CA1080409A - Compositions for pitch control - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Pitch formation in paper mill pulp systems may be inhibited by treating such systems at a point prior to where pitch deposits normally occur with at least 0.5 ppm based on the weight of the pulp of a composition comprising:
Ingredients % by Weight Non-ionic surfactant 50 - 20 Anionic dispersant 45 - 15 Aminophosphonate chelant 45 - 15

Description

~ 4~ -. ,.
I~TRODUCTIo~ . .
Mechanics of Pitch Formation Pitch, as it is first introduced into the papenmaking sys~m~
. is found adsoxbed on ~he fiber ~2%) and contained withi~ ~he part of : the ~iber termed ray cells ~9~/O). Even when it is wi~hin khe xa~
cells, it is in a small p~rticle state, attempting to a~hieve the grea~est surface area v.s. volume pos5i~1e~ When viewed under a . microscopQ~ ths pitch in the ra~ cell appears s~milar to eggs in.a .; fish's egg sac.
~he pit~h is oxced from the fiber sur~ace and from the ray ~? cells during the harsh process of aigesting and during period~ of.
high ~hear (pumps, refiners, etc 1~
. When the oil-loving pitch particles are released fxom the-` fiber, they enter the water system in ~he ~orm of a~ unstable~ crude ~ispersion. In form and activity~ the~ are very slmilar to mice~le.s or a colloidal systems, orming an unstable dispexsion in suspension . in the stock a~d water s~stem used to process paper and pulp Thi~
i unstable dispersion completely des~abilizes or breal~s and the l particles agglomerate when subjected to:

:. 1~ Shear i . 2. Temperature shocX
3. pH shock --Insoluble mineral salts Such as calcium carbonate aggravate the problem by providing sites for the pi-tch particles to adsorb an~
i I the pitch e~entually acts as a birlder, cementing the cr~stals i ¦to~ether into a deposit. Technically, they o:Eer liquid-soli~
interEaces ~,7hich intensify the dispersion destabiliza~tion orces~
¦addiny great y to the bulk of the depos1 t.

Filler materials, fines and fibers can become trapped wi~in the organic matrix formed by the pitc~ coalesence ana compou~ the problem. Oil carriers from ~ash aids and deoamers a~ oleop~ili~
and tend to be attached to ~he oleophilic, crudely ~is?ersea, pi~ch particles causing further des tabili~ation of ~he ~ispersion a~d-adding to the gross deposits.
.' . ' ' , , Factors That Influence Pitch Formation:
: . The composition of pitch and the amount o~ de~osit~bie materials are influenced b~:

1~ Type of wood ~ 2. Seasoning of wood : . 3. Typs o~ pulping process ~ . 4. Process w~ter -: 5. Pulp ~ashing 6~ Pulp bleaching . 7. System additives 8. System design . 1.) Type of Wood ana Its Componants:
Softwood vs Hard~ood .

. contain more atty acids contains mora neu~xal : contain more rosin acids organics (unsapo~ifia~le~
and sterioas)

2) Effect of Seasoninq and Storaqe: ~ ~
The total amount o pitch forming organics that wil~ .
be released during the pulping operation is s Lrongly affected by its seasoning and storage~ Woo~ storea as chips, above freezing, ~7ill "season" more c~uic'~l~ and comple tel~ than lo~s due to the greater sur~ace area ' . - available ~or oxidation. The oxidation of th~ resinous !, matcrials tends to make the resi~s more solu~le and easier . to remove by washi~.g.
., ~ -3-( 108()4~9 A chemical reaction, suchias oxidation, takes place more slowly during cold weather than during warm weather~
It thus follows that wood seasoned in ~he winter will ha~e ;, a higher pitch forming tendency, thi5 bein~ the xeaso~ or the traditional late winter and spring pitch outbreaXs,

3~ Pulpinq Process:
~ he presen~e and ~he relative amo~t of fat~y/rosin acids and neu~ral organics depend upo~ ~he type o~ WOo~-and ~he method of pulping~ These ma~erial5 are respons~ble ~ox most of ~he pitch deposition. . .
. Kraft Coo~s Saponify natural fats completely l~tO fat-t~ aci and glycerine, Sulfite Cooks ~ot as ~evere as Kraft and may lea~e unsaponifie~
. fatsO
Groulldwood Contain great amounts o unsaponified ~ats as ~od .
is hot cooked.
~ eutral organics are found mostly in sulfite an~.
groundwood systems because the acidic pulping systems conditions causes an~ fatty acid, which do formJ ~o be i~
the ~ree acid state.
Free fatty acias are almost insoluble in ~ter~ howe~er the sodium salts of fatty acids (pxesen~ at higher pH~ are true surfac~ants and act to form ~he unsta~le dispersion of

-4-~ 8~ ~V~

neutral organics into a more stable natural dispersion suspendea in the pulp/waste system. If the p~ is lowered, they revert and the fatty acids ~eposit as pitc~. - .
Kraft Cooks of hard~ood pulps are more troubles~me than softwood due to the hig~er percen~age of~ neutral organics. Usually har~wood krafts ha~e i~su~iciellt f~at:t~
acid salts to stabilize the neutral organi~ dispersion~
. 4) ~ ~-. ~he process water is very important in cont~olli~
pitch because it can aid in aggravating pitc~ prob~ems o~
, used to help prevent pitch outbreaXs by providing a ~ami~
. system in which to suspend pitch in ~he form of a stab~e .
emulsion~ . .
. Water hardness~ indigenous to ~he incoming mi~l. w~ker or created by system chemistry, is vexy important to pitch . formation, especially in kraft pitc~ Kraft pUlp7 ~Jhen i~
leavss the digester is quite akaline and has a ver~ hi~. -sodium (salt cake) content~
When it entexs a countercurren~ ~rown stoc~ was~er line, the pulp is washed with cooler and cleaner water~ t~
progessively lower solids content At the high pH's~ ~n ~.
first stages of washing, all of the fat~ acids are presen~ ~
as so~ium salts, t~hich are solu~le and emulsify and non~ r organics, any calcium present in the liquor or the woo~t during tne coo~ would be found as precipitated calciu~
carbonate. IE the proccss water usea in washing is soft (naturally so:Et, chemically softened or boilex condensate), no pitch o-ltbreaks could be expected in the washer system.

-5-1~ ( 108134U9 However~ ~he wash water added at mos~ deckexs or the last stages of washing usually contains a fair amoun~ o~
calcium hardness. The calcium is detrimental to ~rashing and encouxages pitch formation by two aiffQxent ~echanisms:
A. The calcium exchanges wi~h Whe sodium in ~h~
sodium soaps o-f ~he fatty acias ana forms insol-uble calcium soap.
J!~o fatty acid ~ Ca~Ca Fatty PAci~" ~.~a~
~he insolu~le soap (~ike a hara wa~er soap ~
scum) no longer ha~ ~he ability to act a$ a na~u~al surfactant (ik once helped ~eep the pit~h emulsi-. :Eied). The natural pitc~ dispersion therL'becomes destabilized and forms a crude dispersio~ susc~p -$ible to depositing when ~aced with an~ form o shear.
. B. The calcium and bicarbonate alkalini~ c~ he wash water aaa to ~he car~onate and hydroxide alkalinity generated ~uring ~he caustic cooX~
forcing the pxecipi tation of calcium carbonate_ Process Water Ca'~ HCO3 Pulp ~ Liquor CO3 -~ OH
HC03 -1- 0~ -- ~ ,~1 C03 ~ H2 Ca~ CO3 C~ Cac03 .

The calcium carbonate cr~stals are then ava}~-¦ able as addi tional liquid-soli~ interfac~s whic~2 ¦ destabilizes ~he natural dispersion of pitch forming oryanics. The destabilized dispersion ..or

-6-108~409 ~ l crude dispersion...then plates out at the decker or screen room ~ith typical kraft pitch~

Pitch usually doesn't occur before the d~cker or ~h~
last stage of washing because~ in csuntercurre~t washin~, the earliest stag~s have the hig~est amount of natural surfact~nts (sodium fatt~ acid salts) in the ~sh water an~
this enables a natural stable dispersion oE the eit~h form~g materials~ .
In coniuction with this phenomenon~ ~he earlie5'c ~a~h~
ing stages pro~i~a ~ highsr concentration o~ sodium ~soaa~-.r and higher pH in the wash ~ate~3 allowlng ~he s~dium to displace the calciu~ in the fatty aci~ sales formed in ~h~
last stages of tha ~sher~ the fatty acid salts act muc~ ~ik~
the zeolites use~ in water softening in ~heix res~o~se to concentratio~s of sodium ana calcium ions~ .
~ a fatt~ acid ~ Ca~ ~ a~ ~ Ca fa~t~ acid . .
. The freed oalcium ~hen ties up wi~h ~he available car~onate but causes no problems due ~o ~he hi~her level~ of natural surfactants. The CaCo3 and sodium soaps ~hen pass progressively and i~nocuously through to ~he earliest stag~
of washi.ng and then to li~upr recover~, ~) Pulp Bleachinq Syst~:
Pulp bleachinc is important to pi~c~ conLrol becau~e i~provides an additional opportunity ~o ~emove resinous material frol;l the pulp which has not been remo~re~l in w~s'ning~ The naturally occuring ~esin~ are mostly unsa~uraLeda making them ¦
some~l'nat prone to attac~ by oxidi~in~ agents:

.7_ 10804U9 {
A. Chlorine B. Chlorine Dioxide .
C. Peroxides D. Ox~gen ~he oxidation o~ ~he resins yiela compounds which ~re mor~ soluble in watex than ~he original re~ins and are more easil~ removea during caustic axtraction~
Calcium ~ypo~hlorite bleachin~ causes problems because of calcium fat-t~ acid formation and the possibility o~ CaCo~
. :ormation.
63 . System Additives:
Systems additives are ver~ impo~ta~t to pitch co~troL
programs. . , FattY Acid ~e~oamexs - If applied i~correctly or in :
heavy dosages add pitch formi~ material to the ~y~te~l.
:.Paraf~in Oil Carriexs - Found in most ~efoamers are usually non-polar and very h~dxop~obiF and acts to de-. stabilize natural pitch ~mulsions. ~ -L qht Hydrocarbons - Petrochemicals co~taining kerosene . or x~lene are not ~uite as hyd~ophobic as ~he para~f.in oils and tend to act as solvati~g a~ents to couple the natural sur~actan~s and inc~ease the stabilit~ o~.
the resin emulsion. -.
Talc - Controls pitch by providing a h~drophobic sur- ¦
face for the pitch particle to adsorb and thus either de-stabilizing the natural emulsion ox accumulatln~
cruaely dispersed pitch particles on its surface~ It attempts to bring the pitc~l particles together ~ h~ le the Nalco syste~'s goal is to keep them apart~
`/' 1~
. -8-~38~

Talc provides a liquid-solid interface (similar to calcium crystals) on ~Yhich the natural pitch dispersion can deposit without causing deposits on the machinery, providing the proper amount is applied. The pitch coated talc is large enough so that it tends to stay with khe pulp, ;
System design plays an extremely important roll in pitch control. A washer designed to wash 300 TPD of pulp obviously will not be as efficient when 500 TPD are put across it. Minimizing the air-water interfaces in the washers, by proper machine designs and application of ~-good defoamers, will help to stabilize the natural resinous emulsions, ~ ~
Plastic materials in the machinery are more hydrophobic than ~ `
metal parts and provide a greater de-stabilizing effect on the natural pitch emulsions than do metal parts.
This invention seeks to provide a chemical additive capable of acting on a variety of paper mill stocks to prevent pitch formation.
Another aspect of the invention is the furnishing of a pitch control composition which is capable of dispersing and emulsifying pitch particles to an exceptionally fine state of subdivision and allowing such finely dispersed particles to be uniformly distributed throughout the fin- .
ished paper in particles of microscopic size.
Another important aspect of the invention is to provide a pitch dispersant chemical composition which is capable of operating to pre-vent pitch buildup in paper mill systems at low economical dosages.
Another further aspect of the invention is a method of inhi-biting pitch formation in paper mill pulp systems which comprises adding to such systems at a point prior to where pitch deposits normally occur at least 0.5 ppm based on the weight of the pulp of a composition comprising:

g _ iBJ

4~
Ingredicnts % by Weight ~
,:
A. Non-ionic surfactant 50 - 20 ,, ~ .
B. Anionic Dispersant 45 - 15 C. Aminophosphonate chelant 45 - 15 In accordance with the invention, it has been found that pitch formation in paper mill pulp systems may be inhibited by adding to such systems at a point prior to where pitch deposits normally occur at ;~
least 0.5 parts per million based on the weight of the pulplof a 3-component formulation. This 3-component formulation is capable of acting upon the pitch contained within the pulp system to maintain it as a finely divided dispersion or emulsion of pitch particles which frequently have a paxticle size less than 10 microns, with the majority of the particles be- ;
ing in the sub-micron range.
The 3-component composition used in the paactice of the in-vention has the further advantage of being effective in dispersing or emul-sifying pitch which commonly occurs in a wide variety of pulp systems.
More importantly, the compositions of the invention are capable of operat-ing on the paper mill pulp systems in amounts ranging from as little as 0.5 ppm up to about 20 ppm. In certain instances, large amounts may be required, e.g., 100 or 200 ppm, but the lower dosage ranges give good results in most cases. ;
The composition of the invention are primarily designed to prevent pitch buildup in the paper mill systems. It is well known that pitch has favorite places for accumulating on the various apparatus and equipment associated with the processing of pulp. To be effective, the compositions of the invention should be added at a point in the mill system ahead of these so-called problem areas.
;.
Pulp is to~al fiber/water suspension.

-. - 10 - p ' ~ ~J ' '-' .~ ''' ' ~ o~9 ' ~

In certain instances, the compositions may be added a~ mul~iple points throughout the system to insuxe prevention of~pul~ buildup at several points throughout the wet end of the paper-makiny process Sinc~ the compositions of the invention are primarily adapte~
to disperse pitch already contained in pulp rather than remove heavy accumulations thereof from e~uipmentt the best results are obtainea in the practice of the invention ~hen the mill system has been thoroughly cleaned by the use of a cleaning and/or sanitiæing agent such as chlorine~ It should be noted, however, that existing pitch deposits can be removed by prolonged use o these compositions.
~ Pxior art dispersing compositions which oftentimes contain one of the ingredients o~ t~e compositions of this invention, while ~apable of maintaining pitch in a dispersed condi~ion throughou~ a paper mill system, are incapable of produciny micron to sub-micron particles of pitch which will attach themselves to the fibers in kh~
pulp system, thereby allowing the pitch to be incorporated into khe finished product in a Einely dividea state of subdivision. Prior art compos;tions tend to allow the pîtch to remain with the white ater which is reused after sheet formation, thus producing a paper ill by-product which has an undesirable conta~inant. When such itch-containing white waters are redispersed back in~o ~he pulp, the pitch buildup steadily increases, thus aggravating the pitch deposit problem.

Composit;~ns of the Invention As indicated generically above, the compositions of the invention contain 3 components. These components are listed below:
:
. . .

.- . . . .; :.. ~...... ....

(~ '~

Generi.c Formula I
In~redients % b~ Weight A. Non-ionic surfactant 50 - 2Q
B. Anionic Dispersant 45 - 15 C. Aminophosphonate chelant45 - 15 A more preferred com~osition falling ~7ithin the scope o~ ~he invention is set forth below~ .
G~ner~c Formula IT.
Ingredients % by W ght A. Non-ionic surfactant 50 - 30 . .
. Anionic Dispersant 45 - 20 C. Aminophosphonate chelant40 - 20 The on-~onic Surfac~ant This portion of the compos.ition may be selected rom a w:ide variety of non-ionic surfactants.- Examples of such non-ionic surfactants are condensati.on products of higher fatty alcohols w;~h ethylene oxide, such as t~e xeaction product of oleyl alcohol wi~h .
10 ethylene oxide units; condensatio~ products of alkylpheno1s a.nd .
ethylene oxiae, such.as the reaction products of isooctylphenol wi~h 12 ethylene oxide units; condensation products of higher fatty acia amides with five, or more, ethylene oxide units; polyethylene glycol esters oE long chain fatty acids, such as tetraethylene glycol monopalmitate, hexaethyleneglycol monolaurate, nonaethyleneglycol monostearate, nonaethyleneglycol dioleate, tridecaethyleneglyco~
monoarachidate, tricosaethylene glycol mon?behenater tricosaeth~l-eneglycol dibehenate, polyhydric alcohol partial hi~her at-ty acid esters such.as sorbitan tristearate, etnylene oxide co~densatio~
products of polyhydric alcohol partial hicher fatty esters~ and their inner anhydrides (mannitolanhydride, called Mannitan, and sorbitolanhydxide, called Sorbitan3,~ uch as the emulsion even reacted they 10 molecules oE ethylene oxid ~ pentaerythritolmono-::~;
- ~ ; :., ~

~ (. l oleate reacted with 12 molecules of ethylene oxide, s~bitan mono stearate reacted with 10 to 15 molecules of ethylene oxide; long chain polyglycols in whïch one hydroxyl group is esterified with a higher fatty acid and the other hydrox~l group is esterified with low molecular alcohol, such as met~oxypolyethylene glycol 550 monostearate (550 meaning the average molecular weight of the poly-glycol ether). A combination of two or more of these surfactants may be used.
~ preferred group of non-ionic surfactan~s are the alkyl _ phenols containing 4 to 12 car~on atoms which have been reacted wi~h rom 4 to 10 moles o ethylene oxide. A typical ma~eriaf of thi~
type is nonyl phenol which ~as been reacted with 6 moles of ethylene oxlde .

~he Anionic Surfactants T~pical anionic surfactants are sodium and potassium myristate, laurate, palmitate, oleate, stearate, resinate, and hydroabietate, the alkali metal'alkyl or alkylene sul~ates, such as sodium lauryl sulfate, potassium stearyl sulfate, the alkali metal alkyl or alkylene sulfonates, such as sodium lauryl sulfonate, potassium stearyl sulfonate, and sodium cetyl sulfonate, sulfonated mineral oil, as well as the ammonium salts thereoE; and salts o higher means like lauryl amine hydrochloride, and stearyl amine hydrobrQ-mide.
Other examples of suitable anionic surfactants are alkali''metal salts of alkyl-aryl sulfonic acids, sodium dialkyl sulfosuccinate, sulfated or sulfonated oils, e.g., sulated castor oil, sulEonated tallow, and alkali salts of short chain petroleum sulfonic acids.
A particularly pxeferred group of anionic dispersants are ~he alkali metal salts of sulfonated naphthalenes and al~yl substituted ¦napht enes. -13-~ ~ 8~

A particularly p.referxed material of this type would be an ethyl substituted naphthalene sodium sulfonate.

The Aminophosphonate Chelant The aminophosphonate chelant may be selected 1Erom any oE the compounds having the following structural formulas:
. ~ . .

R
R - N - R

II

~ 1 , .
R - N - (CHa)~r-N - R .

. III

R (N-CH2C~2)y N - R

In these formulas, R is CH2PO(OM) 2; n is.l -..6; y is 2 - 4;
~5 is H, NH3 or alkali metal~ .
. Compounds of the above type are known as chelants a~d are described in U.S. 3,336,221.
Compounds of the above t~pe may be prepared by reacting ammonia or certain primary or secondary amines with aqueous solutions o~
phosphorus acid and ormaldehyde. This simple preparatiVe tech~i~ue is set forth in U.S. Patent 3,288,846. A pre-Eerred aminophosphoni~

acid chelant or use in the practice of the invention is hexamëth~l-enediamine tetramethylene phosphonic acid which is prepared by reacting hexamethylenediamine with phosphorous acid and -Eormaldehyde .
in accordance with the teachings oE U.S. 3,288,846- Another pre-lerred phosphonate .is nitrilotrismethylene phosphonic acid which is sold under the name oE Dequest* 2000.

*P~eg. T~l ~lonsan~o CO. -14-.. . . .. .. . ..

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Optional Ingredients ! . . _ _ The above ingredients are conveniently prepared as an aqueous¦ emulsion by dispersing them in water. These concentrakes may con-I tain as little as 5 up to about 45 or 50% by weight of the active ~n~redients.
! Such concentrates may also contain adaitional ingredients as j anti-~oams, emulsi~ying a~ents, p~l adjusting agents for maintaining j formulation stability and the like.' .
l It is oftentimes useful to emplo~ a cationic polyelectro-lyte in the formulation to combat severe instances o pitch out~
brea~ This material which'may be exemplified by examples which include copolymers o~ acr~lamide containing 1-60% by weight oi .~dimeth~laminoeth~lmethacrylate or its water-soluble quaternar~
salts~ Other useful polymers include those prepared using diallyl dimethyl ammonium halides, and acrylamides which have been reac~ed with a secondary amine and aldehyde to form their correspondin~
Mannich'derivatives. Also useul and within the purview of this invention are qu~ternary Mannich derivatives of polyacrylamide These materials, being water-soluble,' may be incorpora~ed direc~ly into the three component pitch control formulation of this .
invention at levels of from .01-20% by ~Jeight. However, since ' these'materials are otentimes of a high molecular weight and wil~
thicken the formulation, it is oftentimes advisable to add them separately along ~ith the three component pitch control chemica~ of this invention. When addin~ these materials separately, it is bot'n convenien~ and desirable to have them in a water-in-oil emulsion form such as that described in Anderson, et al, ~,624,019 -15- ,... .

10~409 ( I 1~
¦ ~ typical composition o khe invention would be the following co~position: ' Generic Formula III
I .
¦ ' Ingredients % By Weight ' ¦ Hexamethylene diamine ¦ tetramethylene phosphonic acid...... ~..... ..8~0 ¦ Ethyl naphthalene sodium sulfonate........ .12.2 Nonyl phenol reacted ~ith'6 moles of ethylene oxide.~O,~ ................... .10 Polydimethyl siloxa~e antifoam...... ~..... ....OS
~ater................................... .. Balance , In order to further illustrate the attributes of ~he insta~
invention, the ollowin~ example is presented: ;"
E~AMPLE I ~
~ he composition shown in Generic Formula III was trialea at a calcium base sulfite mi~l in Wisconsin. The mill, prior to ' introduction of the compound of this invention, was addi~g 75 lbs~
talc per ton of pulp to the system to attempt to disperse pi~ch which was forming. This mill was using as a furnish 40-70% by weight sulfite, 20-4~o Kraft and 10-30~ Broke. Paper yrades produced included bonds and offsets. Dosage o Generic Formula III
was held at 2-4 lbs. per ton to the tray water. In addition, 2-3 lbs. per ton were employed at each of the two different paper machines, while one paper machine was dosed with 2-4 lbs. per ton_ It was found that the addition of the material to the tray water at a dosa~e of 2-4 lbs. per ton gave the best results. After a period of approximately our months running with the composition of this invention adding 2-4 lbs. per ton to the tray water on one paper machine alone~ downtime -to clean up the ta,ble area o pitch deposits was reduced by 90%~ The roils which were cleaned once or twice a shi~t, prior to the introduc~ion o~ the chemical of this invention, were now cleaned only once a month. Prior to the ';

1(~80409 1', in troduc~ion of the chemical treatrnent, the suction boxes had to be cleaned re~uently. Since treatment started, suction boxes ha~e only been cleaned one or two times a month an~ only then to reauce small amounts o deposits on the lip.
A further bene~it of the program of this invention has been the fact that the ~dditi~n of talc and the manpower xequiremen~s ~or handling and feedin~ this material have been eliminated. ~here have also been ~e~er machine breaks, fewer general machine deposl~s and fabric li~e has been increased by an estimated 33~. ~s a ~urther benefit, while the mill previously had to use a separate slimicide dispersant, the use of this matexial was also elimi~ated by the comp~sition of this invention thus providing a further ~aVings- . :
Having thus described by invention, I claLm: .

Claims (3)

1. A method of inhibiting pitch formation in paper mill pulp systems which comprises adding to such systems at a point prior to where pitch deposits normally occur at least 0.5 ppm based on the weight of the pulp of a composition comprising:
Ingredients % by Weight A. Non-ionic surfactant 50 - 20 B. Anionic Dispersant 45 - 15 C. Aminophosphonate chelant 45 - 15

2. A method of inhibiting pitch formation in paper mill pulp systems which comprises adding to such systems at a point prior to where pitch deposits normally occur at least 0.5 ppm based on the weight of the pulp of a composition comprising:
Ingredients % by Weight A. Non-ionic surfactant 50 - 30 B. Anionic Dispersant 45 - 20 C. Aminophosphonate chelant 40 - 20

3. A method of inhibiting pitch formation in paper mill pulp systems which comprises adding to such systems at a point prior to where pitch deposits normally occur at least 0.5 ppm based on the weight of the pulp of a composition comprising:
Ingredients % by Weight A. An ethoxylated phenol 50 - 30 B. Alkyl substituted naphthalene sulfonate 40 - 20 C. Hexamethylenediamine tetra-methylene phosphonic acid 40 - 20