Production of Ethylene Oxide

A porous .alpha.-alumina carrier (supplied by Norton Company) and having a surface area of 0.5 M.sup.2 g.sup.- 1, a pore volume of 0.43 mls per gm, a SiO.sub.2 content of 0.38%, and a sodium content of 121 ppm), in the form of rings of dimensions outer diameter 7.8 mm inner (hole) diameter 3.1 mm and thickness 7.8 diameter, was impregnated with a solution of silver nitrate dissolved in aqueous isopropylamine. The impregnated damp solid was pyrolysed by heating in a flow of nitrogen at up to 240.degree. C.. the product was washed with hot water and dried. The dried catalyst was impregnated with an aqueous solution of potassium formate drained and dried. the final catalyst contained 16% w/w silver and 500 ppm of added potassium.

The catalyst was crushed and sieved to produce 112 g of particulate matter in the size range 1 to 3.35 mms. It was loaded into a stainless steel reactor of 10.8 mm internal diameter and 2,58 metres long. A gas mixture of ethylene (30%), oxygen (8%), carbon dioxide (2.5%) vinyl chloride (12 ppm), ethyl chloride (3 ppm) and 2 nitropropane (20 ppm) with nitrogen to balance was passed at a pressure of 15 bar gauge over the catalyst at a temperature of 252.degree. C.. The gas was passed at a space velocity of 3070 hr.sup.-1. The reaction produced ethylene oxide and carbon dioxide. Oxygen conversion was 20% and the selectivity of the snythesis of ethylene oxide was 87% (i.e. 87 moles of ethylene oxide were formed from 100 moles of ethylene converted).

Catalyst support pellets, comprising porous, high purity .alpha.-alumina containing 250.+-.50 ppm of silica expressed as silicon and 40+10 ppm of sodium compounds expressed as sodium and 12+3 ppm of potassium compounds expressed as potassium in the form of cylinders 8 mm diameter and 8 mm pierced by seven longitudinal holes 1.22 mm in diameter one being central and the others being regularly spaced on a circle of 4.39 mm diameter centred on the axis of the pellet were uniformly coated with silver metal particles as described below. The mean pore diameter of porous alumina was 2-3 microns, its porosity as assessed by water absorption was 0.36.+-.0.03 ml per g and its surface areas was about 0.5 m.sup.2 per g.

Silver nitrate (4,418 g) was dissolved at 70.degree. C. into distilled water (896 ml) and the resulting solution cooled to 50.degree. C.. Monoisopropylamine (4,800 mls) was slowly added to this solution whilst stirring and cooling. The addition of the amine was sufficiently slow to avoid undue temperature rises. The temperature was maintained in the range 40.degree. to 60.degree. C.. The resulting clear solution was cooled to room temperature.

Support pellets (4,200 g) were evacuated and the solution of the silver nitrate-monoisopropylamine complex (5,000 mls) was added. After contacting the solution for 30 minutes, the impregnated pellets were separated from the residual solution and drained.

The support pellets, wet with the impregnated complex solution, were charged to a perforated basket which was then loaded into a reactor. The impregnated support was heated in a stream of hot nitrogen gas, the temperature was initially 100.degree. C. and subsequently was gradually increased to 240.degree. C. over a period of 18 hours. The impregnated complex decomposed to leave particulate silver evenly dispersed on the surface of the porous .alpha.-alumina pellets. The pellets also contained a residue of substances containing carbon and nitrogen.

The silver-coated pellet were subsequently contacted with hot air in a process which began by passing a stream of 5% air in nitrogen over the pellets heated at 150.degree. C.. Subsequently the air content of the gas stream and the reactor temperature were gradually increased to 100% and 280.degree. C., respectively. The rate of both changes were slow enough to avoid uncontrolled rises in temperature of the pellets due to the exothermicity of the process. On reaching 280.degree. C., the pellets were contacted with the air stream for a further 2 hours and then allowed to cool.

The resulting silver-coated pellets, now substantially free of the residues of the silver nitrate - monoisopropylamine complex decomposition process were contacted with a flow of hot water in the temperature range 90.degree. to 100.degree. C. for 16 hours, then cooled, drained and dried by contacting with a stream of hot nitrogen at 150.degree. C.. The product was a catalyst precursor and was characterised as a substantially clean, dry dispersion of silver particles evenly coated on the surfaces, both internal and external, of the porous 2-alumina pellets.

The catalyst precursor (4945 gm) was impregnated with potassium by being contacted at room temperature with 3323 mls of a solution of potassium formate in aqueous methanol.The aqueous methanol solvent contained 0.2% water by volume and 17.9 gms of potassium formate. The contacting was achieved by pumping the potassium formate solution through a bed of the catalyst precursor, collecting the liquor and recycling it through the bed for 16 hours. On completion of this impregnation stage, the catalyst pellets were drained and dried in a stream of warm nitrogen at 150.degree. C.. The finished catalyst contained 500 to 600 ppm potassium.

This preparation was repeated to provide two additional batches of catalyst. The three batches were mixed and tested.

The catalyst was tested as follows. A reactor tube of 39 mm internal diameter was charged with the catalyst to give bed lengths of 10.7 m (bed volume 12.8 1.) and 3 m of tube length above the catalyst was packed with inert alumina pellets. The tube was surrounded by a liquid heat exchange fluid for temperature control. At start-up, a reactor feed gas composition of O.sub.2 6%, C.sub.2 H.sub.4 27%, vinyl chloride 6 ppm, ethane 0.1%, 2-nitropropane 20 ppm, the balance being substantially methane with a small proportion of inert gases, was fed. The feed to the reactor was at 75.degree. C. and 18.5 bar pressure, with a gas hourly space velocity of 3600 hr.sup.-1. Reactor temperatures were then raised to initiate reaction. Oxygen, ehtylene, ethane, methane, 2-nitropropane and vinyl chloride feeds were then mixed with recycle gas to give the desired feed composition. After twenty six days on line 1.03 m.sup.3 /hr oxygen, 1.4 m.sup. 3 /hr ethylene, 6.8 1./hr ethane and 36 ml/hr vinyl chloride in methane all expressed as vapour at standard temperature and pressure plus an intermittent flow of methane sufficient to control the plant pressure plus 2-nitropropane were mixed with recycle gas. The 2-nitropropane was introduced by pumping liquid 2-nitropropane with a positive displacement micro pump having a relief valve set to operate at thirty bars. The temperature of 2-nitropropane in the pump was approximately 20.degree. C. and it was substantially free from gaseous air, oxidising agents, alkalis, acids and water. It was introduced at a point in the process at which the temperature was 70.degree. C., the pressure 18 bars absolute at 3.7 mls/hr of liquid onto a knitted stainless-steel mesh through which all the process gas was passed.

The reactor feed composition was analysed to be O.sub.2 7.5% C.sub.2 H.sub.4 27%, CO.sub.2 0.3%, vinyl chloride 7.2 ppm, ethyl chloride 0.9 ppm, ehtane 0.1%, 2-nitropropane 20 ppm, 0.12% water vapour and an estimated content of oxides of nitrogen of about 3 ppm the balance being substantially methane. Analysis was carried out from the reactor inlet and less inaccuracy of analysis was found due to condensation of water than that which had occurred when NO and NO.sub.2 had been supplied instead of the 2-nitro propane. The reaction feed was at 75.degree. C. and 18.5 bar with a gas hourly space velocity of 3600 hr.sup.-1. the oxygen conversion across the reactor was 28%. The reaction give a selectivity of ethylene converted of 87%. The average catalyst temperature was 255.degree. C.. The product gases were cooled to 75.degree. C. before being contacted with 250.1/hr of water at 20.degree. C., to absorb product ethylene oxide. The resulting gas stream was then split, part being contacted with 250.1/hr of 0.5% w/w caustic soda solution in a carbon dioxide scrubber. The scrubber gaseous product and the bypass stream were combined and then compressed to form the recycle gas stream. No solid deposits resulting from the reaction of nitropropane with ethylene occurred. (Deposits can occur under certain conditions between NO/NO.sub.2 and ethylene even at embient tempertures.) NO corrosion was observed in the reactor feed section of the plant.

A catalyst similar to that of Example 2 but containing 300-330 ppm potassium was tested as follows. A reactor tube of 39 mm internal diameter was charged with the catalyst to give bed lengths of 10. m (bed volume 11.92 1.) and 3 m of tube length above the catalyst was packed with inert alumina pellets. The tube was surrounded by a liquid heat exchange fluid for temperature control. At start-up, a reactor feed gas composition of O.sub.2 6%, C.sub.2 H.sub.4 27%, vinyl chloride 6 ppm, ethane 0.1%, 2-nitropropane 41 ppm, the balance being substantially methane with a small proportion of inert gases, was fed. The feed to the reactor was at 75.degree. C. and 18.5 bar pressure, with a gas hourly space velocity of 3600 hr.sup.- 1. Reactor temperatures were then raised to initiate reaction. Oxygen, ethylene, ethane, methane, 2-nitropropane and vinyl chloride feeds were then mixed with recycle gas to give the desired feed composition. The 2-nitropropane was introduced by pumping liquid 2-nitropropane with a positive displacement micro pump having a relief valve set to operate at 30 bars. The temperature of 2-nitropropane in the pump was approximately 20.degree. C. and it was substantially free from gaseous air, oxidising agents, alkalis, acids and water. It was introduced at a point in the process at which the temperature was 70.degree. C., the pressure 18 bars absolute at 4.8 mls/hr of liquid onto a knitted stainless-steel mesh through which all the process gas was passed.

After fourteen days on line the reactor feed composition was analysed to be O.sub.2 8.2% C.sub.2 H.sub.4 27%, CO.sub.2 1%, vinyl chloride 5.9 ppm, ethyl chloride 0.8 ppm, ethane 0.1%, 2-nitropropane 32 ppm, NO.sub.2 8.3 ppm, NO 2.0 ppm, 0.12% water vapour, the balance being substantially methane. Analysis was carried out from the reactor inlet and less inaccuracy of analysis was found due to condensation of water than that which had occurred when NO and NO.sub.2 had been supplied instead of the 2-nitro propane. The reaction feed was at 75.degree. C. and 18.5 bar with a gas hourly space velocity of 3340 hr.sup.-1. The oxygen conversion across the reactor was 28%. The reaction give a selectivity of ethylene converted of 84.2%. The average catalyst temperature was 250.degree. C.. The product gases were cooled to 75.degree. C. before being contacted with 250.1/hr of water at 20 .degree. C., to absorb product ethylene oxide. The resulting gas stream was then split, part being contacted with 250.1/hr of 0.5% w/w caustic soda solution in a carbon dioxide scrubber. The scrubber gaseous product and the bypass stream were combined and then compressed to form the recycle gas stream. No solid deposits resulting from the reaction of nitropropane with ethylene occurred. (Deposits can occur under certain conditions between NO/NO.sub.2 and ethylene even at embient temperatures.) No corrosion was observed in the reactor feed section of the plant.

ppm means, in the case of liquids or solids, parts per million by weight and in the case of gases, parts per million by volume. Gas hourly space velocities are calculated as at 20.degree. C. and atmospheric pressure.

Throughout this specification, pressures are absolute.