Patent Publication Number: US-RE41341-E

Title: Ester synthesis

Description:
The present invention relates to a process for the synthesis of esters by reacting an olefin with a lower carboxylic acid in the presence of an acidic catalyst. 
     It is well known that olefins can be reacted with lower aliphatic carboxylic acids to form the corresponding esters. One such method is described in GB-A-1259390 in which an ethylenically unsaturated compound is contacted with a liquid medium comprising a carboxylic acid and a free heteropolyacid of molybdenum or tungsten. This process is a homogeneous process to which the heteropolyacid catalyst is unsupported. A further process for producing esters is described in JP-A-05294894 in which a lower fatty acid is esterified with a lower olefin to form a lower fatty acid ester. In this document, the esterification reaction is carried out in the gaseous phase in the presence of a catalyst consisting of at least one heteropolyacid salt of a metal e.g. Li, Cu, Mg or K, being supported on a carrier. The heteropolyacid used is phosphotungstic acid and the carrier described is silica. 
     It has now been found that the process efficiency can be improved significantly by co-feeding water to the reaction mixture. 
     Accordingly, the present invention is a process for the production of lower aliphatic esters said process comprising reacting a lower olefin with a saturated lower aliphatic mono-carboxylic acid in the vapour phase in the presence of a heteropolyacid catalyst characterised in that an amount of water in the range from 1-10 mole % based on the total of the olefin, aliphatic mono-carboxylic acid and water is added to the reaction mixture during the reaction. 
     A feature of the invention is the addition of water as a component of the reaction mixture. Surprisingly, it has been fond that the presence of water in the reaction mixture in an amount of 1-10 mole %, preferably from 1 to 7 mole %, e.g. 1 to 5 mole %, based on the total feed enhances the stability of the catalyst and thereby enhances the efficiency of the process. Furthermore, the presence of water also reduces the selectivity of the process to undesired by-products such as e.g. oligomers and other unknowns, excluding diethyl ether and ethanol. 
     It has further been found that dosing the reaction mixture with amounts of di-ether such as e.g. diethyl ether, as a co-feed also reduces the formation of undesirable by-products. The amount of di-ether co-fed is suitably in the range from 1 to 6 mole %, preferably in the range from 1 to 3 mole % based on the total reaction mixture comprising the olefin, the aliphatic carboxylic acid, water and diethyl ether. The di-ether co-fed may correspond to the by product di-ether from the reaction generated from the reactant olefin. Where a mixture of olefins is used, e.g. a mixture of ethylene and propylene, the di-ether may in turn be an unsymmetrical di-ether. The di-ether co-feed may thus be the by-product of the reaction which by-product is recycled to the reaction mixture. 
     The term “heteropolyacids” as used herein and throughout the specification is meant to include the free acids. The heteropolyacids used to prepare the esterification catalysts of the present invention therefore include inter alia the free acids and coordination type salts thereof in which the anion is a complex, high molecular weight entity. Typically, the anion is comprises 2-18 oxygen-linked polyvalent metal atoms, which are called peripheral atoms. These peripheral atoms surround one or more central atoms in a symmetrical manner. The peripheral atoms are usually one or more of molybdenum, tungsten, vanadium, niobium, tantalum and other metals. The central atoms are usually silicon or phosphorus but can comprise any one of a large variety of atoms from Groups I-VIII in the Periodic Table of elements. These include, for instance, cupric ions; divalent beryllium, zinc, cobalt or nickel ions; trivalent boron, aluminium, gallium, iron, cerium, arsenic, antimony, phosphorus, bismuth, chromium or rhodium ions; tetravalent silicon, germanium, tin, titanium, zirconium, vanadium, sulphur, tellurium, manganese nickel, platinum, thorium, hafnium, cerium ions and other rare earth ions; pentavalent phosphorus, arsenic, vanadium, antimony ions; hexavalent tellurium ions; and heptavalent iodine ions. Such heteropolyacids are also known as “polyoxoanions”, “polyoxometallates” or “metal oxide clusters”. The structures of some of the well known anions are named after the original researchers in this field and are known e.g. as Keggin, Wells-Dawson and Anderson-Evans-Perloff structures. 
     Heteropolyacids usually have a high molecular weight e.g. in the range from 700-8500 and include dimeric complexes. They have a relatively high solubility in polar solvents such as water or other oxygenated solvents, especially if they are free acids and in the case of several salts, and their solubility can be controlled by choosing the appropriate counter-ions. Specific examples of heteropolyacids that may be used as the catalysts in the present invention include:
         12-tungstophosphoric acid—H 3 [PW 12 O 40 ].xH 2 O   12-molybdophosphoric acid—H 3 [PMo 12 O 40 ].xH 2 O   12-tungstosilicic acid—H 4 [SiW 12 O 40 ].xH 2 O   12-molybdosilicic acid—H 4 [SiMo 12 O 40 ].xH 2 O   Potassium tungstophosphate—K 6 [P 2 W 18 O 62 ].xH 2 O   Sodium molybdophosphate—Na 3 [PMo 12 O 40 ].xH 2 O   Ammonium molybdodiphosphate—(NH 4 ) 6 [P 2 Mo 18 O 62 ].xH 2 O   Sodium tungstonickelate—Na 4 [NiW 6 O 24 H 6 ].xH 2 O   Ammonium molybdodicobaltate—(NH 4 )[Co 2 Mo 10 O 36 ].xH 2 O   Cesium hydrogen tungstosilicate—Cs 3 H[SiW 12 O 40 ].xH 2 O   Potassium molybdodivanado phosphate—K 5 [PMoV 2 O 40 ].xH 2 O       

     The heteropolyacid catalyst whether used as a free acid or as a salt thereof is suitably supported, preferably on a siliceous support. The siliceous support is suitably in the form of extrudates or pellets. 
     The siliceous support used is most preferably derived from an amorphous, non-porous synthetic silica especially fumed silica, such as those produced by flame hydrolysis of SiCl 4 . Specific examples of such siliceous supports include Support 350 made by pelletisation of AEROSIL® 200 (both ex Degussa). This pelletisation procedure is suitably carried out by the process described in U.S. Pat. No. 5,086,031 (see especially the Examples) and is incorporated herein by reference. Such a process of pelletisation or extrusion does not involve any steam treatment steps and the porosity of the support is derived from the interstices formed during the pelletisation or extrusion step of the non-porous silica. The silica support is suitably in the form of pellets or beads or are globular in shape having an average particle diameter of 2 to 10 mm, preferably 4 to 6 mm. The siliceous support suitably has a pore volume in the range from 0.3-1.2 ml/g, preferably from 0.6-1.0 ml/g. The support suitably has a crush strength of at least 2 Kg force, suitably at least 5 Kg force, preferably at least 6 Kg and more preferably at least 7 Kg. The crush strengths quoted are based on average of that determined for each set of 50 beads/globules on a CHATTILLON tester which measures the minimum force necessary to crush a particle between parallel plates. The bulk density of the support is suitably at least 380 g/l, preferably at least 440 g/l. 
     The support suitably has an average pore radius (prior to use) of 10 to 500 Å preferably an average pore radius of 30 to 100 Å. 
     In order to achieve optimum performance, the siliceous support is suitably free of extraneous metals or elements which might adversely affect the catalytic activity of the system. The siliceous support suitably has at least 99% w/w purity, i.e. the impurities are less than 1% w/w, preferably less than 0.60% w/w and more preferably less than 0.30% w/w. 
     Other pelleted silica supports are the Grace 57 and 1371 grades of silica. In particular, Grace silica No. 1371 has an average bulk density of about 0.39 g/ml, an average pore volume of about 1.15 ml/g and an average particle size ranging from about 0.1-3.5 mm. These pellets can be used as such or after crushing to an average particle size in the range from 0.5-2 mm and sieving before being used as the support for the heteropolyacid catalyst. 
     The impregnated support is suitably prepared by dissolving the heteropolyacid, which is preferably a tungstosilicic acid, in e.g. distilled water, and then adding the support to the aqueous solution so formed. The support is suitably let to soak in the acid solution for a duration of several hours, with periodic manual stirring, after which time it is suitably filtered using a Buchner funnel in order to remove any excess acid. 
     The wet catalyst thus formed is then suitably placed in an oven at elevated temperature for several hours to dry, after which time it is allowed to cool to ambient temperature in a desiccator. The weight of the catalyst on drying, the weight of the support used and the weight of the acid on support was obtained by deducting the latter from the former from which the catalyst loading in g/liter was determined. 
     Alternatively, the support may be impregnated with the catalyst using the incipient wetness technique with simultaneous drying on a rotary evaporator. 
     This supported catalyst (measured by weight) can then be used in the esterification process. The amount of heteropolyacid deposited/impregnated on the support for use in the esterification reaction is suitably in the range from 10 to 60% by weight, preferably from 30 to 50% by weight based on the total weight of the heteropolyacid and the support. 
     In the esterification reaction, the olefin reactant used is suitably ethylene, propylene or mixtures thereof Where a mixture of olefins is used, the resultant product will inevitably a mixture of esters. The source of the olefin reactant used may be a refinery product or a chemical grade olefin which invariably contain some alkanes admixed therewith. 
     The saturated, lower aliphatic mono-carboxylic acid reactant is suitably a C1-C4 carboxylic acid and is preferably acetic acid. 
     The reaction mixture suitably comprises a molar excess of the olefin reactant with respect to the aliphatic monocarboxylic acid reactant. Thus the mole ratio of olefin to the lower carboxylic acid in the reaction mixture is suitably in the range from 1:1 to 15:1, preferably from 10:1 to 14:1. 
     The reaction is carried out in the vapour phase suitably above the dew point of the reactor contents comprising the reactant acid, any alcohol formed in situ, the product ester and water as stated above. The amount of water is in the range from 1-10 mole %, suitably from 1-7 mole %, preferably from 1-5 mole % based on the total amount of olefin, carboxylic acid and water. Dew point is the temperature at which condensation of a vapour of a given sample in air takes place. The dew point of any vaporous sample will depend upon its composition. The supported heteropolyacid catalyst is suitably used as a fixed bed which may be in the form of a packed column. The vapours of the reactant olefins and acids are passed over the catalyst suitably at a GHSV in the range from 100 to 5000 per hour, preferably from 300 to 2000 per hour. 
     The esterification reaction is suitably carried out at a temperature in the range from 150°-200° C. using a reaction pressure which is at least 400 KPa, preferably from 500-3000 Kpa depending upon the relative mole ratios of olefin to acid reactant and the amount of water used. 
     The water added to the reaction mixture is suitably present in the form of steam and is capable of generating a mixture of esters and alcohols in the process. The products of the reaction are recovered by e.g. fractional distillation. Where esters are produced, whether singly or as mixture of esters, these may be hydrolysed to the corresponding alcohols or mixture of alcohols in relatively high yields and purity. By using this latter technique the efficiency of the process to produce alcohols from olefins is significantly improved over the conventional process of producing alcohols by hydration of olefins. 
    
    
     The present invention is further illustrated with reference to the following Examples and Comparative Tests. 
     EXAMPLES 
     In all the Examples, the reaction conditions used and the results achieved are tabulated below. In these tables, the following abbreviations have been used: 
     
       
         
           
               
               
               
             
               
                   
                   
               
             
            
               
                   
                 HOS 
                 Hours on stream 
               
               
                   
                 Bed (T/M/B) 
                 Bed (top/middle/bottom) 
               
               
                   
                 HAC 
                 Acetic Acid 
               
               
                   
                 C 2 H 4   
                 Ethylene 
               
               
                   
                 H 2 O 
                 Water 
               
               
                   
                 EtAc 
                 Ethyl acetate 
               
               
                   
                 EtOH 
                 Ethanol 
               
               
                   
                 DEE 
                 Diethyl ether 
               
               
                   
                 GHSV 
                 Gas hourly space velocity 
               
               
                   
                 g/Lcat/h 
                 Gram per liter of catalyst per hour 
               
               
                   
                 STP 
                 Standard temperature &amp; pressure 
               
               
                   
                 STY 
                 Space time yield 
               
               
                   
                   
               
            
           
         
       
     
     Example 1 
     A. Catalyst Preparations 
     Catalyst 1 
     Silica granules (Grace 1371 grade, 530 m 2 /g, bulk density 0.39 g/ml, pore volume 1.15 ml/g, ca. 1-3 mm, 70 g, ex W R Grace) were soaked over 24 hours with intermittent stirring in a solution of silicotungstic acid [H 4 SiW 12 O 40 .26H 2 O] (65.53 g, ex Japan New Metals) dissolved in 250 mlo distilled water in order to impregnate the silica support with the silicophosphoric acid catalyst. After this duration, excess catalyst solution was decanted and filtered off. The resultant catalyst impregnated support was then dried in flowing nitrogen gas overnight at 120° C. The supported catalyst so formed was then left in a desiccator to cool and was finally reweighed. The resultant support catalyst had a heteropolyacid catalyst loading of 92 g/liter. 
     Catalyst 2: Silica granules (Grace 57 grade, surface area 510 m 2 /g, bulk density 0.649 g/ml, pore volume 1.0267 ml/g, ca. 5-8 mm, 57.7 g, ex W R Grace) was soaked in a solution of 12-tungstosilicic acid [H 4 SiW 12 O 40 .26H 2 O] (ex Johnson Matthey, 69.4 dissolved in 200 ml distilled water) for 24 hours with intermittent stirring in order to impregnate the support with the catalyst. Thereafter the excess solution of the silicotungstic acid catalyst was removed by decantation and filtration. The resultant catalyst impregnated support was then dried overnight under flowing nitrogen at 120° C. The dried supported catalyst so formed was cooled in a desiccator and had a heteropolyacid catalyst loading of 190g/liter. 
     Catalyst 3: The above process of Catalyst 2 was repeated and was found to have a heteropolyacid catalyst loading of 192 g/liter. 
     B. Catalyst Forming 
     All the catalysts produced above were broken down and sieved to obtain the desired pellet size for loading into the esterification reactor. 
     C. Catalyst Testing 
     The reactor used was a three-zone Severn Sciences reactor constructed of Hastelloy C-276 capable of withstanding glacial acetic acid up to 300° C. and 15000 Kpa (150 barg) pressure (length 650 mm, outer diameter 22 mm, internal diameter 16 mm). It had a thermowell running the entire reactor length (5 mm outer diameter) and 1.77 cm outer diameter Swagelock VCR joints at each end. Gas from cylinders of ethylene and nitrogen were taken off at 1000 Kpa (10 barg) and then compressed to 5000-12000 Kpa (50-120 barg), via Haskel boosters, before being regulated and fed to mass-flow controllers. The liquid feed systems had 2 dm 3  reservoirs maintained under a nitrogen blanket of 10 KPa-80 KPa (0.1-0.8 barg). 
     A cooling jacket was provided to condense products in the gas stream back to liquids prior to collection in a receiver. The majority of the liquid product was collected at room temperature. 
     A pre-heating zone was located upstream of the catalyst bed. The pre-heating zone was separated from the catalyst bed by a plug of glass wool. Another plug of gas wool was used downstream of the catalyst bed to reduce dead volume and help maintain the catalyst bed in the centre section of the reactor. 
     The reaction was started up by pressurising the reactor to 1000 KPa (10 barg) with nitrogen, establishing the desired flow rate (which is the same as that used later for the olefin feed) and then increasing the reactor temperature to the desired operating conditions (170° C. or 180° C.) over a one hour period. The liquid pump for the mixture of acetic acid/water mixture was switched on initially at the desired flow rate and the olefin admitted into the reactor on liquid breakthrough at the collection pots, usually after 2 to 3 hours. The flows were then adjusted to give the desired feed molar ratios and GHSVs. The reactor effluent was collected at regular intervals. Liquid product was drained off, weighed and then analysed by GC. The gas stream was sampled downstream of the liquid collection points and also analysed by GC. Total gas out during a test period was measured using a wet-gas meter. 
     The above process/catalysts were used to esterify ethylene with acetic acid. The relative amounts of each of the Catalysts 1 to 3 used, their bed size and bed length in performing the esterification reaction were as follows: 
     
       
         
           
               
               
               
               
               
             
               
                   
                   
               
               
                   
                 Parameter 
                 Catalyst 1 
                 Catalyst 2 
                 Catalyst 3 
               
               
                   
                   
               
             
            
               
                   
                 Volume (cm 3 ) 
                 25 
                 25 
                 25 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Weight (g) 
                 11.3 
                 (11.4*) 
                 12 
                 12 
               
               
                   
                 Pellet size (mm) 
                 1-2 
                 (0.5-1*) 
                 0.5-1 
                 0.5-1 
               
               
                   
                 Bed length 
                 8.75 
                 (14*) 
                 14 
                 14 
               
               
                   
                   
               
               
                   
                 *Parameters of Catalyst 1 used for the Runs in Table 2   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 1 
               
               
                   
               
             
            
               
                 Run Conditions: (1 Mole % Water added to feed) using Catalyst 1: 
               
            
           
           
               
               
               
               
            
               
                 Parameters 
                 Run No. 1 
                 Run No. 2 
                 Run No. 3* 
               
               
                   
               
               
                 HOS 
                 17-20 
                 42-45 
                 70-73 
               
               
                   
                   
                   
                 (21-24) 
               
               
                 Temperature (° C.) 
               
               
                 Applied 
                 170 
                 170 
                 170 
               
               
                 Bed (T/M/B) 
                 173/—/170 
                 172.5/—/169.5 
                 173/—/168 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
                 1000 
               
               
                 Total feed GHSV/h 
                 980 
                 980 
                 974 
               
               
                 (@ STP) 
               
               
                 C 2 H 4  GHSV/h 
                 905 
                 905 
                 905 
               
               
                 HAC GHSV/h 
                 66 
                 66 
                 69 
               
               
                 H 2 O GHSV/h 
                 9 
                 9 
                 9 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1131 
                 1131 
                 1131 
               
               
                 HAC (g/Lcat/h) 
                 177 
                 177 
                 185 
               
               
                 H 2 O (g/Lcat/h) 
                 8 
                 8 
                 0 
               
               
                 Feed contact time 
                 4 
                 4 
                 4 
               
               
                 [1/GHSV](secs) 
               
               
                 C 2 H 4 /HAC/H 2 O 
                 92.3/6.7/1.0 
                 92.3/6.7/1.0 
                 92.9/14.1/0 
               
               
                 mole % ratio 
               
               
                 C 2 H 4 /HAC/H 2 O wt % ratio 
                 85.9/13.5/0.6 
                 85.9/13.5/0.6 
                 85.9/14.1/0 
               
               
                 C 2 H 4 /HAC mole ratio 
                 13.7 
                 13.7 
                 13.1 
               
               
                   
               
            
           
           
               
            
               
                 *No added water used in this comparative test (not according to the 
               
               
                 invention) 
               
            
           
           
               
            
               
                 Product Analysis 
               
            
           
           
               
               
               
               
            
               
                 Products/Analysis 
                 Run No. 1 
                 Run No. 2 
                 Run No. 3* 
               
               
                   
               
               
                 HAC Conversion 
                 66 
                 64 
                 27 
               
               
                 Product Selectivity (wt %) 
               
               
                 EtAc 
                 97.3 
                 97.8 
                 91.6 
               
               
                 EtOH 
                 0.4 
                 0.3 
                 0.1 
               
               
                 DEE 
                 1.8 
                 1.3 
                 0.0 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 0.3 
                 0.6 
                 1.4 
               
               
                 Others 
                 0.1 
                 0.04 
                 6.8 
               
               
                 EtAc Yield 
                 95 
                 59 
                 25 
               
               
                 EtAc STY (g/Lcat/h) 
                 180 
                 160 
                 44 
               
               
                 Carbon Balance (mol %) 
                 104 
                 105 
                 100 
               
               
                 Oxygen Balance (mol %) 
                 95 
                 102 
                 81 
               
               
                 Mass Balance 
                 103 
                 105 
                 99 
               
               
                 Water recovered (%) 
                 69 
                 73 
                 — 
               
               
                   
               
               
                 *No water used and is hence a comparative test (not according to the invention)   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 2 
               
               
                   
               
             
            
               
                 Run Conditions: (1 Mole % Water added to feed) using Catalyst 1: 
               
            
           
           
               
               
               
               
               
            
               
                 Parameters 
                 Run No. 4 
                 Run No. 5 
                 Run No. 6 
                 Run No. 7 
               
               
                   
               
               
                 HOS 
                 19-22 
                 44-77 
                 68.75-73.75 
                 91-94 
               
               
                 Temperature (° C.) 
               
               
                 Applied 
                 180 
                 180 
                 180 
                 180 
               
               
                 Bed (T/M/B) 
                 181.5/186/182.5 
                 181.5/185/183 
                 181.3/184.5/181.2 
                 181.4/184/181.1 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
                 1000 
                 1000 
               
               
                 Total feed GHSV/h (@ STP) 
                 980 
                 980 
                 980 
                 980 
               
               
                 C 2 H 4  GHSV/h 
                 905 
                 905 
                 905 
                 905 
               
               
                 HAC GHSV/h 
                 66 
                 66 
                 66 
                 66 
               
               
                 H 2 O GHSV/h 
                 9 
                 9 
                 9 
                 9 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1131 
                 1131 
                 1131 
                 1131 
               
               
                 HAC (g/Lcat/h) 
                 177 
                 177 
                 177 
                 177 
               
               
                 H 2 O (g/Lcat/h) 
                 8 
                 8 
                 8 
                 8 
               
               
                 Feed contact time [1/GHSV](secs) 
                 4 
                 4 
                 4 
                 4 
               
               
                 C 2 H 4 /HAC/H 2 O mole % ratio 
                 92.3/6.7/1.0 
                 92.3/6.7/1.0 
                 92.3/6.7/1.0 
                 92.3/6.7/1.0 
               
               
                 C 2 H 4 /HAC/H 2 O wt % ratio 
                 86/13.4/0.6 
                 86/13.4/0.6 
                 86/13.4/0.6 
                 86/13.4/0.6 
               
               
                 C 2 H 4 /HAC mole ratio 
                 13.7 
                 13.7 
                 13.7 
                 13.7 
               
               
                   
               
            
           
           
               
            
               
                 Product Analysis 
               
            
           
           
               
               
               
               
               
            
               
                 Products/Analysis 
                 Run No. 4 
                 Run No. 5 
                 Run No. 6 
                 Run No. 7 
               
               
                   
               
               
                 Ethylene conversion (%) 
                 5.3 
                 3.9 
                 4.1 
                 6.0 
               
               
                 HAC Conversion 
                 71 
                 64 
                 60 
                 54 
               
               
                 Product Selectivity (wt %) 
               
               
                 EtAc 
                 95.9 
                 97.2 
                 97.8 
                 98.1 
               
               
                 EtOH 
                 0.7 
                 0.6 
                 0.5 
                 0.6 
               
               
                 DEE 
                 2.3 
                 1.8 
                 1.3 
                 1.0 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 0.8 
                 0.3 
                 0.6 
                 0.2 
               
               
                 Others 
                 0.3 
                 0.1 
                 0.0 
                 0.0 
               
               
                 EtAc Yield 
                 68 
                 63 
                 59 
                 53 
               
               
                 EtAc STY (g/Lcat/h) 
                 194 
                 183 
                 164 
                 148 
               
               
                 Carbon Balance (mol %) 
                 100 
                 199 
                 100 
                 97 
               
               
                 Oxygen Balance (mol %) 
                 94 
                 89 
                 93 
                 88 
               
               
                 Mass Balance 
                 100 
                 99 
                 99 
                 96 
               
               
                 Water recovered (%) 
                 53 
                 56 
                 62 
                 65 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 3 
               
               
                   
               
             
            
               
                 Run Conditions: (1 Mole % Water added to feed) using Catalyst 2: 
               
            
           
           
               
               
               
               
            
               
                 Parameters 
                 Run No. 8 
                 Run No. 9 
                 Run No. 10 
               
               
                   
               
               
                 HOS 
                 14.75-17.5 
                 38.5-41.5 
                 62.5-65.5 
               
               
                 Temperature (° C.) 
               
               
                 Applied 
                 180 
                 180 
                 180 
               
               
                 Bed (T/M/B) 
                 179.5/189/ 
                 179.6/187.5/ 
                 179.4/186.5/ 
               
               
                   
                 182.8 
                 182.9 
                 182.8 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
                 1000 
               
               
                 Total feed GHSV/h (@ STP) 
                 981 
                 981 
                 981 
               
               
                 C 2 H 4  GHSV/h 
                 905 
                 905 
                 905 
               
               
                 HAC GHSV/h 
                 66 
                 66 
                 66 
               
               
                 H 2 O GHSV/h 
                 10 
                 10 
                 10 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1131 
                 1131 
                 1131 
               
               
                 HAC (g/Lcat/h) 
                 177 
                 177 
                 177 
               
               
                 H 2 O (g/Lcat/h) 
                 8 
                 8 
                 8 
               
               
                 Feed contact time 
                 4 
                 4 
                 4 
               
               
                 [1/GHSV](secs) 
               
               
                 C 2 H 4 /HAC/H 2 O 
                 92.3/6.7/1.0 
                 92.3/6.7/1.0 
                 92.9/6.7/1.0 
               
               
                 mole % ratio 
               
               
                 C 2 H 4 /HAC/H 2 O wt % ratio 
                 85.9/13.5/0.6 
                 85.9/13.5/0.6 
                 85.9/13.5/0.6 
               
               
                 C 2 H 4 /HAC mole ratio 
                 13.7 
                 13.7 
                 13.7 
               
               
                   
               
            
           
           
               
            
               
                 Product Analysis 
               
            
           
           
               
               
               
               
            
               
                 Products/Analysis 
                 Run No. 8 
                 Run No. 9 
                 Run No. 10 
               
               
                   
               
               
                 Ethylene Conversion 
                 7.3 
                 3.9 
                 3.3 
               
               
                 HAC Conversion 
                 81 
                 77 
                 75 
               
               
                 Product Selectivity (wt %) 
               
               
                 EtAc 
                 92.7 
                 95.2 
                 96.0 
               
               
                 EtOH 
                 0.8 
                 0.7 
                 0.7 
               
               
                 DEE 
                 3.8 
                 2.8 
                 2.2 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 1.6 
                 0.9 
                 0.8 
               
               
                 Others 
                 1.1 
                 0.5 
                 0.3 
               
               
                 EtAc Yield 
                 75 
                 73 
                 72 
               
               
                 EtAc STY (g/Lcat/h) 
                 213 
                 211 
                 201 
               
               
                 Carbon Balance (mol %) 
                 100 
                 102 
                 103 
               
               
                 Oxygen Balance (mol %) 
                 99 
                 96 
                 98 
               
               
                 Mass Balance 
                 100 
                 102 
                 103 
               
               
                 Water recovered (%) 
                 45 
                 43 
                 51 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 4 
               
               
                   
               
             
            
               
                 Run Conditions: (5 Mole % Water added to feed) using Catalyst 2: 
               
            
           
           
               
               
               
               
            
               
                 Parameters 
                 Run No. 11 
                 Run No. 12 
                 Run No. 13 
               
               
                   
               
               
                 HOS 
                 90.5-95.5 
                 134.5-137.5 
                 158.5-161.5 
               
               
                 Temperature (° C.) 
               
               
                 Applied 
                 180 
                 180 
                 180 
               
               
                 Bed (T/M/B) 
                 179.3/188.5/ 
                 179.6/188.5/ 
                 179.5/188.5/ 
               
               
                   
                 182.4 
                 183.4 
                 183.4 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
                 1000 
               
               
                 Total feed GHSV/h (@ STP) 
                 975 
                 975 
                 975 
               
               
                 C 2 H 4  GHSV/h 
                 866 
                 866 
                 866 
               
               
                 HAC GHSV/h 
                 61 
                 61 
                 61 
               
               
                 H 2 O GHSV/h 
                 48 
                 48 
                 48 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1083 
                 1083 
                 1083 
               
               
                 HAC (g/Lcat/h) 
                 164 
                 164 
                 164 
               
               
                 H 2 O (g/Lcat/h) 
                 38 
                 38 
                 38 
               
               
                 Feed contact time 
                 4 
                 4 
                 4 
               
               
                 [1/GHSV](secs) 
               
               
                 C 2 H 4 /HAC/H 2 O 
                 88.8/6.3/4.9 
                 88.8/6.3/4.9 
                 88.8/6.3/4.9 
               
               
                 mole % ratio 
               
               
                 C 2 H 4 /HAC/H 2 O wt % ratio 
                 84.2/12.8/3 
                 84.2/12.8/3 
                 84.2/12.8/3 
               
               
                 C 2 H 4 /HAC mole ratio 
                 14.2 
                 14.2 
                 14.2 
               
               
                   
               
            
           
           
               
            
               
                 Product Analysis 
               
            
           
           
               
               
               
               
            
               
                 Products/Analysis 
                 Run No. 11 
                 Run No. 12 
                 Run No. 13 
               
               
                   
               
               
                 Ethylene Conversion 
                 4.4 
                 4.0 
                 4.3 
               
               
                 HAC Conversion 
                 68 
                 72 
                 72 
               
               
                 Product Selectivity (wt %) 
               
               
                 EtAc 
                 85.2 
                 82.9 
                 82.0 
               
               
                 EtOH 
                 3.7 
                 3.7 
                 3.9 
               
               
                 DEE 
                 10.5 
                 13.0 
                 13.6 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 0.6 
                 0.4 
                 0.5 
               
               
                 Others 
                 0.01 
                 0.02 
                 0.07 
               
               
                 EtAc Yield 
                 58 
                 60 
                 59 
               
               
                 EtAc STY (g/Lcat/h) 
                 203 
                 215 
                 210 
               
               
                 Carbon Balance (mol %) 
                 102 
                 103 
                 103 
               
               
                 Oxygen Balance (mol %) 
                 87 
                 87 
                 89 
               
               
                 Mass Balance 
                 101 
                 102 
                 102 
               
               
                 Water recovered (%) 
                 43 
                 39 
                 42 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 5 
               
               
                   
               
             
            
               
                 Run Conditions: (5 Mole % Water added to feed) using Catalyst 3: 
               
            
           
           
               
               
               
               
            
               
                 Parameters 
                 Run No. 14 
                 Run No. 15 
                 Run No. 16 
               
               
                   
               
               
                 HOS 
                 16-19 
                 40-43 
                 112.5-115.5 
               
               
                 Temperature (° C.) 
               
               
                 Applied 
                 180 
                 180 
                 180 
               
               
                 Bed (T/M/B) 
                 179.1/191/ 
                 179.1/190.5/ 
                 179.2/190/ 
               
               
                   
                 183.2 
                 183.5 
                 183.8 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
                 1000 
               
               
                 Total feed GHSV/h (@ STP) 
                 980 
                 980 
                 980 
               
               
                 C 2 H 4  GHSV/h 
                 866 
                 866 
                 866 
               
               
                 HAC GHSV/h 
                 64 
                 64 
                 64 
               
               
                 H 2 O GHSV/h 
                 50 
                 50 
                 50 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1083 
                 1083 
                 1083 
               
               
                 HAC (g/Lcat/h) 
                 170 
                 170 
                 170 
               
               
                 H 2 O (g/Lcat/h) 
                 40 
                 40 
                 40 
               
               
                 Feed contact time 
                 4 
                 4 
                 4 
               
               
                 [1/GHSV](secs) 
               
               
                 C 2 H 4 /HAC/H 2 O 
                 88.4/6.5/5.1 
                 88.4/6.5/5.1 
                 92.3/6.7/1.0 
               
               
                 mole % ratio 
               
               
                 C 2 H 4 /HAC/H 2 O wt % ratio 
                 83.7/13.2/3.1 
                 83.7/13.2/3.1 
                 86/13.4/0.6 
               
               
                 C 2 H 4 /HAC mole ratio 
                 13.6 
                 13.6 
                 13.6 
               
               
                   
               
            
           
           
               
            
               
                 Product Analysis 
               
            
           
           
               
               
               
               
            
               
                 Products/Analysis 
                 Run No. 14 
                 Run No. 15 
                 Run No. 16 
               
               
                   
               
               
                 Ethylene Conversion 
                 6.6 
                 7.6 
                 6.3 
               
               
                 HAC Conversion 
                 86 
                 85 
                 83 
               
               
                 Product Selectivity (wt %) 
               
               
                 EtAc 
                 73.4 
                 74.0 
                 73.2 
               
               
                 EtOH 
                 3.7 
                 3.7 
                 3.5 
               
               
                 DEE 
                 22.0 
                 21.5 
                 22.9 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 0.6 
                 0.7 
                 0.5 
               
               
                 Others 
                 0.2 
                 0.1 
                 0.0 
               
               
                 EtAc Yield 
                 63 
                 63 
                 60 
               
               
                 EtAc STY (g/Lcat/h) 
                 219 
                 221 
                 224 
               
               
                 Carbon Balance (mol %) 
                 106 
                 104 
                 105 
               
               
                 Oxygen Balance (mol %) 
                 103 
                 101 
                 95 
               
               
                 Mass Balance 
                 105 
                 104 
                 104 
               
               
                 Water recovered (%) 
                 40 
                 40 
                 36 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 6 
               
               
                   
               
             
            
               
                 Run Conditions: (5 Mole % Water added to feed) using Catalyst 3: 
               
            
           
           
               
               
               
               
            
               
                 Parameters 
                 Run No. 17 
                 Run No. 18 
                 Run No. 19 
               
               
                   
               
               
                 HOS 
                 160.5-163.5 
                 208.5-211.5 
                 285.5-288.5 
               
               
                 Temperature (° C.) 
               
               
                 Applied 
                 180 
                 180 
                 180 
               
               
                 Bed (T/M/B) 
                 179.2/190/ 
                 179.3/190/ 
                 179.3/190/ 
               
               
                   
                 184.1 
                 184.3 
                 184.2 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
                 1000 
               
               
                 Total feed GHSV/h (@ STP) 
                 980 
                 980 
                 980 
               
               
                 C 2 H 4  GHSV/h 
                 866 
                 866 
                 866 
               
               
                 HAC GHSV/h 
                 64 
                 64 
                 64 
               
               
                 H 2 O GHSV/h 
                 50 
                 50 
                 50 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1083 
                 1083 
                 1083 
               
               
                 HAC (g/Lcat/h) 
                 170 
                 170 
                 170 
               
               
                 H 2 O (g/Lcat/h) 
                 40 
                 40 
                 40 
               
               
                 Feed contact time 
                 4 
                 4 
                 4 
               
               
                 [1/GHSV](secs) 
               
               
                 C 2 H 4 /HAC/H 2 O 
                 88.4/6.5/5.1 
                 88.4/6.5/5.1 
                 88.4/6.5/5.1 
               
               
                 mole % ratio 
               
               
                 C 2 H 4 /HAC/H 2 O wt % ratio 
                 83.7/13.2/3.1 
                 83.7/13.2/3.1 
                 83.7/13.2/3.1 
               
               
                 C 2 H 4 /HAC mole ratio 
                 13.6 
                 13.6 
                 13.6 
               
               
                   
               
            
           
           
               
            
               
                 Product Analysis 
               
            
           
           
               
               
               
               
            
               
                 Products/Analysis 
                 Run No. 17 
                 Run No. 18 
                 Run No. 19 
               
               
                   
               
               
                 Ethylene Conversion 
                 8.8 
                 8.7 
                 8.4 
               
               
                 HAC Conversion 
                 85 
                 86 
                 88 
               
               
                 Product Selectivity (wt %) 
               
               
                 EtAc 
                 73.2 
                 73.0 
                 73.7 
               
               
                 EtOH 
                 3.6 
                 3.9 
                 3.7 
               
               
                 DEE 
                 22.6 
                 22.6 
                 22.1 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 0.5 
                 0.5 
                 0.5 
               
               
                 Others 
                 0.1 
                 0.1 
                 0.1 
               
               
                 EtAc Yield 
                 62 
                 63 
                 65 
               
               
                 EtAc STY (g/Lcat/h) 
                 217 
                 217 
                 225 
               
               
                 Carbon Balance (mol %) 
                 104 
                 104 
                 104 
               
               
                 Oxygen Balance (mol %) 
                 103 
                 103 
                 103 
               
               
                 Mass Balance 
                 103 
                 104 
                 104 
               
               
                 Water recovered (%) 
                 40 
                 41 
                 38 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 7 
               
               
                   
               
             
            
               
                 Run Conditions: (5 Mole % Water added to feed) using Catalyst 3: 
               
            
           
           
               
               
               
               
            
               
                 Parameters 
                 Run No. 20 
                 Run No. 21* 
                 Run No. 22* 
               
               
                   
               
               
                 HOS 
                 375.5-378.5 
                 448.5-451.5 
                 472.5-475.5 
               
               
                 Temperature (° C.) 
               
               
                 Applied 
                 180 
                 180 
                 180 
               
               
                 Bed (T/M/B) 
                 179.3/190/ 
                 179.3/186.5/ 
                 179.3/186.5/ 
               
               
                   
                 184.4 
                 183.4 
                 183.4 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
                 1000 
               
               
                 Total feed GHSV/h 
                 980 
                 1001 
                 1001 
               
               
                 (@ STP) 
               
               
                 C 2 H 4  GHSV/h 
                 866 
                 866 
                 866 
               
               
                 HAC GHSV/h 
                 64 
                 64 
                 64 
               
               
                 H 2 O GHSV/h 
                 50 
                 50 
                 50 
               
               
                 DEE GHSV/h 
                 0 
                 21 
                 21 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1083 
                 1083 
                 1083 
               
               
                 HAC (g/Lcat/h) 
                 170 
                 170 
                 170 
               
               
                 H 2 O (g/Lcat/h) 
                 40 
                 40 
                 40 
               
               
                 DEE (g/Lcat/h) 
                 0 
                 71 
                 71 
               
               
                 Feed contact time 
                 3.7 
                 3.6 
                 3.6 
               
               
                 [1/GHSV](secs) 
               
               
                 C 2 H 4 /HAC/H 2 O/DEE 
                 88.4/6.5/5.1§ 
                 86.5/6.4/2.1§ 
                 86.5/6.4/5/2.1 
               
               
                 mole % ratio 
               
               
                 C 2 H 4 /HAC/H 2 O/DEE 
                 83.7/13.2/3.1§ 
                 79.4/12.5/2.9/ 
                 79.4/12.5/2.9/ 
               
               
                 wt % ratio 
                   
                 5.2 
                 5.2 
               
               
                 C 2 H 4 /HAC mole ratio 
                 13.6 
                 13.6 
                 13.6 
               
               
                   
               
            
           
           
               
            
               
                 Product Analysis 
               
            
           
           
               
               
               
               
            
               
                 Products/Analysis 
                 Run No. 20 
                 Run No. 21 
                 Run No. 22 
               
               
                   
               
               
                 Ethylene Conversion 
                 8.7 
                 2.7 
                 2.4 
               
               
                 HAC Conversion 
                 85 
                 81 
                 80 
               
               
                 Product 
               
               
                 Selectivity (wt %) 
               
               
                 EtAc 
                 74.1 
                 71.9 
                 70.8 
               
               
                 EtOH 
                 3.6 
                 5.0 
                 5.4 
               
               
                 DEE 
                 21.6 
                 22.9 
                 23.3 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 0.5 
                 0.2 
                 0.5 
               
               
                 Others 
                 0.1 
                 0.0 
                 0.0 
               
               
                 EtAc Yield 
                 63 
                 59 
                 57 
               
               
                 EtAc STY (g/Lcat/h) 
                 226 
                 226 
                 222 
               
               
                 Carbon Balance 
                 103 
                 105 
                 105 
               
               
                 (mol %) 
               
               
                 Oxygen Balance 
                 98 
                 101 
                 98 
               
               
                 (mol %) 
               
               
                 Mass Balance 
                 102 
                 105 
                 104 
               
               
                 Water recovered (%) 
                 38 
                 60 
                 63 
               
               
                   
               
               
                 *co-fed additionally with 2 Mole % DEE.   
               
               
                 §No diethyl ether used in this Run   
               
            
           
         
       
     
     
       
         
           
               
               
               
             
               
                   
                 TABLE 8 
               
               
                   
                   
               
               
                   
                   Run No. 23 
                 Run No. 24 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
            
               
                 Run Conditions: (5 Mole % Water + 2 Mole % DEE added to feed) 
               
               
                 using Catalyst 3: 
               
            
           
           
               
               
               
            
               
                 Parameters 
                   
                   
               
               
                 HOS 
                 479.5-500.5 
                 544.5-547.5 
               
               
                 Temperature (° C.) 
               
               
                 Applied 
                 180 
                 180 
               
               
                 Bed (T/M/B) 
                 179.3/186.5/183.4 
                 179.4/187/183.4 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
               
               
                 Total feed GHSV/h (@ STP) 
                 1001 
                 1001 
               
               
                 C 2 H 4  GHSV/h 
                 866 
                 866 
               
               
                 HAC GHSV/h 
                 64 
                 64 
               
               
                 H 2 O GHSV/h 
                 50 
                 50 
               
               
                 DEE GHSV/h 
                 21 
                 21 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1083 
                 1083 
               
               
                 HAC (g/Lcat/h) 
                 170 
                 170 
               
               
                 H 2 O (g/Lcat/h) 
                 40 
                 40 
               
               
                 DEE (g/Lcat/h) 
                 71 
                 71 
               
               
                 Feed contact time [1/GHSV](secs) 
                 3.6 
                 3.6 
               
               
                 C 2 H 4 /HAC/H 2 O/DEE mole % ratio 
                 86.5/6.4/5/2.1 
                 86.5/6.4/5/2.1 
               
               
                 C 2 H 4 /HAC/H 2 O/DEE wt % ratio 
                 79.4/12.5/2.9/5.2 
                 79.4/12.5/2.9/5.2 
               
               
                 C 2 H 4 /HAC mole ratio 
                 13.6 
                 13.6 
               
            
           
           
               
            
               
                 Product Analysis 
               
            
           
           
               
               
               
            
               
                 Products/Analysis 
                   
                   
               
               
                 Ethylene Conversion 
                 1.4 
                 1.3 
               
               
                 HAC Conversion 
                 84 
                 82 
               
               
                 Product 
               
               
                 Selectivity (wt %) 
               
               
                 EtAc 
                 70.6 
                 71.1 
               
               
                 EtOH 
                 5.1 
                 5.2 
               
               
                 DEE 
                 23.9 
                 23.5 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 0.3 
                 0.3 
               
               
                 Others 
                 0.0 
                 0.0 
               
               
                 EtAc Yield 
                 59 
                 58 
               
               
                 EtAc STY (g/Lcat/h) 
                 226 
                 224 
               
               
                 Carbon Balance (mol %) 
                 107 
                 106 
               
               
                 Oxygen Balance (mol %) 
                 103 
                 99 
               
               
                 Mass Balance 
                 106 
                 105 
               
               
                 Water recovered (%) 
                 61 
                 63 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 9 
               
             
            
               
                   
               
               
                 LIQUID PRODUCT DATA 
               
               
                 GCMS 
               
               
                 180° C., 1000 Kpa (10 barg), ethylene/acetic acid = 14 
               
            
           
           
               
               
            
               
                   
                  Run No. 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Organics (% by Wt) 
                 7 
                 17 
                 23 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Water (mole % in feed) 
                 1 
                 5 
                 5 
               
               
                   
                   
                   
                   
                 (+2% DEE) 
               
               
                   
                 Acetic acid (unreacted feed) 
                 52.3 
                 21.2 
                 16.3 
               
               
                   
                 Ethyl acetate 
                 46.5 
                 67.3 
                 69 
               
               
                   
                 Diethylether 
                 0.05 
                 3 
                 3.3 
               
               
                   
                 Ethanol 
                 0.65 
                 7.8 
                 11 
               
               
                   
                 Acetaldehyde 
                 0.002 
                 0.04 
                 0.009 
               
               
                   
                 C6 oligomers 
                 0.0015 
                 0 
                 0 
               
               
                   
                 C8 oligomers 
                 0.0055 
                 0 
                 0 
               
               
                   
                 Miscellaneous oxygenates 
                 0.0065 
                 0 
                 0 
               
               
                   
                 Aromatic hydrocarbons 
                 0.045 
                 0 
                 0 
               
               
                   
                 Unknowns 
                 0.11 
                 0.01 
                 0 
               
               
                   
                 BALANCE: others 
               
               
                   
                 (Hydrocarbons &amp; oxy 
               
               
                   
                 compounds) 
               
               
                   
                   
               
            
           
         
       
     
     Example 2 
     Catalyst Preparations 
     Catalyst 4. 12-Tungstophosphoric acid [H 3 PW 12 O 40 .24H 2 O] (175 g) was dissolved in distilled water (250 ml). Lithium nitrate [LiNO 3 .2H 2 O] (0.652 g) was dissolved in distilled water (˜5 ml). The lithium nitrate solution was added dropwise to the tungstophosphoric acid solution to form Solution “A”. 
     Solution “A” was added to pelleted silica support (Grace 1371 grade, 1-3 mm, 99.5 g, ex W R Grace) and left to soak over 24 hours with occasional stirring in order to impregnate the silica with the tungstophosphoric acid catalyst. After this duration, excess solution “A” was decanted and filtered off. The resultant catalyst impregnated support was then dried in flowing nitrogen gas initially at 150° C. for 3 hours and then raised to 200° C. and maintained at that temperature for 5 hours. The supported catalyst so formed was then left in a desiccator to cool and was finally reweighed. The resultant supported catalyst had a final weight of 164.4 g, a net catalyst loading of 64.9 g and had the formula Li 0.1 H 2.9 PW 12 O 40 .24H 2 O/SiO 2  corresponding to a loading of 255 g/l. 
     Catalyst 4. Pelleted silica support (Grace 1371 grade, 1-3 mm, 70 g, ex W R Grace) was soaked in a solution (250 ml) of 12-tungstosilicic acid [H 4 SiW 12 O 40 .26H 2 O] (65.53 g in distilled water) for 24 hours with intermittent stirring in order to impregnate the support with the catalyst. Thereafter the excess solution of the tungstosilicic acid was removed by decantation and filtration. The resultant catalyst impregnated support was then dried overnight under flowing nitrogen at 120° C. The dried supported catalyst so formed was cooled in a desiccator and had a final weight of 86.2 g, a net catalyst loading of 16.2 g and had the formula H 4 SiW 12 O 40 .26H 2 O/SiO 2  corresponding to a loading of 92 g/l. 
     The above catalysts were used to esterify ethylene with acetic acid. The relative amounts of each of these catalysts used, their bed size and bed length in performing the esterification reaction were as follows: 
     
       
         
           
               
               
               
               
             
               
                   
                   
               
               
                   
                 Parameter 
                 Catalyst 4 
                 Catalyst 5 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Volume (cm 3 ) 
                 25 
                 25 
               
               
                   
                 Weight (g) 
                 15.5 
                 11.2-11.4 
               
               
                   
                 Pellet size (mm) 
                 1-2 
                 1-2 
               
               
                   
                   
                   
                 (Table 11) &amp; 
               
               
                   
                   
                   
                 0.5-1   
               
               
                   
                   
                   
                 (Tables 12, 13 and 14) 
               
               
                   
                 Bed length 
                 8.5 
                 8.75 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 10 
               
               
                   
                   
               
               
                   
                   Run No. 25 
                 Run No. 26 
                 Run No. 27 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
            
               
                 (Catalyst 4-15.5 g) 
               
               
                 Run Conditions: 
               
            
           
           
               
               
               
               
            
               
                 Parameters 
                   
                   
                   
               
               
                 HOS 
                 1-3 
                 19-21 
                 25-27 
               
               
                 Temperature (° C.) 
               
               
                 Applied 
                 170 
                 170 
                 170 
               
               
                 Bed (T/M/B) 
                 173.5/—/170.5 
                 172/—/169 
                 172/—/169 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
                 1000 
               
               
                 Total feed GHSV/h 
                 979 
                 979 
                 979 
               
               
                 (@ STP) 
               
               
                 C 2 H 4  GHSV/h 
                 905 
                 905 
                 905 
               
               
                 HAC GHSV/h 
                 65 
                 65 
                 65 
               
               
                 H 2 O GHSV/h 
                 9 
                 9 
                 9 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1131 
                 1131 
                 1131 
               
               
                 HAC (g/Lcat/h) 
                 173 
                 173 
                 173 
               
               
                 H 2 O (g/Lcat/h) 
                 8 
                 8 
                 8 
               
               
                 Feed contact time 
                 4 
                 4 
                 4 
               
               
                 [1/GHSV](secs) 
               
               
                 C 2 H 4 /HAC/H 2 O mole 
                 92.4/6.6/1.0 
                 92.4/6.6/1.0 
                 92.4/6.6/1.0 
               
               
                 % ratio 
               
               
                 C 2 H 4 /HAC/H 2 O wt % ratio 
                 86.2/13.2/0.6 
                 86.2/13.2/0.6 
                 86.2/13.2/0.6 
               
               
                 C 2 H 4 /HAC mole ratio 
                 14.0 
                 14.0 
                 14.0 
               
            
           
           
               
            
               
                 Product Analysis (Table 10 continued) 
               
            
           
           
               
               
               
               
            
               
                 Products/Analysis 
                   
                   
                   
               
               
                 HAC Conversion 
                 51 
                 47 
                 45 
               
               
                 Product Selectivity (wt %) 
               
               
                 EtAc 
                 89.7 
                 98.0 
                 97.7 
               
               
                 EtOH 
                 0.5 
                 0.5 
                 0.4 
               
               
                 DEE 
                 0.9 
                 0.7 
                 1.0 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 7.0 
                 0.4 
                 0.7 
               
               
                 Others 
                 1.90 
                 0.49 
                 0.26 
               
               
                 EtAc Yield 
                 45 
                 46 
                 44 
               
               
                 EtAc STY (g/Lcat/h) 
                 128 
                 122 
                 118 
               
               
                 Carbon Balance (mol %) 
                 102 
                 102 
                 105 
               
               
                 Oxygen Balance (mol %) 
                 86 
                 89 
                 100 
               
               
                 Mass Balance 
                 101 
                 101 
                 104 
               
               
                 Water recovered (%) 
                 90 
                 70 
                 81 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 11 
               
               
                   
                   
               
               
                   
                   Run No. 28 
                 Run No. 29 
                 Run No. 30 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
            
               
                 (Catalyst 5-11.3 g) 
               
               
                 Run Conditions: 
               
            
           
           
               
               
               
               
            
               
                 Parameters 
                   
                   
                   
               
               
                 HOS 
                 1-2 
                 17-20 
                 21-24 
               
               
                 Temperature (° C.) 
               
               
                 Applied 
                 170 
                 170 
                 170 
               
               
                 Bed (T/M/B) 
                 176/—/174 
                 173/—/170 
                 173/—/170 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
                 1000 
               
               
                 Total feed GHSV/h (@ STP) 
                 980 
                 980 
                 980 
               
               
                 C 2 H 4  GHSV/h 
                 905 
                 905 
                 905 
               
               
                 HAC GHSV/h 
                 66 
                 66 
                 66 
               
               
                 H 2 O GHSV/h 
                 9 
                 9 
                 9 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1131 
                 1131 
                 1131 
               
               
                 HAC (g/Lcat/h) 
                 177 
                 177 
                 177 
               
               
                 H 2 O (g/Lcat/h) 
                 8 
                 8 
                 8 
               
               
                 Feed contact time 
                 4 
                 4 
                 4 
               
               
                 [1/GHSV](secs) 
               
               
                 C 2 H 4 /HAC/H 2 O mole % ratio 
                 92.3/6.7/1.0 
                 92.3/6.7/1.0 
                 92.4/6.6/1.0 
               
               
                 C 2 H 4 /HAC/H 2 O wt % ratio 
                 85.9/13.5/0.6 
                 85.9/13.5/0.6 
                 86.2/13.2/0.6 
               
               
                 C 2 H 4 /HAC mole ratio 
                 13.7 
                 13.7 
                 13.7 
               
            
           
           
               
            
               
                 Product Analysis: 
               
            
           
           
               
               
               
               
            
               
                 Products/Analysis 
                   
                   
                   
               
               
                 HAC Conversion 
                 62 
                 66 
                 64 
               
               
                 Product Selectivity (wt %) 
               
               
                 EtAc 
                 86.0 
                 97.3 
                 97.6 
               
               
                 EtOH 
                 2.4 
                 0.4 
                 0.4 
               
               
                 DEE 
                 3.3 
                 1.8 
                 1.4 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 2.4 
                 0.3 
                 0.6 
               
               
                 Others 
                 5.9 
                 0.1 
                 0.1 
               
               
                 EtAc Yield 
                 53 
                 65 
                 62 
               
               
                 EtAc STY (g/Lcat/h) 
                 151 
                 180 
                 171 
               
               
                 Carbon Balance (mol %) 
                 101 
                 104 
                 105 
               
               
                 Oxygen Balance (mol %) 
                 98 
                 95 
                 99 
               
               
                 Mass Balance 
                 101 
                 103 
                 105 
               
               
                 Water recovered (%) 
                 70 
                 69 
                 67 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 12 
               
               
                   
                   
               
               
                   
                   Run No. 31 
                 Run No. 32 
                 Run No. 33 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
            
               
                 (Catalyst 5-11.2 g) 
               
               
                 Run Conditions: 
               
            
           
           
               
               
               
               
            
               
                 Parameters 
                   
                   
                   
               
               
                 HOS 
                 19.25-22.5 
                 23-26 
                 43.25-46.25 
               
               
                 Temperature (° C.) 
               
               
                 Applied 
                 170 
                 170 
                 180 
               
               
                 Bed (T/M/B) 
                 172.5/176/— 
                 172.5/175.5/— 
                 182/187/— 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
                 1000 
               
               
                 Total feed GHSV/h 
                 980 
                 980 
                 980 
               
               
                 (@ STP) 
               
               
                 C 2 H 4  GHSV/h 
                 905 
                 905 
                 905 
               
               
                 HAC GHSV/h 
                 66 
                 66 
                 66 
               
               
                 H 2 O GHSV/h 
                 9 
                 9 
                 9 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1131 
                 1131 
                 1131 
               
               
                 HAC (g/Lcat/h) 
                 177 
                 177 
                 177 
               
               
                 H 2 O (g/Lcat/h) 
                 8 
                 8 
                 8 
               
               
                 Feed contact time 
                 4 
                 4 
                 4 
               
               
                 [1/GHSV](secs) 
               
               
                 C 2 H 4 /HAC/H 2 O mole % 
                 92.3/6.7/1.0 
                 92.3/6.7/1.0 
                 92.3/6.7/1.0 
               
               
                 ratio 
               
               
                 C 2 H 4 /HAC/H 2 O wt % ratio 
                 86/13.4/0.6 
                 86/13.4/0.6 
                 86/13.4/0.6 
               
               
                 C 2 H 4 /HAC mole ratio 
                 13.7 
                 13.7 
                 13.7 
               
            
           
           
               
            
               
                 Product Analysis: 
               
            
           
           
               
               
               
               
            
               
                 Products/Analysis 
                   
                   
                   
               
               
                 HAC Conversion 
                 72 
                 72 
                 72 
               
               
                 Product Selectivity (wt %) 
               
               
                 EtAc 
                 96.0 
                 94.4 
                 94.9 
               
               
                 EtOH 
                 0.5 
                 0.5 
                 0.7 
               
               
                 DEE 
                 2.9 
                 2.7 
                 3.3 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 0.4 
                 1.6 
                 0.7 
               
               
                 Others 
                 0.2 
                 0.3 
                 0.8 
               
               
                 EtAc Yield 
                 69 
                 68 
                 78 
               
               
                 EtAc STY (g/Lcat/h) 
                 203 
                 194 
                 210 
               
               
                 Carbon Balance (mol %) 
                 101 
                 103 
                 108 
               
               
                 Oxygen Balance (mol %) 
                 91 
                 97 
                 104 
               
               
                 Mass Balance 
                 100 
                 103 
                 108 
               
               
                 Water recovered (%) 
                 47 
                 48 
                 48 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 13 
               
               
                   
                   
               
               
                   
                   Run No. 34 
                 Run No. 35 
                 Run No. 36 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
            
               
                 (Catalyst 5-11.2 g) 
               
               
                 Run Conditions: 
               
            
           
           
               
               
               
               
            
               
                 Parameters 
                   
                   
                   
               
               
                 HOS 
                 47-50 
                 67.25-70.25 
                 71-74 
               
               
                 Temperature (° C.) 
               
               
                 Applied 
                 180 
                 190 
                 190 
               
               
                 Bed (T/M/B) 
                 181.5/186.5/— 
                 191.5/196/— 
                 191.5/195.5/— 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
                 1000 
               
               
                 Total feed GHSV/h 
                 980 
                 980 
                 980 
               
               
                 (@ STP) 
               
               
                 C 2 H 4  GHSV/h 
                 905 
                 905 
                 905 
               
               
                 HAC GHSV/h 
                 66 
                 66 
                 66 
               
               
                 H 2 O GHSV/h 
                 9 
                 9 
                 9 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1131 
                 1131 
                 1131 
               
               
                 HAC (g/Lcat/h) 
                 177 
                 177 
                 177 
               
               
                 H 2 O (g/Lcat/h) 
                 8 
                 8 
                 8 
               
               
                 Feed contact time 
                 4 
                 4 
                 4 
               
               
                 [1/GHSV](secs) 
               
               
                 C 2 H 4 /HAC/H 2 O mole 
                 92.3/6.7/1.0 
                 92.3/6.7/1.0 
                 92.3/6.7/1.0 
               
               
                 % ratio 
               
               
                 C 2 H 4 /HAC/H 2 O wt % 
                 86/13.4/0.6 
                 86/13.4/0.6 
                 86/13.4/0.6 
               
               
                 ratio 
               
               
                 C 2 H 4 /HAC mole ratio 
                 13.7 
                 13.7 
                 13.7 
               
            
           
           
               
            
               
                 Product Analysis: 
               
            
           
           
               
               
               
               
            
               
                 Products/Analysis 
                   
                   
                   
               
               
                 HAC Conversion 
                 79 
                 74 
                 72 
               
               
                 Product 
               
               
                 Selectivity (wt %) 
               
               
                 EtAc 
                 95.2 
                 94.7 
                 94.9 
               
               
                 EtOH 
                 0.7 
                 0.7 
                 0.7 
               
               
                 DEE 
                 3.2 
                 2.8 
                 2.2 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 0.6 
                 1.4 
                 1.3 
               
               
                 Others 
                 0.2 
                 0.3 
                 0.8 
               
               
                 EtAc Yield 
                 75 
                 70 
                 68 
               
               
                 EtAc STY (g/Lcat/h) 
                 206 
                 202 
                 191 
               
               
                 Carbon Balance 
                 105 
                 102 
                 104 
               
               
                 (mol %) 
               
               
                 Oxygen Balance 
                 102 
                 94 
                 99 
               
               
                 (mol %) 
               
               
                 Mass Balance 
                 105 
                 102 
                 104 
               
               
                 Water recovered (%) 
                 47 
                 52 
                 54 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 14 
               
               
                   
                   
               
               
                   
                   Run No. 37 
                 Run No. 38 
                 Run No. 39 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
            
               
                 (Catalyst 5-11.4 g) 
               
               
                 Run Conditions: 
               
            
           
           
               
               
               
               
            
               
                 Parameters 
                   
                   
                   
               
               
                 HOS 
                 19-22 
                 44-47 
                 68.75-71.75 
               
               
                 Temperature 
               
               
                 (° C.) 
               
               
                 Applied 
                 180 
                 180 
                 180 
               
               
                 Bed (T/M/B) 
                 181.5/186/182.5 
                 181.5/185/182 
                 181.3/184.5/181.2 
               
               
                 Pressure (Kpa) 
                 1000 
                 1000 
                 1000 
               
               
                 Total feed 
                 980 
                 980 
                 980 
               
               
                 GHSV/h 
               
               
                 (@ STP) 
               
               
                 C 2 H 4  GHSV/h 
                 905 
                 905 
                 905 
               
               
                 HAC GHSV/h 
                 66 
                 66 
                 66 
               
               
                 H 2 O GHSV/h 
                 9 
                 9 
                 9 
               
               
                 C 2 H 4  (g/Lcat/h) 
                 1131 
                 1131 
                 1131 
               
               
                 HAC (g/Lcat/h) 
                 177 
                 177 
                 177 
               
               
                 H 2 O (g/Lcat/h) 
                 8 
                 8 
                 8 
               
               
                 Feed contact time 
                 4 
                 4 
                 4 
               
               
                 [1/GHSV](secs) 
               
               
                 C 2 H 4 /HAC/H 2 O 
                 92.3/6.7/1.0 
                 92.3/6.7/1.0 
                 92.3/6.7/1.0 
               
               
                 mole % ratio 
               
               
                 C 2 H 4 /HAC/H 2 O 
                 86/13.4/0.6 
                 86/13.4/0.6 
                 86/13.4/0.6 
               
               
                 wt % ratio 
               
               
                 C 2 H 4 /HAC mole 
                 13.7 
                 13.7 
                 13.7 
               
               
                 ratio 
               
            
           
           
               
            
               
                 Product Analysis: 
               
            
           
           
               
               
               
               
            
               
                 Products/Analysis 
                   
                   
                   
               
               
                 HAC Conversion 
                 71 
                 64 
                 60 
               
               
                 Product 
               
               
                 Selectivity (wt %) 
               
               
                 EtAc 
                 95.9 
                 97.2 
                 97.8 
               
               
                 EtOH 
                 0.7 
                 0.6 
                 0.5 
               
               
                 DEE 
                 2.3 
                 1.8 
                 1.3 
               
               
                 Acetaldehyde 
                 0.0 
                 0.0 
                 0.0 
               
               
                 Oligomers 
                 0.8 
                 0.3 
                 0.3 
               
               
                 Others 
                 0.3 
                 0.1 
                 0.0 
               
               
                 EtAc Yield 
                 68 
                 63 
                 59 
               
               
                 EtAc STY 
                 194 
                 183 
                 164 
               
               
                 (g/Lcat/h) 
               
               
                 Carbon Balance 
                 100 
                 100 
                 100 
               
               
                 (mol %) 
               
               
                 Oxygen Balance 
                 94 
                 89 
                 93 
               
               
                 (mol %) 
               
               
                 Mass Balance 
                 100 
                 99 
                 99 
               
               
                 Water recovered 
                 53 
                 56 
                 62 
               
               
                 (%)