Material Balance

CHAPTER 1INTRODUCTION 1 1. INTRODUCTION The constant demand for products such as liquid fuels is the main driving force behind the petroleum industry. Indeed, fuel products, for example, gasoline, kerosene, and diesel fuel, are the prime products of the current era. In addition, other products, such as lubricating oils, waxes, and asphalt, have also added to the popularity of petroleum as an important resource. Petroleum products are the basic materials used for the manufacture of synthetic fibers for clothing and in plastics, paints, fertilizers, insecticides, soaps, and synthetic rubber. In fact, the use of petroleum as a source of raw material in manufacturing is central to the functioning of modern industry Base oil is the base stock or blend of base stocks used in American Petroleum Institute (API)licensed oil and a base stock slate is a product line of base stocks that have different viscosities but are in the same base stock grouping and are from the same manufacturer. Base oil (the raw material for lubricants) is the name given to lubrication grade oils initially produced from refining crude oil (mineral base oil) or through chemical synthesis (synthetic base oil). Base oil is typically defined as oil with a boiling point range between 300°C (550°F) and 565°C (1050°F), consisting of hydrocarbons with 18 to 40 carbon atoms. This oil can be either paraffinic or naphthenic in nature depending on the chemical structure of the constituent molecules. Like many petroleum products, there are no longer many (if any) processes that are responsible for the direct manufacture of base oil. The base oil is typically a blend of products from several streams to which additives are added to adjust the properties to meet specifications and desired service life. 1.1 HISTORY Lubricating oil manufacture was well established by 1880, and the method depended on whether the crude petroleum was processed primarily for kerosene or for lubricating oils. Usually, the crude oil was processed for kerosene, and primary distillation separated the crude into three fractions, naphtha, kerosene, and residuum. To Manufacture of Lubricating Oil WE increase the production of kerosene, the cracking distillation technique was used, and this converted a large part of the gas oils and lubricating oils into kerosene. The cracking reactions also produced coke products and asphalt-like materials, which gave the residuum a black color and, hence, it was 2 often referred to as. The rapid evolution of lubricating oil manufacture and use occurred during the early decades of the twentieth century. Petroleum-based oils first became available and as the demand for automobiles grew, so did the demand for better lubricants. By 1923, the U.S. Society of Automotive Engineers (SAE) classified engine oils by viscosity as light, medium, and heavy lubricating oils. However, engine oil contained no additives and had to be replaced every 800 to 1000 miles. In the 1920s, more lubrication manufacturers started “processing” base oils to improve their performance. Three popular processing routes were: • clay treatment • acid treatment • sulfur dioxide treatment Clay treatment was used to soak up and remove some of the worst undesirable components in the petroleum base oil. These compounds were usually aromatic and highly polar compounds containing sulfur and nitrogen. Acid treatment with concentrated sulfuric acid was used to react with the worst components in the base oil and convert them into a sludge that could be removed. Although this process effectively cleaned up the oil, it was expensive and the technology is no longer used in many refineries due to environmental concerns about the acid and the acid sludge (a thick viscous material that separates when petroleum or petroleum products are treated with sulfuric acid) formed in the process. Continuous acid treatment involves the same steps as batch refining with the exception that • the acid and feedstock oil and neutralizing agent are mixed with pumps or static mixers • excess acid and sludge and excess neutralizing agent and soaps are removed using centrifuges or centrifugal extractors • Water washing is conducted using centrifugal extractors, and • Drying of the oil is conducted in continuous strippers. The advantages for the continuous process over the batch process are higher yields of oil, lower chemical consumption, and a reduction in air and water pollution. Sulfur dioxide treatment was a primitive extraction process to remove the worst components in the lubricating oil using a 3 recyclable solvent which, unfortunately, was highly toxic. Although it also has been virtually phased out, it was a useful stepping stone to conventional solvent extraction. Currently, catalytic de-waxing and solvent de-waxing are processes commonly in use, older technologies include cold settling, pressure filtration, and centrifuge de-waxing . 1.2 Used Lube Oil Re Refining Processes • Re-refining removes all the contaminants from used lube oil to recover base lube oil product. During the last years many factors have obliged rerefiners to look for alternative Rerefining process, such as: • Increased use of additive packages in the formulation of finished lube oil and by consequence higher level of contaminants in the used oil. • Increased amount of thermal degradation products due to longer mileage of the lubricants. • Pollution problems related to the disposal of acid sludges and spent clay from the traditional acid/clay re-refining. Among the available today processes, STP Re-refining offers a low energy high yield operation, high quality products and absence of noxious wastes or by products 1.3 STP Re-refining Process • High flexibility towards feedstock quality and composition • High process yield with recovery more than 72%. • High separation selectivity, removal of contaminants and production of high quality base oils. • Low energy and low utility consumption. • High on stream efficiency without corrosion, fouling, coking. • Environment safeguarding operation. • Management of all odorous compounds to eliminate malodorous and toxic emissions. 4 • Capital investment and operating cost highly competitive. Re-refining process removes all the contaminants from the used lube oil and recovers a distillate product as high quality base oil either API Group I by chemical finishing or API Group II by hydro finishing. It does not release harmful or pollutant wastes to be disposed and is therefore environment friend. Process water sent to treatment before disposal and process off gas sent to thermal oxidizer for combustion and destruction according to environmental law and regulations. 1.4 DEMAND AND SUPPLY DATA The generation of Waste Oils in some of the major regions/countries of the world is reported as under. (a) United States The demand for lubricants was forecast to expand 1.3 percent annually to 7.66 MMT in 2014. However, with the present sluggishness in market, this may not be realized. (b) European Union Waste oil generated in selected European countries (Collectable and collected portions of the lube oils in EU) has been reported by U. S. Department of Energy. According to EC resources about 5 MMT base oils are consumed in Europe annually, automotive and Industrial sectors accounting for 65% and 35% respectively. (c) Asia Asian region is the largest lube oil market with 30 % of the global demand; automotive grades have largest segment. The EPA reports that used motor oil alone accounts for 0.67 MMT of waste oil per year. Used motor oil can be recycled to create virgin lubricating oil at a much more efficient rate than production from crude oil, claims the EPA. The Lube oil growth potential 2005-10 for Asian countries was projected to be in the range of 0.5% to 4.8%, with Japan at the lowest level with 0.5% and China at 4.8% followed by India at 4.6%. Also, in Group II base oils, Asia is moving to Group II / II+. Asia’s strong lube oil demand growth is driven by China. Strong growth rates were reflected in projections for 2010, where lube demand in China were estimated to reach 5.5 MMT which was close to 40 % of the Asian lube market. 5 The regional sales of automotive lubes in the total base oils demand. 0. which are estimated to account for over 50% of base oils consumption. the amount of collected used oil in Mexico can be estimated to be 0.122 MMT of base oils in 2008. This makes India a big market for Group II/III oils. giving an estimate of approx. Assuming that only 50% of virgin lube oil is collectible as used oil out of which only around 70% is actually collected. 0. China remains the engine of growth in the Asian base oils market. the impressive industrial production recovery in China in 2009 has kept growth in industrial lubes strong. the amount of collected used oil can be estimated by the same process used for Mexico above.122MMT per annum each. Automotive and marine applications in India are lesser than in China. Many blenders in China used Group II / III base oils initially because of better regional availability. oil change centers. particularly of South Korean origin. India is also a large base oils market .Economic growth has led to grassroots refining investments in Asia. This means that there will be a big scope for Waste Oils recycling facilities in Asia. Venezuela also consumes about 0.605 MMT per annum. too. transformer oils and petroleum jelly. Using 15 collection centers located across Brazil and a fleet of more than 200 trucks. car repair shops and industries. 6 . however. Mexico produced about 0. Nearly a third of Indian base oils demand comes from specialty oils. Brazil's largest re-refiner of used lubricating oils collects more than 50% of the waste lubricants collected under current environmental standards in the country. (d) Latin America Brazil consumed more than 1. For these two countries.350 MMT / year of base oils.106 MMT/year of used lubricants from service stations.albeit with slightly different characteristics to the Chinese market. supplying about 40% of Mexican demand.210 MMT per annum. the collection touches 0.247 MMT of base oils in 2008. Additionally. are estimated to be 40%. such as white oil. Argentina's lube market is 0. Higher quality requirements for automotive lubricants in these markets are driven by original equipment manufacturers for Japanese/US and European automotive brands.350 MMT per year. The remainder was imported totaling to approx. The burgeoning Chinese car sales overtaking that of the US has boosted Chinese base oil demand for automotive lubricants. In 2008. most waste lubricating oils are recycled for use as heating fuels rather than being 7 . February 2009 (f) New Zealand : Used oil is the single largest non-watery liquid waste stream in New Zealand. The major oil companies operate nationwide collection networks and supply waste oil to Milburn. successful recovery of over 70% of waste oil was reported. Lubricants Marketing Research ( http://researchwikis.2011) # Freedonia Industry Study. An unknown but possibly small quantity of waste oil is land filled or dumped in the environment. Highest generators are trucks and buses due to their high share in transportation and high engine oil requirement.24 MMT of waste oil only was collected and recycled in.920 MT of lubricating oil are sold each year. such as two-stroke lawn mower engines burn oil completely. Even though this rate is high. where it is burned at high temperatures. burned or otherwise lost during use.194 MMT of their waste oil in 2004–05.06.27 MMT of waste oil was generated by industry and the community and was available for recycling but about 0. 21. (Approximately 52. Industry study with forecasts for 2012 to 2017. 0.09 MMT of waste oil remains unaccounted for. Currently. New Zealand's Westport cement kiln. #Researchwikies. Supported by the Australian Government's Product Stewardship for Oil Program. The burning of waste oil in high temperature kilns is good practice environmentally because it deals effectively with contaminants. While some engines. (g) South Africa: An estimated 0.460 MT are generated each year. An estimated 26. Study #2454.com/Lubricants_Marketing_Research.106 MT of waste oil is generated in South Africa in a year.05 to 0. burning in asphalt plants and road oiling.) Used oil recovery programmes have been in place for some years. World Lubricants. In some areas.(e) Australia: Around 0.32 MMT of Waste Oils per year. (h) Turkey Turkey generates around 0. During 2008-09 about 0.45 MMT of lubricating oil is sold in Australia each year. Australia recycled approximately 0.225 MMT of waste oil in Australia each year. others like motor vehicle engines and machinery produce large volumes of waste oil that can be reclaimed and reused. local operators collect oil for low temperature burners (which often do not require resource consents). About 50% is leaked. Industry and the community generate at least 0. Industry study with forecasts for 2012 to 2017. February 2009) 8 . concerns over depleting oil reserves. 21. However.078 MMT for re-processing or re-refining.converted back into base oil that can be sold back into the lubricants industry.com/Lubricants_Marketing_Research. Study #2454. Assuming that at least 80% of these base oils are blended into different grades of virgin oils. Recovery to base oil is energy intensive and so is not necessarily the best option. Assuming that used oil generation could be estimated at 50% of virgin oil while the collectible used oil could be as low as 30%. (Researchwikies. Thus. ever increasing carbon emissions and climate change.260 MMT per annum.332 MMT per annum of base oils (year 2004) into the country. the virgin oil market is estimated at about 0. are now driving re-assessment of best practice in waste oil industry.2011) # Freedonia Industry Study.06. Lubricants Marketing Research ( http://researchwikis.130 MMT. the volume of used oils in Nigeria is estimated at about 0. collected oil could be is as low as 0. (i) Nigeria25 Nigeria imported a total of 0. World Lubricants. CHAPTER 2 LITERATURE REVIEW 9 . small acid droplets as well as sulphonic acids and oxidized or sulphurized products resulting from acid action in suspension are coalesced and adsorbed. A part of the oil is injected at the top of the upper section where dehydration is achieved.1. and is even prohibited in industrialized countries. it remains the most globally applied. Heat is supplied by steam or heated fluid through a heat exchanger.1 Dehydration Dehydration is almost always the first step. Diesel and spindle oils are removed at the top and the oil at the bottom is cooled to a maximum of 120°C before filtration. According to this process. for example.1. The pressure in the vessel is 80 mmHg. dehydrate the oil in the upper section. the oil is processed as follows: 2. (high-speed flash boiler). finally. The dehydration column is in two sections: in the lower section. clay consumption is of the order of 3.5 wt% of the settled oil (fig. 2.1.1.2 Acid treatment and clay adsorption Dehydrated oil is cooled to about 30°C before reacting with sulphuric acid. >3 mm. This column helps to eliminate variable amounts of water in the lower section and. The lighter fractions removed at the top are used as fuels (fig. 2.1 MEINKEN PROCESS: A Standard Process Involving Sulphuric Acid and Clay Considered for a long time as the standard process. oil is pumped at a high flow rate to avoid formation of deposits and oil cracking by ensuring a good heat transfer.1Process description After a coarse filtration to eliminate particles. Decanted oil is mixed with clay before injection into the high temperature vessel. heated at 270°C by a heated fluid to avoid superheating of the oil. Settling time is of the order of 24 h. its application is on the decline. During clay treatment.1. for ecological reasons.CHAPTER 2 LITERATURE REVIEW 2. However. A). The temperature is of the order of 160-180°Cat atmospheric pressure. 10 . B). 1 11 . The acid withdrawal.Several solutions were proposed. because ofthe acid sludge production and the cost of used clay elimination. • Used clay (oil retention 100%): 31 kg/t. andpossibly of deasphalted vacuum residue in the most complete rerefining scheme[2]. has led to the installationof a vacuum tower upstream and the use of catalytic hydrogenation of distillates. which ensures the notabledestruction of phenols. In Sweden. Acid sludge and used clay are burned in a furnace equipped witha dust removal system and Hme washing. Finally. the Meinken process was and remains a widely used process.2. It is an optimizedversion of the standard acid and clay process. The sodium sulphate formed was transformedinto sodium sulphide used in the manufacture of cellulose in the firing reactor. Storage and elimination of calcium sulphite andsulphate resulting from the previous treatments must be properly done. and then channelled to a sulphate production plant where it was incineratedwith paper mill black liquor. application in the cement industry is often mentioned. acid sludge was neutralized with a 50% soda solution. Fig1.000°C.1. Anotherapplication consisted of introducing acid sludge into pyrite roasting furnace for theproduction of sulphuric acid.To conclude. • Acid sludge: about 170 kg/t. Waste water and gas are fed into a furnace heated to 1. • Gas production (gas recovered in vacuum circuits): about 40 Nm^/t.2 Waste production The nature and amount of waste produced by the Meinken process are as follows: • Process water rejected: about 130 kg/t of waste oil. However.2. and Scori (10 %). the essential characteristics of which are described in Section 4. Total (10 %). the Matthys-Garap collaborationworked on a process. Elf (10 %). with a correspondingly marked decline inthe selling price of rerefined base oils. At the same time. In the 1980sthe technical collaboration of CBL with Total and CEA aimed at developing UF (see the Regelub process . the 12 . owing to the declines in the price of crude petroleum and the dollar.2 ECOHUILE PROCESS The information reported here results from the different contacts established in the pastwith this company and also from the data supplied to Ecobilan for a study based on thelife cycle analysis carried out in 1997-1998 at the request of ADEME. This process couldnot be industrially applied and was practically abandoned in 1986.2 2.12) followed by catalytic hydrotreatment. currently operated by Ecohuile. this company has realized an important investmentin the vacuum distillation column and stopped clay treatment[2]. several companies havebeen active in the field of regeneration.1 History On Lillebonne's site (Rouen).Fig1. 2. In the 1960s.Condat (14 %).Section 4.The site was then operated by CBL: the principal shareholders were Burma (34 %).2. Motul (10 %). More recent informationis not available. In addition. • Development of instrumentation and automation of various equipments.Lillebonne's site was taken over by a holding company (Financiere 97). In 1992. this simultaneously increased the oilyield and made the treatment of the corresponding oil waste unnecessary 2. and vacuum residueas supplement) by combustion in a rotating furnace and effluent gas cleaning in electrofilters.2 Process flow sheet (updated in 2001) A simplified process diagram is shown in 4. after SOPALUNA. which eliminates the problem of combustionof sludge containing on average 14 wt% sulphur.this new company proceeded to update the vacuum column to improve the quality of distillates and reduce the column bottom residue from 40 to 15-20%. IMPERATOR. In 1994-1995. • Clay adsorption was banned on 1 January 2001. the following technical and environmental improvements were made: • Prohibition of the use of sulphuric acid.3 and includes the following sequences: • Waste oil settling and emulsion treatment.2. CBL went bankrupt as well [2]. Soon. • Vacuum distillation feed heated by the rotating furnace effluent coming from the combustion of wastes[2] 13 .parafiscal tax on new oil was implemented in order to finance the collection of waste oil. CBL was the only company still operating apartially obsolete rerefining plant. • Light hydrocarbon and water elimination (preflash column). • Mixing with an additive before treatment in the dehydration column (or preflash). waste water. with a vacuum distillation producing a bottom residue representing 40 % of the feed to the column. • Energy recovery from various effluents (used clay. Then. and UFP closed down. supplies technology and equipment for the rerefining of lubricating oils.3 Simplified production scheme of the Ecohuile plant.Fig 1. CEP licensed the Mohawk pretreatment step in 1989. CEP and Mohawk collaborated on processes to reduce catalyst poisons and addressed the problems of short hydrotreatment catalyst life.CEP abandoned the Mohawk pre-treatment process and adopted a simplified approach to address fouling and corrosion problems in rerefining. After the CEP-Mohawk collaboration ended in 1994-1995. Mohawk first developed a pre-treatment step. Later. Efforts were made by companies to improve regeneration processes. 2.MOHAWK PROCESS CEP. indeed. an affiliate of Evergreen Oil Inc.3 CHEMICAL ENGINEERING PARTNERS (CEP) .. the direct combustion route was no longer authorized in the State of California and the province of British Columbia in 14 . This situation explains why the Mohawk process was first operated in these two regions[2]. calledSB-86. and PCBs. metals. which have been in existence for a long period of time (old permits). for concentrations of halogens.Canada. It is true that a permit for even the controlled burning of used oil in California would be very difficult to obtain for a new operation. Direct combustion of used oil is still possible in the state of California but only in certain permitted heaters and furnaces. The oil that was burned met a certain standard. First version of the Mohawk process 15 . the Mohawk plant in Vancouver and the plants of Evergreen Oil in California and Safety Kleen in Chicago. In the oil rerefining.000 t/year) were planned in the USA (Evergreen considered building a plant in Southern California in the early 1990s.000. which requires suitable operating conditions in order to ensure quality for the different fractions at the final separation. has been involved inwaste oil collection and rerefining since 1978. CA. Canada. To get better product separation. and 50. In 1991. a TFE is coupled to the vacuum distillation unit. Notably. hydrotreatment is applied to the bulk oil. shows the steps involved in the process. Application of a chemical treatment to the oil. 16 . detrimental to reliable operation. the installation of intermediate storage between vacuum distillation and hydrotreatment. however. Another way to proceed is to first separate the oil fractions and to apply a hydrotreatment adjusting the conditions for each fraction. produced 18. Canada. Mohawk researchers had noticed that some organometallic additives were thermally unstable and formed polymers leading to frequent plugging and corrosion of equipment.but did not actually do so) and Breslube near Toronto.000-150. seemed tosolve such problems well. Two-large capacity plants (80. 30. USA. developed by MOC. of Vancouver. A second flash under vacuum eliminates diesel oil at the top of the column. An antideposit agent is added to the oil before preflash.Its position so reinforced. MOC licensed the Mohawk process to Evergreen Oil inNewark.000. and to Breslube (acquired by Safety Kleen in 1987) near Toronto.The Mohawk Oil Company (MOC) Ltd. This solution necessitates.000 t of baseoil. respectively. In the following section an improvement of the Mohawk process applied at Evergreen Oil and consisting of a simplification of the process is described[2]. 4 Mohawk process . spent clay is disposed to brick kilns .Fig1. large quantities of spent clay Residue from settling & course filtration of waste oil. Acid Sludge and spent clay Fuel products ( utilized in the plant itself as fuel) Acid activated clay treating process Residue from settling & course filtration of waste oil . . cement plants Vacuum distillation based Fuel products ( utilized in the plant itself as fuel) 17 Distillation residue may be disposed to cement plants or mixed with asphalt for road construction.first version (including an additional vessel for diesel oil separation2.4 COMPARISON OF VARIOUS RE-REFINING TECHNIQUES Process /Technology Waste produced By-products utilization Waste disposal Acid.Clay re-refining Residue from settling & course filtration of waste oil. Distillation Fuel products ( utilized in the plant itself as fuel) Major problem is of acid sludge which is to be neutralized with lime before disposal . cement plants Spent clay ( increased amount) is disposed to brick kilns. Due to loss of oil in sludge as well as clay since higher dosage of clay is required. Can be set-up for very small capacity. As most of the government has adopted stringent pollution control . This is a Proven technology worked for many years worldwide.residues Extraction Based Residue from settling & course filtration of waste oil. in some cases up 5% Features Acid-Clay Process for used oil recycling / reprocessing is Old and popular. Makes it most cost effective for small and tiny scale plants.Clay Process (Typical consumption: Bentonite 1 to 2%: However. concentrate from membranes Fuel products ( utilized in the plant itself as fuel) Spent clay – disposed to brick kilns Regeneration of clays is also an option and is started now Extraction residue to cement plants / mixed with asphalt for road construction. Drawbacks Causes Environmental pollution due to generation of acid sludge and acid gas emission. Disposal of acid sludge is a problem. No Causes corrosion of equipments reducing its life. No advanced instruments. Low Capital investment. Very simple process. 18 Gives Lower yield. Simple to operate. extraction residues Fuel products ( utilized in the plant itself as fuel) Membrane based Residue from centrifugation.disposed to brick kilns or regeneration[5] Concentrate from the process may be disposed to cement plants 2. Non sophisticated.5 A COMPARATIVE STATEMENT OF VARIOUS GENERIC TECHNOLOGIES FOR WASTE OIL RECYCLING 1. Technologies Acid . Spent clay . . Disposal of large quantity of spent clay is an environmental problem[5]. low yield. As it has very sophisticated equipments. No acid is required 2. Simple pipe furnace. Operating at high vacuum and normally used for high value and heat sensitive products. 19 Plant has to be of a higher capacity to make it economically viable. High cost of heating fluid and High operational costs. Vacuum Distillation (a)Thin/Wiped Film Evaporator Thin film evaporator is capable Requires high capital of investment. Very high clay consumption. this process is on its way out.skilled operators required. Higher Fuel Cost. inconsistent quality. convection heating at low heat flux by recirculating flue gases. Process is dependent on a particular type of clay which may not be available from all the sources[5]. Suitable only for very small capacity plants. Due to multiple stage of distillation involving heating & cooling. Suitable for high capacity plants. Require special/expensive thermic fluids & heating system. Does not cause pollution. Acid Activated Clay Process It is simple process Suitable for small capacity plant regulations. Operates at high temperature & very high Vacuum. Require highly skilled & Operational Maintenance Staff. Sophisticated Equipments & Process Produces good quality Base Oils 3. Solvent is recyclable. 4.No moving part on process side.(making system expensive and complicated) Involves operational solvent losses and highly skilled operating and maintenance personnel and system is required. In this process propane is used as solvent to remove bitumen. Simple instrumentation. metals and tar etc. Fire & explosion hazard is associated with this process [5]. . Economical only for high capacity plants. ) at ambient temperature (27°C ) require high pressure sealing systems. Solvent Extraction Process Does not cause pollution. additives. Propane being very hazardous. Produce Good quality Base Oils. 20 Has to operate at higher pressure ( 10 atm. Vacuum Distillation (b) Pipe Furnace Vaporizer No prior removal of gas oil is required. a gasoil of low grade is separated by fractionation from the lube oil. together with an amount of the bottoms from this pre-distillation column which is recycled. under reduced pressure. Part of the preheated bottoms stream is recycled through conduit and mixed with the dry spent lube oil in conduit as previously described. A 21 . The bottoms stream before arriving in the lm evaporator is mixed with part of the bottom product coming from the film evaporator which is cycled in conduit by means of pump.2. After that the stream is sent to the pre flash column here light hydrocarbons and water is removed. where this stream is preheated. Spent lube oil freed from sludge-forming impurities and from water and light components is fed to a pre-distillation column. and is pressed through a heat exchanger by means of a pump. The remainder of the bottom product from the film evaporator is discharged through conduit. The gasoil vapors escape through conduit are condensed in heat exchanger and are partly recycled as a reflux through conduit . the rest being discharged via line by means of pump and further used as described below. Spent lube oil freed from gasoil leaves column as a bottoms stream through conduit.6. In the pre-distillation column. The remainder of the pre-heated bottoms stream flows through conduit to a wiped film evaporator. 2.6 PROCESS DISCRIPTION: The KTI process (Kinetics Technology International). combines vacuum distillation and the hydrogenation treatment to eliminate most of the polluting substances in used oil. also known as KTI Relube Technology.1 BASIC STEPS OF THE PROCESS: Waste oil collected is first fed to the heater where its temperature is raised. The condensate is pumped by pump into a vessel.heavy fraction. in which this mixture of hydrocarbons is separated into a diesel oil fraction which leaves the column at the top. The condensate in vessel from which impurities have been separated as a heavy fraction. light lube oil components are evaporated. and. the temperature being maintained as high as possible. after having been mixed with hydrogen. is discharged after the hot-soak via conduit and pump. is mixed with the gasoil fraction which was formed in the pre distillation (column 2) and discharged by means of pump as described above. is mixed with the preheated bottoms stream in conduit. where this condensate under goes a hot-soak. this heavy fraction is recycled as a blow off (drain) stream via conduit and as previously described. In this hot-soak treatment impurities present in the condensate are separated as a heavy fraction. a light lubricating base oil fraction leaving the column as a middle fraction and a heavy lubricating base oil fraction. These vapors escape through conduit and are condensed in the heat exchanger. 22 . described below. The hydrogenated hydrocarbon mixture is discharged from the bottom of the separator and is passed via conduit to a fractionation column . which operates under vaccum. it is recycled via conduit and is mixed with the mixture of hydrocarbons fed through conduit. The product stream from the hydrogenation reactor is passed through conduit to a separator in which the residual hydrogen is separated and is discharged through conduit in order that after increasing the pressure in compressor and mixing with replenishing (make up) hydrogen which is fed through conduit. is mixed with the bottoms stream in conduit which is fed as a blow-off (drain) stream from a hot-soak via conduit. In the film evaporator. where the mixture is hydrogenated. is passed via conduit and heat exchanger to a reactor filled with hydro generation catalyst. Fee d Vacuum distillation Prefash Condensor Pum p mixer Heat Exchanger Hot soak vess el TF E Reboile r Fuel Gas H2 Makeup Diesel oil Compres sor High Pressur e Vessel Light Oil Heavy Oil Fig1.5 Process flowsheet of KTI Process 23 Fixed Bed Reactor . CHAPTER 3 MATERIAL BALANCE 24 . 018867925 .000 TPA • Number Of Days For Which The Plants Operates = 330 Days • Total Waste Lube Oil Refined = 4580 Kg/hr 1. PREFLASH: Waste Lube Oil Preflash Column Input Water Output 200 Light Hcs Output 100 Lube Oil Output 5000 Components ṁ (Kg/hr) %Water Water+ Light HCs 5300 25 0.3. MATERIAL BALANCE • Capacity Of Plant = 36.037735849 %Light HCs 0. 2.8 OC PREFLASH (I) ṁ=5300 kg/ hr Fig.Waste Lube Oil ṁ=5300 kg/ hr 148.1 : Prefash ṁ=5000 Kg/hr Material balance of Preflash 26 Table 1 : . 2. VACUUM DISTILLATION: VACUUM DISTILLATION ṁ= 410 Kg/hr 27 . Lube Oil Diesel oil (8.2%) (From Condenser) ṁ= 5046 Kg/hr Fig 2. 3 : Vacuum Distillation Lube Oil (From Reboiler) 28 . Lube Oil (From VDU) Table 2 : Material Balance of Vacuum Distillation Vacuum Distillation Unit ṁ (Kg/hr) Lube Oil Lube Oil (To SettlingVessel) Residues(6. THIN FILM EVAPORATOR: ṁ= 4590 Kg/hr Lube Oil (From SettlingVessel) ṁ= 5289 Kg/hr Thin Film Evaporator ṁ (Kg/hr) Input 209 Lube Oil Input 4590 Bottom Stream (TFE) Input 800 Asphaltenes (Residues) Output 310 Lube Oil(From TFE) Output (Recycled N FILM EVAPORATOR Bottom Stream (Impurities) 5289 29 Table 3Stream) : Material Balance of Thin Film Fig 2.36 %Diesel=0.36 Components Reflux Ratio=5:1 3.2%) InputAsphaltenes5046.36 Recycled Stream (Reboiler) Input 46. 4: Thin Film ṁ= 310 Kg/hr Evaporator .082 Overhead (Lube Oil+ Gas Oil) Output 2460 Gas Oil Output 410 Reflux Stream (Condenser) Input 2050 Lube Oil Output 4636. SETTLING VESSEL: Lube Oil ṁ= 4389 Kg/hr ṁ= 4180 Kg/hr 5-30% of Overhead Product Settling Vessel Components Lube Oil 180 oC TFE Input (lll) ṁ (Kg/hr) 4389 Fig 2.4.5 : Settling Bottom stream (Impurities) Output Vessel 209 Lube Oil Output 4180 Bottom stream (Impurities) ṁ= 4180 kg/hr SETTLING VESSEL (lV) Table 4: Material Balance of Settling Vessel Lu 30 . 6 : Hydrofinishing Reactor ṁ=4930 Kg/hr Table 5: Material Balance of Hydrofinishing Reactor 31 . HYDROFINISHING REACTOR: Assumptions1) Fixed bed reactor 2) Co/Mo or Co/Al Catalyst Diesel Oil (From Settling Vessel) Lube Oil Hydrofinishing Reactor Make Up Up H2 H2 + Diesel Oil Lube Oi l+ Make HYDRO FINISHING REACTOR Lube Oil Lube Oil ṁ (Kg/hr) Input 4930 Output 4930 ṁ= 4930 kg/hr Fig 2.5. HIGH PRESSURE SEPARATOR: ṁ= 4880 Kg/hr HIGH PRESSURE SEPARATOR ṁ= 300Kg/hr Fig 2.7 : High Pressure Separator Separator ṁ (Kg/hr) Naphtha Input 4880 Make Up H2 Output Naphtha Output Components Table 6 : Material Balance of High Pressure Separator 32 Naphtha (From Hydro finishing) Naphtha 300 ṁ= 4580 Kg/hr (To Fractionation Coloum) 4580 .6. FRACTIONATION COLUMN: Fuel Gas Heavy Oil ṁ= 4580 Kg/hr Components Naphtha Fraction Heavy Oil + Light Oil FRACTIONATION COLUMN ṁ= 40 Kg/hr Fractionation Column Input ṁ= 520 ṁ= 4020 Kg/hr ṁ (Kg/hr) 4580 Fig 2. 8: Output 4020 Fractionation Column Table 7: Material Balance of Fractionation Column Diesel Oil Output 520 Output 40 Fuel Gas 33 .Diesel Oil 7. CHAPTER 4 ENERGY BALANCE 34 . ENERGY BALANCE 1.°C-1) 3.4.Kg-1.8 OC PREFLASH (I) 2.096 T (oC) 148.096 Tr 148.8 ΔT 25 Q=ṁCpΔT(Kwatt) 123. HEATER: Water+ Light HCs Lube Oil ṁ= (200+100) Kg/hr Table 8: Energy balance of Heat duty across Heater ṁ Cp 5300 T 3.°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) Output StreamWater ṁ(Kg/hr) 35 .8 Tr (oC) 25 ΔT (oC) 123. PREFLASH: ṁ=5000 Kg/hr Table 9 : Energy Preflash balance of Energy Balance across Preflash Input StreamWasteLube Oil ṁ(Kg/hr) 5300 Cp(KJ.Kg-1.8 Q=ṁCpΔT(Kwatt) 564.2804 Waste Lube Oil ṁ=5300 kg/ hr 148.8 564.2804 Cp(KJ. 8 555.8 25 123.23 148.°C-1) ṁ(Kg/hr) 5000 3.253333 Cp(KJ.200 Output StreamLHCs ṁ(Kg/hr) 100 4.931 Cp(KJ.844582 Q=ṁCpΔT(Kwatt) 123.°C-1) T (oC) Tr (oC) ΔT (oC) Q=ṁCpΔT(Kwatt) 1.32 148.3806 .Kg-1.8 36 25 Tr(oC) 25 123.Kg-1.8 8.8 ΔT 1.8 T(oC) 148. 37 . 38 . 39 . 40 . 41 . 42 . HEATER: 43 .3. 44 . Table 10 : Energy Balance of Heater 2 45 . °C-1) 3.7917 .Kg-1.Heat Duty Of Heater 2 ṁ(Kg/hr) 5000 Cp(KJ.23 T (oC) 220 46 Tr (oC) 25 ΔT (oC) 195 Q=ṁCpΔT(Kwatt) 874. 47 . 48 . °C-1) T (oC) Tr(oC) ΔT(oC) 2460 3.27 180 25 155 ṁ Cp(KJ.497216 220 195 ṁ(Kg/hr) Cp(KJ.754 Qd Q=ṁCpΔT(K watt) 308.Kg-1.°C-1) T (oC) Tr(oC) ΔT(oC) 2460 2.217 320 25 ΔT(o Q=ṁCpΔT(Kwatt) C) Qf-Qd-Qw-Qc -1507.7917 Qv 25 Q=ṁCpΔT(K watt) 332.Kg-1.2%) (From Condenser) -1 ° -1 o Cp(KJ.Kg .Kg-1.6229 Qv-Qd-Ql -263.°C-1) T(oC) Tr(oC) ΔT(oC) 2050 3. VACUUM DISTILLATION: Table 11 : Energy Balance of Vacuum Distillation Energy Balance across Vacuum Distillation Unit: Input Stream-Waste Lube Oil ṁ(Kg/hr) Diesel oil (8.27 Q=ṁCpΔT(K watt) 874.9039 Qw ṁ= 5046 ṁKg/hr (Kg/hr) 4590 Qb Cp(KJ.°C-1) T(oC) Tr(oC) 6.Lube Oil 4.71 49 295 2338.23 220 25 195 ṁ(Kg/hr) Cp(KJ. C ) T( C) Tr (oC) ΔT(oC) 5000 3.035 Ql VACUUM DISTILLATION Qc 180 41025Kg/hr155 ṁ= Q=ṁCpΔT(K watt) 288.3691 Lube Oil (From Reboiler) .Kg-1. 2845 180 25 155 223.Kg-1.°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 5599 4.0567 ṁ(Kg/hr) Cp(KJ.Lube Oil (From VDU) ṁ= 5599Kg/hr Table 12 : Energy Balance of Thin Film Evaporator Energy Balance TFE Lube Oil (To SettlingVessel) Asphaltenes Residue (6.THIN FILM EVAPORATOR: ṁ= 4590 Kg/hr ṁ= 5289 Kg/hr (Recycled Stream) 148.2%) Input ṁ(Kg/hr) Cp(KJ.°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 1210 4.4057 Output ṁ(Kg/hr) Cp(KJ.7385 320 25 295 2174.21055 Output 5.Kg-1.Kg-1.7835 320 25 295 1720.8 OC PREFLASH (I) Lube Oil (From SettlingVessel) 50 ṁ= 310 Kg/hr .°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 4389 4. 6. MIXER: Table 13: Energy balance of Mixer Heat Duty of Mixer ṁ(Kg/hr ) 5599 Cp(KJ.7 2134.7385 314.Kg-1.°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 4.9974 7.7 25 289. SETTLING VESSEL: Lube Oil ṁ= 4389 Kg/hr TFE (lll) ṁ= 4180 SETTLING VESSEL (l Kg/hr 5-30% of Overhead Product 180 oC Bottom stream (Impurities) ṁ= 4180 kg/hr 51 . 165 180 25 Vessel 8.94198 4.°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 155 37.89713 CP(KJ.7835 180 25 155 860.479215 Output stream Output stream ṁ(Kg/hr) Table 14: Energy Balance of Settling 209 4.°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 4389 4.94198 ṁ(Kg/hr) Cp(KJ.Energy Balance Across Hot Soak Vessel Input stream ṁ(Kg/hr) Cp(KJ.Kg-1.°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 4389 180 25 155 903.7835 180 25 155 903. HEATER Table 15: Energy balance of Heater 3 Heat Duty Of Heater 3 ṁ(Kg/hr) CP(KJ.Kg-1.Kg-1.7835 52 .°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 4180 4.Kg-1. 735 320 25 295 1912.10799 53 . HYDROFINISHING REACTOR: Diesel Oil (From Settling Vessel) Lube Oil Make Up H2 HYDRO FINISHING REACTOR Lube Oil ṁ= 4930 kg/hr ṁ=4880 Kg/hr Table 16: Energy Balance of Hydrofinishing Reactor Energy Balance Across Reactor ṁ(Kg/hr) CP(KJ.°C-1) 4930 4.Kg-1.Kg-1. HEATER Table 17 : Energy Balance of Heater 4 Heat Duty of Heater 4 ṁ(Kg/hr) Cp CP(KJ.°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 4930 4.735 T(oC ) 320 Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 25 295 162.8742 10.9. HIGH PRESSURE SEPARATOR: ṁ= Energy Balance Across Separator 300Kg/hr Input stream ṁ(Kg/hr) CP(KJ.Kg-1.°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 4930 4.735 320 25 295 162.Kg-1.°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 4590 4.735 320 25 295 1780.952 ṁ= 4880 Kg/hr HIGH PRESSURE SEPARATOR ṁ(Kg/hr) Naphtha (From Hydro finishing) Naphtha ṁ= 4580 Kg/hr (To Fractionation Table 18 : Energy Balance of High PressureColoum) Separator 54 .°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 340 14.Make Up H2Make Make Up H2 11.Kg-1.8069 Output stream Lube Oil CP(KJ.35 320 25 295 399.108 Output stream Gas ṁ(Kg/hr) CP(KJ. Kg-1.735 T(oC) o Tr(Fuel C) Gas ΔT(oC) Q=ṁCpΔT(Kwatt) 320 25 1780.444444 175 ṁ= 4020 Kg/hr Tr( C) ΔT(oC) Q=ṁCpΔT(Kwatt) 25 175 61.°C-1) T(oC) 40 200 2.1 200 25 175 410.17222 o ṁ(Kg/hr) CP(KJ.°C-1) T(oC) Tr(oC) ΔT(oC) Q=ṁCpΔT(Kwatt) 4020 2.952 Heavy Oil Output Stream Fuel Gas ṁ(Kg/hr) CP(KJ.375 Table 19: Energy Balance of Fractionation Column 55 .Naphtha Fraction (From HP Separator) Diesel OilLube Oil 12.Kg-1.Kg-1.8 Output Stream Diesel ṁ(Kg/hr) CP(KJ.Kg-1.42 o Output Stream Heavy Oil FRACTIONATION COLUMN ṁ= 4580 C (KJ.°C-1) P Kg/hr ṁ(Kg/hr) 295 ṁ=ΔT 520 Tr(oC) (oC) Q=ṁCpΔT(Kwatt) 25 5. FRACTIONATION COLUMN: Energy Balance Across Fractionating Column Light OilLight Light ṁ= Oil 40 Kg/hr Input Stream 4590 4.°C-1) T( C) 520 200 2. Pergamon Limited. Alladdin H. Journals of Materials Processing Technology. ISBN-13: 978-14665-5150-3 2. Canizares. J. R. Academy Press. Octobre 2001. 2013. Taha and Gordon McKay. 2059-2065 5. 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