PROCESS FOR PRODUCING ETHYLENE GLYCOL

Abstract: Ethylene glycol is prepared by reacting methanol, for­ maldehyde and from greater than 6 to 25 weight percent of an organic peroxide in the presence of 0.5 to 35 weight percent of water based on the feed composition, the amount of water within said range being correlated with the peroxide content. The organic peroxide has the formula R-O-O-R¹ wherein R and R¹ are each an alkyl or aralkyl group having 3 to 12 carbon atoms.

Description: PROCESS FOR PRODUCING ETHYLENE GLYCOL This invention relates to a process for. producing ethylene glycol' from methanol. Dwindling petroleum. reserves and increasing prices have placed an increased emphasis on the use of. synthesis gas in place of oil as a starting material for producing various chemicals, such as methanol, formaldehyde and ethyl ene glycol. The advantage-of synthesis gas is that it can be produced from raw materials other than petroleum, such as natural gas or coal, and potentially from oil shale and tar sands. An example of an industrial process for the production of ethylene glycol utilising synthesis gas as a starting material is the reaction of.for'maldehy'de with carbon monoxide and water at high pressures (over 300 atmospheres) in the presence of an acid catalyst to produce hydroxyacetic (glycolic) acid, which is then reacted with methanol 'to 'give the methyl ester; the latter is then converted to the glycol by cetalytic hydrogen ation. See ü.S. Patents 2,316,'564 of Cockerill; 2,153,064 of Larson and 2,152,852; 2,385,448 and 2,331,'094 of Loder. Another proposed process utilising synthesis gas for the production of ethylene glycol 'i-s the reaction of methanol and carbon monoxide using a rhodium-catal-ysed, high pressure pro ce.ss; see U.S. Patents 4,115,428 of Vidal at al, and 4,115,433 of Cosby et al. With respect to the type of process for the production of ethylene glycol 'disclo'sed and claimed herein, it should be noted that the oxidative dimersation or dehydrodimerisation of a large variety of organic compounds by peroxides is very old art that was pioneered by the pre-eminent free radical theoret- ician M.S.Kharasdi and his students. These studies became the fou'ndations of much subsequent fre'e radical chemistry. Kharasch et -al in JACS 65, 15 (1943) sho'w' the dehydrodimerisation of acetic acid to succinic acid with -acetyl peroxide in a 50 mole percent utilisation selectivity based on acetyl peroxide, utilisation selectivi.ty being defined as the moles of dehydrodimer product. made div-i.ded by the moles of peroxide converted. Isobutyric acid produced tetramethylsuccinic acid in a 42.4' mole' perc'ent utilisation selctivity. Kharash et al in J. Org. Chem. 10, 386 (1945) .show the -ester methyl :chldroacetate being dimerised to dimethyldichloro succinate by acetyl- peroxide in a 41 percent utilisation selectivi-ty.- Kharash et al in J. Org. Chem. 10, 401 (1945) show the dimerisation of cumene and ethylbenzene wi-th acetyl 'peroxide in 61.9 mole percent and 32.1 mole' percent -respectively to their dehydrodimers. Wiles et -al in -1, E : & & C, August 1949, page 1682, tell of the efficacy of di-t-butyl peroxide and 2,2bis(t-butylperoxy) butane -for the -dimerisation of cumene to 1,1,2,2-tetramethyl ' 1,2-diphenylethane. The -benzoate ester of benzyl alcohol was dimerised to the dibenzoate ester of the corresponding glycol, 1,2-diphenylene ethylene glycol, with di-t-butyl peroxide by Rust et al, JACS 70, 3258 (1948). The literature contains many other example's showing production of dehydrodimers at very low concentrations at utilisation selctivities of generally from 20-50 mole percent, based on the peroxide con-sumed. Such selectivi-ties are generally too low for a pro-cess to be considered for commercial development. In connecti-on with' ethylene glycol, two-'tea-chings involvi-ng peroxide-i-nduced reactions should be menti-oned. The first -is found in Schwetlick et al, Angew. Chem. 72, No 21, 779 - 780 (1960), and involves he'ating a mixture of di-tertiary-butyl peroxide and methanol in a molar ratio of 1:20 in an autoclave and/or under reflu'x for a period of 10 hour's at 140 C. A 26 percent -yield of ethyle'ne glycol is reported, and it is stated that- an increase in the alcohol exce.ss raises the yields. The second and more important of such other reactioin paths to ethyle'ne glycol', in. terms of its relevance ta the present invention, is described by Oyama in J. Org. Chem. 30, 2429-2432 (July 1965). In particular, Oyama shows the re-action' -of 9 mol'e's of methanol, 1.8 moles of 15 percent aqueou's formaldehyde and 0.45 moles of t-butyl 'peroxide (di-tertiary-butyl peroxide) at -14-00C. for 12 hou.rs to give 0.21 moles of ethylene glycol (see Table I at the top of the right-hand column on page 2430) and states immediately below Table .I: "The yield of ethylene glycol in the reaction of formaldehyde with 'methanol is higher than that of butyl peroxide induced dimerization of methanol. This fact suggests that hydroxymethyl radical :(D) adds to formaldehyde". Oyama describes in greater detail flow this reaction was run and the products obtained, and .contrasts it with the dehydrodimerisation of methanol in the presence of t-butyl 'peroxide -and the absence of for'maldehyde, i-n the "Experimental" section beginning at page 2431 (particularly the secti-ons headed "Reaction' of Methanol 'with Formaldehyde" and Dimerization of Methanol" on page 2432). The' yields of ethylene glycol 'obtained by Oyama are fairly low. Oyama's only run with methanol (that involving the above-described reaction of methanol, aqueous formaldehyde and butyl peroxide at 1400C. for 12 hours) gave only 1.86 weight' p ercent o f ethylene glycol. Th'e -above-described reaction can be -ma'de -to produce higher yields of ethylene glycol by substantially decreasing the amount of organic peroxide employed, -relative to the amounts of formaldehyde and metha'nol present, from that employed by Oyama. Moreover, increasing the'-amount of methanol and decreasing the amount of water, relative to the other components of the reaction mixture, in contrast to the amou'nts employed by Oyama, -also 'appear to contribute to the production of higher yields of ethylene glycol.. Thus, for--example, heating a mixture -of 78.5 weight per'cent of metnanol, 1.5 weight percent of di-tertiary-butyl per- oxide, 6.9 weight percent of formaldehyde and 13.1 weight percent of water at -1550C. for 2 hours gave a yield of 4.5 weight percent of ethylene glycol in the product mixture. Th'is is equivalent to a yield of about '7.1 'moles of ethylene glycol per 'mole of di-tertiary-butyl 'peroxide' emplo'y'ed. (Oyama obtained 0.466 mole of ethylene glycol per mole of di-tertiary-butyl peroxide in- his reaction).. This improvement in which the amount of peroxide employed is up to 6% by weight 'of the reaction mixture, is new. It is descri-bed in a pen-ding Patent application, U.S. 'Serial No. 183,537. filed September 2, 1980. It is pos.sible' to produce ethylene glycol' from methanol 'and an organic peroxide, alo'ne or' in the presence .of formaldehyde and water reacted in the presence of a basic material :in an amount sufficient to reduce the' hydrogen ions that are being formed in the reaction without unduly' reducing ethylene glycol production du.e to by-product form- ation. The basic material in the reaction reduces the acids, such as formic acid, formed in the reaction which cataly'se the formation of methylal from metha'nol and formaldehyde. Weeping the' -for'm'ati-on' of methyla'l to minimum is highly desirable in or'der to avoid unduly la'rge or expensive distillation re'qui-rements necessary for' the' purification of the ethylene glycol product. This procedure is new. It is described in a pending U.S. Patent appli'cation¯, U.S-. Serial - No. 286,721, filed July 28, 1981.' In accordance with the present invention, ethylene glycol is produced by reacting methanol, an organic peroxide (as defined below) in an amount -greater than 6 up to 25 weight percent, formaldehyde, and water in an amount from 0.5 to 35 weight percent, these amounts being based on the total weight -of these fou'r 'reactants in the reaction mixture; the amount of water used is dependent on the' amount of peroxide used in accordance with Table A below. The amount of ethylene glycol produced by thi's proc'ess is larger than that 'produced by the process described in the Oyama reference di'scussed earlier which employs 40.5% methanol, 7.55% formaldehyde, 9.18% di-te-rtiary-butyl peroxide and 42.77% water based on the weight -of the reaction mixture. It has been discovered in this invention that if the water content of the reaction is 'redu'ced in accordance with Table A, substantial 'improv'emente in amounts of ethylene glycol to di-tertiary-butyl peroxide (mole ratio basis) are achieved over that of the Oyama preference. using peroxide amounts greater than 6 up -to 25 percent. In addition to the ethylene glycol improvement, hi'gher amou'nts of tertiary-butyl alcohol to di-tertiary butyl peroxide (mole ratio .basis) are achieved in the process of this invention compared to the Oyama reference. The mole ratio of acetone to di-tertiary-butyl peroxide was generally higher in the Oyama reference than the acetone/di tertiary-butyl peroxide ratio of the present invention. Tertiary-butyl alcohol 'production is of particular signifi- - cance in its 'use as an intermediate for gasoline additives as well 'as a gasoline additive itself. The Drawing is a graph illustrating the correlation' of di-tertiary-butyl peroxide (weight 'percent) with the mole ratio of the ethylene glycol produced to said peroxide. It is further discussed in connection with the Exampl-es. For' purposes of this invention, the amounts (weight percentages) of or'gani-c peroxide and water used must be within the' range of Table A which follows. TABLE A Peroxide . Water greater than 6 up to 12 0.5 to 35 greater tha'n 12 up to 15 0.5 to .25 greater than 15 up to 20 0.5 ta 15 greater than 20 up -to 25 0.5 to 10 The amount of formaldehyde contained in- the reaction mixture is nor'm'all.y from 0.5 to '13. weight percent, preferably from 2 ta '12 weight percent. Th'e' amount of metha'nol present in the' reaction mixture is the amount necessary to make the mixture up to 100%. For example, -the' ranges of amounts (weight perc'entages) of reactants in Table B can be used. TABLE B Peroxide Water Formaldehyde Methanol greater than 0.5-35 2-12 41-91.5 6 up to 12 greater than 0.5-25 2-12 48-85.5 12 up to 15 greater th.an 0.5-1.5 2-12 53-82.5 . 15 up to 20 greater than 0.5-10 2-12 53-77.5 20 up to '25 A preferred set of ranges of amounts (weight percentages) is given in Table C. TABLE C Peroxide Water Formaldehyde Methanol greater tha'n 6 5-:10 2-12 68-87 up to 10 The reaction will generally. be carried out at a temp erature of from' 1000C. to 2000C., preferably from 125 C. to 1750C., with 'a residence time which is not -greater 'tha'n 8 hours, usually from 0.25 to 8 hours, and preferably from 0.5 to '4 hours. Generally, the higher the temperature, the lower the reaction time necessary to bring the reaction to a desired state of completion. There is li'ttle or no critic- ality in the pressure at -which the reacti-on is carried out. In ge'neral, pressures from autog'enous pressure up --to 600 psig can be utilised. The organic peroxide' employed in the process of this invention is defined as one which has the formula R-O-O-R1 wherein R and R (which may the same or different) are each an alk:yl or aralkyl .group having 3 to 12 carbon atoms. Organic peroxides which' 'may te employed inclu'de, for example, di-tertiary-butyl peroxide, di-cumyl peroxide, tertiary butyl cumyl peroxide and tertiary-butylethylbenzyl per oxide. The preferred organic peroxide is di-tertiary-butyl peroxi'de. An inert solvent may be employed in the' process, although in most cases it is preferred to operate without one. Any solvent whi'ch 'does not 'react under conditions of the process may be employed, e.g. benzene and tertiary butyl alcohol. When a solvent is employed, it will generally be in an amount up to '25 percent by weight' of the total reaction medium, alt'hou'gh larger amounts can be used in some . instances. The reactions may be carried out batchwise wherein a reactor such 'as a stirred autocla've is charged with the initial 'reaction mixture which is then subjected to reaction, after which the entire reaction mixture is withdrawn and pu,ri'fied. Anothe'r batchwi'se pro'c'essing technique is to charge the methanol, water and portions of the formaldehyde (usuall'y mixed with 'some water) and peroxide as the initial reaction mixtu're and the'n add the remaining portions of the formaldehyde and peroxide and in some cases basic material, whi'ch 'are -s'equentially' and incrementally added to the methanol reaction medium. After all of the portions of reactants are added, the reaction is continued until 'the desired degree -of reaction ha's taken place, after whi'ch the product mixture is withdrawn and purified. Another technique is a semi-continuous method in which the initial reaction mixture and incremental 'additio.ns of reactants are cha'rged to the methanol reaction medium, reaction takes place and the' product mixture periodically withdrawn from the reactor and purified. In 'chis connection, reference is made to our co-pending European Patent Application fil-ed togethe'r with the present application and identified as c-5957A/5957B. A continuous redaction. can be carried out in a reactor constructed so that under -the conditions of reaction, a glycol concentration gradient occurs between the poi'nt where the first portions of peroxide and fo'rmal'dehyde are added and that at which the glycol-containing product is withdrawn. Thus, subsequent portions of peroxide and formaldehyde are ad'de'd between these two points. Fo'r example, a continuous process may be carried out by causing the liquid reaction medium to flow through a pipe and adding portions of the formaldehyde and peroxide reactants at intervals along the pipe, forming a moving reaction medium containing a concentration gradient of glycol as it travels through the pipe. Thu's, the' individual portions of the reactants are added in a controll.ed manner along the' pipe to the specific moving 'reacti-o-n medium until all :the' portions of the reactants have been added. At the end of the' pipe reactor, the' re'action' of each portion of the react.ants in the reaction medium has occurred at a conversion level to provide a product stream containing the desired amount of ethyl'e"ne 'gly'c'ol'. Alternatively a baffled reactor' may te employed containing a liquid reaction medium with a glycol concentration gradient between the point of entry of the initial feed stream and the point of exit of the product stream, wherein additional portions of peroxide and formaldehyde are added between the two points. In each 'case, the product mixture may then be purified using conventional techniques such as distillation or solvent extraction to obtain ethylene glycol in the desired purity, preferably fibre grade, and by-products such as tertiary-butyl alcohol, methylal, methyl formate, glycerine and aceto'ne. The follo-wing Examples illustrate the invention. EXAMP-LES' 1-14' An initial reaction mixture containing methanol (MeOH), di-tertiary-butyl peroxide (DtBP), formaldehyde (CH20) and water were charged into a stirred autoclave in the following manner: all but about -20 weight' percent of the methanol' in the initial charge, formaldehyde and water were added to a stirred autoclave at room temperature. The mixture was then heated up to reaction temperature and- a solution of diterti-ary-butyl peroxide in the remaining 20 wei-ght percent of methanol was added to the autoclave to initiate -the reaction. A reaction pressure of 500 psig was maintained with nitrogen. After -a reaction ti-me of one hour, -th-e product -mixture was removed from the autoclave and analysed for ethylene glycol (EG), acetone (A), tertiary-butyl alcohol (TBA), unreacted di-tertiary-butyl 'peroxide and othe'r pro'ducts present in minor amou'nts. The amounts of the reactants and of the products, and the temperatur-e, pressure and' reaction time, of each Example are shown in Table I. EXAMPLES' i'5'-18' These were comparativ.e Example's. As a basis for comparison of thi's invention with the Oyama reference described previously, Example 15 illustrates the results of the Oyama process. Th'i's run ',was made by charging methanol, di -tertiary-butyl 'peroxide, formaldehyde and water to 304 stainless steel Hoke reactor at atmospheric pressure. The reactor was capped and placed in a thermostated oil bath held at the stated reaction temperature and allowed to 'react for one hour at autogenous pressure. After the reaction time was completed, the reactor was cooled by quenching, vented, discharged and analysed for ethylene glycol, acetone, tertiary-butyl alcohol, unreacted di-tertiary-butyl peroxide and other products present in minor amounts. Examples 16, 17 and 18 illustrate the use .of water from 35.7 to 45 weight percent with peroxide, formaldehyde and methanol reacted in a 304 stainless steel Hoke reactor at atmospheric pressure. It is to be noted that in each of these runs 0.015 weight percent sodium bicarbonate was added to the initial reaction mixture. The reactor was capped and placed in a tharmostated oil bath held at 755"C. for one hour at autogenous pressure. After the reaction was completed, the reactor was cooled by quenching, vented, discharged and analysed for ethylene glycol, acetone, tertiary-butyl alcohol, unreacted di-tertiary-butyl peroxide and other products present in minor amounts. In Example 16, the analysis of ethylene glycol and unreacted di-tertiary-butyl peroxide was determined by acetone and tertiary-butyl alcohol 'were not determined. The results of Example's 14-18 are' als'o 'show'n in Table I, which sets out the composition of the initial 'charge, temperature, pressure and reaction time employed for the reaction. The' results of Example 15 according to the Oyama reference for ethylene glycol production is similar to the result's given in the reference itself. Comparing the results of Example 15 with Examples 1-14 which illustrate the results of the present invention, it should be noted that Examples 1-14 all produce highe'r mole -ratios of ethyle'ne gly'c-ol/di -tertiary-butyl perox'ide. and tertiary-butyl alcohol/di-tertiary butyl peroxide than does the Oyama reference run of Example 15. In- regard to acetone, Example 15 pro'duces a higher mole ratio of acetoneXdi-tertiary-butyl peroxide than the runs of Examples 1-14. Examples 16-18 illustrate the use of over 35 weight percent of water itv the reaction mixtu're' whi'ch is outside the scope of this invention. Even though a base, i.e. '0.015 weight' -percent -of sodium bicarbonate, was employed in the reaction mixture which., as mentioned abov'e, has the effect of reducing the formation o.f by-product methylal and raising the production of ethylene glycol, the amount of glycol ¯produced in Examples 17 and 18 was below' that obtained by the Oyama method, but the mole ratio of glycol to di-tertiary-butyl peroxide was hi'gher. than in the' Oyama method. In Table II, the yields of the products of all the Examples are' expressed as mole ratios based on the di-tert- iary-butyl peroxide consumed. TABLE I Ethylene Glycol Production Initial Charge Wt% Temp era Example DtBP CH2O MeOH H2O ture C 1 6 10 79 5 155 2 9 10 46 35 155 3 12 10 53 25 155 4 6 10 59 25 155 5 10 10 , 65 15 155 6 15 10 60 15 155 7 20 10 55 15 155 8 20 10 60 10 155 9 15 10 65 10 155 10 10 10 70 10 155 11 12 10 43 35 155 12 25 10 55 10 155 13 25 10 62.7 ' 2.3 155 14 25 10 60 5 155 15 9.3 7.6 41.1 42.0 155 16 6.1 10.2 46 35.7 155 17 1.5 10.0 43.5 45 155 18 6.0 6.0 43 45 155 TABLE I (cont.) Ethylene Glycol Production Products Wt % Example EG A TBA DtBP 1 7.90 2.24 2.70 0.25 2 4.10 4.72 1.92 0.29 3 5.3-5 6.-50 -3.20 0.58 4 5.20 3.38 1.94 0.26 5 6.70 4.90 3.90 0.48 6 6,70 7.00 5.60 0.71 7 6.20 9.99 7.60 0.90 8 7.00 8.80 7.90 0.98 9 7.00 7.35 ' 6.'60 0.59 10 7.38 4.20 4.19 0.58 11 3.93 6.43 2.41 ' # 0.67 12 6.05 10.8 10.5 1.50 13 7.36 9.73 11.'7 2.10 14 6.89 10.5 11.1 2.'70 15 1.'59 5.50 1.'73 0.03 16 3.20 -- -- 0.13 17 1.31 1.04 0.38 0.03 18 1.51 3.20 1.61 0.02 TABLE II Ethylene Glycol Production Product Mole Ratios Example EG/DtBP A/DtBP TBA/DtBP 1 3.24 1.02 0.93 2 1.11 1.'41 0.43 3 1.10 1.48, 0.55 4 2.13 1.54 0.67 5 1.66 1.34 0.81 6 1.10 1.28 0.77 7 0.76 1.36 0.79 8 0.88,, 1.21 # 0.82 9 1.14 1.'33 0.90 10 1.84 8.16 0.88 11 0.82, 1.48 0.42 12 0.61 1.20 0.88 13. 0.76 1.'11 1.01 14 0.73 1.23 0.98 15 0.40 1.55 0.37 16 1.26 -- -- 17 2.10 1.: :84 0.51 18 ' 0.59 1.40 0.53 The results of Examples 1-18, illustrating a correlation of di-tertiary-butyl peroxide chargb,d (weight percent) to the mole ratio of ethylene glycol/di-tertiary- butyl perox'ide ob'tained at various levels of water, are plotted on the graph shown in the Drawing. (Example 13. is the only example not plotted on the graph since only' one point of a 2.3 weight percent water run is available) The graph illustrates that as the amount -of water is decreased, higher amounts of di-tertiary-butyl peroxide can be used to achieve better results than those of the Oyama reference. The graph illu'strates the effectiveness of the relationship required by the present invention between the ranges of proportion of peroxide and the ranges of water content. EXAMPLES 19-22-. These Examples illustrate the use of equivalent -total amounts of reactants used in a single stage reaction'and multiple stage reactions to produce ethylene glycol (EG) by the reacti-on of formaldehyde (CH2Q) containing water (H20), di-t-ertiary-butyl peroxide (DtBP) and methanol (MeOH) in the presence of sodium bicarbonate (NaHCO3). The: formaldehyde used in these Examples contained 4.54 parts per million sodium hydroxide per one weight percent formaldehyde used. The reactor was a 316 'stainless steel 1 " .(2.:54 cm) diameter pipe having a capacity of approximately' 85 milljrnetres liquid. In a one stage reaction, all;:the reacting ingredients were placed in the reactor which was seale'd and heated to 155 C. for one hour at autogenous pressure. In a staged reaction, a portion of the reactants of di-tertiary-butyl 'peroxide, formaldehyde and water and sodium bicarbonate were # initlall'y' 'add'ed to 'the' 'reactor' containing all the methanol heated to 15'50C. for one hour. After the first hour of reaction, additional portions of the reactants were added and the reaction was conducted for another hour. # After the second ho'u'r, the remainder of the reactants were ad'ded to the' reactor' and the reaction conducted for' the final hour. After the'reaction was completed in the first stage or in each multiple stage reaction, the reactor was cooled by quenching, vented and discha'rged, and the contents were analy'sed by gas chromatography for' ethylene glycol (EG) and other products. The results of these -Example's are shown in Table III which sets out the compqsition of tot'al amounts of peroxide, formaldehyde and water ch.arged to the reactor containing the methanol in. the various stages. The amounts of reactants used are reported as weight 'percent of the total material in the reactor up to that -stage. The amounts of' ethylene glycol are reported as weight percent of the total product mixture. TABLE III Rectants Added NaHCO3 Ethylene DtBP H2CO H2O Parts Reaction Glycol Examples Type of reaction WT% Wt% Wt% per million time hours Wt% 19 1 stage 7.0 14.0 1.91 100 1 8.75 20 3 stage 1st. stage 3.0 6.0 .8 50 1 6.14 2nd. stage (total) 5.0 10.0 1.36 75 1+1=2 9.28 3nd. stage (total) 7.0 14.0 1.91 100 2+1=3 11.68 21 1 stage 6.42 11.77 1.60 100 1 8.92 22 3 stage 1st. stage 3.0 7.0 0.95 50 1 7.32 2nd. stage (total) 4.77 9.48 1.33 75 1+1=2 9.58 3rd. stage (total) 6.42 11.77 1.60 100 2+1=3 11.48

Claims: 'CLAIMS' 1. A process for producing ethylene glycol by reacting methanol, an. organic peroxide and formaldehyde in the presence of water, said organic peroxide having the formule R-O-O-R1 wherein each of R and.R1 (which may be the same or different) is an alkyl 'or aralkyl group containing 3 to 12 carbon' atoms, characterised in that the amount of the peroxide used is greater than 6 and up -to 25 weight' -percent and the amount of water used is from 0.5 to 36 weight -percent, and the amounts of the peroxide and water used are dependent on each other so that either the amount of the peroxide used is greater than 6 up to 12 weight percent and the amount of water used is from 0.5 to 35 weight percent, or the amount of the peroxide used is greater than 12 up to 15 weight -percent and the amount of water used is from 0.5 to 25 weight percent, or the amount of the peroxide used is greater than 15 up to 20 weight percent and the amount of water used is from 0.5 to 15 weight -percent, or the amount of the peroxide used is greater than 20 up to 25 weight percent and the amount of water used is from 0.5 to 10. weight percent, the above weight percentages being based on the' total weight of the methanol, organic perox'ide, formaldehyde and water present in the reaction mixture. 2. The process of claim 1 whe'rein the organic peroxide is di-tertiary-butyl peroxide. 3. The pro'c'ess of claim 1 'or 2 'where'in the reaction time is no greater than 8 hours. 4. The process of claim 3 wherein the initial reaction mixture contains di-tertiary-butyl 'peroxide as the peroxide, water, 0.5 to 13 weight percent 'formaldehyde and the remain der is methanol, the reaction temperature is from 100 to 2000C. and the reaction' time is from 0.25 to '8 hours. 5. The process.of claim 4 wherein the' amount of formaldehyde is 2- to '12 weight' 'percent,' the reaction temperature is from 1250C. to 1750C. and the reaction time is from' 0.5 to 4 ho'u'rs. 6. The process of claim 5 wherein the' initial reaction mixture contains from 41 to 91.5 weight percent of methanol, greater than 6 up to 12 weight percent of di-tertiary-butyl pero'xide' -and from 0.5 to 35 weight percent water. 7. ' The' process of claim 5 where'in the' initial' 'rsacti'on mixture contains from 48 to 85.5 weight' percent of methanol', greater than 12 up to 15 weight percent of di-tertiary- butyl 'perox'ide and from 0.5 to 25 weight percent of water. 8. The' process of claim 5 whe'rein the initial reaction mixture contains from 53 to 82,.5 weight percent of methanol, greater than 15 up -to 20 weight per'cent of di-tertiary-butyl peroxide -and from 0.5 to 15 weight 'percent water. 9. The' process of claim 5 wherein the initial reaction mixture contains from 53 to 77.5 weight percent -of methanol, g'reater than 20 up to 25 weight percent of di-t-ertiary-butyl peroxide and from 0.5 to 10 weight percent 'water. 10. The process of claim 5 wherein th-e initial reaction mixture contains from 68 to 87 weight percent of methanol, greater than 6 up to 10 weight -percent-of di-tertiary-butyl peroxide, and from 5 to 10 weight per'cent 'water.

Inventors: KOLLAR, JOHN
Applicants: REDOX TECHNOLOGIES INC.
Application year: 1982
Main classification: C07C29
IPC codes: C07C29, C07C31