Q Oman Formaldehyde Chemical Company. _ No. 4297446 Rev. 0 Sohar, Sultanate of Oman Job $-00703 HALDOR TOPSZE A/S 203 MTPD Formaldehyde Plant, Unit 1000 Page 1 of 8 Job S-00703 WBS 40 Process Description \ i Rev. | Deseription Dae | Madeby _[_Chd_| Mond 0 First issue eaJaN2007 | __imT | ROL Ti “Thformaton contained herein is content and may not be wed by or conveyed to ay thd pry without our written autorisstion - Haldor Topsoe4 Oman Formaldehyde Chemical Company. No. 4297446 Rev. 0 Sohar, Sultanate of Oman Job $-00703 HALDOR TOPSGE A/S 203 MTPD Formaldehyde Plant, Unit 1000 1DK-2800 Lyngby, Denmark erratic aimeaenaaa Page 2 of 8 Contents 1. General Preparation of reactor feed gas .. Oxidation of methanol to formaldehyde. .. eYN Absorption of formaldehyde 4,1 Absorption of formaldehyde in water, F 101 .. 4.2 Absorption of formaldehyde in Urea- water solution, F 102 4.2.1 Production of Urea Formaldehyde Pre-condensate. 42.2 Neutralisation with NaOH.. 42.3 Urea to Formaldehyde Ratio . 43° Recycle ga 5. Catalytic Incinerator 6. Heat ‘Transfer Oil System 7. Steam System.. Information contained herein is confidential and may not be used by or conveyed to any third party without our writen authrsstin ~HaldorTopso7m Oman Formaldehyde Chemical Company. No. 4297446 Rev. 0 Sohar, Sultanate of Oman Job S-00703 HALDOR TOPS@E A/S 203 MTPD Formaldehyde Plant, Unit 1000 Page 3 of 8 1. General ‘The plant is laid out in accordance with the following process flow sheets: 240 MTPD AF & 98.7 MTPD UF: HTAS Drawing no. 1288359, 2288361, 2289419 160 MTPD AF & 148 MTPD UF: HTAS Drawing no, 1289472, 2289474, 2289475 203 MTPD AF-37: HTAS Drawing no, 1289308, 2289495 125 MTPD UF-85: HTAS Drawing no. 1289476, 2289478 Besides the process flow sheets, reference should also be made to the relevant piping and instrument diagrams, equipment specifications, etc. ‘The nominal plant capacity is 203 MTPD as AF-37%. ‘The plant is prepared for a future revamp, where a2" reactor is added. Operation after addition of the second reactor is shown on the Flow sheets for 240 MTPD AF & 98.7 MTPD UF and 160 MTPD AF & 148 MTPD UF listed above. ‘The plant can produce aqueous formaldehyde at a concentration of 37% and urea formaldehyde at a concentration of UF-85 also known as UFC. 2. Preparation of reactor feed gas Liquid methanol from the methanol storage is pumped by the Methanol Feed Pump, P 301 AJB and delivered to the plant battery limit at 5.5 kg/em* g. A part of the methanol feed to the plant is mixed with air and recycle gas, circulated by the Recirculation Blower K 101, and led into the Feed/Effluent Heat Exchanger, E 101, where it is evaporated. Downstream E 101 the remaining part of the methanol is injected and vaporised into the process gas. ‘The reaction mixture upstream R 101 has a methanol content of 8.4% by volume and an ‘oxygen content of approx. 9.5% by volume. The mixture after evaporation of methanol and preheating in E 101 is approximately 164°C. 3. Oxidation of methanol to formaldehyde. The preheated gas enters the Reactor, R 101, in which it passes through tubes containing Topsoe metal oxide catalyst type FK 2. The principal reaction, the catalytic oxidation of methanol into formaldehyde, occurs according to the equation: CH3OH + 1/2 02 > HCHO + 1,0 A limited amount of formaldehyde is further oxidised to carbon monoxide by the following side reaction: HCHO + 1/2 02» CO+H;0. Information contuined herein f confidential and may not be used by or conveyed to any third party without our writen authorisation -HaldorTopsaerr Oman Formaldehyde Chemical Company. No. 4297446 Rev. 0 Sohar, Sultanate of Oman Job $-00703 HALDOR TOPS@E A/S D Formald Mant, Unit 1000 eee 203 MTPD Formaldehyde Plant, Unit Page 4 of 8 Also minute amounts of dimethyl ether and formic acid are formed. These reactions are strongly exothermal, and in order to maintain optimum temperature conditions and to limit the formation of by products, the heat of reaction has to be removed during the reaction. This is done through heat transfer from the catalyst tubes to a bath of heat stable boiling oil. ‘The reactor effluent gas leaving R. 101 is cooled to 130°C in E 101, before it enters the Absorbers, F 101 and F 102 4, Absorption of formaldehyde The flow of process gas passed on to the absorbers is divided into two streams one for each absorber. Each flow is controlled by a flow control valve inlet the absorber thus allowing controlling the production rate in each absorber. AF-37 is produced in the AF Absorber, F 101 and UF-85 is produced in the UF Absorber, F 102. Each absorber is designed for production of 240 MTPD as AF-37. ‘The absorption system is made from stainless steel throughout. Also the bottom of I* reactor as well as the equipment between the 1* reactor and the absorbers is made of i stainless steel for all parts in contact with the reactor effluent gas. The choice of this ' material is made to avoid corrosion and to obtain a maximum purity of the product. 1 4.1 Absorption of formaldehyde in water, F 101 ' The formaldehyde containing gas passed on to the AF Absorber, F 101 is absorbed in counter-current flowing process water. | ‘The absorber is divided into two tray sections and three packed beds. The heat of the solution as well as the sensible and latent heat of the reaction gas is removed in the packed beds by recirculating externally cooled solution. | ‘The process gas enters at the bottom of the absorber, where it is passed through the first a packed bed. Aqueous formaldehyde is withdrawn from the bottom of the absorber, and the Product | Circulation Pump, P 108 A/B, returns the solution at the top of the 1 packed bed. Product solution is withdrawn from the discharge of P 108 A/B. Information contnined herein f confident! and may not be used by or conveyed to any thi party without our wien auhorstion ~ HaldorTopsnerr HALDOR TOPS@E A'S 203 MTPD Formaldehyde Plant, Unit 1000 Page 5 of 8 42 Oman Formaldehyde Chemical Company. No. 4297446 Rey. 0 Sohar, Sultanate of Oman Job $-00703 Formaldehyde and methanol are removed from the gas by countercurrent washing with process water in the 1* tray section above the bottom packed bed. ‘The second packed bed where the main part of the heat is removed is placed above the 1** tray section. Solution is withdrawn from the take off tray at the bottom of the packed bed and recirculated by the AF Circulation Pump Il, P 107 A/B, and cooled in the AF Circulation Cooler II, E 107, before it is returned to the top of the 2"! packed bed. The 2" tray section is placed above the 2"! packed bed. Formaldehyde and methanol are removed fiom the gas by counter-current washing with process water. ‘The last packed bed is placed at the top of the absorber where the remaining trace of HCHO js absorbed. Solution is withdrawn from the bottom of the packed bed and recirculated by the AF Circulation Pump I, P 106 A/B and cooled in the AF Circulation Cooler, E 106, The concentration of the product is controlled by mixing the solution with process water from battery limit before returning at the top of the upper packed bed. The selection of optimum conditions is governed by the reactions taking place. A description of these reactions is given below: ‘When formaldehyde is absorbed in water, the following reactions take place: 1 CHOH+H,0 > » CH,(OH): + heat Methylene glycol Practically all methylene glycol will polymerize to a varying degree according to: HT nCHA(OH» > — (Cth), E20 + (n~ 10 whereby polyoxyethylene glycols are fornied. The degree to which this polymerisation takes place depends on concentration (increasing progressively with concentration) as well as temperature (decreasing with increased temperature). The solubility of the polyoxymethylene glycols decreases with increased degree of polymerisation and precipitation occurs when the concentration exceeds the solubility in the solution media at the prevailing temperature and concentration. Such precipitations are normally referred to as paraformaldebyde. Absorption of formaldehyde in Urea- water solution, F 102 The UF absorber is divided into a tray section and three packed beds. Each of the packed beds is provided with an external cooling circuit for removal of the sensible and latent heat of the reaction gas as well as the heat of the solution. Information contsined herein i confidential end may not be used by or conveyed to ny tid party without our writen authorisation ~Haldor Topsnerm Oman Formaldehyde Chemical Company. No. 4297446 Rev. 0 Sohar, Sultanate of Oman Job $-00703 HALDOR TOPS@E A'S — 203 MTPD Formaldehyde Plant, Unit 1000 9 DK 2800 Lyngby, Denman emaete aneieuaae tie Page 6 of 8 42.1 Production of Urea Formaldehyde Pre-condensate The process gas enters the bottom of the absorber, where it is passed through the bottom packed bed. Urea formaldehyde pre-condensate is withdrawn below the bottom packed bed, and the UF Product Circulation Pump, P 111 A/B, returns part of the solution at the top of the bed through the UF Circulation Cooler, E 111. Urea solution is added to the circulation loop downstream E 111. Product solution, withdrawn from the discharge of P 111 A/B, is cooled to 36°C in the UF Product Cooler, E112. In the second packed bed solution is withdrawn from the bottom of the packed bed. The solution is circulated by the UF Circulation Pump II, P 110 A/B, and cooled in the UF Circulation Cooler II, E 110, and then returned to the top of the packed bed. ‘The tray section is placed above the 2" packed bed. Formaldehyde and methanol are removed from the gas by counter-current washing with a dilute urea solution being added to the 4th tray from top and by pure water on the uppermost 3 trays The last packed bed is placed at the top of the absorber; solution is withdrawn from the bottom of the packed bed. The sotution is circulated by the UF Circulation Pump I, P 109 AJB and cooled in the UF Circulation Cooler 1, E 109, the solution is mixed with process water from battery limit before returning at the top of the upper packed bed. 42.2, Neutralisation with NaOH Formic acid is a by product in the formaldehyde process. To prevent precipitation of high molecular urea formaldehyde compounds the formic acid must be neutralised when absorbing formaldehyde in a urea solution. ‘The pH Dosing Pumps, P 104 A/B/C, keeps the pH value at approx. 7 by continuously adding NaOH to the two lower circulation loops. Under these conditions the absorption will result in low molecular weight urea formaldehyde addition products, The following typical reactions will dominate: I 2NEhCONF2+HCHO > —NH,CONH.CO.NHCONH, methyloldiurea I NH,CONH,;+HCHO] > HOCH,NHCONH2 methylol urea mm NH,CONH)+2HCHO > HOCH, NHCONH.CH,0H dimethylol urea Information contained herein is confidential and may not bo used by or conveyed to any third party without our written authorisation = Hldor Tope7 HALDOR TOPSZE A/S 203 MTPD Formaldehyde Plant, Unit 1000 DK-2800 Lyngh Oman Formaldehyde Chemical Company, No. 4297446 Rev. 0 Sohar, Sultanate of Oman Job 8-00703 Page 7 of 8 enark 42.3 Under the conditions foreseen in the bottom of the absorber, where there will be surplus of formaldehyde, reaction no. II will dominate, whereas in the tray part of the column, where urea is in surplus, reaction no. I will most likely be dominating. If acidic conditions were present a number of different undesirable reactions would take place. A typical reaction is as follows: NE,CONH)+HCHO) = > =~ NECON:CH2 + H,0 Methylene urea ‘Under mildly acidic conditions complex transparent resins will be formed, but in presence of strong acids, insoluble condensation products are precipitated from the urea mixture. As the pH is an essential parameter it should be monitored not only in the circulation oops, but also on some selected trays in the upper part of the column, There is a risk of formation of formic acid during prolonged storage of the urea formaldehyde solution according to the Canizzaro reaction: 2HCHO + H20 > — CH,OH + HCOOH Therefore the pH of the stored solution should be monitored periodically, and in case the pH drops NaOH must be added. Urea to Formaldehyde Ratio When the urea to formaldehyde molar ratio is above 1:4 the solution shows a tendency to get turbid and after some hours or days precipitation takes place. In the product UF-85 this ratio is 1:4.8, Consequently, there is no risk of development of turbidity. Nor will there be any risk in the lower circulation loop of the absorber, where the liquid is identical to the product. In the upper part of the tray section the urea to formaldehyde molar ratio is above 1:4. However as the mean residence time for the formaldehyde in this section is very limited there will be no precipitation. Recycle gas ‘The purified gas that leaves the absorber in the top is split into: 1. Recycle gas, which after separation of condensate in the K.O, Drum, B 103, is mixed with the process air and recycled back to the reactors by the Recirculation Blower, K 101. 2. Tail gas which is vented after further purification by a catalytic combustion unit. [Information contined herein i confidential snd may not be used by or conveyed to any ti party without our written authssation - Haldor Topsoerr ‘Oman Formaldehyde Chemical Company. No. 4297446 Rev. 0 -_ Sohar, Sultanate of Oman Job $-00703 HALDOR TOPSZE A'S F it eo eee 203 MTPD Formaldehyde Plant, Unit 1000 Page 8 of 8 Process condensate from B 103, is retumed to the absorber F 101, reused elsewhere in the plant or sent to the incinerator through E 113. 5. Catalytic Incinerator ‘The scrubbed tail gas from the absorber is heated to approx. 250°C in the Tail Gas Heater, E 108. At this temperature the gas enters the Catalytic Incinerator, R 103. Here the Topse catalyst makes the combustible compounds, CO, CH;OH, HCHO and (CH;),0 bum with the Op present in the tail gas. Thereby the gas temperature is increased to approx. 470°C. 6. Heat Transfer Oil System The heat from the exothermal process in the reactor are removed by boiling a heat stable oil, the oil is then condensed in the Waste Heat Boiler, E 102, where the heat is utilised for steam production. The liquid oil is returned to the reactor. Control of the oil bath pressure and thereby also the boiling temperature of the oil is obtained by means of a pressure controller, which act by throttling on the inlet to E 102. The oil circulation is obtained by gravity. The boiling pressure for the selected heat transfer oil is moderate in the whole operating, temperature range (between approximately 0.2 and 1.4 kg/em’g). For storage of the heat transfer oil for make up, etc. an Oil Tank, T 101, has been installed. At start-up the Start-up Oil Pump, P 103 A/B, circulates oil, through the Electrical Start-Up Heater, E 104, to the reactor. The reactor is heated by the hot oil from E 104. P 103 A/B is also used for charging heat transfer oil to the system from the oil tank, T 101. Furthermore, the heat transfer oil system includes an Oil Vent Condenser, E 105, which has capacity to condense all vapour escaping from the system even in case the safety valve opens. The liquid effluent from E 105 is collected in the above-mentioned oil tank, T 101. 7. Steam System The steam produced in the Waste Heat Boiler, E 102 is condensed in the Steam Condenser, B 114 or used to evaporate excess water in the Evaporator, E 113, before the steam condensate is retumed to the Waste Heat Boiler. The steam system is designed to operate up to a pressure of 12 kg/cm’ g. Information contained hers is confidential and may aot be used by or conveyed to any third pat without our written suhrisaton - Haldr Topsoe