Glyoxal Operating Equipment at (:arbitle and Carbon (b., Soiith t;liarlestoii, W. \-a. Tall column i * reactor: qucmcher is on ground floor at right and r o n v e r t e r on upper bel: drum-loading huilcling in Iiackgruund
,J. F. BOHMFALK, J R . rlssoriute Editor
H . W. \ I C \ ~ ~ \ I E EO D K. P. BARR'I i n collaboration u i t ti
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Carbide a n d Curbori Cheniiculs Co., Division of I niori Carbide und Carbon Corp.. Sotith Charleston, Ip. I ( 1 .
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drvelopiiig a chenlical for a conteniplated ni:irlict or ikvelopirig a market for a special chemical. These proccdurw ;in' coniplementary :znd neither iieeds to predoniinatc. Product devc~lopmentis the logical extension of thr, research la~)or:itor'y. :mil by reverse reasoning, surcessful applicatiori of prixluct tlt~vrlopnit~nt guarantew niore efficient and fruitful ri irch. R-ith thi, diwovery of a rieiv chemical or with apprwiatioii of :I neeti for a chemical, a proper balance and close coordinatiori bctnccn chemical research and market resc~arch niwt I w inaiiitained froni the very beginning of the market dc~vc~1opnic.iit pingram ( 6 ) . History of Glyoxal
Conhider the story of glyoxal----the first di:ildrliytIc~ t ii l i i b produced and sold on a commercial scale. It is tlir s i n i p l i ~ ~ t tlialdehyde, but its chemistry has fascinated research I\ orliw. siricr its discovery. Although the chemistrv of its s p t h is rrlntively simplr, the skill of rrsearch chemists arid prni 786
r~rigiiic*c'r.s tind thr too ol'tc'ri u n r t ~ i g ~ i i z cgcjiiius ~ t l of the productiriii 1ii:iii wt'ri, wll required t o make this cht~niicalcommercially avail:il)lc. In :t lei\- short years it hap gro\vii from a research photographic c.heniic;tl selling for 830.00 pt'r pound to a full-fledgrd indust r i d rau- material? u d ~ d i n approximately 50 differen1 US('S. F'roin the bonding of cork s h t ~ tto the mothproofing 0 1 i,:iiyi,ts. froin the manufwcturr~of disposable diapers to t h r enil d n i i n g ot' cadavers (5---literdly from the cradle to the gravv. g1yi)x:il h:~r found its ~vwyinto ninny products which are integral parts of o u r daily lifcx. Thc nati,r-r&atant match we carry iii o u r poc!,r.t and the washable \vallpaper or1 our living room w I * o havia p r o h b l y been treat,ed with glyoxal. C;Iyox;il \vas originally syntherized by Debus ( 4 ) in 1856 it1111 ~ ~ c ~ i i i a i i i:I r dcuriosity on the laboratory shelf fo: almost 80 years t1ieri~:iftc~r. Ththn, i n 1036, tn-o chemists, R. W. RIcNamee :m . i r i :i \vide variety of applications including I III. ni:iniifacture of gaskets, wateri i i x i c l i t , ? , iv:tshable wallpapers, and cor a i i ( l sheczting. In nearly all cases the (!e.;iretl i(..iiIt can he ncconiplished hy mixing the prot t 3 i i i and glyoxal, applying the mixture, drying, : I I I I ~Iwat curing i t if necessary. The degree of ill-~iluhilizationobtained varies n-ith the conditions C I i~ , w c t i o i i , In general, the inore glyoxal used ; I I I I I the lunger the heat cure or the higlirr thc’ c,iii,ing tc,iiiperature, the more complete the ini i 1 1 ~ iilizat 1 ion. For protein insoluhilizstion, i n gt,iit,riiI,flnni 1 t o 37, b y weight of contained gl! o ~ a lizised l on the protein solids is customary. Iri gvnrral, t,his type of application may be ii)Ilii\vrd through for all protein glues which req i i i n , :ihnoriiially high water resistance. For ex:t!iiplr, \\-ashable wallpapers are prepared by -1itxying a glyoxal formulation on a printed n.al1 ~ i ; i l ) t 1~hic11 ~r has been aftercoated with a protein. Special type. o t ]xiper such as blueprint paper are sized with glue, then t,reattvl \vir I1 glyoxal t o permit usage under high humidity conditions. lisiit CXUPC~~
Insolubilization of Polyhydroxy Materials iii~olubilizationof polyhydroxy materials, such as starch, iujlyvinyl alcohol, and partially hydrolyzed polyvinyl acetate, i. LL cross-linking reaction similar t o the insolubilization of protvins. In this case, however. glyoxal reacts vr-it,h the hydroxyl groulis of the material being insolubilized t o form acetals or hemiscetals. The two materials are mixed, applied, and then subjccrrcl to a heat cure t o drive off the nat,er of reaction. In :ilitlition to those mentioned above, several typical materials t h t c a n be insolubilized b y reaction with glyoxal are viscose or ciipraninionium spun rayon, partial polyvinyl butyral resim, :ind Cellosize hydroxyethylcellulosc. Shrinkproofing rayon provides one of the major markets f o r g l > ~ ~ s a lInsolubilization . of the rayon fibers is accomplislictl padding a solution of glyoxal, about 4% by n-eight, on tlw clr!tli i r i the presrnce of acidic catalysts, after which the clotli i.3 tlricd and cured. Fabrics treated in this way shrink less th:tti “C after forty launderinge, yet the cloth does not beconit, Ijiisrtiy and stiff. I n addition, the treatment gives minimuni cliliirinc retention, a n improvement in dye fastness, and masii i i u i i i re4atance t o shrinkage. . h i important use for glyoxal results from its ability t o reart I Iit11 st:irch arid related substances, such as dextrin, to make them 1v:ttt’r resistant,. For example, in the manufacture of envelopes. ‘e dext.rin adhesives are used for the closures, three problems - thickening of the dextrin solution on standing, curling 13f tlics paper coated with adhesive, and self-sealing of the finishcd c.lo-urtx under conditions of high humidity. The addition of :ipprosirnately 3% by vieight of commercial glyoxal based on thtl .nlitls content of the dextrin solution overcomes these problenis r ( i n considerable extent. The dextrin solution viscosity remain.-tu1 )le on storage, the humidity resistance of the plasticized glue i l high r3iiough t o prevent self-sealing even a t 90% relativt. liuniidity. and sufficient plasticizer can be used to prcvent curling , I i rhr p:cper. Other applications in which glyoxal-modified starch adhesivc; :ii’t, u ~ t d iiiclude: the manufacture of paper boxes, such as soap pmvder boxes, which are liable t o become !vet during use; sealing cienrette papers; and affixing tax stamps or other labels t o cont:iiners that may be subjected t o high moisture conditions. ‘lli(,
Glyoxal Tank Farm ( ; l j ~ s : t l is also used to modify starch in coatiiig paperboard, Pigmented starch coat,ings can be made insoluble by a siiiipltt glyoxal treatment t,hat yields a good water-rl?sist,antfinish which will perniit offset printing. Glyosal is an insolubilizing agent for partially hydroly7.i~tl polyvinyl rtcetates and partial polyvinyl butyral resins. Fivtd per cent of commercial glyoxal based on the dry w i g h t of the polyvinyl acetate or of the butyral resins is added in iiorrnal commercial processes. Textile sizes prepared from polyvinyl acetate or polyvinyl alcohol can be made more water resistant, under coiiditions of high humidity and elevated temL)eratures by the incorporation of 1 t o 2’7’ glyoxal in the sizing mixture. .I cross-linked thermoplastic resin having escellent resistance t o xater ailti organic solvents is produced from the butyral resins. Sheets milled from this resin can be used for wrapping niatrrials. insulating tape, rainco:it niaterials, and for 1aniin:iting gl p l y ~ o o t l or , nietals.
Cfieniistry of Glyoxal Process
Glyoxnl is manufactured commercially I,- the oxidation of ethylene glycol in the presence of a copper oxide catalyst,. The reactions occurring in the catalytic zone are coiitrolletl by thc qunntit,y and type of inhibitor added and :ire inHur,ncfvl by t h e nature of the reaction tuhe.
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INDUSTRIAL AND ENGINEERING CHEMISTRY
79 1
S S LINE TOCONVERTER R E 1FNl LHIBITOR L TANK7
TEMPERATURE CONTROLLER
I 7 1
Ne H E . E _ R
3 O j S T E A M HEADE!
GAGE G L A S S
7
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PRESSURE GAGE
PRESSURE REGULATOR
Inhibitor System
INDUSTRIAL AND ENGINEERING CHEMISTRY
792
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TABLE IV. IKSTRLME\T ('OXTROI i Sanie
Tyue IiistrinnPiir
Iristrirrrien tation
East Panel ( R e a c t i o n ' r .
Flow controller Flow controllri
Ilei.order, inlet a i r H o v
Flow controller
Recordel,
Floir controller
irJt.r
Vol. 43, No. 4
glycol
HOW
Indicator. Don tlicrii floir
K r c o r d w . converter inlet pressure
Flax controller Pressiire coniro1lt.r
R e i order, inhibitor How
H ~ c o r d n r inhiliitnr . perafurc
tr~n-
Hrcorder. o y y g p n
aria-
ai1 !]ne Slotor v a i r e i n inlet glycol feed l i n p .\larm for lo\\ S)uivt h e r m flonSoiinds Iiifh preesuw alsrni and s h u t s off inlet air a n ? g!ycol 1Ioror i - a l x e i n inlet nirrogcan line t o inhitiitor tank ('onrrols teiiil~eratrirc of inhibitor tank by control oi stenin t o
1 hr. glyoxal titiit is operated on a continuou:: 1 c.~~iiditiori.~ i n nort~iitloperaticin are relatively con 111I . Tlit~iii.truineritation or' thc plyosal unit i3 highi!. c~~iitr:rIix~~~l iii t h c control room. IVith the exception of the ~~1ge.q OII ill[. i~tliylenr~ glycol i r e d tktiiks and glyoxal make and storage ?:iiik.-, n h i r h nre located a t thr base of each tank, and the quc,nch :iiiil reactor liquid flo\vnictrr.s 1ocatt.d on the ground lt.vr.1 o i i 111 c~quipmi~nt, 1 be air-actuated controls are situated on the ( ' a c t ri'action pnnc.1 :ultl i v w t rrcoverj- panel in the control rooin. AIsI, lorated in thc. end of thr: control room between t,he II:IIW xlariii panc.1 \vhic,h iiitli~atesin(lividua1 equipnwiit f:r ?vent of : i t 1 crnt'rgc'licy. J l i i t e r i u l s i f Constructiorz
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Indivarnr. c o n r e r t e r inlet preseure I n d i c a t o r , converter o u t I P t pressure Rrt,oriier, Domtiierm cirrilla t ing t e m p e r a t u r e
In t l A i , ilt,sigii of t l w glyoxal unit thew :ire t h r t ~ .- i t t i x t i i i i i Iiich rcyuirc t h t : u i c ( i f staiiikss stwl 01' oth1.r ~ [ J l T i : i l :1l10) .-. ('IN. glyictil vapor R t elevated temperatriri~.i t 1 thi. l i r t ' > ' g ~ i ih:~sa tt~ti~1ixiicy t u discompose t o l " i ~ r n ~ : i I ( I C Y $ :icc~cl(~i,atrii b y tlic presence of iron iil \the is n i i n i n i i z e r ~by T).p' 3-17 staiitltw steel. ThfJrefortA.t l i c tiient on t h e cwnvi,rtczr irilet is construct,ed of Type 347 st:~iiili,..c steel for ii .*hiJrt diitanw prwcding the ethylem: gl?.i~)li*i11iy t u the rollvi!rler &J that no iron is carried into t1ii.- JJ:II'I of t ) i i . 5ystem from t.he primding steel equipment, glass-vm11 t l':lpd art' i l l s t a h d on the c y c k HIJW line rind ill the inlet air h a : :xiid c c J t t l U i packed screen filters arc installed on the inlet glycol l i i i i s to the I: I valves, andequipment betn.cv*ritllt,-i.gl il the c'onverter inlet are constructid Secondly, glyoxal in the varar phase i n t h t . converter has a inarked tendency to decoinposc to i ~ ~ ~ i n : i l ~ l r ~ h ~ i i ( : . This deconiposition is ertrenir in the presence of iroii; i t I S It,:. i n the presence of s t a i n l e s s steel; and it is least i i i r l l c . pi'c'.~etic~c~ of Hastelby alloy R. Therefore, the converkr tu1ic.x :iiiiI tfic. m i d e of the heads mid tubr .sheets of the convertrhr i n i*otit:tct \\-ith glyoxal are constructed of t>hisspecial alloy. I3iac-ausi. gl>.1 1 ~ i$ 1 very reactive i i l thr vapor phase in the prear~n('c~ ( ~ i "o x > y i ~ i i xiid h a s a tendency tlJ form a horny polymer in the p ~ ~ ~ ~ Ie I i ~i ~ t ; minute quantities of liquid ivatcr, the converter outlist g:i,.f quenched as quickly :is possible i n the liquid qut!tir,lir~r. the line froiii the coli outlet to the quencht.r isfactory for this wvicc.. Type 347 stainless strc.1 Thirdly, Type 347 rt s stcel iir required in tlir q u t ~ i i r l ~ t ~ r c.yi.1~bccwu~cthe glyiirnl solution contains 0.2 t o O.riYc fortiiii. :icitl, \vhic,h ia very cui.rosive to ordinary steel. Tiit. i,iitii.i. ~ ~ u i ~ ~ atid ~ e h reactor er cycle, consisting of quenclwr. I ~ I , : I ( ~ ~ O I . unips, cooler, valves, and piping, is (wristruvit- I inlc'si; nt~:rl. .llso, the glyoxal make and $tcJr:igi, icous litrw, arid valves are construrteil of t l i i s for t,lieb sanie reason. Ginc :iciti iiw carrird into the f IWI. iliinute :tnd a Ili;ctiargt~ I)wisiire oi 7.5 pounds pi qu:irr i i i i . 1 1 I\
.;lire Contruls t-:rwIafing Dowtherni temperat u r e by operating motor Lalve on Don.thPrrn inlet Yapur OT mutor v a i r e on w a t e r t o Dawt her t i t cooler 1ritlicart.s i.riat!iros ill:t
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