SE128233C1 - - Google Patents
Info
- Publication number
- SE128233C1 SE128233C1 SE128233DA SE128233C1 SE 128233 C1 SE128233 C1 SE 128233C1 SE 128233D A SE128233D A SE 128233DA SE 128233 C1 SE128233 C1 SE 128233C1
- Authority
- SE
- Sweden
- Prior art keywords
- pressure
- catalyst
- increased
- sectional area
- alcohol
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 claims description 62
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 14
- 230000007420 reactivation Effects 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 13
- 230000008901 benefit Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000013529 heat transfer fluid Substances 0.000 description 5
- 230000002779 inactivation Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- MHCVCKDNQYMGEX-UHFFFAOYSA-N 1,1'-biphenyl;phenoxybenzene Chemical compound C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 MHCVCKDNQYMGEX-UHFFFAOYSA-N 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Uppfinnare: E. V. Harlow. Inventor: E. V. Harlow.
Prioritet begard Iran den 7 september 1946 (Amerikas farenta stater). Priority was given to Iran on September 7, 1946 (United States United States).
Foreliggande uppfinning hanfor sig till Tramstallningen av butadien och avser mera speciellt ett forfaringssatt for framstallning av butadien av en gasformig blandning av acetaldehyd och alkohol eller alkohol enbart. The present invention relates to the preparation of butadiene and more particularly to a process for the preparation of butadiene of a gaseous mixture of acetaldehyde and alcohol or alcohol alone.
Vid framstallning av butadien av alkohol ar det brukligt all lata en blandning av alkohol och acetaldehyd, av wilka den senare erhallits genom oxidation av alkohol eller ph annat satt, passera over en butadienbildande katalysator av lfimplig ,sammansfittning. FOr ,detta andamal liar silikagel aktiverat med tantaloxid (Ta20) befunnits tillfredsstallande. Katalysatorn kan framstallas genom indunstning av silikagel med en losning av ett sonderdelbart salt av tantal oak upphettning av katalysatorn vid omkring 300-400° C. Impregneringen kan aven utforas genom neddoppning av silikagel i en losning av det sonderdelbara saltet, varvid citrater oak oxalater aro effektiva salter for detta andamal. In the preparation of butadiene from alcohol, it is customary to pass a mixture of alcohol and acetaldehyde, from which the latter has been obtained by oxidation of alcohol or otherwise, over a butadiene-forming catalyst of liquid fitting. For, this andamal liar silica gel activated with tantalum oxide (Ta20) has been found satisfactory. The catalyst can be prepared by evaporating silica gel with a solution of a decomposable salt of tantalum oak. Heating the catalyst at about 300-400 ° C. salts for this purpose.
Vanligen an-vandes ett lagt inmatningsforhallande, d. v. s. omkring 3 mol alkohol per mol acetaldehyd, ehuru hoga inmatningsforhallanden (20 till 1) eller till och med ren alkohol kan komma till anvandning med nagra katalysatorer. Usually a given feed ratio was used, i.e. about 3 moles of alcohol per mole of acetaldehyde, although high feed ratios (20 to 1) or even pure alcohol may be used with some catalysts.
Det as att formoda, att acetaldehyden forst kondenseras till krotonaldehyd, vilken i sin tur reduceras till krotylalkohol av den valeavgivande foreningen, etylalkohol, och att den salunda bildade krotylalkoholen avvattnas till 1,3-butadien. Vilka detaljerna i forfaringssattet och vilken dess mekanisin an ma vara, far den inmatade blandningen kontinuerligt passera Over katalysatorn under lampliga betingelser, tills katalysatorn blivit sa inakti-verad, att en tillfredsstallande produktion av butadien lake langre erhalles. Darefter reaktiveras katalysatorn genom upphettning till en temperatur, som as tillrackligt hog f8r att utfallt kol skall forbrannas, yarigenom ett kretslopp fullbordas. Katalysatorn är darefter fardig att inforas i ett nytt kretslopp. Varje kretslopp bestar av en tillstromningsfas, katalys, en bortstromningsfas och reaktivering. It is assumed that the acetaldehyde is first condensed to crotonaldehyde, which in turn is reduced to crotyl alcohol by the valence-releasing compound, ethyl alcohol, and that the thus formed crotyl alcohol is dehydrated to 1,3-butadiene. Whatever the details of the process and what the mechanism may be, the feed mixture may be passed continuously over the catalyst under suitable conditions until the catalyst has become so inactivated that a satisfactory production of butadiene lake is obtained. The catalyst is then reactivated by heating to a temperature which is sufficiently high for the precipitated carbon to burn, thereby completing a cycle. The catalyst is then ready to be introduced into a new cycle. Each cycle consists of an inflow phase, catalysis, an outflow phase and reactivation.
Foreliggande uppfinning liar till andamal att astadkomma ett forbattrat forfaringssatt av angivet slag, att underlatta katalysatorns reaktivering, att erhalla ett jamnare arbctsforlopp under hela katalysen, att undvika olagenheter, som aro f8rbundna med tidigare fOrfaringssatt, och att uppna fordelar, som komma att framgd narmare i fortsattningen av beskrivningen. The present invention has for its object to provide an improved process of the type indicated, to facilitate the reactivation of the catalyst, to obtain a smoother course of action throughout the catalyst, to avoid irregularities associated with previous procedures, and to obtain advantages which will become apparent the continuation of the description.
Dessa andamal uppnas enligt uppfinningen darigenom, att en blamlning av acetaldehyd och alkohol i fingfas kontinuerligt ledes Over en butadienbildande katalysator -vid en ternperatur, vid vilken reaktion ages ruin, i ett cykliskt forfarande innefattande katalys och reaktivering av katalysatorn, och att trycket okas foretradesvis, utan motsvarande okning av volymen gas per volym av katalysatorn, som genomledes under katalysen. These purposes are achieved according to the invention in that a mixture of acetaldehyde and alcohol in the fine phase is continuously passed over a butadiene-forming catalyst - at a temperature at which reaction is ruined, in a cyclic process comprising catalysis and reactivation of the catalyst, and that the pressure is preferably increased. without a corresponding increase in the volume of gas per volume of the catalyst passed through the catalyst.
Man har hittills =sett, att framstallning av butadien av alkohol skall forsigga vid atmosfartryck eller lagre tryck for att basta resultat skall erhAllas, oak att det lake skulle vara mojligt att arbeta vid hogre tryck an atmosfartryck ph grund .av alltfor stor utfallfling av kol pa katalysatorn och darav fororsakad minskad omsattningseffektivitet. It has hitherto been seen that the production of butadiene from alcohol should proceed at atmospheric pressure or lower pressure in order to obtain the best results, also that it would be possible to work at higher pressure than atmospheric pressure due to excessive precipitation of carbon on the catalyst and the consequent reduced sales efficiency.
Det har emellertid nu befunnits, att ovantade fordelar erhallas genom forfaringssattet enligt uppfinningen. Genom utforande av den forsta delen eller fasen av katalysen yid relativt lagt tryck, som kan ligga vid eller i narheten av atmosfarstrycket, i overensstammelse ,med mom tekniken bruklig praxis, eller vid hogre tryck an atmosfartryck i enlighet med det svenska patentet 123 915, samt en senare fas av katalysen vid relativt Mgt tryck, d. v. s. genom okning ay trycket under katalysen är man i stand att draga fordel av Rad kolutfallning, beroende pa okat tuck, 2- - och att samtidigt uppratthalla en hOgre genomgaende halt av butadien i katalysatet under katalysen. However, it has now been found that the above advantages are obtained by the method of the invention. By performing the first part or phase of the catalytic conduction yd relatively added pressure, which may be at or near the atmospheric pressure, in accordance with practice customary in the art, or at higher pressures than atmospheric pressure in accordance with the Swedish patent 123 915, and a later phase of the catalyst at relatively high pressure, i.e. by increasing the pressure under the catalyst, one is able to take advantage of Rad carbon precipitation, depending on increased tuck, 2- - and at the same time maintain a higher continuous content of butadiene in the catalyst during the catalyst .
Det Sr brukligt att utf8ra katalysen i varmeutbytare, i vilka temperaturregleringen forsiggar genom cirkulation av ett varmeoverforingsfluidum I indirekt viirmeutbyte med katalysatorn. DS den temperatur, som fir erforderlig for reaktiveringen, är avsevart hog-re fin den temperatur, soin erfordras f8r katalysen, har det hittills yarit Midvandigt att valj a varmeoverforingsfluidet i overensstdmmelse med den erforderliga reaktiveringstemperaturen, eller att f8rvarma luften, som an- vandesregenereringen, eller att pa annat salt tillfora det ytterligare varme, som erfordrats for att bringa katalysatormassan upp till reaktiveringstemperaturen. It is customary to carry out the catalyst in heat exchangers, in which the temperature control proceeds by circulating a heat transfer fluid in indirect heat exchange with the catalyst. Since the temperature required for the reactivation is considerably higher than the temperature required for the catalysis, it has hitherto been difficult to select the heat transfer fluid in accordance with the required reactivation temperature, or to preheat the air used. or to add to other salt the additional heat required to bring the catalyst mass up to the reactivation temperature.
Enligt foreliggande uppfinning är det m8jligt att vaija varmeoverforingsfluidet med hansyn till katalystemperaturen. Det ytterli- garesom erfordras for att bringa ka- talysatormassan upp till regenereringstempe-raturen, erhalles genom forbriinning av den stfirre mangd hot, som utfalles vid genomforandet av processen vid Rat tryek-. For att uppna denna fordel är det endast nocivandigt att Oka tryeket, foretradesvis utan en motsvarande aiming av volymen genomledd gas, raknat pa katalysatorvolymen, nara slutet av tillstromningsfasen eller katalysfasen av kretsloppet med na.gra tiondels kg per cm', t. ex. 0,7 kg per cm ° eller mera, och tillrSckhg mfingd kol for kornpensering av bristen upphettningskapacitet hos varmeoverf8- ringsfluidet saint for stegring av temperaturen Iran arbetstemperaturen vid katalysen till den erforderliga reaktiveringstemperatuTen kommer att utfallas pa katalysatorn. Det Sr onskvart, att detta fOrsiggar endast under de sista 15 % och mera, upp till 7av tillstromnings- eller katalysfasen av kretsloppet, am katalysatorns ,aMivitet Sr lag vid kretsloppets borjan, for att den totala effektiviteten av forfaringssattet icke shall pa.- verkas ogynnsamt. According to the present invention, it is possible to select the heat transfer fluid with respect to the catalyst system temperature. What is further required to bring the catalyst mass up to the regeneration temperature is obtained by combining the greater amount of threat which results from the implementation of the process at Rat pressure. In order to achieve this advantage, it is only necessary to increase the pressure, preferably without a corresponding measurement of the volume of gas passed through, calculated on the catalyst volume, near the end of the inflow phase or the catalytic phase of the cycle by a few tenths of a kg per cm 2, e.g. 0.7 kg per cm ° or more, and sufficient carbon for granulation to compensate for the lack of heating capacity of the heat transfer fluid saint for increasing the temperature Iran the working temperature at the catalyst to the required reactivation temperature will be precipitated on the catalyst. It is important that this occurs only during the last 15% and more, up to 7 of the inflow or catalytic phase of the cycle, at the catalyst's activity at the beginning of the cycle, so that the overall efficiency of the process is not adversely affected. .
Okning av trycket under katalysen utan motsvarande Okning av volymen genomledd gas i forhallande till katalysatorvolymen liar som effekt en kompensering av den minskade aktivitetet hos katalysatorn, som fororsakas genom kolutffillning eller andra 'slag av in- aktivering, som sa smaningom intrader 'under tillstrOmningsfasen eller katalysfasen av _kretsloppet. Effekten av katalysatorns inaktivering Sr, att den giver ett katalysat med alltjthnt lagre butadienhalt, alltefter som tillstrSmningsfaseri eller katalysfasen av kretsloppet fortskrider. Denna ogynnsamma omstfindighet komplicerar bearbetningen av kataivsatet for utvinning av dess butadienhalt. Increase in the pressure during the catalytic converter without corresponding Increase in the volume of gas passed in relation to the catalyst volume has the effect of compensating for the reduced activity of the catalyst, which is caused by carbon deposition or other 'types of inactivation which gradually enter' during the inflow or catalytic phase. of the _circulation. The effect of the inactivation of the catalyst is that it gives a catalyst with an ever lower butadiene content, as the feed phase or the catalyst phase of the cycle progresses. This unfavorable circumstance complicates the processing of the kataivsate to recover its butadiene content.
Enligt foreliggande uppfinning Sr det mojligt att reglera trycket under katalysen, sS att denna tendens has butadienhalten i kata lysatet att sjunka atminstone delvis kompenseras, och am .sa. Sr Onskvart kan trycket under katalysen progressivt 'Ras, med lfimpliga tidsmellanrum, .sh. att katalysatets butadienhalt bibehalles vid ett praktiskt taget konstant varde. According to the present invention, it is possible to control the pressure during the catalysis, so that this tendency of the butadiene content in the catalyst to drop is at least partially compensated, and so on. Sr Onskvart, the pressure during catalysis can progressively 'Ras, with lfimpliga time intervals, .sh. that the butadiene content of the catalyst is maintained at a practically constant value.
Uppfinningen beskri-ves nedan utforligare i foljande utforingsexempel, i vilka de augurna delarna aro viktsdelar, savida joke annat sarskilt angives. The invention is described in more detail below in the following exemplary embodiments, in which the auger parts are parts by weight, unless otherwise stated.
Exempel 1. Example 1.
En blandning av etanol och aeetaldehyd leddes genom en multipelrorvarmeutbytare, I vilken var anbragt en silikagelkatalysator aktiverad med 2 % tantaloxid, yid en temperatur ay 350° C och under de betingelser, som aro angivna nedan i tabellernaGrund- tryeket, d. v. s. trycket, .som bestammes av det inre motstandet i systemet, var 0,63 kg per cm' av tvarsnittsarean. Mangden genomledd gas i fOrhallande till katalysatorvolymen halls konstant under varje kretslopp vid den vittskestrOmningshastighet per timme, som är angiven i tabeIlerna. A mixture of ethanol and acetaldehyde was passed through a multiple tube heat exchanger, in which was placed a silica gel catalyst activated with 2% tantalum oxide, at a temperature of 350 ° C and under the conditions given below in the basic pressure tables, i.e. the pressure determined. of the internal resistance of the system, was 0.63 kg per cm 2 of the cross-sectional area. The amount of gas passed in in relation to the catalyst volume is kept constant during each cycle at the velocity flow rate per hour indicated in the tables.
Tabell 1. Table 1.
Inmatningshastighet: 0,-volymer per malymkatalysator per timme. Total tid for tiltstrOmningsfasen: 120 timmar per kretslopp. Feed rate: 0, -volumes per maly catalyst per hour. Total time for the tilt flow phase: 120 hours per cycle.
Tim. till-stromnings-fas efter senaste reaktivering 3 25,8 ea 0,63 9,0 29 26,2 »0,63 9,1 26,3 »0,63 8,4 71 25,8 »0,63 7,6 98 25,7 »0,63 6,9 Tabell 2. Tim. inflow phase after last reactivation 3 25.8 ea 0.63 9.0 29 26.2 »0.63 9.1 26.3» 0.63 8.4 71 25.8 »0.63 7, 6 98 25.7 »0.63 6.9 Table 2.
Inmatningshastighet: 0,42 volymer per volymkatalysator per timme. Total tid fOr tillstromningsfasen: 110 timmar per kretslopp. Feed rate: 0.42 volumes per volume catalyst per hour. Total time for the inflow phase: 110 hours per cycle.
Tim. till-strtimnings-fas efter senaste reaktivering 4 26,2 ea 0,63 8,2 25,8 »0,63 8,6 26,7 »0,88,7 72 26,2 »1,8,4 98 25,8 »1,48 8,2 Trycket okades yid den. 47, 69 och 95 timmen. Tim. start-up phase after last reactivation 4 26.2 ea 0.63 8.2 25.8 »0.63 8.6 26.7» 0.88.7 72 26.2 »1.84 98 25 , 8 »1,48 8,2 The pressure increased okid the. 47, 69 and 95 hours.
Am de data, soon aro angivna i ovanstfiende tabeller, framgar, att dh man arbetar vid grundtryeket i systemet butadienhalten i katalysatet sh smaningom sjunker efter den 29 timmen. Om man utgar ifran den 29 timmen, sa är hastigheten, med vilken butadien- acetal- dehyd i at- gangs- materialet Tryck p5 konvertern i kg/cm2 tvarsnitts- area butadien I produkt- gaserna acetaldehyd i ut- gangs- materialet Tryck p5 konverten I kgicm2 tvarsnitts- area butadien I produktgaserna — —a halten sjunker, praktiskt taget linear. label' 2 visar effekten av en Ruing av trycket under tillstrornningsfasen .eller katalysfasen av kretsloppet. Ay tabellen framgar, att en &- Ring av trycket med c:a 0,21 eller 0,28 kg/em2 tvarsnittsarea varje 20 eller 25 timme efter den 30 timmen resulterat 1, att katalysatet har praktiskt taget konstant butadienhalt. The data, soon to be given in the above tables, show that ie the basic pressure in the system is used, butadiene content in the catalyst gradually decreases after 29 hours. If one starts from the 29 hour, then is the rate at which butadiene-acetaldehyde in the starting material Press the converter in kg / cm2 cross-sectional area butadiene In the product gases acetaldehyde in the starting material Press the converter In kgicm2 cross-sectional area butadiene In the product gases - —a the content decreases, practically linear. label '2 shows the effect of a Ruing of the pressure during the inflow phase .or the catalytic phase of the cycle. The table shows that a & - Ring of the pressure with about 0.21 or 0.28 kg / cm2 cross-sectional area every 20 or 25 hours after the 30 hour resulted 1, that the catalyst has practically constant butadiene content.
Apparaten, i vilken forsoken enligt ovanstaende exempel utfordes, upphettades riled Dowtherm. (en eutektisk blandning av difenyl och fenyloxid) som varmeoverforingsfluidum. Eftersom arbetstemperaturen vid anyandning av Do-wtherm normalt ligger omkring mid 350° C for katalysen, utnyttjas det extra kol, som bildats sasom result at av tryckokningen, med fiirdel for uppnaende ay de onskade temperaturerna av 400-420' C for reaktivering av katalysatorn. Andra fordelar, som uppnas genom fiirfaringssattet enligt uppfinningen, aro okad produktion, i det att det Sr mojligt att producera fran 10 till 20 % mera butadien per kretslopp, och att utvinna mera butadien per sats eller charge fran destillationsanlaggningen ph grund av den Rade butadienhalten i katalysatet, yilken Sr aft hanfora till okningen av trycket, samt vidare en okning av kapaeiteten hos eirkulationskompressorerna. Dessa kompressorer arbeta amen med mindre temperaturhojning, da mindre arbete utfores for en given gasmassa. En ytterligare fordel Sr, att storre mangder av den icke omsatta alkoholen och acetaldehyden kunna kondenseras fore kompressionen, och att denna kondensation kan ske med mindre mangd kylvatten. The apparatus in which the experiments according to the above example are challenged was heated riled Dowtherm. (a eutectic mixture of diphenyl and phenyloxide) as a heat transfer fluid. Since the operating temperature when inhaling Do-wtherm is normally about mid-350 ° C for the catalyst, the extra carbon formed as a result of the pressure increase is used, with the advantage of reaching the desired temperatures of 400-420 ° C for reactivating the catalyst. Other advantages obtained by the process according to the invention are increased production, in that it is possible to produce from 10 to 20% more butadiene per cycle, and to recover more butadiene per batch or batch from the distillation plant ph due to the Rade butadiene content in the catalyst, which Sr aft hanfora to the increase of the pressure, as well as a further increase of the capacity of the circulating compressors. These compressors work amen with less temperature rise, as less work is done for a given gas mass. A further advantage is that larger amounts of the unreacted alcohol and acetaldehyde can be condensed before compression, and that this condensation can take place with a smaller amount of cooling water.
Ehuru uppfinningen ovan beskriyits 1 samband med en sarskild utforingsform dãrav, Sr det underforstatt, att detta endast skett som exempel, ,och att variationer kunna foretagas i forfaringssattet, utan att man for den skull avviker fran uppfinningens ide och andamal. Although the invention has been described above in connection with a particular embodiment thereof, it is to be understood that this has been done by way of example only, and that variations may be made in the method without departing from the spirit and spirit of the invention.
Uppfinningen Sr speciellt tillamplig vid processer, som forsiggh mid atmosfarstryck, ehuru densamma, shsom ovan ornnamnts, Sven kan anyandas mid processer, som forsigga yid lagre eller hogre tryck an atmosfarstryck. Med atmoslarstryckprocesser ayses sadana processer, som forsigga eller genomforas mid det normala rnottrycket i apparatsystemet, utan anordnande av .speciella tryekregleringgapparater. Satillvida som de konvertrar, som -vantigen anvandas yid framstallning av butadien av alkohol, ham a relativt Mgt mottryck, koramer det normala arbetstrycket att vara relativt hogt, t. ex. fran c:a 0,63 kg/cm' tvarsnittsarea i exempel 1 upptill omkring 0,s5 kg/cm' tvarsnittsarea. The invention is particularly applicable to processes which process at atmospheric pressure, although the same, as mentioned above, may be used in other processes which process at lower or higher atmospheric pressures. Atmospheric pressure processes are used to process such processes which proceed or are carried out at the normal rated pressure in the apparatus system, without the provision of special pressure regulating apparatus. To the extent that the converters used in the production of butadiene by alcohol have a relatively high back pressure, the normal working pressure is expected to be relatively high, e.g. from about 0.63 kg / cm 2 cross-sectional area in Example 1 at the top about 0.5 kg / cm 2 cross-sectional area.
Graden av tryckokningen kan variera mom yida granser, ehuru vanligtvis relativt snail okningar, t. ex. av storleksordningen frau omkring 10 % till omkring 100 %, foretradesvis fran 25 till 100 % ay det absoluta arbetstryc ket, befunnits vara mest Onskvarda. Foretradesvis bOr den totala tryekokningen vara Stminstone 0,7 kg/cm' tvarsnitts,area, ehuru varje tryekokning bidrager till uppnaendet av uppfinningens andamal. Vid mindre tryckokningar kan emellertid graden, i vilken uppfinningens andamal uppnas, icke alltid anses betecknande. For atmosfarstryckprocesser Sr det onskvart att Oka trycket under katalysfasen av kretsloppet till atminstone 0,7 kg/cm= tvarsnittsarea utover .det normala arbetstrycket, men foretradesvis icke till mera an .omkring 1,76 kg/cm= tyarsnittsarea. The degree of pressure increase may vary with yida limits, although usually relatively snail increases, e.g. of the order of about 10% to about 100%, preferably from 25 to 100% of the absolute working pressure, has been found to be most onskvarda. Preferably, the total pressure boiling should be at least 0.7 kg / cm 2 of cross-sectional area, although each pressure boiling contributes to the attainment of the spirit of the invention. At smaller pressure increases, however, the degree to which the spirit of the invention is achieved cannot always be considered significant. For atmospheric pressure processes it is advisable to increase the pressure during the catalytic phase of the cycle to at least 0.7 kg / cm = cross-sectional area beyond the normal working pressure, but preferably not to more than about 1.76 kg / cm = tire average area.
Tryckokningen kan foretagas yid yilkensom heist tidpunkt under katalysfasen ay kretsloppet. FOr att mera fullstandigt realisera uppfinningens andamal Sr det emellertid att foredraga alt icke fiiretaga tryekokningen, fOrran en avsevard del av katalysfasen ay kretsloppet har utforts yid det normala arbetstrycket i systemet. Foretradesyis bar atminstone omkring de forsta 25 % air katalysfasen av kretsloppet utforas yid vanligt arbetstryek och trycket darefter Ras i .enlighet med °van angivna principer. The pressure increase can be carried out at any time during the catalytic phase of the cycle. However, in order to more fully realize the spirit of the invention, it is preferable not to undertake the pressure cooking until a considerable part of the catalytic phase in the cycle has been carried out at the normal working pressure in the system. Preferably, at least about the first 25% of the catalytic phase of the cycle is carried out under normal working pressure and the pressure is then applied in accordance with the principles set forth.
I shdana fall, da huyudandamalet Sr att utfalla kol for att underlatta katalYsatorns reaktivering, bOr trycket lampligen Ras endast under de sista 15 % ay katalysfasen ay kretsloppet. I sadana fall foretages okningen ay trycket till det onskade vardet lampligen i ett enda steg. Om emellertid huvudandamalet Sr att kompensera katalysatorns inaktivering for att Oka butadienhalten i katalysatet, Sr det att foredraga att Oka trycket stegvis under en tid, som .stracker sig over atminstone de sista 60 rilokretsloppets ha- talysfas. In such cases, since the main purpose is to precipitate carbon to facilitate the reactivation of the catalyst, the pressure should probably only rise during the last 15% of the catalytic phase in the cycle. In such cases, the increase in the pressure to the desired value is suitably carried out in a single step. However, if the main purpose is to compensate for the inactivation of the catalyst to increase the butadiene content of the catalyst, it is preferable to increase the pressure stepwise over a period of time which extends over at least the ha-lysis phase of the last 60 cycles.
Mangden utgangsmaterial som tillfores, raknat i volym ph katalysatorvolymen, kan variera alltefter den speciella reaktion, som skall genorafOras. Vanligen genomledes en mangd mellan 0,4 och 0,6 volymer per volym katalysator per Emilie, vilket befunnits vara tillfredsstallande. I -sa.dana fall, da huvudandamitlet Sr att underlatta katalysatorns reaktivering, Sr den genomledda mangden icke en utslagsgivande faktor, medan detta daremot Sr fallet, oin huvudOndamedet Sr att kompensera katalysatorns inaktivering. I sistnamnda fall bibehalles lampligen mangden, som genomledes, konstant under hela katalysen. Den kan emellertid ocksh yarieras, utan att man for den skull avviker fran uppfinningens ide och andamal, forutsatt att okningen icke Sr sa stor, att den motsvarar tryckiikningen. The amount of starting material fed, calculated in volume and volume of the catalyst, may vary according to the particular reaction to be reacted. Usually an amount of between 0.4 and 0.6 volumes per volume of catalyst per Emilie was passed through, which was found to be satisfactory. In such cases, when the main element is to facilitate the reactivation of the catalyst, the amount passed is not a decisive factor, while this is the case, in the main case it is to compensate for the inactivation of the catalyst. In the latter case, the amount which is passed through is suitably maintained constant throughout the catalyst. However, it can also be varied without departing from the spirit and spirit of the invention, provided that the increase is not so great as to correspond to the pressure equation.
Eftersom hatalysen utfores i angfasen, Sr kontakttiden en funktion av den genomledda mangden och av trycket. Om trycket okas och den genomledda mangden Ras i mot- svarande grad, kommer kontakttiden att bliva densamma. Satillvida som andamalet med tryckokningen Sr att Oka kontakttiden och 4— — ,darigenom kompensera katalysatorns inaktiTering, är det darfor onskyart, att den. genomledda mangden bibehalles praktiskt taget konstant under hela katalysen eller att den atminstone icke okas i en grad, som motsvarar tryekokningen. Since the hate analysis is performed in the ang phase, the contact time is a function of the amount passed through and of the pressure. If the pressure is increased and the conducted quantity Ras to a corresponding degree, the contact time will be the same. To the extent that the purpose of the pressure increase is to increase the contact time and thereby compensate for the inactivation of the catalyst, it is therefore uncommon for it. the amount passed through is maintained practically constant throughout the catalyst or at least is not increased to a degree corresponding to the pressure boiling.
Claims (8)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE128233T |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SE128233C1 true SE128233C1 (en) | 1950-01-01 |
Family
ID=41926247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE128233D SE128233C1 (en) |
Country Status (1)
| Country | Link |
|---|---|
| SE (1) | SE128233C1 (en) |
-
0
- SE SE128233D patent/SE128233C1/sv unknown
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102091679B1 (en) | Separation processes using divided columns | |
| JP6208249B2 (en) | Alkanol production equipment | |
| US20120123172A1 (en) | Production Method Of Trans-1,3,3,3-Tetrafluoropropene | |
| EP3214062B1 (en) | Distillation method for the separation of n-butanal and iso-butanal | |
| US10513492B2 (en) | Process for conversion of dimethyl sulfide to methyl mercaptan | |
| EP3390350B1 (en) | Recovery column control | |
| JP5722771B2 (en) | Crystallization method of (meth) acrylic acid | |
| US3272875A (en) | Surface crystallization process | |
| JP4831553B2 (en) | Method and equipment for producing 1,2-dichloroethane | |
| JP2004066222A (en) | Method and equipment for separating mixture by distillation | |
| SE128233C1 (en) | ||
| SG175661A1 (en) | Fluidized bed method and reactor for carrying out exothermic chemical equilibrium reactions | |
| CN103922891B (en) | Energy integration method for producing benzyl chloride by two-stage reaction rectification series connection | |
| CA2938370C (en) | Process for the manufacture of hydrochlorofluoroolefins | |
| TWI613179B (en) | Process for the manufacture of ethylene dichloride (edc), and process for the manufacture of vinyl chloride monomer (vcm) and of polyvinyl chloride (pvc) | |
| EP3389812B1 (en) | Recovery column for the purification of acrylonitrile/acetonitrile mixtures | |
| CN104829452B (en) | Energy-saving production system of ethyl acetate and corresponding energy-saving production technology | |
| CN104591956B (en) | Tetrachloro-ethylene method is produced the system and method for trifluorobichloroethane and tetrafluoro monochlorethane | |
| CN108069824A (en) | The device and its technique that a kind of octyl alconyl raffinate recycles | |
| CN215427361U (en) | Heat-sensitive material solvent recovery system | |
| KR20170074666A (en) | Separating and recovering method of unreacted alcohol | |
| KR101434462B1 (en) | Batch type distillation apparatus for the purification of lactide, and the distillation method for the purification of lactide using the same | |
| CN102407090B (en) | Device and method for lowering influences of sublimates on reaction | |
| CN211561855U (en) | Chemical product purification system | |
| SE193471C1 (en) |