Material Balance

CHAPTER 1 INTRODUCTION

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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

Economic growth has led to grassroots refining investments in Asia. Many blenders in China used Group II / III base oils initially because of better regional availability. Higher quality requirements for automotive lubricants in these markets are driven by original equipment manufacturers for Japanese/US and European automotive brands. India is also a large base oils market - albeit with slightly different characteristics to the Chinese market. Nearly a third of Indian base oils demand comes from specialty oils, such as white oil, transformer oils and petroleum jelly. This makes India a big market for Group II/III oils, particularly of South Korean origin. China remains the engine of growth in the Asian base oils market. The burgeoning Chinese car sales overtaking that of the US has boosted Chinese base oil demand for automotive lubricants, which are estimated to account for over 50% of base oils consumption. Additionally, the impressive industrial production recovery in China in 2009 has kept growth in industrial lubes strong. Automotive and marine applications in India are lesser than in China. The regional sales of automotive lubes in the total base oils demand, however, are estimated to be 40%. This means that there will be a big scope for Waste Oils recycling facilities in Asia, too. (d) Latin America Brazil consumed more than 1.122 MMT of base oils in 2008. 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. Using 15 collection centers located across Brazil and a fleet of more than 200 trucks, the collection touches 0.106 MMT/year of used lubricants from service stations, oil change centers, car repair shops and industries. Mexico produced about 0.247 MMT of base oils in 2008, supplying about 40% of Mexican demand. The remainder was imported totaling to approx. 0.605 MMT per annum. Assuming that only 50% of virgin lube oil is collectible as used oil out of which only around 70% is actually collected, the amount of collected used oil in Mexico can be estimated to be 0.210 MMT per annum. Argentina's lube market is 0.350 MMT per year. Venezuela also consumes about 0.350 MMT / year of base oils. For these two countries, the amount of collected used oil can be estimated by the same process used for Mexico above, giving an estimate of approx. 0.122MMT per annum each. 6

(e) Australia: Around 0.45 MMT of lubricating oil is sold in Australia each year. While some engines, such as two-stroke lawn mower engines burn oil completely, others like motor vehicle engines and machinery produce large volumes of waste oil that can be reclaimed and reused. Industry and the community generate at least 0.225 MMT of waste oil in Australia each year. Supported by the Australian Government's Product Stewardship for Oil Program, Australia recycled approximately 0.194 MMT of their waste oil in 2004–05. Even though this rate is high, 0.05 to 0.09 MMT of waste oil remains unaccounted for. During 2008-09 about 0.27 MMT of waste oil was generated by industry and the community and was available for recycling but about 0.24 MMT of waste oil only was collected and recycled in. #Researchwikies, Lubricants Marketing Research ( http://researchwikis.com/Lubricants_Marketing_Research, 21.06.2011) # Freedonia Industry Study. World Lubricants, Industry study with forecasts for 2012 to 2017, Study #2454, February 2009

(f) New Zealand : Used oil is the single largest non-watery liquid waste stream in New Zealand. An estimated 26,460 MT are generated each year. (Approximately 52,920 MT of lubricating oil are sold each year. About 50% is leaked, burned or otherwise lost during use.) Used oil recovery programmes have been in place for some years. The major oil companies operate nationwide collection networks and supply waste oil to Milburn, New Zealand's Westport cement kiln, where it is burned at high temperatures. The burning of waste oil in high temperature kilns is good practice environmentally because it deals effectively with contaminants. In some areas, local operators collect oil for low temperature burners (which often do not require resource consents), burning in asphalt plants and road oiling. An unknown but possibly small quantity of waste oil is land filled or dumped in the environment. (g) South Africa: An estimated 0,106 MT of waste oil is generated in South Africa in a year. In 2008, successful recovery of over 70% of waste oil was reported. (h) Turkey Turkey generates around 0.32 MMT of Waste Oils per year. Highest generators are trucks and buses due to their high share in transportation and high engine oil requirement. Currently, most waste lubricating oils are recycled for use as heating fuels rather than being 7

converted back into base oil that can be sold back into the lubricants industry. Recovery to base oil is energy intensive and so is not necessarily the best option. However, concerns over depleting oil reserves, ever increasing carbon emissions and climate change, are now driving re-assessment of best practice in waste oil industry. (i) Nigeria25 Nigeria imported a total of 0.332 MMT per annum of base oils (year 2004) into the country. Assuming that at least 80% of these base oils are blended into different grades of virgin oils, the virgin oil market is estimated at about 0.260 MMT per annum. Assuming that used oil generation could be estimated at 50% of virgin oil while the collectible used oil could be as low as 30%, the volume of used oils in Nigeria is estimated at about 0.130 MMT. Thus, collected oil could be is as low as 0.078 MMT for re-processing or re-refining. (Researchwikies, Lubricants Marketing Research ( http://researchwikis.com/Lubricants_Marketing_Research, 21.06.2011) # Freedonia Industry Study. World Lubricants, Industry study with forecasts for 2012 to 2017, Study #2454, February 2009)

8

CHAPTER 2 LITERATURE REVIEW

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CHAPTER 2 LITERATURE REVIEW 2.1 MEINKEN PROCESS: A Standard Process Involving Sulphuric Acid and Clay Considered for a long time as the standard process, it remains the most globally applied. However, its application is on the decline, and is even prohibited in industrialized countries, for ecological reasons. 2.1.1Process description After a coarse filtration to eliminate particles, for example, >3 mm, the oil is processed as follows: 2.1.1.1 Dehydration Dehydration is almost always the first step. The temperature is of the order of 160-180°Cat atmospheric pressure. Heat is supplied by steam or heated fluid through a heat exchanger. The dehydration column is in two sections: in the lower section, oil is pumped at a high flow rate to avoid formation of deposits and oil cracking by ensuring a good heat transfer. A part of the oil is injected at the top of the upper section where dehydration is achieved. This column helps to eliminate variable amounts of water in the lower section and, finally, dehydrate the oil in the upper section. The lighter fractions removed at the top are used as fuels (fig. A). 2.1.1.2 Acid treatment and clay adsorption Dehydrated oil is cooled to about 30°C before reacting with sulphuric acid. Settling time is of the order of 24 h. Decanted oil is mixed with clay before injection into the high temperature vessel, (high-speed flash boiler), heated at 270°C by a heated fluid to avoid superheating of the oil. During clay treatment, small acid droplets as well as sulphonic acids and oxidized or sulphurized products resulting from acid action in suspension are coalesced and adsorbed. 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. The pressure in the vessel is 80 mmHg. According to this process, clay consumption is of the order of 3.5 wt% of the settled oil (fig. B).

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2.1.2 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. • Gas production (gas recovered in vacuum circuits): about 40 Nm^/t. • Acid sludge: about 170 kg/t. • Used clay (oil retention 100%): 31 kg/t. Waste water and gas are fed into a furnace heated to 1,000°C, which ensures the notabledestruction of phenols. Acid sludge and used clay are burned in a furnace equipped witha dust removal system and Hme washing. Storage and elimination of calcium sulphite andsulphate resulting from the previous treatments must be properly done.Several solutions were proposed. In Sweden, acid sludge was neutralized with a 50% soda solution, and then channelled to a sulphate production plant where it was incineratedwith paper mill black liquor. The sodium sulphate formed was transformedinto sodium sulphide used in the manufacture of cellulose in the firing reactor. Anotherapplication consisted of introducing acid sludge into pyrite roasting furnace for theproduction of sulphuric acid. Finally, application in the cement industry is often mentioned.To conclude, the Meinken process was and remains a widely used process. It is an optimizedversion of the standard acid and clay process. The acid withdrawal, because ofthe acid sludge production and the cost of used clay elimination, has led to the installationof a vacuum tower upstream and the use of catalytic hydrogenation of distillates, andpossibly of deasphalted vacuum residue in the most complete rerefining scheme[2].

Fig1.1

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Fig1.2 2.2 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. More recent informationis not available. However, this company has realized an important investmentin the vacuum distillation column and stopped clay treatment[2]. 2.2.1 History On Lillebonne's site (Rouen), currently operated by Ecohuile, several companies havebeen active in the field of regeneration. In the 1960s, the Matthys-Garap collaborationworked on a process, the essential characteristics of which are described in Section 4.2.The site was then operated by CBL: the principal shareholders were Burma (34 %),Condat (14 %), Elf (10 %), Total (10 %), Motul (10 %), and Scori (10 %). In the 1980sthe technical collaboration of CBL with Total and CEA aimed at developing UF (see the Regelub process - Section 4.12) followed by catalytic hydrotreatment. This process couldnot be industrially applied and was practically abandoned in 1986, owing to the declines in the price of crude petroleum and the dollar, with a correspondingly marked decline inthe selling price of rerefined base oils. At the same time, the

12

parafiscal tax on new oil was implemented in order to finance the collection of waste oil. In 1992, after SOPALUNA, IMPERATOR, and UFP closed down, CBL was the only company still operating apartially obsolete rerefining plant, with a vacuum distillation producing a bottom residue representing 40 % of the feed to the column. Soon, CBL went bankrupt as well [2]. Then,Lillebonne's site was taken over by a holding company (Financiere 97). In 1994-1995,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%. In addition, the following technical and environmental improvements were made: • Prohibition of the use of sulphuric acid, which eliminates the problem of combustionof sludge containing on average 14 wt% sulphur. • Energy recovery from various effluents (used clay, waste water, and vacuum residueas supplement) by combustion in a rotating furnace and effluent gas cleaning in electrofilters. • Development of instrumentation and automation of various equipments. • Clay adsorption was banned on 1 January 2001; this simultaneously increased the oilyield and made the treatment of the corresponding oil waste unnecessary 2.2.2 Process flow sheet (updated in 2001) A simplified process diagram is shown in 4.3 and includes the following sequences: • Waste oil settling and emulsion treatment. • Mixing with an additive before treatment in the dehydration column (or preflash). • Light hydrocarbon and water elimination (preflash column). • Vacuum distillation feed heated by the rotating furnace effluent coming from the combustion of wastes[2]

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Fig 1.3 Simplified production scheme of the Ecohuile plant. 2.3 CHEMICAL ENGINEERING PARTNERS (CEP) - MOHAWK PROCESS CEP, an affiliate of Evergreen Oil Inc., supplies technology and equipment for the rerefining of lubricating oils. Mohawk first developed a pre-treatment step. CEP licensed the Mohawk pretreatment step in 1989. Later, CEP and Mohawk collaborated on processes to reduce catalyst poisons and addressed the problems of short hydrotreatment catalyst life. After the CEP-Mohawk collaboration ended in 1994-1995,CEP abandoned the Mohawk pre-treatment process and adopted a simplified approach to address fouling and corrosion problems in rerefining. Efforts were made by companies to improve regeneration processes; indeed, the direct combustion route was no longer authorized in the State of California and the province of British Columbia in 14

Canada. Direct combustion of used oil is still possible in the state of California but only in certain permitted heaters and furnaces, which have been in existence for a long period of time (old permits). The oil that was burned met a certain standard, calledSB-86, for concentrations of halogens, metals, and PCBs. 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. This situation explains why the Mohawk process was first operated in these two regions[2]. First version of the Mohawk process

15

The Mohawk Oil Company (MOC) Ltd. of Vancouver, Canada, has been involved inwaste oil collection and rerefining since 1978. In the oil rerefining, Mohawk researchers had noticed that some organometallic additives were thermally unstable and formed polymers leading to frequent plugging and corrosion of equipment, detrimental to reliable operation. Application of a chemical treatment to the oil, developed by MOC, seemed tosolve such problems well.Its position so reinforced, MOC licensed the Mohawk process to Evergreen Oil inNewark, CA, USA, and to Breslube (acquired by Safety Kleen in 1987) near Toronto, Canada. In 1991, the Mohawk plant in Vancouver and the plants of Evergreen Oil in California and Safety Kleen in Chicago, produced 18,000, 30,000, and 50,000 t of baseoil, respectively. Two-large capacity plants (80,000-150,000 t/year) were planned in the USA (Evergreen considered building a plant in Southern California in the early 1990s,but did not actually do so) and Breslube near Toronto. shows the steps involved in the process. An antideposit agent is added to the oil before preflash. A second flash under vacuum eliminates diesel oil at the top of the column. To get better product separation, a TFE is coupled to the vacuum distillation unit. Notably, hydrotreatment is applied to the bulk oil, which requires suitable operating conditions in order to ensure quality for the different fractions at the final separation. Another way to proceed is to first separate the oil fractions and to apply a hydrotreatment adjusting the conditions for each fraction. This solution necessitates, however, the installation of intermediate storage between vacuum distillation and hydrotreatment. 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].

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Fig1.4 Mohawk process - 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, 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 , large quantities of spent clay 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 , spent clay is disposed to brick kilns , cement plants Spent clay ( increased amount) is disposed to brick kilns, 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,

residues

Extraction Based

Residue from settling & course filtration of waste oil, extraction residues

Fuel products ( utilized in the plant itself as fuel)

Membrane based

Residue from centrifugation, 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, Spent clay - disposed to brick kilns or regeneration[5] Concentrate from the process may be disposed to cement plants

2.5 A COMPARATIVE STATEMENT OF VARIOUS GENERIC TECHNOLOGIES FOR WASTE OIL RECYCLING 1.

Technologies Acid - Clay Process (Typical consumption: Bentonite 1 to 2%: However, in some cases up 5%

Features Acid-Clay Process for used oil recycling / reprocessing is Old and popular.

Drawbacks Causes Environmental pollution due to generation of acid sludge and acid gas emission. Disposal of acid sludge is a problem.

This is a Proven technology worked for many years worldwide. Can be set-up for very small capacity. Low Capital investment. Makes it most cost effective for small and tiny scale plants. Non sophisticated, Very simple process. Simple to operate, No advanced instruments, No

Causes corrosion of equipments reducing its life.

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Gives Lower yield. Due to loss of oil in sludge as well as clay since higher dosage of clay is required. As most of the government has adopted stringent pollution control

skilled operators required. No acid is required

2.

Acid Activated Clay Process It is simple process Suitable for small capacity plant

regulations, this process is on its way out. Very high clay consumption, low yield, inconsistent quality. Disposal of large quantity of spent clay is an environmental problem[5]. Suitable only for very small capacity plants. Process is dependent on a particular type of clay which may not be available from all the sources[5].

Suitable for high capacity plants. Operates at high temperature & very high Vacuum. Require special/expensive thermic fluids & heating system. 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. Operating at high vacuum and normally used for high value and heat sensitive products. Does not cause pollution. Sophisticated Equipments & Process

Produces good quality Base Oils 3. Simple pipe furnace, convection heating at low heat flux by recirculating flue gases. 19

Plant has to be of a higher capacity to make it economically viable. Require highly skilled & Operational Maintenance Staff. As it has very sophisticated equipments. Higher Fuel Cost. Due to multiple stage of distillation involving heating & cooling.

No moving part on process side. Vacuum Distillation (b) Pipe Furnace Vaporizer

No prior removal of gas oil is required. Simple instrumentation.

In this process propane is used as solvent to remove bitumen, additives, metals and tar etc. Solvent is recyclable.

4.

Solvent Extraction Process

Does not cause pollution.

Produce Good quality Base Oils.

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Has to operate at higher pressure ( 10 atm. ) at ambient temperature (27°C ) require high pressure sealing systems.(making system expensive and complicated) Involves operational solvent losses and highly skilled operating and maintenance personnel and system is required. Economical only for high capacity plants. Propane being very hazardous, Fire & explosion hazard is associated with this process [5].

2.6 PROCESS DISCRIPTION: The KTI process (Kinetics Technology International), also known as KTI Relube Technology, combines vacuum distillation and the hydrogenation treatment to eliminate most of the polluting substances in used oil.

2.6.1 BASIC STEPS OF THE PROCESS: Waste oil collected is first fed to the heater where its temperature is raised. After that the stream is sent to the pre flash column here light hydrocarbons and water is removed. Spent lube oil freed from sludge-forming impurities and from water and light components is fed to a pre-distillation column, together with an amount of the bottoms from this pre-distillation column which is recycled. In the pre-distillation column, under reduced pressure, a gasoil of low grade is separated by fractionation from the lube oil. 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, and is pressed through a heat exchanger by means of a pump, where this stream is preheated. Part of the preheated bottoms stream is recycled through conduit and mixed with the dry spent lube oil in conduit as previously described. The remainder of the pre-heated bottoms stream flows through conduit to a wiped film evaporator. 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. The remainder of the bottom product from the film evaporator is discharged through conduit. A 21

heavy fraction, described below, 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, which operates under vaccum, light lube oil components are evaporated. These vapors escape through conduit and are condensed in the heat exchanger, the temperature being maintained as high as possible. The condensate is pumped by pump into a vessel, where this condensate under goes a hot-soak. In this hot-soak treatment impurities present in the condensate are separated as a heavy fraction; this heavy fraction is recycled as a blow off (drain) stream via conduit and as previously described, is mixed with the preheated bottoms stream in conduit. The condensate in vessel from which impurities have been separated as a heavy fraction, 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, and, after having been mixed with hydrogen, is passed via conduit and heat exchanger to a reactor filled with hydro generation catalyst, where the mixture is hydrogenated. 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, it is recycled via conduit and is mixed with the mixture of hydrocarbons fed through conduit. The hydrogenated hydrocarbon mixture is discharged from the bottom of the separator and is passed via conduit to a fractionation column , in which this mixture of hydrocarbons is separated into a diesel oil fraction which leaves the column at the top, a light lubricating base oil fraction leaving the column as a middle fraction and a heavy lubricating base oil fraction.

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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

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Fixed Bed Reactor

CHAPTER 3 MATERIAL BALANCE

24

3. MATERIAL BALANCE •

Capacity Of Plant = 36,000 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

0.037735849

%Light HCs 0.018867925

Waste Lube Oil ṁ=5300 kg/ hr

148.8 OC PREFLASH (I)

ṁ=5300 kg/ hr

Fig. 2.1 : 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(6.2%) InputAsphaltenes5046.36 %Diesel=0.082

Overhead (Lube Oil+ Gas Oil)

Output

2460

Gas Oil

Output

410

Reflux Stream (Condenser)

Input

2050

Lube Oil

Output

4636.36

Recycled Stream (Reboiler)

Input

46.36

Components

Reflux Ratio=5:1

3. 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

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Table 3Stream) : Material Balance of Thin Film

Fig 2. 4: Thin Film ṁ= 310 Kg/hr Evaporator

4. 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 2.5 : 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

5. 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 2.6 : Hydrofinishing Reactor

ṁ=4930 Kg/hr Table 5: Material Balance of Hydrofinishing Reactor

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6. 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

Diesel Oil 7. 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

CHAPTER 4 ENERGY BALANCE

34

4. ENERGY BALANCE 1. HEATER:

Water+ Light HCs Lube Oil ṁ= (200+100) Kg/hr

Table 8: Energy balance of Heat duty across Heater ṁ

Cp

5300

T 3.096

Tr 148.8

ΔT 25

Q=ṁCpΔT(Kwatt)

123.8

564.2804

Waste Lube Oil ṁ=5300 kg/ hr

148.8 OC PREFLASH (I)

2. 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.°C-1) 3.096

T (oC) 148.8

Tr (oC) 25

ΔT (oC) 123.8

Q=ṁCpΔT(Kwatt) 564.2804

Cp(KJ.Kg-1.°C-1)

T(oC)

Tr(oC)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

Output StreamWater ṁ(Kg/hr)

35

200 Output StreamLHCs ṁ(Kg/hr) 100

4.32

148.8

25

123.8

8.253333

Cp(KJ.Kg-1.°C-1)

T (oC)

Tr (oC)

ΔT (oC)

Q=ṁCpΔT(Kwatt)

1.931 Cp(KJ.Kg-1.°C-1)

ṁ(Kg/hr) 5000

3.23

148.8 T(oC) 148.8

36

25 Tr(oC) 25

123.8 ΔT

1.844582 Q=ṁCpΔT(Kwatt)

123.8

555.3806

37

38

39

40

41

42

3. HEATER:

43

44

Table 10 : Energy Balance of Heater 2

45

Heat Duty Of Heater 2 ṁ(Kg/hr) 5000

Cp(KJ.Kg-1.°C-1) 3.23

T (oC) 220

46

Tr (oC) 25

ΔT (oC) 195

Q=ṁCpΔT(Kwatt) 874.7917

47

48

Lube Oil

4. 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 (8.2%) (From Condenser) -1 ° -1 o Cp(KJ.Kg . C )

T( C)

Tr (oC)

ΔT(oC)

5000

3.23

220

25

195

ṁ(Kg/hr)

Cp(KJ.Kg-1.°C-1)

T (oC) Tr(oC)

ΔT(oC)

2460

2.497216

220

195

ṁ(Kg/hr)

Cp(KJ.Kg-1.°C-1)

T (oC) Tr(oC)

ΔT(oC)

2460

3.27

180

25

155

ṁ

Cp(KJ.Kg-1.°C-1)

T(oC)

Tr(oC)

ΔT(oC)

2050

3.27

Q=ṁCpΔT(K watt) 874.7917

Qv

25

Q=ṁCpΔT(K watt) 332.754

Qd Q=ṁCpΔT(K watt) 308.035

Ql

VACUUM DISTILLATION

Qc

180 41025Kg/hr155 ṁ=

Q=ṁCpΔT(K watt) 288.6229

Qv-Qd-Ql -263.9039

Qw

ṁ= 5046

ṁKg/hr (Kg/hr) 4590

Qb

Cp(KJ.Kg-1.°C-1)

T(oC)

Tr(oC)

6.217

320

25

ΔT(o

Q=ṁCpΔT(Kwatt)

C)

Qf-Qd-Qw-Qc -1507.71

49

295

2338.3691

Lube Oil (From Reboiler)

Lube Oil (From VDU) ṁ= 5599Kg/hr

Table 12 : Energy Balance of Thin Film Evaporator Energy Balance TFE

Lube Oil (To SettlingVessel) Asphaltenes Residue (6.2%)

Input

ṁ(Kg/hr)

Cp(KJ.Kg-1.°C-1)

T(oC)

Tr(oC)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

5599

4.7385

320

25

295

2174.0567

ṁ(Kg/hr)

Cp(KJ.Kg-1.°C-1)

T(oC)

Tr(oC)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

4389

4.7835

320

25

295

1720.4057

Output ṁ(Kg/hr)

Cp(KJ.Kg-1.°C-1)

T(oC)

Tr(oC)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

1210

4.2845

180

25

155

223.21055

Output

5.THIN FILM EVAPORATOR: ṁ= 4590 Kg/hr ṁ= 5289 Kg/hr

(Recycled Stream)

148.8 OC PREFLASH (I)

Lube Oil (From SettlingVessel)

50

ṁ= 310 Kg/hr

6. MIXER:

Table 13: Energy balance of Mixer Heat Duty of Mixer ṁ(Kg/hr ) 5599

Cp(KJ.Kg-1.°C-1)

T(oC)

Tr(oC)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

4.7385

314.7

25

289.7

2134.9974

7. 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

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

4.7835

180

25

155

903.94198

ṁ(Kg/hr)

Cp(KJ.Kg-1.°C-1)

T(oC)

Tr(oC)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

4180

4.7835

180

25

155

860.89713

CP(KJ.Kg-1.°C-1)

T(oC)

Tr(oC)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

155

37.479215

Output stream

Output stream ṁ(Kg/hr)

Table 14: Energy Balance of Settling 209 4.165 180 25 Vessel

8. HEATER

Table 15: Energy balance of Heater 3 Heat Duty Of Heater 3 ṁ(Kg/hr) CP(KJ.Kg-1.°C-1)

T(oC)

Tr(oC)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

4389

180

25

155

903.94198

4.7835

52

9. 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.Kg-1.°C-1)

T(oC)

Tr(oC)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

4930

4.735

320

25

295

1912.8742

10. HEATER

Table 17 : Energy Balance of Heater 4 Heat Duty of Heater 4 ṁ(Kg/hr)

Cp CP(KJ.Kg-1.°C-1)

4930

4.735

T(oC ) 320

Tr(oC)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

25

295

162.10799

53

Make Up H2Make Make Up H2

11. 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

162.108

Output stream Gas ṁ(Kg/hr)

CP(KJ.Kg-1.°C-1)

T(oC)

Tr(oC)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

340

14.35

320

25

295

399.8069

Output stream Lube Oil

CP(KJ.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

Naphtha Fraction (From HP Separator) Diesel OilLube Oil 12. FRACTIONATION COLUMN:

Energy Balance Across Fractionating Column Light OilLight Light ṁ= Oil 40 Kg/hr Input Stream 4590

4.735

T(oC)

o Tr(Fuel C) Gas ΔT(oC)

Q=ṁCpΔT(Kwatt)

320

25

1780.952

Heavy Oil

Output Stream Fuel Gas ṁ(Kg/hr) CP(KJ.Kg-1.°C-1)

T(oC)

40

200

2.8

Output Stream Diesel ṁ(Kg/hr) CP(KJ.Kg-1.°C-1)

T( C)

520

200

2.42

o

Output Stream Heavy Oil

FRACTIONATION COLUMN

ṁ= 4580 C (KJ.Kg-1.°C-1) P Kg/hr

ṁ(Kg/hr)

295

ṁ=ΔT 520 Tr(oC) (oC)

Q=ṁCpΔT(Kwatt)

25

5.444444

175

ṁ= 4020 Kg/hr Tr( C)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

25

175

61.17222

o

ṁ(Kg/hr)

CP(KJ.Kg-1.°C-1)

T(oC)

Tr(oC)

ΔT(oC)

Q=ṁCpΔT(Kwatt)

4020

2.1

200

25

175

410.375

Table 19: Energy Balance of Fractionation Column

55

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