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470 I N D U S T R I A L A N D ENGINEERING CHEMISTRY Vol. 23, No.

Trisodium Phosphate-Its Manufacture and Use'


Foster D. Snell
130 CLINTON N.Y.
Sr., BROOKLYN,

I n the manufacture of trisodium phosphate, phosphoric tion of double salts in the product or by spray-con-
acid is added to a solution of soda ash to form disodium gealing.
phosphate, with evolution of carbon dioxide. The solu- The value of trisodium phosphate a s a detergent is due
tion is diluted and extraneous matter removed by filtra- to its high pH value in solution, its ability to lower inter-
tion. Sodium hydroxide, added to t h e filtrate, converts it facial tension against oils or solids, and its marked power
to trisodium phosphate. This solution is diluted, filtered of emulsifying oils. Trisodium phosphate is used a s a
hot, and crystallized. The crystals of trisodium phosphate detergent in households, laundries, factories, hotels,
are separated from the filtrate, dried, meshed, and aged. dairies, and garages. I t is used a s a water softener and
A spray-congealed product may also be prepared from the boiler compound because of its ability to precipitate cal-
clear trisodium phosphate solution. cium and magnesium phosphates. It has many other
Caking of the crystals may be avoided either by forma- miscellaneous uses.
.....
HE tertiary sodium salt of phosphoric acid finds use in liberated. As the neutralization proceeds, steam is used for

T industry because of various applications of two proper- heating the batch to boiling. Slightly more phosphoric acid
ties. The salt in water hydrolyzes to give a solution is added than that required to convert all the soda ash to
of reasonably high pH value, well buffered a t that level disodium phosphate. The solution is then boiled until
against neutralization. This pH value is higher than that of all the carbon dioxide has been eliminated. Since the pH
soda ash and modified soda, the principal competitive alkalies. level at which the third hydrogen of phosphoric acid is
The salt forms insoluble phosphates under conditions which neutralized is higher than that a t which the second hydrogen
permit its use for removal of heavy metal ions from solution. of carbonic acid is converted to form sodium carbonate, it is
The manufacture of trisodium phosphate is essentially not to be expected that phosphoric acid can be neutralized
the neutralization of phosphoric acid and subsequent crys- further than to the disodium stage with sodium carbonate.
tallization. For economic reasons it is desirable to neut.ra1- Plant experience confirms this since, if just sufficient phos-
ize in two stages as follows: phoric acid is added theoretically to convert all the soda ash
to disodium phosphate, some remains unconverted in the mix.
The practically complete elimination of carbon dioxide
by boiling is insured by laboratory control. At suitable in-
The phosphoric acid may be of variable purity and concen- tervals the batch is sampled. One portion of the sample is
t r a t i o n . The process de- further boiled in the labora-
scribed in this paper is one used tory; another is not. Both
with electric furnace acid by are then titrated. Agreement
the Swann Chemical Company. shows c o m p l e t e removal of
An outstanding feature of the carbon dioxide in the plant.
process is the absence of con- By addition of mother liquor
centration or e v a p o r a t i o n from a previous crystalliza-
steps. With some modifica- tion of trisodium phosphate
tion it is applicable to acid the specific gravity of the mix
made by the Dorr process. is suitably lowered. This gives
a solution of disodium phos-
MANUFACTURE
?
phate, the excess alkalinity of
Production of Disodium Tri s o d i urn P h o s p h a f e the trisodium phosphate crys-
Phosphate Liquor tallizing liquor having neutral-
Solutlon
ized any deficiency in the
I n a 4000-gallon tank (right, batch below the disodium
Figure 1) equipped with an [ T i t e r
I I phosphate stage. This solu-
agitator, 7000 pounds of 58 per tion of disodium p h o s p h a t e
cent soda ash are suspended carries in suspension any solid
in 900 gallons of hot liquid. 1 i impurities from the phosphoric
This liquid may be water, but acid, as well as iron, aluminum,
is more commonly wash liquor and calcium which were in the
from filtration of previous phosphoric acid and soda ash
batches of disodium phosphate solutions.
or mother liquor from diso- The diluted disodium phos-
dium phosphate manufacture. phate s o l u t i o n is filtered
Phosphoric acid containing ap- through a deeply recessed
proximately 45 per cent PzO6 plate-and-frame filter p r e s s
is added a t the surface of the (left, Figure 1) and the filtrate
tank so that the carbon dioxide pumped directly to storage
evolved can be more readily t a n k s . This f i l t r a t i o n is
1 Received December 9, 1930. Flow Sheet for Trisodium Phosphate carried out at 85-100° C. The
allay, 1931 INDUSTRIAL A N D ENGINEERING CHEMISTRY 471

PiCure 1 -Tanks and Filter Pres8 I'ned In Manufacture of Figure Z--CausfIc Pot8
Disodium Phoaphafe

result,iug dear solution uf di- produce uniimn crystals in


sodium phosphate contains the cry8tallieing units. The
14.5 per cent I'& and 13 per solution goes to the crystal-
cent K:&. The press cake lieers through steam-jacketed
is washed with water and tlie pipes a t an average tempera-
dilute disodium p1iosphat.e so- ture of 70" C. with a ratio of
lution so obtained used as phenolphthalein t.o m e t h y l
make-up water for the first orange end points of 0.527.
stage of the process. Tlie By analysis it shows 9.25 per
cake from the press is waste. cent 1'20s and 13.2 per cent
NasO. The crystallizers are
Conversion to Trisodium
Phosphate of the Swenson-Walker type
(Fiyre 3), water-cooled,
I n order to c o n v e r t di- and are installed in banks
sodium p h o s p h a t e to tri- of three, each 24 feet long.
s o d i u m p h o s p h a t e it is Four such banks in parallel
necessary to use sodium hy- produce 175,000 pounds of
droxide. For this causticie- trisodium phosphate per 24
ing operation 1500 gallons hours. The liquor is fed to
of disodium phosplra.te solu- tlie c r y s t a l l i a e r s through
tion are pumped
. . into a 4000- a visible-feed Wier box at
gallon iron tank. To this are added approximately 2800 the Iread of the nracliine to give volume control. I n the
pounds of sodium liydroxide in 300 gallons of water at 90" C. crystallizers the temperature is reduced from 60' C. to 30" C .
(Figure 2). An additional 1000-gallon quantity of disodium at a uniform rate.
plrosphate solution is tlien added. The evolution of heat by The crystals discharge to a separating pan and are dried
rrnction of disodium plrosphate and sodium hydroxide neces- in a centrifuge (Figure 4). The discharge liquor a t 30" C. has
sitates venting these tanks through the roof of the building a specific gravity of 1.235 and contains 5 per cent P,O, and
t,o enrry off caustic spray. Tlie boiling point of this liquor 7.1 per cent Illia2O. In tlie crystallizcrs 70 per cent of the
isabuiit 112" C. trisodium pliospliate has been separated as crystals and oiily
As a coiitr(i1 on tlie solution a sample is titrated to plicnol- 30 per cent l e f t in the mot!ior liquor. This liquor is slored
i?!itlitileiii mid methyl orange end points. At this stage i n R submerged sump for use in suhseqiient. iiatclies.
an excess of sodium hydroxide over that for exact neutrali- '?tie crystals pass froni the centrifuge to a rotary drier
ible. The ratio of the reading using lilicnol- (Figure 5 ) . Warm crystals from the drier pass into a rotary
plitlialeiii to the total reading should lie between 0.51 and cooler arid thence to a screen (Flgiire ti), where they are
0..54. screened and distributed to storage bins in four six-coarse,
The solution of trisodium phosphate is next dilutcd wit11 medium, fine, and powdered. Wticn screened t!ie crystals
mother liquor from the crystallizers to a spccifie gravity of have cooled nearly to room temperature. Aft.er screening
1.34-1.40 a t 90" C. At that stage it contains 10.5 per cent they are aged 3 or 4 days by storage in piles.
1hOs and 15 per cent Na20. It is then filtered through a The product then goes to packing and is placed in 1 2 6
press wliieh is efficiently heatlagged. 'I'his filtration re- pound kegs, 200-pound bags, or 325-pound barrels.
moves any precipitate introduced with the sodium hydroxide.
The trisodium phosphate solution must be kept hot through Spray-Congealing
this operation or it will freeze i u the press. A spray-congealed grade is also produced. The clear,
Crystailization filtered solution of trisodium phosphate is adjustcd to a con-
centration approximating NaJ'OI.12ILO, which will congeal
The trisodium phosphate solution is then pumped to a to a solid at room temperature. This liquid trisodium phos-
common feed t,ank, where the temperature is adjusted bo phate is pumped into the top of a spray chamber. A motor-
driven ntouuzer discliargw it and duriiig :I rrec iirll of 70 fei:L Production and Consumption
the liquid particles assiii~ica splierieal form and congeal. r l
Various sizes are pnrduoe:I by variation of temperature and 1b e most recent production figures available are given ill
concentration of the liqirid. The product collected on con- 'l'abk I.
veyor belts is scrcciicd to give a close classification as to size.
This globular form sells without premiuni as a competitiw
grade for the package-goods t.rade.

Physical Properties 1927 63,581 $4,624,695 571


1929 82,046 5.WS.815 61

As with all crystalliiie prodiicts, oiic problem is that of h decline in average value in a pcriud of generally advancing
caking. h i general, coarse crysials arc produced because t h i prices is indicated. The distribution of consumpt,ion in 102
caking tendencies are less. Government specifications requin is shown iii Table 11.
that a t least 50 per cent of the product pass 10 mcsh and Ix
retained on 100 mesh (.5). Table 11-Consumption of Trisodium Phosphate in 1927
Paundr % of T o l d

Iinpxts iu 1926 totaled only 064 tons as compared wit11


exports of 1000 tons, mainly to Canada.
USES
Detergents

A material niay be valuable as a detergent if it possesses


m e or more of the following properties: high pH value, well
buffered in fairly dilute solution; marked lowering of inter-
facial tension against oils and solids; marked emulsifying
power.
The relative pH values of SohItions of Sever231 common
alkaline detergents are giveu in Table 111. It is evident that a
higher pH value may he obtained with a reasonable amount
of trisodium phosphate than with any detergent available
to the public other than sodium hydroxide. The comparative
practical value is not so clearly shown in terms of pH, a
logarithmic function,las in terms of C O X .

Table Ill-Compsrative PH and Con Values of Allisllne Detergents


DBTBRCBNI. 0.038% SOLIITEION 0.66% SOLUTION
Flsure 4-Centrifugal Drier for Trlaadium Phosphate PX COB PH COB
CrYStai* Sodium bydroridr 11.85 0.0071 12.80 0.0784
Trisodium phosphate 10.80 0.0006 11.45 0.0028
Sodium carbonate 10.65 0.0006 11.20 0.W18
The iiitn,duc,tion of ot.liar salts to form double salts wit!) Sodium oleate 10.20 0.0002 10.20 0.0002
trisodium phosphate tends to reduce this caking. At least Modified soda 10.00 0.0001 10.00 o.Uoii1
one nianufacturer's product rontains sodium fluoride for
that purpose. Other double mlts with sodium chlorirlr. As a detergent thc conceutrat,ion used in practice does uot
sodium borate, sodium hypochlorite, etc., have been pro- ordinarily exceed 1 per cent, a common figure being I ounce
duced, a typical one having approximately the fonnultr per gallon of water.
5(Sn81'04,12H20), NaCI ( I ) . As iniglit be predicted, tlic The lowering of interfacial tension against oils or solids
eleetrometric titration curve of this salinc trisodium plios- by trisodium phosphate is not mnrked a$ compared with
phate falls uniformly below that of normal trisodium plios- other detergent alkalies. It is not sufficiently poorer, how-
piiate. ever, to react against its use.
I t is highly desirable th%tthe crystals have sharp, even sur- For the emulsification of oils it has repeatedly been stated
faces. Caking can be predict,eil when crystal surfaces are that trisodium phosphate has remarkable properties. Ex-
rough and uneven. Moisture almrption by trisodium phos- perimental work to be published in detail later has shown that
phate does not start a t room temperature until the relative it approaches in emulsifying power the properties of a colloidal
humidity is 60 to 65 pcr cent. At 100 per cent relative hu- emulsifying agent. No satisfactory explanation of this emul-
midity it is rapid, but in all cases is lower than with anhydrous sifying power is available.
wdium carbonate. Trisodium phosphate has almost entirely displaced borax
Another method of obtaining desirable physical properties as a household detergent and is definitely displacing sodium
has been to spray-congeal the product. This gives a smooth, carbonate for that purpose. It is probably impossible to
globular product with few points of contact, which is corre- estimate the number of manufacturers of hausellold detergent
spondingly free-flowing. An offsetting disadvantage is that products having trisodium phosphate as a base. One large
a lower ratio of surface to mass causes it to dissolve in water manufacturer packs i t without admixture and advertises on a
more slowly than the erystallinr form national scale. Another product sold similarly differs only
4 74 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 23, No. 5
phthalein, to be sure that sufficient trisodiunl phosphate is Other uses include soaking of hides, stripping of color
present to maintain the alkalinity above pH 8.0. from leather, clarification of sugar, and photographic appli-
The use of trisodium phosphate as a boiler compound is cations. It is used to inhibit corrosion of steel (4). It has
closely related to its use as a water softener. Its function been used for control of pH during perborate bleaching (6).
in boiler-water treatment is to precipitate salts which cause When added t o chlorine bleach liquor, it increases its effi-
scale formation. The conditions to be overcome in a boiler ciency as an ink eradicator against an iron tannate ink (2).
are scale formation, corrosion, and foaming. Trisodium Added to loaf cheeses it is an alternate for trisodium citrate,
phosphate will have no effect in preventing foaming or serves as an emulsifying agent, and does not give such a
corrosion, but properly used in a boiler compound will salty taste to the cheese (3).
prevent scale formation. Where this problem is the only The claims for its virtues are so broad and numerous that
one to be met, treatment with trisodium phosphate may be one manufacturer states, “Trisodium phosphate is the uni-
sufficient. versal cleaner.”
Either as a water softener or in boiler compounds trisodium An enterprising advertiser offers a formula for a marvelous
phosphate is effective, but its use is justified only when in- cleaner which will sell itself. The information available on
telligently prescribed. It is no more a wonder worker than payment of five dollars is a list of manufacturers of trisodium
are other materials similarly recommended. phosphate. Perhaps this is the last word in using trisodium
phosphate to “clean up.”
Miscellaneous Uses
As a paint remover, trisodium phosphate is used a t about Literature Cited
1 pound to the gallon, in contrast with the use of 1 ounce per
gallon in cleaning. So applied it softens the paint readily (1) Booth, Gerber, and Logue, U. S. Patent 1,688,112 (1928).
so that it can be removed with a scraper. It does not raise (2) Cappon, U. S. Patent 1,475,932 (1923).
the grain as caustic soda would. A closely related package- (3) Dave1 and Retiel, Science Bull. 68 (1927).
(4) Evans, J . SOC.Chem. I n d . , 46, 347-65T (1927).
goods business is its sale as paint-brush cleaner. (5) Federal Specification Board, Spec. 168.
Another use of large crystals of trisodium phosphate is as (6) Ring, U. S. Patent 1,633,213 (1927).
bath salts, although it is probably used less for this purpose (7) Levine and Buchanan, A m . J . Pub. Hcallh, 18, 1351-8 (1928).
than sodium chloride and sal soda. (8) Levine, Buchanan, and Toulouse, Zowo State ColZ. J . Sci., 2, 19-29
(1927).
Trisodium phosphate is recommended as a cleaner for (9) Levine, Peterson, and Buchanan, IND.ENC.CHBM.,19,1338-40 (1927).
the face and hands and as a shampoo, although the justifica- (10) Parker, Am. J . Pub. Health, 19, 761-7 (1929).
tion for these uses is subject to question. (11) Sprague, Power, 66, 321-2 (1927).

Cheaper Power for the Chemical Industry’


W. S. Johnston2
BOSTON,MASS.

HE chemical industry probably uses as much steam and provided yorld peace obtains. Upon the return of commerce

T electricity per ton of finished product as any industry


in this country. Many of the manufacturing units
are small and widely scattered geographically, but others
and industry to normal volumes, the world consumption of
goods will probably increase in proportion to the growth of
population, with no abnormal ratio of demand to supply,
are very large owing either to their own natural growth or Hence, in general, the price one obtains for one’s product is
the amalgamation of a number of smaller ones. I n any likely to be less in the future than it has been in the past.
case the expense of production reflects the cost of the steam Those manufacturers that were hard-pressed to show a profit
and electric services required. I n the smaller and less modern heretofore will be facing a deficit unless production costs are
establishments the steam necessary for process is generated rigorously pared by using only the most modern facilities
locally in part of the manufacturing plant and the,electricity in their establishments. With this thought in mind there
needed for driving the machinery is purchased from the will be outlined some of the methods used by leading chemical
public utility serving that section. plants to effect savings by changing the method of developing
The costs of both these services are doubtlessly much higher steam and electric services.
than they might be under more favorable circumstances.
The boiler plant which makes the steam is probably of such Efficient Steam and Electric Energy in Chemical Plant
poor efficiency that were it actually known the plant would Ten years or so ago a concern making a well-known and
be immediately and thoroughly renovated and modernized. widely distributed commercial fertilizer built a chemical
Owing to the characteristics of the electric load, the monthly plant along conservative lines, but owing to the success of
power bills are much higher than they should be. All of their particular brand additional plant facilities were re-
which is directly attributable to the fact that the methods peatedly needed. Over two years ago the establishment
of manufacture of the product and the machinery required found itself greatly handicapped in meeting price competition
have been foremost in the mind of the management and have by expensive steam costs to which had to be added the power
received greater attention in the effort to decrease manu- company’s charge for electrical energy. Steam was being
facturing costs to meet the keen competition of rival concerns. generated a t 120 to 130 pounds in a number of small boiler
The United States, if not the entire world, is in the midst units, none of which was modern and efficient or suitable for
of an era of falling commodity prices. The downward trend the increasing demands of the manufacturing departments.
will probably continue for another decade, maybe longer, At this pressure i t was delivered to the autoclaves used for
1 Received January 24. 1931.
digesting the chemical fertilizer and a t lower pressures to
’Mechanical engineer. other manufacturing processes. At the same time electricity