PATENT SPECIFICATION Inventors: FREDERICK FARLOW RUST, LEE MARION PORTER and WILLIAM EUGENE No, 4425/54. Index at acceptance : Class 1(2), A7. VAUGHAN. 751.508 Date of Application and filing Complete Specification Feb. 15, 1954. (Patent of Addition to No, 708,339 dated Nov. 30, 1950). Compete Specification Published June 27, 1956, COMPLETE SPECIFICATION ~ Process for the Production of Hydrogen Peroxide and the Hydrogen Peroxide so Produced We, Naawsooze Vanvoorsaur DE Batadescus Porwovewat MaarscxAarey, of 30, Carel van Byandiaaa. The Hague, ‘The Netheeinds, 4 Company orgeised unde the 5 laws of The Netheslands do hereby declare SR aventiln, fr whith we payne nay be granted t0 Us, ind the method which ie i to be performed, to be partict- Tnely described and by the folowing stte- 10 oi pertains wed s invention pertains to an improved pro- cess forthe prodscton of hydrogen peroxide by oxidation of secondary alecbols im liquid ste with molecular eaygen i ‘Application No, 29383/50 (Serial No. 708339), there is. described a Process for she prodscton of hydrogen pet SiC by un ep dat, ch 8 isopropyl alobl, in guid state by’ weat 20 ment with molecular onpgen-containing sas at elevated temperatures of about 70 10 160" C. preferably beoween 90° C. and 140” C, The Process is carried out by passing a steim of Ecularcrygenconsining gi og mle 25 ct onpgc or aii arog « gun tly of the liquid secondary aleshol at rate Such that che liguidaloool is substanclly saturated with mleclas oxygen at all mes oe seat ny Be ae st unde spe atmospheric pressure f necessary desirable 2 he Tecios eo, wai deay i of Spherical or eter form which i characterised low ratio of surface azea to volume dest sbi 3 oe which Ba. een revue 5 ditoned, eg. by repested use in non-atalyic ae ase or by teatment with a. sabilser for gen peronde. A reaction iat, such ts an orginic peroxide or hydrogen petoxide 40 lle, dearably is added to the. secondary 1 cof at the ue a ator of the ‘necessary reaction, In butchwise operation the process, asthe oration of the secondary Heobal propreses hydrogen peroxide is 45 formed aad accumulates inthe lige reaction tixtze uni the concentration may be as High a: 15% or 20%. ‘The process my be a ~—— operated in a continuous manner, for example, - bby continuously adding the alcohol to the liguid reaction mixture and withdrawing 50 liquid reaction mixture from, the reaction vetsel at rates adjusted to maintain constant volume of reaction mixture and constant con by centration of hydrogen peroxide therein. The ing the reaction mixture containing Peroxide with water and fractionally dist the diluted mixture or by other suita ‘methods. Yields of hydrogen peroxide better than 90% based upon the amount of 60 secondary’ alcohol consumed, are’ readily hycogen penis may be recoeed by dut- 55 ‘The present invention is based upon the observation ‘that under otherwise identical sonditions the reaction can be produced at an 65 increased rate when these are present in solu tion in the secondary alcohol undergoing oxi= dation, which is sometimes used in the form of an alcohol/water azcotropic mixture, (a) @ heavy metal salt soluble therein, the amount 70 ich salt is such that the tofal concentra- by weit ofthe dente aed @) secure by weight of the leohol, a sequestra~ tive stabiliser for hydrogen peroxide in an amount at least equivalent to the total amount 75. of Denny metal present. Expressed otherwise thero is obtained a higher rate of consumption, of molecular i or a higher over-all feacdon rate, without material decease in yield of hydrogen peroxide, The favourable 80 effect of the heavy’ metal is dependent upon the simultaneous presence of the sequestrative hhydrogen_ peroxide stabiliser. Thus, the pre- sence of heavy metal alone, even in the stall amounts contemplated according to the inven 85 tion, is inimical to the formation of hydrogen peroxide, an observation which appears to be in full accord with the well-known fact that fom of many ety metals ae extremely active catalysts for decomposition of hydrogen 90 peroxide. ‘The addition of a sequestrative hhydrogen peroxide stabiliser to inhibit’ the deleterious effect of heavy metal ions has already been described in our copending2 : 751,508 Application No, . 35725/53 (Serial No. 731,238). In cases where the alcohol contains heavy ‘metal impurities, the amount of heavy metal 5 added in accordance with the present inven- ‘on will have to be adjusted so that the result- fog total hesvy metal content of the alcohol does not exceed 0.001%" by weight. The total concentration of heavy metal in the secondary 40 aleobol undergoing ‘axdston should prefer ably not exoced 000015% by weight. As itl as 0.000039 by weight of cobalt (added jin the form of a soluble salt) employed in as cect ih esate sie fr rogen peroxide, such as orthophosphoric acic Bas Born observed to have @ proneunced. effect upon the desired reaction. Amounts of chromium as low as 0.000001 94) by weight of the secondary alcohol have been observed to 20 noticeably increase the cate of production of Jpdogea pode when pete! with sodium pyrophosphate or with orthophosphoric acid, ‘The minimum practical concentration of ‘heavy ‘metal difers somewhat between the 25 different heavy metals and thus cannot be stated in terms of a precise generally applic- is «abl fig, Te may be snd tht cnet: tions of heavy metal greater than 1% 10-"% by weight generally are used according to the 30 present invention, “The Reavy metal ordinarily i added to the seaction mixture as by direct addition to the “nize undergoing oxidation or to the liguid eed, in the form of «soluble salt or more ean 235 veniently a dfute solution of the soluble set. Mluswative salts of heavy metal that can be <, employed include, among others, inorganic salts such as chlorides or other halides, sulphates, nitrates or carbonates, and organic salts such 40 a3 carboxylic acid salt, eg. acetates, propion- ates, butyrates, laurates, nephthenates or ben- ies, butyates,laurates, naphthenates or ben + zoates, and chelate salts, or chelate complexes ‘with dicarbonyl compounds, eg. with beta- ddikctones, such, as acetylacetonate, isovalery- 45 lacetonates or ‘butyrylacetonates. Since the ‘only requirement is thatthe salt be sufcient Soluble to provide an. voludon he small amount of heavy metal defined hereinabove it vwill be apparent that other salts of heavy 50 metalg containing a wide variety of anionic radicals can be used. It also will be noted that ‘the salt may be formed im sity os by reaction beeen he eae mc el or oxide o& wydroxide, and the acid corsesponding to 5 desied anionic radical ‘As the heavy metal there may be employed, broadly speaking, any metal of the lass gener” ally knowa and referred to as the heavy metals. ‘The base heavy metals of Groups V, VI, VII 6 an VI ofthe Pvc Table the Berens ie included within the scope of the present < nention: Although cobalt. is a. prefered theavy metal because ofthe high reaction rates and yields of hydrogen peroxide that may be ‘65 obtained therewith in accordance with the pre- ‘sent invention, iron, chromium, manganese, nickel and vanadium are also included among the heavy metals that have been found to be satisfactory for the joses of the present: invention.” ical compounds which 70 say be employed for introduction of the heavy meal foto the reaction mixture include, among others, cobelt acetate, naphthenate, ovalerybacetonate, butyrate; iron” chlor -acetonylacetonate, valerate; nickel nitrate, pro- 75 jonate, sulphate; manganese accfate, lactate, sedan’ A segs bevy rol oa piaiy of cant A singe heavy metal or «platy heavy metals may be employed. Sequestrative. stabiliser for hydrogen 80 peroude if employed in an amount suficent to combine with, sequester, or unite with the - heavy metal which is present in solution, Tt thus is empl in an amount at least equal fb and preeeeby greater tan the amount tht 85 {8 sihiomettally equivalent to te heary ‘metal in solution. Since the presence of an Gross of de stbiber does no harm and fe Geniy is geen benccal, en exten stoichiometric basis, of the stabiliser desirably 90 Bp provided. ‘The sublicer can be employed tian up 10 003%, by weight of te tear Mn mine or efeh me hough & pe ferred general maximum is about 001% by weight. 95 ‘the purposes of. the present invention organic stabilisers are consic to be less eevee than norgense ables because Se gy og ns oe cess the argnie compotnds ae prone 19 100 ‘destoyed, whereas the inorgaaie com pounds are resistant to such destruction. ‘Shitable inorganic stabilisers that can be used in i Ecce ot eae ‘fall into {mo general Houpe ‘ba Seat group compete 108 salts, eg. alkali meal selts of the oxy acids of fin aninony, lon and aluminas andthe Ibydrous anides of these elements, eg. sodium stannate, sodium aluminate, ium silic sodium ineu-samate, alphemetestannc ac, 110 Srtcweaptiay oy ey pecan isi adie anata ma Phe second group cone Pune Ge eapacels of phogohen wat cay thereof, particularly the dlkalt metal salts, and 115 incdes"for exugple'onbopheephrte "ac, pyrophosphocie acid, sodium pyrophosphate, Eioltum orhophospate, aiden, hone. Bogen atorinpiay sacs ddan 1ophosphate, potassium dihydrogen 10> 120 ‘howphate and’sodium hexametphephates Jn the preferred method of carrying out the process of te preset invention the Scondary Alcohol, eg. isopropyl alcohol, secondary buty! ‘cohol, @ secondary amyl alcohol, oF other 125 Secondary alcohol wherein the Bydroxyl group {5 the only funcional group, i charged to 8 cemefully cleaned ancl ‘conditioned pressure resistant reaction vessel constructed ‘of of at feast lined with gess, aluminium, tn, stainless 130steel or other corrosion resistant material, eg. resin, The vessel is equipped with an inlet for introduction of gas below the surface of the ap comer, a ult fo gts which 5S preferably leads through a condenser for con- densing and returning to the vessel. any entrained or voatlised. portion of the liquid mixture, and the customary thermometer, ancillary pieces of apparatus such a5 a pres- Jo sure gauge, bestng ad cooling means. Ifthe process is” to be effected ina continuous ‘manner, the necessary inlet and outlet for charging the alcohol feed and withdrawing reaction mixture are, of course, provided. The 15 charge to the reactor is made up to the desired concentration of soluble heavy, metal com ‘and stabiliser, for example, an amount Of a dilute solution of cobalt isovalerylaceton- ate in the alcohol equivalent to about 20 0,00000% ‘by weight of cobalt and about 0.00359" by weight of HPO, based on the total change may” be added.‘ In continuous s, wherein additional alcohol is 10 be to the reactor, it will be apparent that 25 the feed may contain pr dissolved therein the requisite amounts of heavy metal compound and stabiliser. The system is brought to the reaction temperature and pres- sure, temperatures of about 70° C. to about 30 160° G. preferably 90°C, to 140°C. and SES tp To 1000 pounds er square inch Si oe Ea, bai by rane Cis ow is ait, ‘reason of its tot aid beonse when tng a explosive 35 compositions liable to be encounted when ‘oxygen (90—100%5) is used, can more readil bbe avoided. A » such as an eg. 22-{tertiary-butyl-peroxy) utane, or hydrogen peroxide may be, added 40 to the reaction mixture as initiator for, the desired reaction, The peroxide may be added i a ons fom, shoe OO0S% thug 3%, or more by weight. A vigorous stream ugetrcontaining as; eg a Jo passed under pressure into sh the liquid alcohol ‘whereby the sloohol js agitated and i saturated with molecular oxygen at the operating perature and pressure and is s0. maintained uring the oure ofthe run | During the 50 period that the flow of oxygen-containing gxs E continued hydrogen peroxide is formed and ‘accumulates in the mixture until the concen tration may be 20%. anit lowing inl of the mayo whieh 55 the process present invention may carried into effect further illustrate the present invention and the comparative dats given show the advantages of the process of the present invention. Exanpue 1 Each of the experiments was certied out by charging to carefully cleaned and condi- tioned glass vessel 300 parts by weight of dis- tiled isopropyi alcohol containing added (65 cobalt isovalerylacetonate in varying amounts 751,508 & and 0.00359’ by weight added H,PO,. Gescous oxygen under 25 stmospieres pret Sure wes cetlated in a. vigorous ‘team through the liquid alcohol at 166° C., thence through a water-cooled condenser arranged for 20 return of condensate 0 the resction ves, and then via a pump back to the reaction vessel. During the run oxygen was added to ‘the system from a calibrated reservoir as required to maintain the pressure constant. 25 ‘The course of the reaction was followed by teasuring. the volume of oxygen. consumed durin; oe FP yd the Ca a fun te yield of hydrogen peroxide was detet- mined by analysis of ‘fe reaction mixture. ‘From ‘L of the accompanying draw- ings, it will be seen that the rate of absorp- tion of oxygen increases substantially with F obalt concentration. up 10. about 0.000125 cobalt and then rapidly decreases 85 as the concentration of cobalt is further loeesed As is sea from gue 2 of the accompanying dravings, ydrogen peroxide apilly decreased ap the cobalt con Eentration vas ineressed above - about 90 S.C he ie foes reaction tine en. peroxide, ee a ‘concentration of about 0.00009% to be opti- fun in ths series of experiments 95 ‘For Purposes of comparison, a run was car- ied out in the presence of 0.0001% by weight ‘of cobalt added as cobalt isovalerylacetonate but with no added stabiliser, the other condi- tons being the same. No formation of hydso- 100 gen peroxide was observed during the reaction ‘time of 24 hours. Exaweze IL To a carefully cleaned glass reactor which a bun coined by pir we the dason of peop al 1 to produce hyo: seca tes ai neous opropyl ca weight of water) aud ebout 10% by weight of HO, (90% solution) as initiator, A vigorous stream’ 110 Gf gascous oxygen under § atmorpetes Dres- suse was pasol through the mixture at 125° Cifor 6 Hours, vapour from the reactor being passed through 2 glass water-cooled condenset Fer condensation and return to. the reactor. 115 ‘After 6 hours operation the run was di tinued and the amounts of hydrogen peroxide td acetone produced. were, determined ‘A second sun was caried out under iden tical conditions except that 0.003%, by weight 120 Of etophonpse ad ata he propyl alcool prior to the commencement of the run, "A third run was the same as the frst un except that 0.00019 by. weight of iron (as 125 ferie sulphate) was added to the inital mice ture, ‘A fourth run was the same as the third run except that 0.0003% by weight of orhopos- 105& S1SdB- phoric acid also was added to the initial mix- ‘ture, ‘The results shown in the following table ‘were observed in the four runs. EG, peta — weight per cent, | based upon total | weight of reaction Amount of additive mixture 5 Fe | HPO, none mone 48. none | 0.008% 59 0.001% | none 34 0.001% | 0.0003% a1 1t will be seen from the table that, while the presence of but 0.0001% of iron alone led {9 aad dere i th yd ond none yzogen peroxide prodated, te addition 10 of both .0001% of ton and” 0.0003% of cr (0.0003 5 ‘none 0.000001 | 0.0003 % What we claim bs col A porns oan ok ‘process ction ogen peroxide by the oxidation with oxygen of secondary alcohols in the liguid phase at a ‘temperature of about 70 to 160° C, described and claimed in the Specification “of Patent ication numbered 29383/50 (Serial No. 339) which consists in adding to the alco- hhot"undergoing oxidation (a) a heavy metal salt soluble therein, the amount of which salt is such that the total concentration of heavy 45 metal does not exceed 0.001% by weight of the alcohol, and (b) a sequestrative hydrogen peroxide sttbiliser in an amount at least equi valent to the total amount of heavy metal ‘resent. 50 | 2. A process claimed in claim 1, in which the gnonnt of elles dow ‘not ezoted 0.059% by weight of the alcohol 3. process as cained ja cli 1 or 2, in which the heavy metal is added in the form 55 of an inorganic salt, a carboxylic acid salt, a chelate compound of a dilute solution thereof. 4, A process as claimed in any one of claims 1 to 3, in which the heavy metal is a metal of the’ groups V, VI, VI and VIIL of the 60 Periodic Table of the lements. '. A process as claimed in claim 4, in which the heavy metal js cobalt, iron, nickel, man 4” ‘Amount of additive HPO, led to a substantial (greater than 40%) inate inthe smounto¢ Gpdropen pecs Getincaa i ain wile om dt Sop experiments. Tt seen that despite sence of he on og vii ot 6 ce ‘was obisiged in the run Cini the prsnee of book the ‘eon tnd the BPO, thaa inthe ran conducted with neither iron nor H,PO, and thatthe yieid was | Substantally as igh athe yield observed in 20 the run employing only the HPO, Exampue I. “The experiments described in this example, ‘which illustrate the effects of chromium, were Carried out in the same manner as the experi 25 ments described in Example IL In two of the experiments, sodium pyrophosphate deca- hhydrate was substituted for’ the orthophos- photic acid. The results shown in the follow ing table were observed, ‘The chromium was 30 added in the form of chromium acetate HO prodiced weight per-cent, based upon total weight of reaction mixture ‘mixture thereof, process as claimed in claim 5, in which the lcavy metal salt is cobalt isovalerylaceron- 65 ate, ferric sulphate ot chromium acetate. “7. A process as claimed in any onc of the pctediog chin, in which the seuesoaive hydrogen peroxide stabiliser is an acid react- ing inorganic compound. '8 A process as claimed in any one of claims 1. to 6, in which the stabiliser is an oxy-acid of phosphorus or tin or an alkali metal sale of such an oxy-acid. 9.°A, process as claimed in any one of claims 75 1 to 6, in which the stabiliser is orthophos- ‘Photic’acid or sodium pyrophosphate. 10. A process as claimed in any one of the claims 1 to 8, in which the secondary alcohol to be oxidised is isopropyl alcohol. IL. A process for the. production of hydro- gen peroxide as claimed in claim 1 substanti- ally a5 hereinbefore described with reference tothe examples gen, 12, Hydrogen peroxide whenever produced 85 by the procen claed in any one ofthe pre ceding claims, sec ROWNES, for the Applicants, St. Helen’s Court, ‘Great St. Helen’s, ‘London, E.C.3. 7 80 Leamington Spa: Printed for Her Majesty’s Stationery Omce, by the Courler Press 1056. Published at the Patent Office, 25, Southampton Buildings, London, W.C.2, from which ‘copies may be obtained, aew 751,508 COMPLETE SPECIFICATION USHEET This droning ts 0 reproduction of the Original ono reduced scole. ® ii TOTAL NUMBER OF LITERS OF OXYGEN CBNSOMES St 1 HOURS REACTION TIME: 3 0.5086 3001 S01 COBALT CONCENTRATION , Ze Fis. 100 F G0 3 2 | ° Bo | 7H co 33 a4 38 — 3 8 4 OPP by 2 94 23 Fe YS 5 oseaer oo 501 COBALT CONCENTRATION Tow Fie. 2