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High deoxygenation rates of 88-99.9% were achieved in bench-scale experiments. The fractionated products of the production run did not fulfil the requirements for direct use as gasoline and diesel. Pyrolysis upgraded oil by the process tested is significantly more expensive than petroleum-derived oil at present oil prices.
High deoxygenation rates of 88-99.9% were achieved in bench-scale experiments. The fractionated products of the production run did not fulfil the requirements for direct use as gasoline and diesel. Pyrolysis upgraded oil by the process tested is significantly more expensive than petroleum-derived oil at present oil prices.
High deoxygenation rates of 88-99.9% were achieved in bench-scale experiments. The fractionated products of the production run did not fulfil the requirements for direct use as gasoline and diesel. Pyrolysis upgraded oil by the process tested is significantly more expensive than petroleum-derived oil at present oil prices.
&maw and Biocnerg~Vol. 7. Nos. l-6, pp. 237-244, 1994
0961-9534(94)000654 Copyright c1995 Elsevier Science Lid Printed in Great Britain. All rights reserved 0961-9534194 $7.00 +0.00 UPGRADING OF FLASH PYROLYSIS OIL AND UTILIZATION IN REFINERIES W. BALDAUF, U. BALFANZ and M. RUPP VEBA OEL AG, Pawiker Str. 30, D-45876 Gelsenkirchen, Germany Abstract-Flash pyrolysis oil from an ENSYN RTP pilot plant was upgraded in a continuous bench scale unit with commercial CoMo and NiMo catalysts in anticipation of scaling up the process. Large amounts of product were produced in a pilot plant for use in an extended analytical characterisation programme. In bench-scale experiments, high deoxygenation rates of 88-99.9% were achieved. Low liquid and high water yields were obtained. The fractionated products of the production run did not fulfil the requirements for direct use as gasoline and diesel. The process is restricted by several operational problems such as rapid catalyst deactivation, coking and plugging. Due to high feedstock and hydrogen addition costs, pyrolysis upgraded oil by the process tested is significantly more expensive than petroleum-derived oil at present oil prices. INTRODUCTION Pyrolysis oils from biomass are characterized by their high oxygen content. They are also very unstable, and properties like viscosity and water content change during storage and heating. The evidence for this is water formation and polym- erisation initiated by side reactions. The properties and composition of pyrolysis oils mainly depend on the pyrolysis conditions. Rapid or fast pyrolysis processe? are charac- terised by a temperature range of 450-900C and short residence times (< 1 s). Under these conditions very low amounts of char are pro- duced. In the region of 450-6OoC, most of the products are liquids. These liquids contain high amounts of water (approx. 30%) and acids and have low viscosities, especially when compared with slow pyrolysis oils which have high viscosi- ties. Because of their poor quality, the utilisation of raw pyrolysis oils is difficult. Possible appli- cations are their use as fuel oil for electricity production in boilers and gas turbines5 or as feedstock in petroleum refineries. For both routes it is necessary to upgrade the oil, e.g. by hydrotreatment. Recent investigations cover laboratory experiments on a small scale> while the target of the reported project is to investi- gate possible routes for pyrolysis oils from biomass to be processed in standard petroleum refineries. Applied technology and experience from the hydrotreating of conventional coker distillates are the background to this study. PETROLEUM REFINERY A petroleum refinery is a very complex se- quence of processes, which convert petroleum crude oils into lighter marketable fuels and chemical feedstocks. A simplified scheme is shown in Fig. 1, which shows only the major processes and major product streams. The crude oil enters the refinery via the desalting unit. After desalting the crude oil is atmospherically distilled and fractionated into naphtha and middle distillate. The naphtha cut is either routed to the naphtha pool, reformed to produce high-octane naphtha components, or treated in olefin plants to produce ethene and propene. The middle distillate can be directly routed to the middle distillate pool, or disul- phurised prior to this. These pools supply gaso- line, jet fuel, diesel and fuel oil to the market. The high boiling residue from the atmos- pheric distillation tower is further distilled in a vacuum tower. The resulting distillates are cata- lytically cracked in hydrocrackers or fluid cat crackers, respectively. The residues are ther- mally cracked in visbreaking or coking units, or in thermal hydrocracking processes. The lighter products are treated in the same way as the straight-run distillates. 237 238 W. BALDAUF et al. Atm. Disttllatton v&z. Diiillatton Fig. 1. Refinery schematic. Raw pyrolysis oils are not miscible with con- ventional petroleum crudes or any fractions and this leads to the need for a pretreatment step prior to processing pyrolysis oil in the refinery. FEEDSTOCK Flash pyrolysis oil was provided by ENSYN (Canada). The oil was produced from mixed hardwood sawdust (maple/oak). The pyrolysis plant operated at a temperature of 525C and a residence time of 0.35 s. The ENSYN oil was analysed with standard analytical methods. Results are listed in Table 1. Depending on the quality of the pyrolysis oil after pretreatment, it can be routed to either atmospheric or vacuum distillation, from where it ends up very diluted in the three distillate streams. Another possibility is to feed it directly into the conversion units. If pretreating product qualities allow, it could also be possible to distil the hydrotreated oil separately and to feed the distillates to the corresponding conversion units or to the corresponding product pools. The possible feed points for pyrolysis oils are indicated in Fig. 1. Table 1. Characterisation of raw pyrolysis oil Water content % 29.85 Density (30C) g cm- 1.192 HHV MJ kg- 16.23 LHV MJ kg- 14.47 Pourpoint C - 30 Flashpoint C 51 Elemental analysis (solids free) C wt% 39.17 H wt% 8.04 S ppm 5 N wt% 0.05 0 wt% 52.74 Solids Acetone insolubles wt% 2.2 Pyridine insolubles wt% 2.1 Ash content wt% 0.15 Because the crude pyrolysis oil contained 2% of char the oil had to be filtered prior to hydrotreating. EXPERI MENTAL The upgrading test runs were performed in a continuously operating bench-scale catalyst testing unit. The unit is designed for pressures of up to 30 mPa, temperatures of up to 500C and flow rates up to 300 g h-. Especially for pro- cessing pyrolysis oil the unit was modified for an optional down- or upflow mode operation. A simplified flow scheme of this continuous-flow fixed-bed unit is shown in Fig. 2. The make-up hydrogen was supplied from a high-pressure hydrogen supply and the liquid feedstock was fed by means of a high-pressure pump. Both feed rates were continuously measured by flowmeters. After contacting gas and liquid the reactor was charged in the se- lected mode. The reactor (30mm internal diameter and 1130 mm long) had a volume of 7 16 cm3, minus the volume of a central thermowell which con- Upgrading of flash pyrolysis oil 239 Reactor Stab. Gas Fig. 2. Bench-scale unit for catalyst testing. tained thermocouples for measuring the temperatures along the reaction section. The reactor was externally heated by five heating zones which were independently con- trolled and monitored by means of the thermo- couples. Preheating was performed in the first part of the reactor, which was filled with inert SIC. The centre part of the reactor was filled with cata- lyst. The feedstock was further heated up to the reaction temperature in the first third of the reactor which was isothermal in the remaining catalyst zone. The catalysts were standard refin- ery catalysts in their sulphided form. To prevent desulphiding and thus deactivation of the cata- lyst small amounts of DMDS (dimethyldisul- 240 W. BALDAUF et a l . WHSV:0.40 * ,z, WHSV:0.80 340 350 360 370 Temperature I [Cl Fig. 3. Influence of temperature on deoxygenation. 380 phide) were added to the feed to ensure a minimum H, S partial pressure. The product leaving the reactor was cooled down at pressure. The offgas was separated from the liquid phase in the high-pressure sepa- rator and depressurised by a control valve which established the operating pressure of the unit. The liquid phase was depressurised and separ- ated into a liquid product and stabilisation gas in the stabiliser. The production run was performed in a hy- drotreating pilot plant which was designed for oil flow rates of up to 10 kg h-. The configur- ation of the plant is similar to that of the bench-scale unit described above. A detailed description of the plant is given in ref. [8]. Material balances were performed by sampling the liquid and gaseous products. The observation of mass balance was 48 h after establishment of stable conditions. Raw mass balances were corrected by a calcu- lation procedure which closed elemental bal- ances of carbon, hydrogen, oxygen, sulphur and nitrogen. Hydrogen consumption was calcu- lated as the difference in hydrogen content of the product streams minus hydrogen content in the liquid feed. H,S, NH3 and additional H,O were calculated by balancing S, N and 0 in liquid product and feed (water in feed oil and DMDS were taken into account). Finally flow rates were corrected by closing the carbon balance. C,-C,, CO, CO*, and C,, were calcu- lated from corrected flow rates and the compo- sitions of liquid products, off gases and stripper gases. RESULTS During the experiments the effects of tem- per at ur e (350-37OC), s pace vel oci t y (0.154.80 kg (kg h))), up- and downflow mode, and different catalysts (CoMo, NiMo) were investigated. In order to reduce the number of independent variables (temperature, space velocity) the severity parameter deoxygenation rate was introduced for the following interpretation of the test results. Deoxygenation rate represents the reduction of concentration of organic oxy- gen in product oil related to organic oxygen concentration in the feed. Depending on the operating conditions, deoxygenation rate in- creases with increasing severity which is illus- trated in Fig. 3. The results of analytical inspection of product oils are summarised in Table 2. The correspond- ing balances and product distributions are listed in Table 3. Oil yields decrease from 36 to 32% with increasing deoxygenation. Water shows the highest yields. In addition to the water in the feed, 21-25.5 wt% of water was produced. Gas and water yields increase at higher severities. In addition to water formation, significant amounts of oxygen were removed as CO and c o, . With increasing deoxygenation the amounts of CO and CO* decrease. This means that, at higher severity, oxygen removal shifts more and more to water production instead of CO, production. Oxygen rejection via water increases hydrogen consumption. As deoxy- Upgrading of flash pyrolysis oil Table 2. Characterisation of product oils 241 Run no. 540 Flow direction downflow Catalyst type CoMo Temperature (C) 370 Space velocity (kg(kg h))) 0.25 Deoxygenation 99.92 rate (X) Elemenial analysis (water .free) c (wt%) 86.79 H (wt%) 13.17 s (wt%) 0.070 N (wt%) 0.003 0 (wt%) 0.021 Density (g cn-) 0.83 H,O content (ppm) 50 CCR (wt%) 0 arom. C (wt%) 10.0 HHV (MJ kg-) 45.96 LHV (MJ kg-) 43.09 Boiling range 0-200c (wt%) 200-350C (wt%) 350-500C (wt%) > 5OOC (wt%) 40.8 38.5 20.7 541 downflow CoMo 370 0.40 98.53 87.22 86.84 86.50 85.94 86.93 86.82 86.47 12.35 11.82 11.23 10.79 11.87 11.52 12.90 0.004 0.004 0.008 0.055 0.055 0.007 0.021 0.033 0.082 0.021 0.152 0.129 0.23 0.009 0.39 1.25 2.14 3.06 1.06 1.20 0.60 0.86 0.896 0.928 0.94 0.90 0.93 I 0.866 210 510 1900 4200 350 351 102 0.09 1.40 3.39 5.52 1.79 1.60 0.28 17.0 18.8 25.9 27.0 18.8 22.7 9.8 45.26 44.46 43.43 41.20 44.38 43.44 44.83 42.60 41.87 40.99 38.87 41.68 40.91 42.00 40.0 30.6 27.6 25.3 29.8 21.4 38.5 36.2 31.4 29.6 29.2 30.2 32.1 36.3 21.2 23.1 23.0 21.6 23.8 27.6 22.3 2.6 14.9 19.8 23.9 16.2 18.9 3.0 542 543 544 downflow downflow downflow CoMo CoMo CoMo 350 350 370 0.25 0.40 0.80 95.17 91.78 88.32 545 551 557 downflow upflow downflow CoMo CoMo NiMo 370 370 370 0.40 0.40 0.15 95.88 95.25 97.20 genation increases from 88 to lOO%, hydrogen consumption increases by about 50%. Product properties show the following depen- dencies with decreasing severity: ?? specific gravity increases from 0.83 to 0.94 g ml-; ??water content in product oil increases from 50 to 4200 ppm; ??higher and lower heating value decrease from 46.0 (43.1) to 41.2 (38.9) MJ kg-; ??Conradson Carbon Residue (CCR) content increases from 0 to 5.5%; ??aromatic carbon content increases from ap- prox. 10 to 27%; ??naphtha and middle distillate concentrations in the liquid product decrease from 41 and 39% to 21 and 29%, while vacuum gas oil remains relatively constant at approx. 20-22% and residue > 500C increases from 0 to 24%. In order to get a measure of catalyst stability, run 541 was repeated at similar operating con- ditions after approx. 150 h (run 545). A signifi- cant drop of deoxygenation rate from 98.5 to 95.9% indicates the rapid catalyst deactivation Table 3. Mass balances and yields Balance no. 540 541 542 543 544 545 551 557 Flow direction downflow downflow downflow downflow downflow downflow upflow downflow Catalyst type CoMo CoMo CoMo CoMo CoMo CoMo CoMo NiMo Temperature (C) 370 370 350 350 370 370 370 370 Space velocity (kg(kg h))) 0.25 0.40 0.25 0.40 0.80 0.40 0.40 0.15 Deoxygenation 99.92 98.53 95.17 91.78 88.32 95.88 95.25 97.20 rate (X) Gases (total) (wt%) 16.69 18.47 18.53 16.72 15.85 16.76 17.12 16.90 c, (wt%) 3.22 3.32 3.12 2.67 2.57 3.35 3.53 3.68 c, (wt%) 4.06 4.04 4.27 3.69 2.62 3.81 3.61 3.63 c, (wt%) 2.70 2.49 2.20 1.76 1.25 1.81 1.85 2.32 c.$ (wt%) 2.04 1.88 1.66 1.29 0.90 1.31 1.34 0.57 co (wt%) 0.13 0.16 0.11 0.15 0.32 0.15 0.15 0.55 co, (wt%) 4.46 6.53 7.11 7.15 8.20 6.33 6.51 4.70 Water (wt%) 55.51 53.61 52.89 52.45 50.97 53.58 53.14 54.53 Oil (wt%) 32.81 32.28 32.68 34.51 36.34 33.78 33.75 33.58 Total products 105.01 104.42 104.10 103.68 103.16 104.12 104.01 105.01 (wt%) H, consumption 5.01 4.42 4.10 3.68 3.16 4.12 4.01 5.01 (wt%) 242 W. BALDAUF et al. Table 4. Characterisation of product oil from the oilot plant production run Product Total product Naphtha Diesel VGO Residue >sooc <18oC I go-350C 350-500C Elemental analysis c (wt %) H (wt%) S (ppm) N (ppm) 0 (wt%) Ca @pm) Ni (ppm) V (ppm) Mo (ppm) Fe @pm) Na (ppm) Density (g cm-) n-Paraffins (wt%) iso-Paraffins(wt%) Naphthenes (wt%) Polynaphthenes (wt%) Aromatics (wt%) Mono aromatics (wt%) Diaromatics (wt%) Polycyclic aromatics (wt%) MOZ/ROZ (-) Cetane number (-) Cetane index (-) Cloudpoint (C) CCR (wt%) Stability test (ASTM D 2274) 86.45 85.45 87.08 13.22 14.72 12.88 851 130 109 83 2 51 0.2 0.05 0.07 0.8503 0.7517 20.56 12.52 61.41 I .47 4.03 62162 87.54 12.26 426 162 0.4 <I <I < I <I <I <I 0.8739 0.9303 0.9316 29.3 0.6 neg. 0.7 45 39.7 - 34 0.02 which is not acceptable for technical fixed-bed reactor systems. The result of rapid deactivation was proved by the fact that the test run was terminated due to pressure build-up in the reac- tor caused by plugging. While the test runs 540 to 545 were performed with downflow mode and with a CoMo catalyst, in additional test runs the influences of a differ- ent catalyst (NiMo, run 557) and of upflow mode (run 551) were tested. The influences on liquid product qualities can be interpreted as follows: ??at similar operating conditions, deoxygenation rate in the upflow mode is less than in the downflow mode; odeoxygenation with the NiMo catalyst is less than with CoMo catalyst; @in upflow mode at the same deoxygenation rate, lower amounts of naphtha and higher amounts of vacuum gas oil are formed; conse- quently the liquid product density in the upflow mode is higher; ??nitrogen removal in the upflow mode is signifi- cantly less than in the downflow mode; sul- phur content in the liquid product is influenced by sulphur injection to the feed and does not represent the behaviour of the hydro- treating process; ??the content of aromatic carbon is lower with NiMo catalyst; ??test runs with CoMo catalyst were terminated by coking and plugging in the low-tem- perature catalyst zone, whereas the test run with NiMo catalyst ended due to plug- ging of product lines with a gum-like sub- stance; ??all other properties are only determined by deoxygenation rate or severity, but are inde- pendent of flow mode and catalyst. Despite operational problems during bench- scale test runs, the potential of upgraded pyrol- ysis oil as feedstock for petroleum refineries should be demonstrated. To provide large amounts of upgraded oil, a production run was performed in a pilot plant. The bench-scale experience led to operation in downflow mode with NiMo catalyst. Operational parameters were adjusted for a medium deoxygenation rate of 97.3%. The product from the pilot plant test run was used for characterisation of total crude and its related fractions with respect to refinery requirements. Results are shown in Table 4. Total liquid product and fractions can be defined as follows. Upgrading of flash pyrolysis oil WV 243 01 I 0 50 104 150 Pyrolysis Oil I ECU/t Fig. 4. Economics of upgrading. Total liquid product The product oil is a light brown low viscosity liquid with a boiling range from 35-535C. Naphtha (boiling range < 180C) High naphthene content and low octane num- ber reduce its suitability as a gasoline pool component. Only small amounts can be blended as gasoline. Further upgrading in the reformer plant and conversion to olefins in steam crack- ers are more promising routes. Diesel (boiling range 180 -350C) The diesel fraction is characterised by high density, low cetane number and high aromatics content. This fraction does not meet the specifi- cations of a marketable diesel product. The oxygen stability test was negative. The need for further upgrading of this fraction for stabilis- ation and aromatics reduction prior to use as a diesel pool component is evident. Vacuum gasoil{ VGO (boiling range 350 -500C) CCR and metals content of VGO are at the limits recommended for feedstocks for hydro- cracking (HC) and fluid cat cracking (FCC) plants. Alternatively, the fraction might be used without further upgrading as heavy fuel oil. Residue ( > 500 C) The residue fraction represents only a very small amount with a final boiling point of 535C. Commercial vacuum distillation units will not separate this fraction because VGO cut points usually are > 535C. That means that the residue will be part of the VGO fraction and is treated as described above. Restrictions might occur if CCR and metal contents of vacuum gas oil are significantly changed by the shift of the cut point. Results of yield structure and fraction qual- ities indicate that the total liquid product cannot be fed to a single further upgrading process. Separate fractionation or feeding to the pet- roleum crude oil distillation unit (which is more economic in an existing refinery) is necessary to split the oil into the main fractions. The reported possible suitability routes are to be evaluated on the basis of the major analytical properties of the fractions. The final decision for suitability has to be confirmed by experimental test programmes. ECONOMICS OF UPGRADING Low yields and high hydrogen costs are re- sponsible for the high cost of upgraded pyrolysis oil. In Fig. 4 the costs for highly upgraded oil are shown as a function of raw pyrolysis oil price. Product costs are calculated as the sum of the feedstock cost, upgrading cost and hydrogen cost, minus a credit for the hydrocarbon gases on the following basis: ??raw pyrolysis price is varied between 50 and 15OECU t-; ??upgrading costs are 15 ECU t- feedstock at a hydrotreating plant capacity of 0.8 x lo6 t year-; ??hydrogen costs are 0.09 ECU Nmd3 for steam reforming of natural gas; ??hydrocarbon product gases are credited at a price proportional to their heating value which leads to approx. 30-50 ECU t- of gas. The result is that upgraded pyrolysis oil is more expensive by a factor of 1.5-3 than equiv- alent petroleum oil products. At typical feed- stock costs of 100 ECU t- for raw pyrolysis oil, 1 t of upgraded oil costs about 450 ECU t-l, compared with 18&220 ECU t- for petroleum- 244 W. BALDAUF et al. derived naphtha and middle distillate and SO-100 ECU t- for fuel oil. The major contri- bution to this cost is the feedstock price (3 t of feedstock are necessary to produce 1 t of up- graded pyrolysis oil); about 150 ECU t- of product has to be expended for hydrogen. Credits for the hydrocarbon product gases and the upgrading costs offset each other. The situation is similar for partially upgraded oil, compared to prices of conventional fuel oils. The value of extenuities such as CO, tax or a credit for zero sulphur content can improve the price relations for biomass resources. These benefits are reduced if the hydrogen and process energy production by fossil resources are taken into account. CONCLUSIONS Catalytic upgrading of flash pyrolysis oil in a fixed-bed reactor system was realised for short run times. High deoxygenation rates were ob- tained. Water is the major product and the oil yield is only 30-35%. The products are light liquids with low oxygen and water content and high heating values. At lower severity of lower deoxygenation rate the solubility of product oil in water is increased and the separation of aqueous and organic phases is increasingly difficult. The catalyst deactivated very rapidly and steady-state conditions could only be obtained for a short period. Several operational problems caused by the instability and coking potential of the pyrolysis oil made processing difficult. Tubes and valves were plugged or covered with gum-like deposits. Operating and control sys- tems such as flow meters and level controllers were disturbed by adhesive deposits. With CoMo catalysts the catalyst bed plugged and coked in the preheater, whereas with a NiMo catalyst the reactor outlet was plugged by gum- like substances. Although the products are already hydrogen- ated, some fractions did not fulfil the required product specifications. The naphtha fraction is unsuitable for direct use as gasoline. Only very small amounts could be routed to the gasoline pool. An additional upgrading (e.g. in a reformer) or the use of the naphtha fraction as a feedstock for olefin pro- duction should be more promising. Low cetane number (45) high density (0.873 g ml-), and oxygen instability illustrate the poor potential of the diesel fraction for direct use as a pool component. Further upgrad- ing is necessary. Total liquid product from the pretreatment step is recommended to be routed to the crude distillation tower, where the fractions end up diluted in the naphtha, diesel and VGO cut and are further upgraded in subsequent conversion units together with petroleum-derived products. A fixed-bed reactor system is not recom- mended, since the rapid catalyst deactivation must be compensated by continuous regener- ation. 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