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    9 views13 pages

    Paten HDO Petrobras

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    Adhisya Salma Khairunnisa

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    © All Rights Reserved
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    ‘US 2006) cu») United States 8602081 2) Patent Application Publication co) Pub. No.: US 2006/0186020 A1 Gomes (54) VEGETABLE O1L. HY! PROCESS ROCONVERSION Jefferson Roberto Got Taneino RI (BR) (73) Inventor: Rio de Comespondence Address: NIXON & VANDERIYE, PC 901 NORTH GLEBE ROAD, 11TH FLOOR ARLINGTON, VA 22203 (Ui Petroleo Brasileiro S.A. = PETRO- BRAS, Rio de Janeiro, IR (BR) (93) Assignee: 1) Appl. Nos 11290,486 (22) Filed Dee. 1, 2005 G0) Foreign Application Priority Data Feb. 18, 2005 (BR). PI 0s00S91-4 (43) Pub. Date: Aug. 24, 2006 Publication Classification G1) Inte Bos 2970 62) USC (2006.01) 208/46 6 AB TRACT A vegetable oil hydroconversion process is described for hhydroconverting a mixture between I 10 75% in mass of il ‘or natural fat (1) and the rst mineral ol 2), hydroconvertd na actor (208) under conditions of pressure, temperature hhyelogen (flow 119) and sulfide catalyst of Groups VITI and VIB, obtaining, affer sour water separation (low 111) and rectification (low 112), a specified diesel product (4). The product (4) has an ITQDEN (eetane number) higher than a product oblained from a pure mineral based ol would have ower density than fom a base oil and a plugging point depending on the mineral oil Dow, as well as grater ‘oxidation stability than the base ol. Patent Application Publication Aug. 24,2006 Sheet 1 of 6 US 2006/0186020 A1 Patent Application Publication Aug. 24,2006 Sheet 2 of 6 US 2006/0186020 A1 IQT/DCN FIG. 2 o 10 20 30 leo de mamona (%massa) FIG. 3 50 + 46 42 40 A 0 5 10 15 Gleo vegetal (%massa) Patent Application Publication Aug. 24,2006 Sheet 3 of 6 US 2006/0186020 A1 FIG. 4 lQT/DCN & 8 6 N oO 2 4 6 Oleo de mamona (%massa) FIG. 5 BE 3 2s coo fo Temperatura(C) 2 4,0 0 10 20 30 40 Oleo de mamona(% massa) Patent Application Publication Aug. 24,2006 Sheet 4 of 6 US 2006/0186020 A1 Temperatura (C ) Cc) Temperatura ( FIG.6 3,5 3,0 25 1 2,0 1,5 10, 9 >> 0,5 0,0 0 5 10 15 Oleo vegetal(%massa) FIG.7 -20,0 2 4 6 8 -25,0 1————+ -30,0 - -35,0 40,0 Oleo de mamona (%massa) Patent Application Publication Aug. 24,2006 Sheet 5 of 6 US 2006/0186020 A1 FIG.8 0,9000 0,8900 Se 0,8800 2 0,8700 ——— 0,8600 | 0,8500 | — 0,8400 — 355 360 365 370 375 380 385 Temperatura ( C) Densidade FIG.9 0,8800 + 038750 ‘ 0,8700 ee %@ 0,8650 | 2— & 0,8600 ——S— 0,8550 a 0,8500 345° «350 4355 360 365 370 375 Temperatura ( C) Patent Application Publication Aug. 24,2006 Sheet 6 of 6 US 2006/0186020 A1 Densidade 0,8358 0,8337 0,8316 0,8295, mg/100mI FIG.10 ,— 0 . 2 4 6 Oleo de mamona (%massa) FIG.11 15 75 10 Oleo vegetal (%massa) US 2006/0186020 AI VEGETABLE OIL, HYDROCONVERSION PROCESS PIELD OF INVENTION [0001] This invention belongs to the field of hydrocon- version processes, more specifically tothe hydraconversion processes 0 oblain diesel ol fom vegetable oils combined with ol BASIS FOR THE INVENTION {0002} Throughout Brazil, agriculture is an important motivating factor in promoting socioeconomic develop- ‘ment, as well as contributing to improving environmental ‘conditions world wide, which isbeing greatly affected by the ‘economic activities of modern civilization, principally by the use of non-renewable fosil Tues in detriment 0 fuels ‘derived Irom vegetable matter. In Prazil for some decades, ‘ethanol, produced on a large scale, has been suecessflly ted asa substi however it wasat possible, ilar program for diesel [0003] Therefore, there is a great efor to make the use of ‘what is known as “biodiesel, trans fatty acids with alcohol (methanol o ethanol) viable. However the production of this Tel requires the development af simple, low cost technol- ‘ogy in order fr itto be used by small agricultural producers, [0004] The main source of these fatty acids is vegetable cil, also called fatty acid tryglicerids. They are extracted directly from vegetable sceds by a pressing process andor ‘exirction with organic solvent, Inaktion to applications i the food industry they are mainly used inthe production of soaps, pats, lubricants and plastis, [0005] The Brazilian fuel market is greatly dependent on the supply of diesel, due to the truck and bus eet, the main means of transport for eargo and people. Therefore, the fcurch for alternative sources has driven many areas of research, and renewable sources have been of partculae Jnerest, 2s they contribute towards improving the envis ‘ment and may be an extra source of resources in some repions ofthe country. [0006] Some work was carried out sing the oils dicectly jn diesel engines. The idea of using pre vegetable oils, oF a mixture, directly in diesel engines has been around for a Tong time, Rudolph Diesel himself used peanut oil in one of his engines atthe 1900 Paris Exposition, However long tem ‘engine testing showed that the conventional engine is not ‘suitable for using tis fue, both in pure form or mixed with ‘mineral ol, at the engines used in the tests showed earhon deposit formation, ashes, fucl chamber wear and the forms: tion of gum in the fel lines, a cited by Recep Alin, Selim (Cetinkaya, Hiseyin Serdar Yacesa ~The potential of wsing vegetable ol a fuel for diesel engines. Energy Conversion and Management, 42, pp 529-538, 2001 [0007] Another important market that is also seeking to substitu diesel with a renewable source is Canada, a can be seen in the anicle by Mark Stumbors, Alwong, Ed Hogan—Hydroprocessed. vegetable oils for diesel fuel improvement, Bioresource Technology, 56, pp. 13-18, 1996. [0008] To convert vegetable ol direetly into extra quality diesel, a bydrorefining technology was developed, based of known technology, sing existing commercial catalysts. The Aug. 24, 2006 vegetable ils used were: rape seed oil, soya ol and residual oil fiom cellolose production using pine trees (or any resinous plan), The ols used are low quality, ie. they have ‘not having bon through any type of teatment, except filtering. The study resulted in the development of a new lhydrotrcatment process for pure vegetable wils, for produe- sion ofa hydrocarbon flow with a high cetane number, 3 per G.N. da Rocha Filho, D. Brodzki and G., Djgga-Mariadas- sou—Formation of alkyleyeloatkanes and alkylbenzenes Garing the catalytic hydrocracking of vegetable ils, Fue, 72, pp. 543-549, 1993. Hydrocracking reactions are used for reducing the number of carbon atoms inthe chain, hydrottsatment for removing oxygenated compotinds and unsuration hydrogenation for removing double bonds, for ‘whieh were used NiMo and CoMo commercial gama alte mina supported sutided catalysts [0009] The diesel obtained amounts to 80% of the load processed, with good results in rolation to the catalyt's ‘seful life, however with 2 Forcast of eaalyst regeneration ‘over the period. The prodict obtained has @ ctane number varying between 5S and 90, withthe production of subprod- vets: C, to C, gas, CO, and water. The liguid product is ible in al proportions in the minecal diesel how and, therefore, may be added 10 the refinery’s diesel pool, ‘improving the ceane number, but pejudicing the low tem: perature specifications of the final produc [0010] Generally, the product contributes to improving emissions from diesel engines, this improvement being inversely proportional to the quality ofthe diesel fuel base, i.e the worse the emissions caused by the diesel are, the ‘better isthe return by the addition ofthe generated product, ‘mainly inthe reduetion of NOx and CO emissions [0011] The hydrorefining provess (HDR), also Known as hhydroprocessing, consists of mining oil’ fractions with hhydeogen in tho presence of a catalyst, which under deter ‘mined operational conditions produces specified diesel. This process is gaining importance throughout the world and Principally in Brazil, as despite being a catalytic process, inder severe operational conditions (high temperatures and pressures) and which consumes hydrogen, a high production cost consumable, the advantages obtained with this refining technology outweigh the cost, allowing better use of heavy Toads, improved produet quality and environmental protee- sion by removing polluants such as sulfur and nitrogen ‘Therefore, resistance tothe HDR process because of its high investment and operational costs, are outweighed by the ‘benoit obtained. [0012] Hydrotreatment (FIDT) units, when sed in more complex refining schemes, are intended 10 improve load quality, by eliminating the contaminants of subsequent pro fesses. The product from the unit as essentially the same load distillation range, although there is secondary progue- ‘ion of lighter products by hydrocracking. Typical loads of these units vary from the naphtha range up to heavy vacuum szsoil (GOP), [0013] Some patent documents cover this area, [0014] The hydrogenation of vogetable oils combined ‘with minora oil is mentioned in US. Pat. No. 2,163,563, which processes vegetable oils mixed with a mineral oil ow in the presence of fydmgen al high pressure (50 to S00 atmospheres) and uses a reduced Ni alumina supported US 2006/0186020 AI ‘catalyst. The converted vegetable ol is separated by distil-, Jation and the mineral oil reeyeled, Havsever this patent ‘doesn't deal withthe hydrotreatment of a combined ofl and vezetable oil load by a HDT process [0015] US. Pat. No. 4,300,009 describes the catalytic ‘conversion of anaboites (substances formed in the anabolic process) such as resins, vegetable oils and fats in liquid hydrocarbons, in the presence of olites with an elfective pore size greater than 5 Angstrom. The generated products have a boiling point in the gasoline range. [0016] U.S. Pat. No. 5,283,109 describes a synthetic enue ‘il produced by the catalytic erackng fa biomass material such a Vegetable or animal oi inthe presence ofa catalyst ‘which is oF alumina, wth of without silica andlor a zeohiic ‘component andr rare earths andor sium oxide. The reaction takes place inte presence ofa carrer gas that can be a, nitrogen, argon, kydrogen and a hydrocarbon ‘biained fom oi sting [0017] U.S. Pat, No, 5,705,722 deseribes 9 process 10 produce additives for diesel fuels with «high eetane number ‘and serving. 88 fel ignition improvers. Ia the process, biomass containing « high proportion of unsaturated fatty acids, wood ols, animal fats ad other mixtures is submitted to hydroprocessing, placing the load in contact with hydro- gen gas inthe presence ofa hycdroprocessing catalyst under hydroprocessing conditions, to obtain « product mixture ‘This mixture is then separated and fractioned to obtain a hydrocarbon product witha boiling point in the diesel range, ‘and this product isa high eetane number additive, There is ‘no meation in this document of the addition of eil hydro- ‘carbons 10 the biomass load being hydroprocessed, [0018] U.S. Pat. No, 4,992,605 uses hydrorefning pro- ‘cess with a sulfided catalyst (NiMo and CoMo) in the presence of hydrogen (4 10 15 Mpa pressure) and temper ture varying between 350° C. and 450° C. and processes pure vegetable oils such as rape sed, sunflower, soya, palm ‘and wood oil, which is @ residue’ from the wood pulp industry. The final objective isto obtain a flow with a high cetane number to be added to the refinry"s diesel pool, however the low temperature specifications are prejudiced “This patent doesn’t cover the mixing of a hydrocarbon with the vegetable oil in hydroretining, [0019] U.S. Pat, No. 5,972,057 describes the transesteri= fication of vegetable oils principally oils use for fying with methanol and ethanol, withthe objective of producing 2 fucl similar to miperal_ diesel, however the process involves the consumption of an expensive reagent (alcohol) and the subproducis (glycerine, et.) have to be separated in ‘onder not 10 damage the engine [0020] Therefore, despite the technologieal developments there is sil the teclnical need of a process forthe hydro- ‘conversion of vegetable oils in order to obtain diesel is Which a vegetable oil flow in a proportion between Tank 75% in mass, combined at between 99% and 25% ia mass swith a hydrocarbon flow, is submitted to hydotreatment under hydeotreatment conditions, the product flow with a boiling point in the diesel range has an improved eetane index and density les than that obtained by processing the usual hydrocarbon ows themselves, the same hydrocon- version process being deseribed ad claimed inthis request. Aug. 24, 2006 INVENTION SUMMARY [0021] Ia broad maaner, the invention process for vege table oil hydroconversion includes hydoteating a low of oils and/or natural fats ina proportion between I and 75% in mass combined at between 9% and 25% in mass to & hydrocarbon flow, hydrotreated ina hydroteatment reactor, under hydrotreatment conditions, which involve an opera ing pressure of 4 MPa to 10 Mpa, a catalytic bed average temperature between 320° C. and 400° C., spatial speed of OS to 2h and @ NiMo oe CoMo catalyst, the hydrogen Joad ratio varying Irom 200N I of hydrogea/load liter 1000 NT of hydrogen/oad liter, obtaining 4 product with a boiling point in the diesel range with an improved cetane index, and a density less than that obtained by hydrotreat- iment of a pie hydrocarbon load, [0022] Therefore, the invention provides a vegetable oil hhydeotteatment process in which a proportion of Ito 75% ia is hydrotreated under hydrotrestment condition ‘obiain diesel ofl with an improved cetane index in relation to the hydrotreatment of mineral oil alone. [BRIEF DESCRIPTION OF THE DRAWINGS [0023] FIG. 1 attached, isa process schematic fowehart ofthe invention. [0024] FIG, 2 attached, is « grap illustrating the 1QT/ DEN of heavy diesel (HD) by easior ol content and reaction temperature. Curve 1 represents the data at 360° C., while Curve 2 the data at 380". [0025] PIG. 3 attached, is a graph that illustrates the IQH/DCN of the REPLAN load by the vegetable oil (VO) content and the reaction temperate. Curves 1 and 2 rep- resent the data for the castor oil at 380° C. and 370° C. respoctvely, while Curves 3 and 4 are te daia Tor soya ol, atthe same temperatures of 350° C, and 370°C. respectively [0026] FIG. 4 attached, is a graph that illustrates the IQUIDCN of light diesel (LD) by castor oil content and action temperature. Curve 1 represents the data for 40° Cy while Curve 2 the data for 360° C. [0027] FIG, § attached, is a graph that illustrates the plugeing temperature of « diesel fuel system for a heavy Giosel (FD) by castor oil content and reaction temperature (Curve I represents the data for 360° C., while Curve 2 the data for 380° C. [0028] FIG, 6 attaches, is graph that illustrates the plugaing temperature ofa diesel fol system for a REPLAN oil by vegetable ol content and reaction temperature. Curve 1 represents the data for 350” C. ia the presenoe of castor oil and soya ol as well as soya oil at 370°C. while Curve 2 the data for castor oil at 370°C. [0029] FIG. 7 attached, is a graph thot illustrates the plugging temperature of a diesel fel system for a light iesel (LD) by castor oil content and reaction temperature Curve I represents the data for 340° C, while Curve 2 the data for 360° C. [0030] FIG. 8 attached, is a graph that illustrates the density variation of the product obtained from pure heavy ‘ese and mixed with eastor ol. Curve I represents the data Tor heavy diesel, Curve 2 the daa for heavy diesel plas 10% US 2006/0186020 AI ss of castor oil and Curve 3 the data for heavy diesel ‘30% in mass of castor ol, [0031] FIG. 9 attached, is a graph that illyrates the density variation of the product obtained from a pare REPLAN oil and med with different vegetable oils, Curve 1 represents the data for the pure REPLAN oil, Curve 2 the REPLAN oil plus 10% soya oil ($0), and Curve 3 the REPLAN oil pls 109% castor cil [0032] FIG. 10 attched, is » graph that illustrates the ‘density vacation ofa product obtained rom light diese, by the content in mass of castor el aad reaction temperature ‘Curve I represents the data for 340° Cand Curve 2 the data lor 360° C. [0093] FIG. 11 attached, is a graph that illustrates the Stability of products obtained from @ REPLAN oil by the content in mass of vepetable oil for different oils and ‘illerent temperatures. Curve I represents he dats for castor oil at 350° C., Curve 2 castor oil at 370° C,, Curve 3 soya, ‘ll at 350° Cand Curve 4 soya ol at 370° DETAILED DESCRIPTION OF THE PREFERRED MODEL [0034] The coprovessing of vegetable oils mixed with mineral oil, in existing HDT units, is an altemative for ‘ncomporating a low aided value flow to the refiney’s diesel pool, not only fr having 2 high cetane number but also for reducing the density, as normal parallins have low density and the HDT process as limitations for attaining this specification with very aromatic loads (high LCO conten). [0035] Another important feet isthe use of eastor oil, ‘which unlike other vegetable oils hydrocracks, producing C10 and CH parang as well as C17 and C18 parafin, therefore having lower density than other vegetable oils studied iD tb © Where Ale [0036] _ Another important factor is, that diluted with vex ‘table ol (VO) the industrial unit ean operate at temperature ranges below 340° C, whieh is lower than the temperatures shown by process patents with pure VO. [0037] Also highlighted is the improved phigging point Tor diesel oils used in Bruvl, whichis contrary to the results in existing patents. possibly because in countries with ‘older climate, diesel oli lighter than that used in tropical [0038] The hydrotreatment of vegetable ois in aecondance ‘withthe invention includes, therefore, hydrotreatment under Aug. 24, 2006 Ibydrotreatment conditions, of a mineral load with between ‘Vand 75% in mass of a vegetable oil or snimal ft load [0039] |The usefil vegetable oils for the invention’s pro- cess includes soya oil (Glycina max), castor oil (Ricinus communis), palm oil (Flaeis guincensis) and peanut oil (Arachis hypogaea), Among these, castor oil isthe prefered [0040] The useful vepetble Joad for the process can be any vegetable or animal oil, without the ned af purification, except Tor particulates, water and dissolved sll [0041] Castor il is obtained from pressing. the sovds produced by the plant Ricinus Communis, which is found in practically all tropical or subtropical countries, and can be propagated from seeds. The fundamental characteristic of te ol isis Tow variability, both inthe quantity of oi from ‘mature seeds and the composition of the obtained oil, the production of which varies between 45 and 49% per sood ‘ats, Castor oil contains around 87 to 90% Ricinolei Aci, 1% palmitic acid and 4.2% linoleie acid. [0042] The most commonly used recovery process firstly presses the seeds followed by extraction with solvent and, ‘when pressing is done a high temperature, itis necessary to purify the oil by removing toxie proteins (riin). The races elcieney i from 75 to 85%, 10 to 20% is retained inthe presse solid reside, [0043] For purifying vegetable oil a centrifugal process is normally used for removing proteins in suspension (degum- sing process), [0044] Soya oil is also the prefered vegetable Toad, prin- cially aimed st recycling used oils from restaurants, for example [0045] ‘The mineral loads used and their analysis is show in Table 1 below: TABLE 1 on is Si Be nD is aw ian : é Ss 93 10 sa sa26 Ng ‘6s ‘cfnsion Ine ASTM D 1318 ant ANTER T= Fl Nope ASIN Daa [0046] ‘The loads are selected in onder to determine the ‘rackabilty of the vegetable oil andl to verily the synergic clfets in relation to the other important process reactions, {determining if any important diesel specification may not be oblained, due to the impact of the vegetable oil on the catalyst, [0047] ‘The useful mineral loads in the process ae: heavy ‘diesel (HD) which isthe largest components of the refinery"s pool: light diesel (LD), to verify the impact on the low ‘emperature specifications and the REPLAN load. The REPLAN load is a mixtuee of a LCO flow andlor coking US 2006/0186020 AI processes gasoil used inthe REPLAN HDT un Sens. atypical load at Petrobras, of a HDT uns ‘ity diesel production. [0048] is equally possible to combine vegetable oil and simul fat Ioads in any proportion [0049] The catalysis used in hydrotreatment (HDT) are basically metal oxides, totally or partially converted t0 ‘y-alumina (j-A1,0,) supported sulfides (active phase). The Conversion ofthe oxides to sulfides (sulfidation) is made in the hydrotrestment reactor itself. The active phase has the hydrogenolysis and hydrogenation processes. The support has the basic role of providing a specific igh are, where the sctive eomponents are found dispersed in the form of stall panicles. Additionally, the support provides mechanical resistance and thermal stability, impeding sintering (active phase agglomeration). The y-alumina has a specific area between 200 and 400 m*/g, pore volume of from 0.5 to LO wg and acidity elasifed as from weak to moderate There is a synergic effect between the metal sulfides of groups VI-B (Mo and W) and VII (Co and Ni), to various reactions involved in the hydrotreatment process, so that the activity ofthe eatalysts containing suides, of both groups, js much greater than the activity ofthe individual sulfides Therefore, the mixed sulfides are normally used asthe active phase (Co--Mo, Ni—-Mo, Ni--W, Co-W), as the optimum relationship between the Group VIII meal and the Group VEEB metal is in the range 0.33 wo 0.54 [0080] In the diesel production hydrotreatment process, the reaction oceurs in the presence of hydrogen at high pressure, in the operation range of 4 MPa to 10 MPa, preferably 5 MPa to 8 MPa, The average temperature of the Catalytic bed can vary between 320° C. and 400° C preferably between 340° C. and 380° C., with spatial veloe- Sty varying from 0.5 8"! to 2, preferably 0.8 hr! to 1.2 he, The catalytic bed may be divide into two oF more stages with an injection of eold nitrogen between stages for temperature contro, hydrogen load ratio varying fom 200N Tot hydrogenvload liter to 1O00N 1 of bydrogen/lad liter [00S1] The bydrotreatment reaction experimental condi tions are determined from the typical conditions of a HDT Uunstables unit. in this way the Variables: pressure (9 MPa) LHSV ("and the Hyload relationship (800 NUtoad fer) are maintained constant. The temperatures are adjusted Jn accordance with the oad’s refrotivit, that is loads with a higher boiling point, or LCO conten, are tested at higher temperatures. The tests are planned in order that there is always, for the same experimental condition, atest with pure ‘mineral (MO) without the adltion of Vegetable vil (VO), to determine the difference inellicieney due to the presence of the vegetable oil sti. [0082] ‘The invention process will be described below, With a reference o the attached Figures [0083] In FIG. 4, the mineral oil (2) is diven via line (101) to the pump (201), which rises the Now's operational pressury, afer which the ol is sent by line (102) to the set ‘of heat exchangers (204) and (203), which heat the oil, recovering heat from the process products. The heated product is pressurized and sent by Tine (103). The vegetable ‘il (1) enters the unit via Tine (104) and is pumped by the pump (202), which pressurizes the flow (105) to the eit’s pressure, Then flow (105) is mixed with fow (103), forming and repre Ses unit for Aug. 24, 2006 is in tum mixed with the hydrogen rieh 119), starting the Now (107). Flow (107) is sent 10 the firnace (208), where ow (107) is heated, Torming flow (108), upto the reactors (206) inlet tempers. tore [0084] The reactions are exothermic and, therefore, there fs an increase in temperature along. the catalytic bed, there- fore the outlet product is at a higher temperature than the inet temperature, giving rise to flow (109) where part ofthe beat is covered by the exchangers (204) and (203) which heats the mineral oil (2) load. The flow (109) i cooled again, this time with eooling water, to condense the light products formed, which are separated from the yas flow in vessel (208), where a flow (111) of produced water from the proeess isa separated, whichis sent to the refinery's sour ‘water system (3) for reutment [0085] The hydrocarbon flow (112), containing the prod- ‘et from VO hydreracking, is set tothe retiller wwer (not represented), where the hydrogen sulfide gas and the amma ni, produced by the HDS and HDN reactions respectively, fare removed. The propane is recovered and the specif diesel (4) i sent for storage. The gas flow (113) arising from (208), is rich in non-reacted hydrogen, but may also have a high hydrogen sulfide gas content, which may prejudice the reactions. Therefore the hydrogen sulfide gas content is ‘maintained below a minimum range by a blow down (8) Flow (114), The blows dossn flow (115) passes vessel (209) Tor resining any liquid compound that may have boca carried, givin rise to flow (116) which is compressed by the compressor (210) up to the fumace (208) inlet pressure starting low (117). Flow (117) is mixed with flow (118), ‘contains pure hydrogen to compensate forthe hydro gen consumed. The hydrogen rich flow (119) is then mixed ‘with flow (106) at the fraace (205), [0086] Proof of the technical viability of the proposed process will described below. based on the evaluation of the parameters, such as IQU/DCN (equivalent t0 the cetane number) density of the products obtained from coproces ‘ng and temperature ofthe plugging point ofa diesel eng running with hydrotreated oil obtained from the invention's process [0087] Evaluation ofthe parameters is illustrated by ref fereace 10 FIGS. 2 10 I [oss] 1Qr/DeN [0089] Diesel quality is associated (© its auto-ignition ‘capability, for this purpose a device called an IQU/DCN nition Quality Tester) was used, which allo the ignition ‘quality ofa fuel to he determined in aconrdance with ASTM 1D 6890.03 and 1P 498/03. The results are shown inthe form fof the DCN (Derived Cetane Number) which isthe equiva- lent of the CN (Cetane Number) obtained in a diesel eycle engine, as per ASTM D6I3. [0060], ‘This parameter shows that the hyerotreatment of ‘vegetable and miner loads brings a shaep improvement of the desl oils specification, as was expected bythe concept fof the invention, as the ‘liquid product from the VO hhydrotreatment would be basically linear hydrocarbons and, therefore, with a high IQT/DCN, so te greater the quantity ff VO the higher the product's IQTIDCN, as shown in FIGS, 2 and 3. The effect of temperature, relatively redue- US 2006/0186020 AI ing the IQUDCN, can be explained by the cracking of higher paralins into lower parafins, which have lower IQH/DCN. [0061] Another relevant fact is that in accordance with FIG. 4, low content with 5% results i improved sensitivity of this specification, Therefore, the processing of small ‘quantities of VO in existing HDT snstables units requires le investment, whereas the processing of lager qua regjires a more detailed study of the sit’s characteristies such as excess hydrogen, recycle compressor: maximum flow rate, et [0062] Diesel Engine Plugging Point [0063] One ofthe problems that ean be caused by oma paralin arises from their high melting point, which can lead to plugging of the engine's fuel system. Analysis of the plugging point reflects the quantity of filtered particulate ormed with the lowering of the temperature, therefore the Jower the plugging point is, che lower the ambient tempera- lure is in which the vehicle can operate, making this speci fcaton extremely important, mainly ifthe fuel is used in gongriphical ara with cold climates [0064] In the eases of heavy diesel (HD) and from the REPLAN load, FIGS. 8 and 6 respectively, ak they are heavy fuels and appropriate for @ country with s tropical climate, the base load has @ high plugging point, and the ‘generated paraffins may even improve the phigging point of the final product, dve tothe dilution effect. However, for 2 Fighter load, similar to that use in counties with & cold climate, the effect is prejudicial, as shown by the graph in G7) [0065] Feet oa Product Density [0066] Analysis of product density reveals a very sharp ‘decrease in density, indicating that the vegetable oil (VO) ‘racks producing lighter hydrocarbons than the peodict fom hydrogenated castor oil (CO). An equivalent redvction can be seen forall loads, therefore, as shown by FIGS. 8,9 and 10, there is no interference to the quality of CO withthe crackability of VO. [0067] LPR Analysis [0068] One of the big problems of using vegetable oils, ‘even vegetable oil esters, as a fuel, isthe low oxidation Stability duc to the presence of olefins. The HDT process not ‘only eliminates the oxygen heteroatoms but also hydroge~ nates ll in saturations, therefore the specification that mea- ‘res stability of fuel to oxidation, LPR, i improved wher ‘compared with the base ol, with a lower insolubles content, as shown by the graph of FIG. 11 [0069] Volumetsic Eficieney [0070] The volumetric elcieney shown by vegetable oil HDT, has an important production of propane (asin com- ponent of domestic gos) and the production of one liter of diesel oil for each liter of VO processed, This fact is 9 ‘consequence of the lower prodct density relative to the therefore thre is an increase in volumetric le 2 below, shows the volumetric efficiency Jor eastor and soya ol Aug. 24, 2006 ae ee ‘Pre quality of oer proceed oe [0071] Based on the kinetic mechanism developed from ‘he experimental dat obtained itis possible wo ealeutate the {quality of the products obtained from processing vegetable oils other than castor and soya oil. As ean be seen in Table 3 below, where the [QT/DCN values and density of the ‘oblained products i listed, There are imporant differences in oth the density and IQU/DCN value, indicating that the best oil to be processed depends not only on its availability and market value, but also on the refinery’s objectives in particular, i. if the speifiaton limitation isin the 1QT/ DEN or the density TABLE 3 we [0072] ‘The description in this report, as wells the accom panying Figures and Tables, prove the excellence of the Jvention, inthe sense that t presents a process where the addition ofa proportion of an olor a natural Lt, to an oi hydrocarbon load in a hydrotreatment process, produces a diesel oil wth various improved charactristies, as well as fn environmental interest when saya ol is used. Addition: ally, itis possible to adjust the vegetable oj] wed to the refinery’s objectives, im terms of the IQT and density of the product obtained 1. Process for the hydroconversion of vegetable vils, in the presence ofa hydrogen flow, hydroconversion catalysts ‘and hydroconversion conditions, to obtain dese ol the said process is characterized by the following: 8) Provide an oil or natural fats; ») Provide a hyetrearbon cil ©) Ina hydrocoaversion reactor and in the presence of 3 catalyst and hydrogen flow, pressure and temperature, effect the hydroconversion: 4) Recover a diesel ol low, in whieh: i) The IQT of the diese oil obtained is higher than for

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