MXPA95001075A - Fluid bed process for the acetoxylation of ethylene in the production of vin acetate - Google Patents

Abstract

A fluid bed process for the preparation of vinyl acetate from ethylene, acetic acid and oxygen, comprising feeding ethylene and acetic acid into a fluid bed reactor through one or more inlets, introducing oxygen into the reactor through at least one other inlet, and collecting the oxygen, ethylene and acetic acid in the reactor in contact with a fluid bed catalyst, to produce vinyl asyacetate. The particle size diameter of the catalytic particulate material is preferably such that 60% of the particles are less than 200 microns (0.2 mm) and no more than 40% of the particles are less than 40 microns (0.04 m)

Description

V f -i- PROCESS IN FLUID BED FOR THE ACETOXYLATION OF ETHYLENE IN THE PRODUCTION OF VINYL ACETATE BACKGROUND OF THE INVENTION Field of the Invention This application is a continuation in part of the US application txQ of series 08 / 252,874 filed &June 2, 1994. This invention relates to a fluid bed process for the synthesis of olefins or diolefins. In particular, the present invention is directed to a fluid bed process for the production of vinyl acetate from d? ethylene, acetic acid and a gae quo oontiono opígono cn resan * ia of a fluid bed catalyst. More particularly, the present invention is directed to a fluid bed process for the production of vinyl acetate using a fluid bed catalyst from palladium-frc-potasiot. The oom? Oidal production of aoot is already known? "to 3T vinyl poar - reaction of ethyl ester, acide ecé" tlco and OKÉgeno eo? vju? tameiyfcft in f? &? I already had my piAuula from a fixed-bed catalyst containing palladium, a promotional metal and an alkaline metal. Mormalmßnto, loo components of the fixed bed catalyst are supported «on a support or bear such as silicone, airpnnnn n alumina. There are several patents such as the US Patent 3. 759,839 and British Patent 1,266,623 which describe the preparation of vinyl acetate using a catalyst promoted with palladium. In each of these patents, mention is made of the use of a fluid bed process. However, none of these patents mentions any technique or aspect of fluid bed methods that would produce unexpectedly superior or economically beneficial results as compared to the process in fixed form. Of heehß, in each of these refs, the typical conditions under which it leads to ?? b? ? l p¿ < í? jét?, r > What is it? What is it? dt-sl l? vl? hu 11 j u. There are numerous disadvantages in relation to the process of preparing vinyl acetate in a fixed-bed process. Some of these disadvantages are: 1, The catalyst used continuously is deactivated in the fixed bed reactor with the service time. This leads to a decrease in the production of vinyl acetate. In this way, the product and the aißt mß. The efficiency of the production process should be such that the high initial yields of vinyl acetate are governed and as the yields of vinyl acetate decrease, a portion of the product recovery train is not used and capital is wasted. 2. Fixed bed catalyst experiences uneven temperatures throughout the length of the reastor Catalyst exposed to excessively high temperatures normally experiences premature aging. The catalyst that is in areas below the desired operating temperature will not react optimally to produce the maximum amount of vinyl acetate. 3. Ethylene conversion is limited by the level of oxygen fed to the fixed-bed reactor. * In a fixed-bed operation, the oxygen is mealated pre iamRn R r.np p.l and acetic acid stream before entering the reactor. This compfsi? Ii n. d.e the melee t2s alimp.nt? pi? n p, nt, ftr¡ =? ? php being outside the flammability zone or there will be explosion / fire hazards. Therefore, the amount of fuel that can be fed to the reactor is limited by the flammability limits of the mixture. 4. The reaction of vinyl acetate in a fixed bed is severely limited by diffusion. Therefore, h? flß flfi? imrßa ora esrf? mrtn rnr-n pinnfnr nni-ril i? iUs where the active components are in a WP * eüstBima fine over. ? ñ piipnrripip. fip, more partíruine Fixed-bed catalysts that have a uniform dispersion of active material throughout the particle produce A.o. tic.l.iMái? l: e a few fewer kilograms of vinyl acetate per kg of noble metal, compared with catalysts that have an outer layer. 5. In a typical fixed bed procedure, a catalytic activator must be added continuously (aßJS.tß.'teF JiA'fe? .B-LfiA) & AUb -Liílt !. iljuni: v on-io what? ca? -. t-.l ??? . Rt »L < j means that the activator is added at the input to the "1000 * 010 do Ißßkß fixed pii ** uiiMpltMaLu a.1 m ^ iLMaütu ¡? salt © reactor. This method of adding the activator is translated. in a non-uniform distribution of the activator on the catalyst which, in turn, results in less active and more active catalyst ions. The fluid bed process of the present invention solves many of the disadvantages of typical commercial surface operation, which is surprisingly superior compared to fixed bed processes. The advantages of the fluid bed process of the present invention will be described in detail below. SUMMARY OF THE INVENTION The main object of the present invention is to provide a pre-defined purpose for the ov.accession of olefins or diolefins. Another object of the present invention is to provide a fluid bed process for the piecing of vinyl acetate from ethylene, acetic acid and oxygen.

A further object of the present invention is to provide a fluid bed process for the preparation of vinyl acetate using a bed catalyst IIUIÜO to D is ae paiaaio or oase ae paiaaio-oro-po-casiu. Other objects and advantages of the invention are lii-s & iirA? d-bir? .. - -, ßr. parts, of the next deaeriTpeió? 'and, in part, will be evident from the description?> g © educir n of. ln pup.R n The invention and the objects and advantages of the invention can be realized and achieved by means of the arrangements and combinations particularly indicated in the appended claims, wherein the invention and the present invention, the invention, the invention, the invention and the invention. The process of preparing vinyl acetate in a fluid bed reactor comprises feeding ethylene and acetic acid into the fluid bed reactor through one or more inlets, feeding an oxygen containing gas into the fluid bed reactor through the at least another entry, join? _iu? ju-.Let ?? ifc; nl.fc5 ye-s quts u.-Lißuts uxíy «iiu,« 1 wLilßii? and the acetic acid in the fluid bed reactor while pit n P? pont-Arvtn pn a native mñl-prinl fien of fluid bed to allow ethylene, acetic acid and oxygen to react to produce vinyl acetate, and recover the vinyl acetate from the bed reactor luido In a preferred embodiment of the present invention, ethylene and acetic acid are fed into the reactor as a gaseous mixture through S uriñ n mññ .n rñdf-ñ. In another embodiment of the present invention, the oxygen containing gas is fed to the reactor through more than one inlet. In a further preferred embodiment of the present invention, the gaseous mixture of ethylene and acetic acid contains oxygen below its flammability limit in the mixture. In another preferred embodiment of the invention, the fluid bed catalyst used for ñ nnnpr P? nr? r.f.ipp ñl nrnpññn rtp, l? nrññn, invp.npi? n comprises a catalyst of the following formula Pd-MA wherein M comprises Ba, Au, Cd, Bi, Cu, Mn, Fe, Co, Ce, U and mixtures e thereof and A comprises a alkali metal or mixtures thereof (preferably potassium), 0% by weight, the percentage by weight of the podode and the alkali metal in the catalyst is as follows: 0.1 to 5% in the case of a phthalate, , to 10% by weight of alkali metal, preferably 0.01 to 5% by weight. In addition, the weight percentage of M can range from 0 to 5% by weight approximately, with preference more than O to 5% by weight, especially 0.1 to 3% by weight. The fluid bed catalyst is prepared according to the procedures set forth in co-pending US Patent Application Serial No. 08 / 252,800, assigned to the assignee of the present application and incorporated herein for reference purposes only. Rn or a pfefe modality of. the prese and invention, the amount of catalyst including other fluidizable solids (e.g., inert particulate materials such as silica) present in the fluidized bed reactor is maintained at a sufficient level already. Cijiqui Lij- la di? i? iwi'i the? il? 'fti'ift'? i-l? diAir &? tft. the reaction, in order to allow the reaction to proceed without damage &Z? the oatalima o. According to yet another preferred embodiment of the present invention, the fluid bed catalyst contains at least 60% of the catalyst particles with a diameter of less than 200 microns (0.2 mm) and not more. less than 40 microns (0.04 m). Preferably, the diameter of the particles of the catalyst is such that at least 50% of the particles are less than 100 myrrhs (0.1 mm), moreover the particles have a diameter that is less than 40 microns ( 0.04 mm). The operation of the fluid bed process of the ¿JJ. ,? LJ, LLW &? I? we.eue.lME nlguíiiß ia loa di.o * ir? * oo disadvantages described previously in the current commercial operation in fixed bed in prnrinci r nr.pfpfn? p vinyl. In the fluidized-bed process, the catalyst is made available to me, and thus to a significant improvement in the homogeneous addition of the promoter, even if it is introduced through of a single exit. In addition, the fluid bed operation allows the continuous separation of a portion of the deactivated catalyst and the continuous replacement of the catalyst during operation. This translates into an aoportant year. ? da aa, a roaotor do looho fluid is almost isothermal by design, which minimizes the deactivation of the heat and rinnfipmipnpin of the exposure to excessive heat. Finally, in the fluid bed process of. In the present invention, oxygen is normally not mixed with the hydrocarbon hññtf. up. Thus, the catalyst is present when the feed is first mixed at the reaction temperature and the reaction proceeds immediately. This means that the partial pressure of oxygen begins to fall in the ac-co. In addition, oxygen can be increased with a hydrogen-containing gas, as in a fixed-bed operation, while it can more oxygen is sprayed into the reactor through the separate inlet. This unique feature of the fluidized bed process makes it possible to use significantly higher oxygen levels at the same time in the use of acetic acid and ethylene to vinyl ßßetat, without danger of flammability. The use of higher levels of oxygen allows eustanoially higher levels of conversion of ethylene and acetic acid than possible in the fixed-bed process. The ratio of the sum of ethylene, acetic acid to oxygen-containing gas entering the reactor can be within the flammability limits of said mixture. BRIEF DESCRIPTION OF THE DRAWING Figure 1 is a schematic illustration of the process of the present invention. DETAILED DESCRIPTION OF THE INVENTION In general, the > taa & is & of the invention, the invention comprises the preparation of vinyl acetate in a fluid bed reactor comprising feeding ethylene and acetic acid into the fluid bed reactor, preferably in the gaseous state, through at least one entry; feeding a gas containing oxygen into the fluid bed reactor through at least one second inlet; gather the gas containing oxygen, ethylene and acetic acid in the reactor fluid bed while in contact with a fluid bed catalyst, to allow ethylene, acetic acid and oxygen to react to produce aeß * a, ugly. vinyl, and recover the vinyl acetate from the 5 fluid bed reactor. With reference to Figure 1, the general outline of the fluid bed process of the present invention for the ethyoxylation of acetyl to produce vinyl acetate (or the o-oxyacylation of olefins or diolefins in general) will now be described in detail. The fluidized bed reactor 7 containing a fluidizable microspheroidal catalyst is equipped with cooling coils 9 which provide heat transfer from the reactor. In reactor 7, a mixture of ßLilenu and Jisμc sa JenLj-u from the reactor by means of a grid or sprayer (no • 1 i! ** .- * ti * *) ne ta »* _.__ * _. "*? Ia * ii * l to att aal i? *__to_. Acetic acid can be supplied partially by acetic acid and ethylene recine by line 31. In addition, oxygen can be added to the stream sent by line 3 provided that the concentration of oxygen in the stream is maintained below that which would result in the formation of a flammable mixture. _-_ r DI _ _. j_y -.- i_j _ »c¡ cil-Liirc --- Lgi s.1 i ?? Lc_lu- dc; l J?? s _ c _ (_. Lu_- through line 1 as a separate stream and dispersed in the reactor by means of a grid or lUt-X £ tUU¿ 1IU llus LJ-ClJ-Wi 5 »and read lea dls ^ c- SiliS-i J < = 1 yuo and < ~ > ? separated. Oxygen can be added in pure form or as. -. IJ-JI.I l? ni i? i a * -.-, a? -iinñpnn n rli? nn end carbon. This stream of oxygen can be mixed t-smhion pnn hajnß1 niThrathia da hi prrr rirnir ale? rnmn ßthylene or acetic acid always, again, the mixture is still outside the limits dp. inflammability. Because the gaseous streams provided by lines 3 and 1 never mix before entering the reactor and once the reaction by the catalyst in the reactor has begun, flammable gas mixtures are not obtained. The gaseous effluents produced in the reactor 7 are passed through a cyclone and / or filtration system 13 which separates any solid catalyst that escapes from the gaseous product obtained. The catalyst is then recycled to the reactor via line 15 or collected for the recovery of metals through line 16. In a preferred embodiment, new catalyst can be supplied together with the catalyst recycled through line 14. In addition, the promoter material can be added completely or partially to the catalyst system together with the new catalyst through line 14, thereby the need to add promoter is eliminated or supplemented by line 5. The gaseous reaction product stream leaving the top of the cyclone or filter 13 is directed towards the product separation unit 19 by i__ i ____ "_. 1C ».- v..i? _-? J- __iuuj_Lμ. * _? ace. ks * u «jß áa aao-ßa% o da. vinyl is recovered through line 21. Any proc.eml.ntn can be used. rf.c.up "ration and purification known in the art, including those described in US Patent 3,759,839 incorporated herein for reference purposes only or in British Patent 1,266,623, The remainder of the stream containing ethylene, acetic acid, carbon dioxide (and / or other inerts) and oxygen, unreacted, is transported via line 20 for re-circulation to the fluid bed reactor. In order to avoid excessive accumulation of inerts, including e & amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amp; amphetamine, it can t.ansp.f'teatfs? A small creep current through line 23 to an inert separation station. where the inerts are separated and transported by line 27 for distribution, while the remaining current is transported by line ß oe new to line 31 for reentry into reactor 7. It can be supplied - Add new ethylene to the charcoal of I-cycle 01 through line 29. Acetic acid can be supplied new through line 4 to the recycle stream for entry into the Loj area: 7 through line 3. The process is usually carried out at high pressures. Typically, pressures of from about 3.5 to 14 kg / cm 2, preferably from about 5.25 to 10.5 kg / cm 2, are employed. t.a t.p.tn.p.rn urft of the reactor can generally range between 100 and 25QaC, with temperatures of 135 to 190'C being more preferred. In general, higher temperatures may be more readily used when using lower pressures, such as ethylene, acetic acid and oxygen may vary. Normally, the useful concentration ranges are as indicated below: Ethylene - 30 to 70%, preferably 35 to 65%, plus prp.fornntnmnr.tr. 40 r. fiO ^ i Acetic acid - 10 to 25%, preferably 12 to 22%, more preferably 15 to 20%; 0_ví¿)? _ '. O - 0 a 2CÍ ,, 9 a. fifteen%. The rest of the currents are constituted by m? Tpri? L inprfp f? L or rlpp? Rhnnn. nitrogen, argon and helium. The main limitation on the feed composition is that the oxygen level in the effluent stream leaving the reactor must be sufficiently low so that the gas stream that leaves the fluid bed reactor is outside the flammability zone. This level is controlled by the amount of oxygen in the feed, by the ¡H_? Or < sie sß? we? 'uiúiüL úa? nít! j_i - ü den ro dol rontortor jr for the concentration of inerts in the effluent stream. The following examples are given below for the purpose of illustrating the present invention. EXAMPLES Ji__U5__iPJtQmJ_: as indicated in US Patent No. 5,185,308. A fixed bed catalyst representative of the composition was prepared as follows: 0.91% by weight Pd, 0.3% in PC3? Au and 3.2% e cocoa K aobrt. oílioe cofacae KA-160 (5 m): The appropriate weights of Na2PdCl4 and IIAuCli were dissolved in 0.7 ml of distilled a.ua and the solution was impregnated on 15 g of silica spheres KA-160 - El fiñl in hu .dn fifi de. jó p.n rfipnfin dujra ñ va iañ hours. An aqueous solution of sodium metasilicate was then poured onto the wet solid. Again at. dtíj? cl -.úlldu c-ii xejjuau duJ- ai? t_ the nw_-ts > . S > ? s > then added an aqueous solution of hydrazine hydrate to the solution covering the catalyst spheres. The wet solid was allowed to stand overnight. The solid was then drained and washed until free of chloride with distilled water. The solid was dried at 60 ° C, then the appropriate amount of potassium acetate in aqueous solution was impregnated on the solid and the finished catalyst was dried at 60 ° C. The final evaluation ñp RR e, p? T? L 1 Tipdnr bf_jn the following conditions: Feeding: C2H4: HOAc: 02: He = 53.1: 10.4: 7.7: 28.6 ÍHSV: j? O? nr Temp: 150 ° C (in hot zone) Pressure; 8.05 kg / cm2 relative CctJ-y-i d? ¿L_? Li __-_ < _l «_» -,.,.?., 50 g Dilution of catalyst: 30 ce of 4 m glass spheres produced a selectivity of 94.2% to vinyl acetate at an ethylene conversion of 8% ( calculation based on the registered oxygen conversion of 32.2%). Example 2 i Preparation of fluid bed catalyst. A catalyst with the desired composition corresponding to 0.90% by weight Pd, 0.40% by weight Au, 3.1% by weight K was prepared by the preferred method using read to »indicated above. Na2FdCl4 (8.57 g) and HAuCl4 (2.18 g) were dissolved in 128 g of water flp¡ = ¡ti Iñd ?. This solution was then added slowly to 210 g of the spherical silica support (A-160, Sud Chemie), The solution-support mixture was swirled and then BU? V uyuLo μ __- was applied to ensure a homogeneous coating. Egt mixture was left for 2 hours at room temperature and it was then observed that the totality of the oxidation had practically been absorbed on the impregnated solution, and a solution of 15.1 g of etasilicide was discharged. or sñpicn disup.lnp, n 7ñ ?, a de. distilled water • This mixture was allowed to stand for 3 hours. At this time, 26.8 g of hydrazine hydrate was added and the mixture was allowed to stand overnight. The solid spheres were then thoroughly washed with distilled water from the solid. The solid Sfe dried at 60 ° C during the night, which brought about the crushing of the spheres «smells aeaao. The crushed oatuiis-aor (.0Q g) was ground overnight with 133 g of silica sol (30 wt.% D.SiO.) And sufficient water to provide an olturable consistency. The catalyst slurry was then spray dried to form microspheroidal particles. A portion of the microspheroidal solid (15 g) was then impregnated with 0.75 g of acetate dissolve-bß in 10 g of deethylated water. This solid was dried at 60 ° C overnight. Microscopic examination of the finished catalyst revealed the existence of well-shaped microspheroidal particles. The evaluation of the catalyst was carried out in a 40-c fluid bed reactor under the conditions specified in Example 1, except that the catalyst bed was composed of 7, 5 g of catalyst diluted with sufficient support of fluid bed of inert silica paire ps-saueir a volume of looho total of 30 ce. An ethylene conversion of 5 was obtained, 2% with a selectivity to acetate dp vinyl dp, 3.7%, i nrt.Loando that the method of preparation used turned out to be effective. Examples 3-7: Effect of process variables on the performance of the catalyst. bed. The catalyst prepared in Example 2 was tested in order to determine the effect of the concentration of oxygen feed, space velocity and temperature on the temperature of the cycler. The percentage of ethylene in the feed remained constant and at the level of the nitrogen content. feed was adjusted downward as oxygen or acetic acid levels increased. HE. They noted the following observations: TABLE 1 iUlem lp a Ü á z% Oa Food 7.7 15.4 15.4 15.4 15.4 % HOAc Alim. 10.4 10.4 15.8 10.4 10.4 T (° C) 160 160, 160 160 170 GHSV 3080 3850 3850 3080 3080 C2 tion (%) 6.0 7.4 7.7 8.5 10.2 VAM 93.0 90.6 92.5 91.2 86.4 Selectivity (%) Table I above shows that good levels of selectivity and conversion are maintained in a broad Ormiri dp, nrli ni? TIP.S de. the imp.ntf_i.ion n. Example 8: Fluidized bed catalyst pre-salt 6.80 g of Na ^ ACl was dissolved, and 1, 7 or GP HAuCl4 in 110 g of distilled water and the solution was impregnated «ohrf», 200 g dr. fifi p.rfiñ fi fiílirifi KA-lfiO (ñ mm). The wet solid was allowed to stand for 2 hours, after which a solution of 12 g of Na2Si3 in 240 g of distilled water was added thereto, mixed gently and the solid left again for 2 hours. To this mixture was added 21.3 g of 55% hydrazine hydrate. This mixture was allowed to stand for 2 hours. The OD oolion was rotated solid and the solid was washed with fresh distilled water until a test was obtained. negative regarding chloride. The precursor spheres were heat-sealed overnight on 60 * C, 200 g of this catalytic precursor were ground and mixed with 19.05 g of ground KA-160 (wash to remove chloride), 202.8 g of silica sol Snotßx-N-30 (36% by weight solids) and sufficient water to provide a grindable consistency in the slurry. This. The grout was milled overnight and then spray dried. The icroesfeiuid catalytic particles were then dried in an oven at 110 ° C. an pooo nd and 0.25% by weight Au, 1.66 g of potassium acetate was dissolved in 3 3, g g of distilled water and this solution was dissolved in 15.85 g of the anterioireß icosphenoidal particles. After drying, the agar contained 0.5% by weight of potassium acetate. Examples 9 to 12 end ni nenaptnr. The mixture of 14.5 g of the catalyst of Example 8 and sufficient lucerizable silica was placed to provide 30 cc. The conditions and results are as follows; _j_á_amplo 1 IX 12% C2H4 Alim. 50, 2 48, 4 45, 6 45, 9% 0Z Aüm, 5, 3 8, 6 9, 7 8, 9 % H0As Alim. 10.3 9.9 13.5 13.7 % N2 Alim. 34.3 33.1 31.2 31.4 Total flow 380.8 394.3 418.5 415.9 Temp. (° C) 156 157 165 158 Pressure (relative kg / cm2) 8.05 8.05 8.05 8.05 nftn? Rftr,? 1? N rIS¡TT4 (*) 12, 0 17.5 20.5 16, 2 Selectivity VAM (%) 90.0 87.7 86.1 89.3 Example 13. A portion of. 16 g of the catalyst prepared in Example 8 was calcined at 640 ° C in air for 2 hours. To this calcined solid was added 1 6 g of potassium acetate dissolved in 13.5 g of water. The catalyst was then dried at 60 ° C. E? EmpAQ.3_ Ll_ > __ _5_ 16.05 g of the catalyst of Example 13 was mixed with enough inert microspheroidal silica to give 33 co. The t-tt-litici-t mixture was introduced into a fluid bed reactor with the following results. Example 14. 15.% C2H4 Alim. 47.2 45.2% 02 Alim. 6.7 '10.5% H0Ac Alim. 14,0 13.4% N2 Alim. 32.2 30.9 Total flow 405 422 ,5 Temp. (• C) 154 168 Pressure (kg / cm2 8, 05 8, 05 relative) Conversion C, H4 (%) 11, 1 16, 9 Selectivity VAM (%) 91, 8 83, 7 Example 16 A catalyst was prepared spray drying as described in Example 8 except that it contained 17% by weight of silica derived from the sun and the levels of the palladium and gold reagents were increased to give 0.69% by weight of Pd and 0.25% by weight of Au (without potassium acetate). 16 g of this microspheroid solid were calcined for half an hour at 400 ° C, followed by 2 hours at 640 * c 1.57 g of potassium acetate was dissolved in 13.5 g of distilled water and the solution was impregnated on 15 g rlp.l sñlirtn and pyridinium. fifi p. A final alliance was se ó __ 60ßC 13.3 g of the catalyst of Example 6 was mixed with enough inert ionosulphuric acid to yield 30 cc. This catalytic mixture was tested in a fluid locus reactor with the eiguiontoe reected: Example 12 13. Xa % C2H4 Food 47.9 45.6 44.8% 0Q Food 5.1, 9.7 11.1 % N2 Alim, 32.7 31.0 30.6 Total flow 399 419 426 Tem. (* C) 151 158 167 fie_-x ?? _ (ky /? -? U 0.03 0.0C or, or relative) conversion C2n4 (%) 11.5 15.5 i?, 7 Seler i iriñrl Vñ (%) «.? .. n fi9.3 ßti.Q

Claims (2)

1. REVINDICATIONS &PROCEDURES 1.- A process for the preparation of vinyl acetate in an eac or fluidized bed, because it comprises feeding ethylene and acetic acid to the intqt? Io_? The sprayer will have a fluid flow to one more inlet, feed a gas containing oxygen into the milk reactor through at least one other inlet, flow the oxygen-containing gas, ethylene and acetic acid into the reactor. of fluid bed while in contact with a fluid bed fluidic ai aic to allow ethylene, acetic acid and oxygen to react to produce vinyl acetate, and recover the vinyl acetate from the fluid bed reactor.
2. 2. A process according to claim 1, characterized in that the ethylene and the acetic acid are broken down to the rp? Rvror nomo nnn mp? ¡Nl ft fj? Si ftñ ñ travéi ñp, one or more entries. 3. - A process according to claim 2, eß-ffietenfiaíadß poique the gaseous acetone and acetic acid aceo contains oxygen below its limit of flammability in the mixture. 4 - A process according to any of the preceding claims, characterized in that the gas that cuA-tits-ue uj-i env alluiente- al icavL? I a tj-avés dw more of an additional entry. 5. - A process according to any of the preceding claims, characterized in that the fluid bed catalyst has the formula Pd-M-A wherein M rnm? Ran? _ Rñ. ftii rfl. Ri. . Mu. FP. end. or. TI n mpTinlpñ of them and A comprises an alkali metal or mixture thereof. C. - Uir. j5-jrß «* ß & ß * gú? _ cuslqu-.ßse. Read the previous claims, characterized in that it comprises maintaining the quantity of fluid bed catalytic material in said reactor in a sufficient volume to allow the dissipation of the heat generated during the reaction of ethylene, acetic acid and oxygen-containing gas, thereby allowing quft said reaction proceeds without any damage in the fluid bed catalyst. 7. A process according to claim 6, ca aoterl-sadu because dlohu fluid bed catalytic material comprises a mixture of catalytic material in parc .. and matori l unbound on pittíaulac. 8. A process according to any of the preceding claims, characterized in that at least 60% of the particulate fluid bed catalytic material has a particle size diameter of less than 200 mi iao and? _? _? ui? ßi d «¡l -i0 > of the »| j lí? ulab LIOLQIÍ Llt-at. They have a diameter of less than 40 microns. 9. - A process according to any of the preceding claims, characterized in that at least 50% of the particulate fluid bed catalytic material has a particle diameter of less than 100 microns and no more than 40% of the catalytic particles have a diameter smaller than 100 microns. 40 microns. 10. A process according to any of the preceding claims, characterized in that the xelaion of the sum of etxleu ?, acetic acid to oxygen-containing gas entering the reactor is found mixture. 11. A process according to any of the preceding claims, characterized in that the concentration of ethylene in the combined gas feeds, which a_? L _.-__ oa or ol r_._. Uuu? uu du 30 to 70% one volume. 12. A process according to any of the preceding claims, characterized in that the concentration of gaseous acetic acid in the combined gaseous feeds entering the reactor is 10 to 25% by volume. 13. - A process according to any of the -!, '&.vi-i? aißa-5S.í _'_- ft? S -._ vL _. *!' _ > _.'_ ¡? _ > , _.?__.cu_/l.c7-.i--c ?, li- UUAUUC the concentration of oxygen in the gaseous feed The process according to any one of the preceding claims, characterized pprgμe further comprises recycling at least a portion of acetic acid, ßtlleno and oxygen. , unreacted, inside d & Lttis? Lox t3 «fluid bed. 15. A process according to any of the preceding claims, characterized in that it further comprises recovering at least a portion of the fluid bed catalytic material that escapes from the fluid bed reactor and recycling said material into the fluid bed reactor. 16. ™ A process according to any of the preceding claims, characterized in that the pressure ranges between 3.5 and 14 kg / cm2 relative and the temperature oscillates between 100 and 250 * C.