . m- 3
VtJ.:= m4 4.=-P4
4 A4 := V4 . τ-
U4
d5 := 0.4 . 10- 9 . m
M 5 := 180.10- 3 . kg. mol- I
7r ‘ a5 := x d;
A4 n 5 :=-
a5
NA := 6.02 . 1023 . mol - I
n5 5 '"
A
m 5 := N5 . M 5
m 5 = 3.4 x 1 0- 3 kg
You need a measurable amount, if only to cover all fibres. In reality you would need substantially more to get a rapid penetration and to displace dirs t: perhaps ten times as much.