RECENT DEVELOPMENTS IN THE PHOSPHATE FIELD ,
Several of the more recent developments in the phosphate industry are bridy reviewed. Defluorinated phosphate rock as a phosphatic fertilizer, tricalcium phosphate as a water-treating agent for the removal of dis30lved fluorine, alkali metal meta- and polyphosphates as calcium sequestering agents, tetrasodium pyrophosphate as a soap powder ingredient, and several of the orpmic phosphorus compounds are among the developments reviewed. Coated anhydrous monocalcium phosphate as a baking acid and salts of alkyl polyphosphates 8s wetting agents and methods for their manufacture are reported. Phosphorated oils, fodder preservation, rust-pro&g of steels, flotation of ores, fortifioation of cereals with respect to iron, calcium metaphosphate, and the catalytic u s e of phosphoric acid and its compounds, me mentioned as phosphate developmente.
R many the word “phosphate” P principally sssociated with the suhject of fertiliaers. Later it b k on added yema
was
significance in the field of dete-cy and as an ingredient in food produck. More IBcently ita siepificance hss extended and @ being further extended as time pwes over the broad 6eld of ahemical progress. The era of chemical progre~sin the field of phasphatm and phosphorus-contsining compounds has been promoted thrwgh the renearoh dorta of both the phosphate manuf a c t m and other chemical manufacturers. The phosphate manufacturers have improved their pto such an extent that it is now possible to prcduce commercially a large number of highly purifies phosphorwcontaining compounds which may be emplcyed aa such or as reagenta in the prepsrstion of other p d u c k . Without a t t e m p h to cover the entire M d of phoephorus h h n o l o ~a, few of the more r m n t developmenta have been seleded for consideration here.
De9uorinated F’hosphate Rock (17) That the inmluble and unavailable cadition of the PO, in phosphate rook is due to the presence of fluorine is fairly
HWRY W. EASTERWOOD Victor Chemical W&,
Cbkaga Heights. IU.
well eetabliahed. Genarslly, phosphate rook is comprised largely of a fluorapatite having the formula 3C@,.CaFI. Other principal compamta of phosphate rook include silica, iron,and aluminum phosp-. The fsrwirer a d a b H t y of the PO6 in phosphate rock is substantially dependent on m e pro ing up the apatite com-. Of breakThe principal mema employed hy the fertdimr fnduehy is to treat the rook with an acid suah as d u r i c 4ptwphmig. This treatment converta the cslcium phaspaSte to the soluble monocaloium phosphate constituent of the annmer4 phosphate fertilkmknown as superphosphate and triple aupeaphoephate. It is Bignificant nteut of phcephate rock that in these -the msae a# gasmua comis largely elirmnated from pounds. In the past nix to even years a conaiderable amount of work bas been done by Jacob and mworkera in the United S b h Department of Agriculture and by Curtis,C o p n , and others in the TVA on methods of directly m o v i n g the flu+
”$”
-
INDUSTRIAL A N D ENGINEERING CHEMISTRY
14
rine from phosphate mck. Jamb and cc-workem have demon&rated that the fluorine can be aubatantislly wm&t.ely removed by calcining phosphate rook in the p m c e of silica and water vapor at about 1400' C. They found that the fluorine wan removed in two stagea. The first half of the fluorine was relatively easily removed but dd not greatly atiect the citrate availability of the P,Or. However, when the calcioation was carried further and the second atom of fluorine evolved, the
&DA
Asa
W E mim
MANUPA-
PHOSPHATES IS STORED IN A
or & D ~ U SILO
apatite structure waa broken down and t h ~Prol beaame oitrate nvailahle. The citrate solubilitJr appesls to inin~pmportiontothepsrtoftheseoondhalfofthefluorine eliminated from the apatite compound. Jacob f d the citratea.rraikbiltytobeashighas@6parcentwhemthefluorind wi+g s u b t i a l l y c o m p l e t d y m d from the rock. The iwwtigation hy the 'lVA waa undertaken on a laga scsle in an &ort to develop a practical furnacemethod of uLl$ug aut the proc&. They found that when ordinary phosp8ste~wihuttheadditionofexcessilicawanfd kiln at about M)-170° C. higher than the fusion p c e of water vapdr, thq fluoriue oould be The f d phosphate produced contained lecur thsn low cant of ita original fluorine, and over W p e r cant of ita P A content wan rendered citrate available. workem have contributed much to the development of t h e m ,but thelimited mpe of the present paper doer not permit a detailed review of their work. of Fluorine from Water ( I )
amas. S m i t h r e p 1931. Since then a number of investigators have worW on
V d 34, No. 1
the prublem of removing or redunng the fluorine content of fluorineannt9ining waters to a d e limit. Generally it is believedthat the fluorine must be reducedto less than 1 p. p. m. to render the water harmless. Of the several methods proposed for removing the fluorine, the one which &em great& promise appesra to be the use of tricalcium phosphate. The fluorine-containing water is w e d through a bed of granular tricalcium phosphate, usually of the hydroxy type. The fluorine is adsorbed or taken up by chemical reaction with the tricalcium phosphate and gives an efauent water which may be controll4 so as to contain less tban 1 p. p. m. of fluorine. The chief d i 5 d t y with the p r o m waa the fact that the tricalcium phosphate would take up only a limited amount of fluorine hefore becoming eaturated. To overcome this defeat, Adler developed a regeneration proces for re moving the fluorine from the spent tricalcium phosphate. This regeneration was accomplished by washing the fluorine saturated tricalcium phosphate with a dilute solution of caw tic soda to dwolve out the fluoride. The excw caustic soda remaining in the adsorbent waa then neutralized with a small amount of dilute acid. In this way the original tricalcium phosphate could be r e d many times with only a d loae due to partial solutiin by the acid in 4 regeneration. Behrmsn improved on the regeneration by the we of carbonic acid to neutraliza the excaustic, and thereby greatly inm a d the number of poasible regenerations and made the p r o m more economical. The tricalcium phosphate employed in the process is made by neutdizing a dilute solution of phosphoric acid with a weak slurry of milk of lime to a pH of approximately7.0. The precipitated product is a hydroxy type of tricalcium p h w phate having the composition 3CdO4.Ca(OH),. Smith developed a suitable bone phosphate for the p u r p a ~ by boiling bone in dilute caustic soda, neutralizing the excaustic, calcining the product, and retreating it with a dilute acid. Smith olaima the resulting product is &cient as a fluorine hating agent. Elvove of the National h t i t u t e of Health waa among the early inveatigators and waa probably the first to suggest the UII)of tricalcium phosphate for removing fluorine from water.
.Alkali Metal Mew- and Polyphoaphatea In the laat d e d e a great amount of researoh and commemid development hss taken plsce in the broad field of manufadue and we of the me& and polyphoephates. PasaiMy the principal development in this lield wan the application of soluble alkali metal metaphosphatea for water softening and other purposes. The J3aU Labratorha, ha., wan a pioneer in thin development, particularly in the we of the slksli metal hexametsphosphates for water softening purpoea. Their rraearch men have bean mccasaful in d e doping many new industrial applications involving the UII) of the hexametaphosphatea. The basic principle involved in most of them is that the hexametaphosphatecombineswith a lage number of metal ions, such as the aLkaline earth met&,to form complex compoundsin which the calcium or other sllcsline earth metals me held in solution probably in a complex anion structure. Hall (93) Buggested that the resulting dcium containing compound might have the formula N&(Ca,P&) which in aqueous solution ionize8 to sodium oations and the complex anion group CaS&. At any rate the faot remains that in aqueous solutiom containing calcium theaddition of nodium hexametaphosphate d l sequester and hold the calcium in solution in the presence of moh strong dcium-precipitating agents as the fatty acid soap. Sodim hexametaphosphate is produced by fusing monoscdiwn orthophosphate at appry5mately 700" C. and quickIy cooling the fused maw. Thia in acoomplished by pouring the
JM-8
1942
INDUSTRIAL A N D ENGINEBRING C H E M I S T R Y
M m r m on a water+mled m e a plate to form BlsasJr plates of the proauot having h thiohbm of about '/, inoh, or the molten m a t e d may be p o d batwtm rapidly d v i n g owled &to produce thin hkea only a few t h o d t b e of aninahthiolc Bothmeansaraused~wmmmdy ,butthe thin fteLes ara p ? f d where r8ady solllbiity of the metaphosphate is dpsired The qui& cooling of the prcduet is enscmtiel for the prcduotion of the soluble hexa-polpwised
.
metephosphate.
A wahinwluble sodium metapbphate may be prcduced by dehydrstieg the monomdium dophosphate at about aKu00' c. Thil type of mebes been uaed Mmmeauidyfor W d yeersaa a dentifriceby one of the large
tootb paste manufactunmr.
BytbedebydratonofsuitaMemi.turrsofmrnwand disodium orthophospbatm, a Spaj, d oompa&ioma called 'Lpolyphosphstcs" may be psodaosa. Tbe principal polyphospbatf.mrpltioned in the tsohnidd and patent Literatwe m y be daigmted by the follonipof o r m h : Nd& tripolrphosphate) N d . 0 . cmdi~m )etThere hss been oonsidfpsble aontmvpoay on the quedtim of whether theee polphQphates BJB true &.mid oompounde ormselymirtureeofmets-andpyrophonphateu.A d e t d d ab& of thin quesoion wan made by wrtridge, fi&, and Wtb (so). The only definite c l r y & d h polgphmphate theminveetigshwere able to psoduoem thesodiumtripdyphphate. other inveatigatiom on this Subjeat we5e made by H u h and by Andress and W W (8.9). To produce the s o d i p tripolyphosphate a definitetermpershue oontml is neoeesary. When mono- and disodium pbmphata in correct proportions or equivalent mixtuw of other phosphates are heated for a ~ u b s t s n t time i batweem 800' and Woo C. and slowly cooled, the produat will praotioally dl be in the form of the tripolyphosphate. If, however, the mixture is fused and rapidly cooled, the product will be autb atentially a mixture of meta- and pyrophosphates. This mixture may be c o n W to the tripolyphosphateby rebeating and t e m m at a tsmpesstureabove 300" C.but below the fusion point The ehemiad properties of the alkali metel tripolyphoophata would appear to place them amnewhere between pym and metsphoephate, having less d c i u m and mom magnesium represing d u e than the metaphoophate, and mom adeium and less maimeaium I W D I W E ~value than the DVT+
18
and tend to cling to fabrics being washed in such solutions. With the intrcduotion of a m5cient amount of tetraaalium pyrophosphste, d of the magmsium hsrdneEs and l ~ r m aof the oalcium willbe 6w.por bound in mob manner that no swp willbe required to eliminate themagneejum and part of the adcium ions. The dcium soap which forma is in such B dispersed condition that it will not deposit on the fibein of the oloth being washed.
[email protected] indicates that the xmwgwim is bound aa sodium pym phosphate (NarMgPtor). Janotp and Hull show that with respeot to magnesium1 pound of t e m m pym phosphate will release appximatdy 2.2 pounds of soap for detergent purposes, and that when used in n o d hard waters 20 to 30 per cent of the soap can be saved by the inclusion of 10 to 15 per cent of the pyrophosphate in the soap compoaition. Unlike trisodium phmphate, the tetrasodium pyrophog phate is not mf&iently slkalineto aot as an e0icient detergent when usad done. However, when used with soap it is dective 88 a water softener. nperimental evidence +own that a mixture of 0.0336 gram of soap and 0.0085 gram of t e b d u m pyrophosphatehas a WataFeOftening capacity quilent to a mixture of 0.0443 gram of soap and 0.0112 gram of trisodium phmphate, when employed with water coutsining 100p.p.m.ofoalciumand50p.p.m.ofmagmsiumhardness. The princtipd reason for this mpriority is the fact that the pyrophosphate prevemte the formation of insduble magneaium soap.
1
meta- and plyphosphatm may b;! had by glancing over m e of the patents on the mbjeot (6, sa).
Tetrasodium F'ymphoaphate Tetwcdium pymphmphate (a is an old oompound and the methods for ita manufaoture ara well known, but only recently hae ita value to the soap manufaotw bean raoognired. In the last threa to foUrye8x-B praotioally all of the h g a produma of soap powdera have inoluded an appmkble a m m t of anhydrous t e t r d u m pyrophosphate in their sopp powder compoaitione. The m n for this phenomenal inin the we of tehmdium pyropwhate is evident whenoneconeideratheadvante.gesit ~ e s i n c ~ ~ n w i the weof soap in hard waters. R a c t i d y all hard w a h ~tainbotharrlciumand~um6ardnesswiththemagd u m repmmting about one tbird of the total hsrdners. W h a soap is used with mob waters, the precipitation of insoluble admum and magnesium map u ~ e eup large amounta of the soap More any md@ or detergent actionis paasible. Furthemore, the h l u b l e soap in thie cwe ara aurdlike
0th applications of d u m pyrophosphate inelude its we 88 a stabilieing agent in hydrogen pmxide solutions, as a disperasng agent for cold water e t a and well drilling muds, in the degumming of raw silk, in dye bathe, eto. Coated Adydrow Monocalcium Phospbte t h A recently developed autogenously coated orgstall'me anhydrouo monoadcium phosphate hae attained a high plaae aa a bsldng acid in the selt-rising flourindwky and as a constituent of baking powders. Tbisspeoial typeofanhydrousmonoasloiumphonphate,dedoped by S d h g e and ~ Knox (q)is ,made by reactinglime with a strong phosphorio mid containing minor amounts of
16
INDUSTRIAL A N D ENGINEERING CHEMISTRY
certain metal cornpounds at a su5ciently high temperature to prevent the formation of any substantial amount of hydrated monocalcium phosphate, and at a temperature low enough to prevent the formation gf any appreciable amount of pyrophosphate. Generally 140-175' C. is employed. The reaction is carried out in a batch mixer equipped with an e5cient agitator. The resulting product is a dry powder cons i s t i i of minute crystals of anhydrous monocalcium phosphate. These minute crystals are then subjected to a temperature of approximately200-220° C. Under this heat treab ment the potassium and several other elements appear to combine with the calcium phosphate d a c e of the crystals to form an autogenous, glasslike, s u b s t a n t i y water-insoluble c o a t i over the crystals. The exact composition of this glassy c o a t i hss not been determined, but it doea have a great effect on the stability and reaction characteristics of the anhydrous monocalcium phosphate particles. As a baking acid or acid constituent of baking powder, this new phosphate depends on its ability to resist decompdtion in moist atmospheres and on its delayed aa well aa slow reaction with 'sodium bicarbonate in dough mixtures. The glaasy c o a t i i protects the anhydrous phosphate from the action of atmosphericmoisture. In wet dough mixtures it permits only a slow penetration of water into the interior of the particle and thereby delaya its reaction with the soda present. As an example of this action, the followingtable shows a direct comparison between the actions of this special anhydrous phosphate and the o r d i i hydrated monocalcium phosphate which for many years had been the principal commercial phosphate baking acid. The table shows the amount of carbon dioxide liberated during different time intervals from a mixture of the baking acid and e d u m bicarbonate in water at 27" C., the amount of sodium bicarbonate present being theoretidy sn5cient to liberate 200 cc. of carbon dioxide on completion of the reaction:
1
BAQQINQ TETU~DIUM h?PHOSPHATE
compounds have already reached a high state of commercial development while others show much promise. It is i m p sible to predict at present what will be the fate of many of the compounds produced in the resesrch laboratories. The types and variations of phosphorus containing organic compounds which are theoretidy possible are unlimited. A few of the general typea include the phosphates, phosphites (5, S), phosphosphorue I), phines (1O), thiophosphorus compounds (.% nitrogen compounds phosphonates, phosphonium compounds, poly- and metaphosphates, phospbinic compounds, etc. The linkage between the phosphorus and carbon of the organic portion of the molecule may be of the following general typea:
(n,
The data show that with ordinary m o n d c i u m phosphate the d o n with sods is about Bo per oent complete within 1 minute, whereas with the special mated anhydrous phosphate the reaction is lea than 10 par cent complete in 2 minutes and not over 50 per.cent complete in 6 minutes. When translated to pis~uitmakingpractice, this information means that the h u i t dough can be mixed, rolled, and cut, and the biscuita placed in the oven before any appreciable loss of the leavening gas takes place. Experimental biscuit bakes under uniform conditions except for the type of baking acid show that the volume of tbe biscuits made with the special anhydrous phosphate is approximately one third grester than when the ordinary monocalcium phosphate is employed. It is not possible within the brief scope of this paper to give a detailed discussion of the research involved in the develop ment of this special anhydrous phosphate. Organic Phosphorus Compounds
A tremendous amount of research hsa been done in conneotion with the organic phosphorus oompounds and their wea. bversl h u n M p h t a have bean taken out in the p a t few years, and one might ssfely my that millions of dobra have been spent on suah -ch. Some of the organic phosphom
CtoP CtoOtoP C to N to P CtoStoP
Phosphines, phosphonium, phosphbic, and phosphonic compound8 &tela
Phosphine amides Thioestera
The phosphorus may be tri- or pentavalent. The bonds may be single, double, or even triple in mme cases. Only a few of the simpler compounds will be considered here. The aryl phosphates, such aa triphenyl and tricregyl, have a well established place as plasticizers in the plastic and lacquer industries; however, new mea are constantly being p r o m , and more complex aryl group than phenyl or cresyl are being added to the list. Martin (P7)proposes the use of neutral phcaphates of polyhydric phenols for inhibiting d amount of an rancidity in fatty oils. Ries ( S f ) adds a akylated triaryl phosphate such aa tri-(plauryl phenyl) phosphate to lubrioatii oil to improve the extreme pressure characteristics of the oil. Bass (6)proposes tri-(ptsrtoOtyl phenyl) phosphate aa a phticimr for ethylcellulose. B p e r (11) u ~ 8 8an aryl phosphate, such ae phenyl biphenyl phosphate, in a hair d r e composition. Webb (58) wea trichlorophenyl phosphate to render dulw acetate non-
J.nw,1942
INDUSTRIAL A N D ENGINEERING CHEMISTRY
&smmsble. Choker (IS)oosta &-6lter fiberswith the visaouS triareeyl phosphate to caw adherence of the dust particlea from the air. Capri0 (IS)rendan wood termibpmf by immothpregnating it with an aryl phosphate. Mills (a) p d wool ~ fabrim with monophenyl di-(o-xenyl) phosphate. Many more citations could he given, but the above will sufficeto give a general idea of the broadnem of the M d of application. The general methd of preparing most of the aryl mtera in by repoting phaephom oxychloride with a phenol or subtituted phenol under mch conditionethat the hydmgen chloride formed in the reaction will he eliminsted. The alkyl phosphates represent another important group of ogsnio phosphates. They may be prepared in a number of types. These compounds are diew a p and rue of cussad by Hochwdt, Lum, Malowan, and Dyer (page 20); however, mention is made here of alkyl polyphoaphates since the pmduotion of these setera m m t a one of the newer develop menta of ow own laboratories. The slkali metal or ammonium aalt of capryl acid tripolyphwphate is a typical wmpound of thii type. It is produced by reactingan appropriate ammt of eapryl alcohol w i t h P& nnder anhydcow conditions, and neutmhing the acid eater with &aaeous ammonia or a ntrong solution of caustio soda. The product is a waxlike solid of light color. It is soluble in water and is an excellent wetting agent. Our testa have shown it to have a wetting-out capmity equivalent to a sinking time of 12 eexnds at 0.2 per oent concentration when testad in accordance with the havea method; the latter cmnprieea the detmhation of the t i required for a 5.O-gram &in of two-ply, unboiled, cotton yarn to sink when weighted with a 1-. sinker and submerged in the wetting agent solution by an anchor. Ita surfnee-temion-reduciog property is marked. The surfem tension of a 0.06 per cent solution in distilled water was found to he 24.5 d y n s per cm.compared to 71.6 dynes for distilled water. Them propertiee will vary with the length of the carbon chain in the a h 1muo. The mteoa may be em&& 68 wett i or emdeifying agenta or in combinstion with alkalins detergent compositions. They have some calcium-ion repression power, though not comparabh to the well-hown d u m hegmetaphosphateinthisrespeot. They rue also suitable 88 fiberdtening agenta and may have some appliwtion as plaatioisere in certain types of resins and aaaddition agenta in lubricating oils. Organic phaephom compounds in which the phosphom atom is in itr t r i d e n t form have bean widely invwtigated as antioxidank or cormeion inhibitom, largelyby the petroleum industry. The litarature in thin field of d e d o p m n t is oonfiaed to patent publications for the most part. The principsl pmducta are the phosphites and thiophosphites. Thes =Y he alkyl (81, aryl (3). ormkedmtern,andtprincipd nea is in lubdcating oils where d amonnta appear to inhibit the cormsion e&% of the oils on met.& and to etabilim the oils againet deteriorationduetothe&dation of eertain oil mmponenta.
.
-
11
No general procedure can be given for the preparation of the various phosphite compounds,but for illustration the following p d u r e for tributyl phosphite may be considered typical: 444 parte of +butanol and 140 parts of metallic d u m are agitated together in an inert liquid hydrocarbon medium until the d u m and butanol rue completely reacted and the d u m butylate formed is diapened 88 a hely divided Buspension in the liquid hydrocarbon medium. This suspension is cooled to below 26' C., and 275 parts of phosp h o m triohloride rue ~Iowlyadded while the agitation is continued and the d i o n temperature is kept below 25" C. After the reactionis completed, the d u m chloride formed in the reaction is waehed out with ice water, and the tributyl phosphite is separated from the hydrocarbon medium by dietilling off the hydrocarbon. The phosphite ster in then purified by fmtional distillation. Yields of above 80 per cent are obtained by thin procem. Without attempting to specify whioh of the t r i d e n t phonphom organic compoundsam most Suitable 88 additive agentu for improving lubricating oils, a partiauy elasaified list in given of the compounds mentioned in the more recent paten@ on this Subjed. It does not include the phosphata esters, many of which are also used with lubricating oils, p a r t i d d y for their BBect on the extreme preeaure charachktias of the oils. The lint inaludm alkyl phosphites (8), phosphites (S), organic phosphine compounds (IO), orgamc phoephorusthiophosphites I), and organic phos nitrogen compounds (& phorus-sullur compounds (0, t r i d e n t phosphom compounds (gened) (1.0, and miscellaneous organic oompwnds (12). M i s d m e o u a Developments
Phosphorated oils (e), such 88 phosphorated castor oil, are finding uw as plssticisers and SOfteniDg agents in Borne typa of rmin pmducta. They rue also d u l in the fat liquoring of leather.
INDUSTRIAL A N D ENGINEERING CHEMISTRY
18
28.72 (1940): Cohbs. H-, and E& 011 d Soap. 1 7 , 4 3 1 (1940): Janota and Hull. IM..17.95100 (1940); MBUer&g, CIk-Ztg., 82. 228 (1938); Vsllaoce. Smp. 15. No. 10. 2 1 4 , 109. 111. I13 (1938); Apthe. C. A.. and B h , R. (to J. R. Qfiw),2,012,462 (Aug. 27, 1936); Boom, J. E. (to du Pont Co.). 2.186.086 (Jan. 9. 1940): Bmk. E. T.. Freelsnd. J. W.. and Lswton. H: C. (to 8hdl Devilowant Co.). 2.211,888 (Aug. 13. 1940): Colomus. H.. and Wolden. F. (to Henkd & Cie.). 2.121.952 (June 28. 1938); h y f w H. and Baden. W. (to CelSnaSe Corn.). 1.926.087 ( s o t . 12. 1958): D d . C. E. (to M o m t o & o m i d a,), 2,687,817 (Nor.2. lO%7); Fddenheier. Wm.. 1,43S.W3 (Dee. 12. 1922). 1,847,212 (March 1.1932); hay.Alben (to EoEmen-Ls Roohe C W oal Works). ~ ~1.381.286 .~~ ~. . (June . 14. 1921): Gilbert. H. N.. .nd &chert. J. 8. (to du Pont c0.j.2,004.808 (J& 11. 1 ~ ) : Hall, R. E. (to aaU Lsh.). 1,985,338 (July 3. 1934); Janob, J. (ta Viotor Chemioal Works). 2,041,473 ( M w 1% 1936); Kline. E.. and Bsrhor. H. (to DuPont Rumn Ca.). 2.012.232 &&.'20. 1936); L i d . Ot& (to Honkel-& Cie.), 2,141,189 @w. 27. 1W); Murphy. 1,196,116 (Muoh 10. 1931); Neupebsuer, W. (to W e & Co.). 2.081.676 (May 26, 1831); Reaton. w..d d. Ita Pmota & Qsmble Co.). 2.083.9374
The application of phosphoric acid for the preemvation of green fodder is well known, but in recent years several new methods of applying the acid have been developed (IS). Ferria buma p h o s p h pentasulfide candles in the silo, the heavy produde bf combustion settling down into the fodder. Benglein employs phosphorus pentachloride and water, the PCL and water being mixed aa it is applied to the gre8n fodder. gerschbsum and Dyhdal employJime-wated, molecularly dehydmtd pbmphoric acids in pellet form. Some of the organic.sulfnr-cont&ing compounds such 88 the &yl or aryl thiophospbatea are considered to be excellent flotation agents for ore separation (4). M u m ferric pppbosphatea are now being used to fortify 00w and other cered pmductg whioh are deficient in iron. Tbeee cornpounds may be used with fat-conhining oereal produde without promoting the development of rancidity. A soluble sodium copper polyphasphate baa recently besn developed ea a spray composition for the control of plant PES@
(88).
In the past few years the TVA baa developed a process for
making calcium metaphospbate (16) by burning phosphorus
in the presence of heated phosphate rook or Iimwtone. The n d u c t is considered to be an excellent concentrated Dbw r---phatic fertiliser. An aldehydephosphorus amide reaction product (83 in now finding commercial w as a corrosion inhibitor for p h w the aoid to be shipped in steel conphoric acid; it @tg
~
k&.
Literature Cited
W.. and Quttwherg. F. H. von und
N
(to Henkd &
Cie.). 2.164.146 (Juoe27. 1989): Wdmm.J. A. (u,Monannta Cbsmiaal Ca3.2.087M (Julv 20. ~.1937). (3) A&hurn, H. V.. C o w , R. E., and Stut&an. P.,S. (to Teura C0.l. 2.226.543 (Doc. 31,1940); CarmU, T.8. (toMonaanto Chemid Ca.).~2.200.712 (May 14. 1940); Conso'. R. E., d d. (to Teiaa Co.). 2,226,662 (Dan. 21. 1940). 2,241.243-4' lMav R 19411: M o m . R. C.. d d. I t 0 Bamnv-Vacuum Oil
.~ ~-
..-- -.
a,) z. .m.a& tootyzo. 1986). a . 1 g 3 . 8 ~coot. ~ 18. 1938).
2.161.300 (Mamh 21. 1938): Moyle. C. L. (taDoa Chemiad 13. 2.220.113 ). and 2,210,846 (Nov. 6,1940): Mluher. 8. (ta M m h m Foundation\. 2.223.941 (De& 3. 1940): PoE.
tainers.
A considerable amount of phosphoric acid is consumed in the rust-prooling of steel and in the preparation of the metal surface for painting. One of the later developmentg in this tield is the uas of a mixtnre of phosphoric acid and sodium dichromate (as). Another development includes the w of wetting agentg with phosphoric acid (E@. Darsey coats the metal with an a d phosphate and an oxide to improve the paint-holding quality of the metai (18). Phosphono acid, silicophosphatea, and vadoue metal d t g of the acids of phasphorus have found extsnsive c o m m e r d UBB as oatalystg within the past ten yeam. outstanding in thia 6eld ia the Univexsal Oil Pmducte Companys develop m a t of a cataly&ic prooeas for the polymerisation of v u e olefins to produce liquid hydwrarbma of the gasoline tm. Another important development is in the oatalytic hydration of oertain hydmcsrbone to produce ald&. Ethyl alcohO4 for example,is d e by the IQdmtion of ethylene in the pres qnca of a phosphate catdpt. A n u m h of other oatalyth p r m employing varion~oompounds of phasphom have been and are still being developed. For example, a recent patent (Sf)propmen the USB of triethyl pbasphate in the EW p @ e to oatalyze the dehydration of glycol^ and o W c alcohols to pmduca diol& such as butadiene. The onhion of any dkmsion on the manufacture of p h w phom, phosphorus acids, and phospborukoontaining intermediatee, much as chlorides, oxychloride, and oxides, ia not inbded to mean that little p r m baa been made in this lnnnch of the industry. Dimmion of this p b might well be the subject of a separate paper.
Vd, 34, No. 1
4, 1940): BaLbsr& P. L. (to du P a t Co.). 2.121.611 (June 21. l958), 2,178,610 (Nov. 7. 1989); Shaemsker. B. H.. and bane, C. M. (to Stsndsrd Oil Co. Ind.). 2,19l.B98 m'ah. 27.1940): Pa&. A. J. van. and M-. F. R (to S h d D&do&nont &3. 2,167,873 ( M w 9. 1939). (&e
(4Bsr&y, 0..snd Heuser. R. V.
(u,American
Cyanamid Co.).
1,888,943 (Den.6, 1932): Chriatmsan. L. J.. d d.. IM, 1.997.280 (April& IW).2.028.166 (JM.28. 1936), 2.W.192 (June 2.1936): Ddaon. 0.E..and Et&, A. C. (to8tand-
kdOilCo.C~l.).2.a28.863(Jan.14.1941)~Derby.I.H...nd cunainghsm. 0. D. (to P. C. BAUY). 2.lM.706 (Nov. 1. 1938): JD. W. (to Amohan Cysnamid Co.). 2.206,IJU~"a. 1840): ~ a c ~ l e M. e . w.. a,om.sis (NOV.17. 1940): Romiau, C. J.. and Wohnsidelsr. H. P. (to A m e r i w cpnsmid Co.). 1,748,619 Web. 26.1830); Whitworth, F. T.. 2aBILMO IA~ril21. 1936).
(s) (6)
Hall L&). 2,182,046 (Dea. 6, 1939); Bomemann. F.. and Bubsl. H.. 2,174,614 (Oot. 3. 1939): Breach. A. M. (to H.u Lab.). 2.a28.158 IJM. 7. ~.19411: BWM. C. 8. (ta Rumlord cbermioal works). a,oss.asi (&t. iz. im); Bwt, R. E. (to 8tandsrd Oil Co. Ohio), 2,063,788 (Don. 8, 1936); BY&. H. T..Frselsnd. J. W.. and Lawton. H. C. (to 8hdl Develop m a t C0.L 2.211.6SS (Aun. 13. ~~.19401: Drsiabsah. F. (to Chem. Fab. J. A. Benakiser). I,897~89~'(Feb. 14. 1833). A d (to E d Lab.). 2.081.617 (Msy 26. 1837). 2.146344 (Jan. 31. 1989). 2,289,284(April 22.1941): DUM, T.H. (to Btaoolind Oil and Qsa Co.). 2,233,813-4 (Mareh 1. 1941); Durgin. C. Q. I t o Monsaota Chemical (3.). 2.087.617 (Nos. 2. 1937); EL&, C.. and 8aanqr. M. W. (to ElLa Lab.). 2.223.316 (Nos. 28, 1940); Fddenheimar, Wm. (laall to W. W. Plowman). I cu1.W (Dee. 18221: M a . A. E ..d d. (to Rumford ,-... 12. ~~, ~~. ,~~ Chamid Works).2.019.6tX-6 (Nov. 5,1936). 2,036,603(Den. 24, 1936). 2.031827 (Fob. 26. 1936). 2,033,913 (Maroh 17. 1936). 2,069,670 (Nos. 3. 1936). 1,067,828 (JM. 12. 1937). 2.078.071 (Aoril 20. 1037). 2.082.913 (SSDt. 14. 1937): Ole6
.~~~~ ~
..~,.
~~
~~
~
~~~~~
~
otherwise Mkd, d rederenoes are to united
F., lod Fi& E. (to Honk01 & Cie.). 2.oR1.27a ( M w 26. 1987); Huhbsrd, F. E.. and McCullon~h,C. (to Morusllta C h s m i o d C0.l. 2.244.168 (J8. 1941): Jon-. E. K. Ita
Jaauarg. 1942
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
P d a n t Co.), 2,010,142 (Oot. 29. 1886); Libbey, A. G.. 2,076,663 (Mamh 30,1937): h d . Otto (to Hankel & Cie.), a.ir1i.m (DW.27. 1938): ~yona,8. c. ( ~ i r dMaahine 2.180.743 (Nov. 21. 1939): Msnaul. P. L.. 2.216.2M (Oot. 1.
Pout Co.). 2,121,811 (June
e.).(18)
1(1901
ai.
1938). 2.178.610 (Nov. 1.
(14)
1940): MG. A. (to h w Gorp.). 2.172.ai6 itbpt. 6. 1939); Miner. C. 0.. 1,837.2ao (Dw. 22, 1931): Mormn. L. C.. 2.128.16C~l ( A u . 23. 1988): Parbidre.. E. P. (to Hall -~ ~. ~Lab.), 2,W.,431 (Nov.-O, 1937);'bkann, A., Ibid., 2.241,868 (May 13, 1841); Rosenstein. L. (to Shell D w l w m e n t Co.). 2,038,316 (April 21, 1936). Reissue 20,764 (June 7, 198% 2.163.0BB (June 20,1839): Sobwsrt.. C. (to H d l Lab.). 2.084.387 (Deo. 16,1888). 2,136.054 (Nov. 1.1988). 2.181.208 (Feb. 20. 1940). 2,216,137 (8ept. 17, 1940); Si&, F. (to (16) I. G. Farbenindustrie), 2,184,846 (Oct. 26. 1838): Bmitb, Q. W. (to Hell Lab.). 2,024,543 (Dec. 17. 1836). 2.108.783 (Feb. 16. 1038). 2.164.082 (June 27.1938): Soem. V. E.. and ~~~~
.~~
(16)
L3n: White. C. E., and Parent, P.-A.;
1,861 (July IS, 1936). 2.041.k I
(MG18.
BG-F.A. (to 8heu Development ~0.). a . i g ' ~ , w(~pril16, 1940); &k. E. W. (to Tide Water hoisted Oil Co.), 2,231,167 (Feb. 11.1841): h m , W. L. (to Booow-Vsouum Oil Co.). 2,188,648 (Feb. 6, 1940): M o m . A. J.;and Zimmer. J. C. (to Standard Oil Development Co.). 2.236.161 (Marob 18, 1841); 8alrbre.P.L. (toduPontCo.).2,121.811 (June 21. 1938). 2,178,810 (Nov. 7. 19.30); Whittier, W. A,, William& N. D., and Moir, H.L. (to Pure Oil Co.). 2,211.3MI (Am. 13.1940). 1940): M o r a R. F..sod h a c i k . A.P. (to Sow&-+souu& Oil Co.). 2,161,300 (Marob 21, 1939): Musher. 8. (to M d w Foundation). 2,223,041 (Deo. 3. 1940): Bhoemaker. B. H.. d d. (to Standard Oil Co. Ind.), z,w.a70 (June 15, loan. 2.191.888 (Feb. 27.1940): Pwki. A. J. and M-, F. R. (to Well Development Co.) 2,167.873 (May9. 1938): Wdnrioh. W. W.(to Gulf Rwesrch and Development Co.). 2.101,632 (Den. 7. 1937): WorLman. A. R. (to Citie %mice Oil (21)
Bh
(22)
(Nov. 26. 1926): Caolsn. 8.. 2.
<&.E. K. (to du Pout Co.), 2,230,371 (Feb. 4, 1841): But& J. G. (to A h t i e Refining Co.), 2,149,271 (Msroh 7. 1939): Jolly. 8. E., and Pemne, J. H. (to Bun Oil COJ. 2,190.716 Web. 20. 1940): Peski. A. J. van, and M e w . J. A. VBD (to Shell Development Cod, 2,lM).349 (Mareh 14, 1889); Workman. A. R. (to Citiss Bervioe Oil Co.). 2.232.421
.___. -..__.,. Bryna. F. (to Dow Chemied Co.). 1.862.231 (April 5.1932): IPah 1R lQAdl\ ~
Chubell, T.L.. and Petew'J. 0. (to Gulf Oil Cow.).2,167,479 (May9. 1839): Conarv. R. E.. Asbburn. A. V.. and S t u t c
(23) (24)
(26) (26)
(27) Martin. 0. D. (to M o m t o Cbemiaal Co.), 2,247,280 (June 24,
1841). (28) M ~ g e l e H.. , and H u h , H.. 2,208,129 (July 23,1940). (20) Milla, L. E.,and Allen. W. A. (toDow Chemical CO.). 2.128.189 (Aw. 23, 1938). (24)Partridge, Hi&, and Smitb. J . A m C h . Sm.. 63, 464-a (1941). (31) Ria,H. E. (to Sinclair Re-p CO.), 2,237,632 (April 8,1841). (32) Webb, W. R.. and Clarke, H. T. (to Eastman &dak Co.). 1.884.433 (Oct. 26. 1832). (38)Woadatook, W. H. (to ViDtor Chsmiasl Works). 1,940,383 (Dw. 19, 1933).
