UNIVERSITA DEGLI STUDI DI ROMA LA SAPIENZA DIPARTIMENTO INGEGNERIA CHIMICA MATERIALI AMBIENTE REPORT ON A TEST EXECUTED ON A KDV DEPOLYMERIZATION PLANT ON JAN 19TH 2012 IN THE ORION ECOSOLUTIONS DEMONSTRATION PLANT IN CITTA DI CASTELLO (PG)- ITALY. The ORION catalytic depolymerization Demonstration Plant is a process applicable to agricultural biomasses, and in general to any organic compound. The attachment n. 1 shows the block process flow diagram of the plant, having a processing capacity of 500 Kg/h of dry biomass. This catalyst aided depolymerization process converts such biomass into light fuel oil, carbon dioxide and water. The theoretical yield is: 1 Kg of cellulose (C 6 H 10 O 5 ) converted to: 0,355 Kg of light fuel oil (C H 2 ) n + 0,513 Kg of CO 2 + 0,132 Kg of H 2 O The expected plant yield is: Dry cellulose on a dry weight basis is converted to: o 28% light fuel oil (diesel oil) o 52 % carbon dioxide + light gases and vapors o 14 % of water o 6% of salts, catalyst, lime, traces of oily organic matters The production test referred to took place on Jan 19 th 2012 in the demonstration plant called above. The charge of the plant consisted in cellulose (saw dust) + 3% lime + 2% of silicoaluminate catalyst dispersed into mineral oil. The amount of mineral oil was that required to make the mixture pumpable, approximately a mixture containing 75% oil is necessary. An hour after the reaching the designed working parameters the following products were recovered: Heavy phase: 38 lt of water + oily products (transparent with light yellow color reflections) Light phase: 56 lt of light oil COD. FISC. 80209930587 - PART. IVA 02133771002
At the end of the run (which is reported lasted about 5 hours) a sample of solid deposits was also taken from the ballast oily products on the bottom of the reflux drum of the distillation column, in order to determine the nature of co-products in the system during the solid to liquid transformation phase. The sample was taken during the process, when the feedstock had not been completely processed. The plant is not yet complete in all its parts: for example the separation of water from oil at the top condensing section on the distillation column of the depolymerization section is not in place as well as the solid waste/liquid separation system. Such sections will be assembled for future tests. The production test performed on Jan 19 th had only the scope of determining the actual developing of the depolymerization reaction, and the quality of the output. Mass and energy balance will be done later on, after the parameters optimization consequent to this preliminary test program. Samples of both fractions were send to our laboratories (Dept of Chemical Engineering Rome Sapienza University), and to the OSI Service Laboratories in ISOLA DEL LIRI (FR). This report analyzes the following documents: OSI Service Test certificates o 57-1E and 57-2E dated 27.02.2012 Rome University report number 1 dated 08.02.2012 Tests on water by OSI Service: Vacuum distillation with water/oil separation Analysis of the oil fraction (Sample N. 3; attachment 3) Analysis of the water fraction (Sample N. 12) Tests on oil by OSI Service: Analysis of the oil fraction as taken from the field (Sample N. 1; attachment 2) Analysis of a mix 50 to 50 of oil taken from the plant and mineral oil used as dispersion for the feedstock + lime + catalyst (Sample N. 2; attachment 4) Tests on oil by Rome University: Analysis of the oil fraction as taken from the field (Sample N. 4) Tests on solid settled from the process ballast by Rome University: Determination of the oil content, elemental analysis of the solid matter (Sample N. 5) COD. FISC. 80209930587 - PART. IVA 02133771002 2/8
CONCLUSIONS 1. Diesel oil (Samples N. 1, 4, attachment 2) The product analyzed has a composition similar but not equal to that of commercial diesel oil. As reported in attachment 2 the hydrocarbon fraction from the plant shows a narrow distribution than that of commercial diesel oil. After the optimum definition of the working parameters no obstacle should arise in order to obtain a product complying the commercial standards for light fuel oils 2. Water (Samples N. 11, 13) The amount of oil separated from the heavy phase is equal to 18% weight (OSI service 57-2E). The recovered oil has an hydrocarbon distribution lighter than that of sample 1 and more similar of that of kerosene (attachment 2). The water after oil separation still contains oxygenated compounds and a treatment before its discharge is needed. Considering the oil in the aqueous phase, the total oil collected during the production test was 62.8 L. 3. Solid from the process settler (Sample N. 5) The product was sampled when the depolymerization process was still on progress. It is a picture of an intermediate phase of the solid transformation to liquid and gas. The test has only the scope to give indications in order to define the optimum working parameters for maximizing the process output. The amount of oil in the settling phase is 54.1 % wt. In the solid matter the amount of organics is approximately 57% with the following elemental composition C: 49.8 % H: 4.3 % O: 2.9 % The solid matter contain still a large amount of organics, more severe conditions or longer residence time on the plant should be tested in order to reduce this amount. Also, a treatment before its discharge for the recovery of mineral oil is necessary. The plant shows, in the actual configuration, some criticism as regards the oil water separation, the amount of organic in the water, and the treatment of the settling phase. As regards the first problem, this is a common problem in oil refineries and an improvement should be obtained with the introduction of the oil/water separation at the top of the condensing section on the distillation column. COD. FISC. 80209930587 - PART. IVA 02133771002 3/8
As regards the water treatment for the reduction of soluble organic compounds (e.g. polyphenols) deriving from cellulose depolymerization, because the relatively low amount of water produced from the process, the suggested treatment is a chemical oxidation step. It is well known that chemical oxidation can reduce the content of organics amount in water to value sufficiently low for its direct discharge in sewer. The settling phase is a by-product of the plant that contain other than basic and zeolite catalyst also the biomass ashes and organic materials (unreacted biomass, carbon, mineral oil). Before the disposal of this product it is convenient to reduce its amount by removing all the oil, so producing a clean dry solid matter. This can be achieved washing the settled material with a part of the light oil produced (that is then recycled to the distillation column) from the plant. Rome 27 02.2012 Prof. Paolo De Filippis COD. FISC. 80209930587 - PART. IVA 02133771002 4/8
Attachemnt 1 COD. FISC. 80209930587 - PART. IVA 02133771002 5/8
Attachment 2 Commercial diesel Diesel from the plant COD. FISC. 80209930587 - PART. IVA 02133771002 6/8
Attachemnt 3 Attachment 3 COD. FISC. 80209930587 - PART. IVA 02133771002 7/8
Attachemnt 4 (mix 50 to 50 % oil from the plant and mineral oil) COD. FISC. 80209930587 - PART. IVA 02133771002 8/8