35th International Conference of Slovak Society of Chemical Engineering, Tatranske Matliare, May 26-30 2008, pp135, Slovak University

of Technology, Bratislava,

WASTE WATER MINIMISATION IN A REFINERY PLANT BY USING PROCESS SIMULATION AND PROCESS INTEGRATION INSTRUMENTS
Gheorghe Bumbac1, Ciornei Cristian1, Adrian Turcu1, Aurelian Toma2 University Politehnica of Bucharest, Centre for Technology Transfer in the Process Industries, 1, Polizu Street, Building A, Room A056, Sector 1, RO-011061, Bucharest, Romania, Phone: +40-21-2125125, Fax: +40-21-2230797, email: cttip@chim.upb.ro 2 PETROM S.A., INCERP Ploiesti Subsidiary, 291A, Republicii Blvd., RO-100072 Ploiesti, Romania, Phone: +40-244-198738, fax: +40-244-198732, popescu@serv.incerp.ro
1

Present tendencies, for the environment protection, long lasting development, pollution prevention and those connected to the increase of the prices of raw materials resources and wastes treatment encourage the process industries to find solutions for diminishing the raw material consumption and the amount of waste produced. According to the systematic methodologies of process synthesis, the topologic process schemes are realized taking in account that they realize a minimum consumption of resources, including the reusing and recirculation of the untransformed raw material by a single pass through the installation concurrent with the achievement of a minimum of the utilities consumption. These things lead to the diminishing of the level of waste generation and material emissions to the environment, as to a diminishing of the production costs and the assurance of a sustained growth of the economic activity. In the last decade there were significant progresses concerning the recirculation and reusing material resources and utilities optimization. Specifically analysis and process synthesis techniques (including retrofit) based on process integration has evolved and developed as an effective instrument in handling and solving problems concerning the resources consumption minimization (both material and energetic). In the present paper is shown the use of simulation and process integration methods for the identification of retrofit solutions for the minimization of fresh water consumption used on a crude oil refining site (only three processing unit were taken in account: crude distillation unit CDU, Fluid catalytic cracking unit FCCU and Delayed Coking Unit DCU) as the reduction of the waste water discharged by this industrial processing site. The paper presents the identified topological solution as well as the performances of this solution compared with those already existing.

1. Introduction The physical and chemical processes specific to the processing units from a refining oil site implies the presence of water. Water acts both as a chemical species that prevents the process of undesirable chemical reactions, specially during the thermal treatments for the raw material processing the crude oil (for instance it prevents carbon deposition on the coil piping inside the super-heating furnaces) and as an energy carrier when it is used as a stripping and/or stripping agent in separation processes. Huge amounts of fresh water are implied and also large quantities of waste water that must be discharged from the processes to the environment. The costs and the efforts for the waste water treatment are very large but the most important problem is that in spite all the efforts the environment is affected because the waste water treated and discharged has not the same quality as the fresh water used. Therefore the more efficient use of water inside the mentioned industrial site is the redeemer solution for reducing operating costs and for fulfilling environment protection legislation. The main idea we developed in this paper was to solve the interconnections between the process units of the refining total site in order to increase the utilization degree of the water inside the site by coupling the water streams (sources and sinks) of its main processing units. As the increase of the degree of utilization of water streams can be realized only by the water

recycle and reuse inside each processing units as well as between them, we have to limit to the choice of process units that have a compositional compatibility of the water streams implied into the respective processes. In the present paper we choose for the integration analysis and the retrofit scheme synthesis the crude distillation unit CDU the fluid catalytic cracking unit FCCU and the Delayed Coking Unit DCU. The water streams of these processes contain approximate the same components (hydrocarbons) that means that there is a compositional compatibility and that can be realized the coupling between the currents with a water shortage from a unit, the currents with water over from the others. For the identification of the specified solution were used the systematic procedures of process analysis and synthesis based on the process simulation and integration. Process integration represents a process analysis and synthesis instrument, used either for grass root design or for retrofit (El-Halwagi, 1997). In the context of pollution prevention, process integration is an element of analysis and synthesis of process schemes that plays an important role in obtaining solutions for process schemes able to fulfill certain performance objectives. In process synthesis, from the point of view of the application methodology two domains are relatively better developed, that is the synthesis methodology of heat exchangers networks (HEN) and mass exchangers networks (MEN). Both domains of mass and heat integration are reported in detail in the literature sources (v. Douglas, 1988; Biegler et al. 1997; Turton et al. 1998; Allen and Shonnard, 2002; Seider at al. 2003; Smith 1995, 2005). Heat and mass integration and more recently the new methodology of property integration (Shelley and ElHalwagi, 2000; Kazantzi Vasiliki and El-Halwagi, 2005; El-Halwagi, 2006) have become together three practical instruments of process integration application, In the case study from the present work, process simulation for the three process units was realized, using the simulator HYSYS, the extraction of the data concerning the water streams, and as instruments for applying Pinch technology for water was first used the Program Table Algorithm of Water Cascade, taking in account a single contaminant and then the procedure based on the optimization, case in which two contaminants in the water streams were considered. 2. Site Process Units description

a. The CDU- Crude oil often contains water, inorganic salts, suspended solids, and watersoluble trace metals. As a first step in the refining process, to reduce corrosion, plugging, and fouling of equipment and to prevent poisoning the catalysts in processing units, these contaminants must be removed by desalting (dehydration). The two most typical methods of crude-oil desalting, chemical and electrostatic separation use hot water as the extraction agent. In chemical desalting, as in our case study, water and chemical surfactant (desemulsifiers) are added to the crude, heated so that salts and other impurities dissolve into the water or attach to the water, and then held in a tank where they settle out. The desalting device is operated continuous. The feedstock crude oil is heated to between 150 and 350C to reduce viscosity and surface tension for easier mixing and separation of the water. The temperature is limited by the vapor pressure of the crude-oil feedstock. In both methods other chemicals may be added. Ammonia is often used to reduce corrosion. Caustic or acid may be added to adjust the pH of the water wash. Wastewater and contaminants are discharged from the bottom of the settling tank to the wastewater treatment facility. The desalted crude is continuously drawn from the top of the settling tanks and sent to the crude distillation (fractionating) tower. Figure 1 gives a simplified CDU process scheme. The first step in the refining process is the separation of crude oil into various fractions or straight-run cuts by distillation in atmospheric and vacuum towers. The main fractions or "cuts" obtained have

specific boiling-point ranges and can be classified in order of decreasing volatility into gases, light distillates, middle distillates, gas oils, and residuum. At the refinery, the desalted crude feedstock is preheated using recovered process heat. The feedstock then flows to a direct-fired crude charge heater where it is fed into distillation column just above the bottom, at pressures slightly above atmospheric and at temperatures ranging from 340 to 370 C (heating crude oil above these temperatures may cause undesirable thermal cracking). To prevent thermal cracking, steam is injected in the crude oil before furnace heater. All but the heaviest fractions flash into vapor. As the hot vapor rises in the tower, its temperature is reduced. Heavy fuel oil or asphalt residue is taken from the bottom. At successively higher points on the tower, the various major products including lubricating oil, heating oil, kerosene, gasoline, and uncondensed gases (which condense at lower temperatures) are drawn off as atmospheric column lateral products. The evaporation, condensing, and scrubbing operation is repeated many times until the desired degree of product purity is reached. Then side streams from certain trays are taken off to obtain the desired fractions. Products ranging from uncondensed fixed gases at the top to heavy fuel oils at the bottom can be taken continuously from a fractionating tower. Steam is often used in towers to lower the vapor pressure and create a partial vacuum. The distillation process separates the major constituents of crude oil into so-called straight-run products. Sometimes crude oil is "topped" by distilling off only the lighter fractions, leaving a heavy residue that is often distilled further under high Vacuum Distillation Tower. In order to further distill the residuum or topped crude from the atmospheric tower at higher temperatures, reduced pressure, and steam injection into system is required to prevent thermal cracking. The process takes place in one or more vacuum distillation towers. The principles of vacuum distillation resemble those of fractional distillation and, except that larger-diameter columns are used to maintain comparable vapor velocities at the reduced pressures, the equipment is also similar. The internal designs of some vacuum towers are different from atmospheric towers in that random packing and demister pads are used instead of trays. A typical first-phase vacuum tower may produce gas oils, lubricating-oil base stocks, and heavy residual for propane deasphalting. A second-phase tower operating at lower vacuum may distill surplus residuum from the atmospheric tower, which is not used for lube-stock processing, and surplus residuum from the first vacuum tower not used for deasphalting. Vacuum towers are typically used to separate catalytic cracking feedstock from surplus residuum. The areas in which the presence of water is implied are stated in Figure 1..

Figure 1 Simplified scheme of CDU process b. DCU - In delayed coking the heated charge (typically residuum from atmospheric distillation towers) is transferred to large coke drums which provide the long residence time needed to allow the cracking reactions to proceed to completion. Initially the heavy feedstock is fed to a furnace

which heats the residuum to high temperatures (460-495 C) at low pressures and is designed and controlled to prevent premature coking in the heater tubes. For this reason steam is injected before heater feeding into processing stream. The mixture is passed from the heater to one or more cocker drums where the hot material is held approximately one day (delayed) at low pressures, until it cracks into lighter products. Vapors from the drums are returned to a fractionator where gas phase species, naphtha, and gas oils are separated out. The heavier hydrocarbons produced in the fractionator are recycled through the furnace. A simplified process scheme is given in the figure 2. After the coke reaches a predetermined level in one drum, the flow is diverted to another drum to maintain continuous operation. The full drum is steamed to strip out uncracked hydrocarbons, cooled by water injection, and decocked by mechanical or hydraulic methods. The coke is mechanically removed by an auger rising from the bottom of the drum. Hydraulic decoking consists of fracturing the coke bed with high-pressure water ejected from a rotating cutter.

Figure 2 Simplified process scheme of DCU. c.) FCCU - FCC process involves mixing a preheated hydrocarbon charge with hot, regenerated catalyst as it enters the riser leading to the reactor. The charge is combined with a recycle stream within the riser, vaporized, and raised to reactor temperature (480-530 C) by the hot catalyst. As the mixture travels up the riser, the charge is cracked at low pressure. In the more modern FCC units, all cracking takes place in the riser.

Figure 3. FCCU a simplified process scheme. The "reactor" no longer functions as a reactor; it merely serves as a holding vessel for the cyclones. This cracking continues until the oil vapors are separated from the catalyst in the

reactor cyclones. The resultant product stream (cracked product) is then charged to a fractionating column where it is separated into fractions, and some of the heavy oil is recycled to the riser. Spent catalyst is regenerated to get rid of coke that collects on the catalyst during the process. Spent catalyst flows through the catalyst stripper to the regenerator, where most of the coke deposits burn off at the bottom where preheated air and spent catalyst are mixed. Fresh catalyst is added and worn-out catalyst removed to optimize the cracking process. In figure 3 a simplified process scheme for FCCU considered in our case study is given. 3. Results and discussions Water stream data characteristics After achieving the simulation modules (more detailed information it can find in source Turcu A, 2008) we extracted the data concerning the water currents of the 3 processes. Thus, Tables 1, 2 and 3 present the data of the water currents for CDU, DCU and, respectively FCCU. Table 1 CDU water streams data
Name Water separated from the heavy gasoline produced in the CDU Water separated from the diesel produced in the CDU Water separated from the vacuum system of the DCU Water after the desalting Fresh water used for desalting Name Desalting Source currents Flow rate, kg/h 2.5 6.3 4857 32870 To calculate Currents in the red Flow rate, kg/h 33750 Hydrocarbons concentration, ppm 10 10 15 5000 0 Hydrocarbons concentration, ppm 3000

Table 2 DCU water streams data

Name Current DW1+DW2+DW3 Source currents Flow rate, kg/h 374 Hydrocarbons concentration, ppm 500

Table 3. FCCU water streams data

Source currents Flow rate, kg/h 2732 9091 To calculate Currents in the red Flow rate, kg/h 9602

Name Water separated from the D 104 vessel Water separated from condenser of the main column Fresh water Name Injection in the main column condenser

Hydrocarbons concentration, ppm 1928 123 0 Hydrocarbons concentration, ppm 2000

In Table 4 are presented the results of the Program table algorithm of water cascade, considering together all the source currents, respectively all the shorts currents of the three processing units of the refining site. Table 4 Program table algorithm of water cascade for CDU, DCU and FCCU

The initial flow rates of fresh water and those discharged from the three units according the process data (emphasized from the simulation modules) are given in Table 5. Table 5 Water import-export flows in the existing units we considered Unit CDU Fresh water, t/h Desalting: 33.75 Discharged water, t/h Desalting :32.87 Lateral products : 0.009 Vacuum system : 4.86 Separator of the main column condenser : 9.091 Water after D104 separator: 2.732 DW1 + DW2 + DW3 : 0.374 Discharged water: 49.936

DCU FCCU TOTAL

Condenser injection: 9.602

Fresh water: 43.352

Carrying out the Program Table Algorithm of Water Cascade for the water currents of the CDU, DCU and FCCU processes (see Table 4) provides information concerning the target values for the necessary of fresh water for the three units: 6.40 t/h as well as the target flow rate of water discharged from the three units : 12.99 t/h. Comparing the target values with those existing nowadays for the three units a serious potential can be observed for reducing the flow rates, by achieving the integration of water resources between the three units, more precisely : for fresh water 43.352 6.40 = 36.952 t/h (meaning a saving of 85.24%) and for the discharged water: 49.93 12.99 = 36.94 t/h. (meaning a saving of 73.98%). The savings obtained are but objectionable due to the fact that they are taking in account only one contaminant. Therefore, in the following analysis, were used the data from the mentioned

simulation modules, taking in account a hydrocarbon (n-C5) and a salt (NaCl). As an analysis instrument was used the procedure based on taking in account the mass transfer, implemented in a numerical algorithm in a software instrument called WATER (elaborated in the Department of Process Integration at the University of Manchester - UMIST). In Figures 4 and 5 are shown the data of the water sources from the three refinery units used in the analysis with two contaminants.

Figure 4. Water source streams data for CDU, DCU and FCCU in analysis with two contaminants

Figure 5. Water sink streams data for CDU, DCU and FCCU in analysis with two contaminants

Using as analysis option water reuse and minimum source water flow rate, according the integrating analysis, taking in account 2 contaminants, the necessary of fresh water for the three units is 36.79 t/h. The differences (savings) of flow rates obtained by integration are: fresh water: 43.352 19.755 = 23.597 t/h; (54.43 % savings) discharged water: 49.936 - 36.79 = 13.146 t/h; (26.32 % savings), obtaining also the topological scheme of interconnections as they are shown in Figure 6.

Figure 6. The topological scheme of the interconnections between the source water streams and short streams arisen for the case when there are taken in account two contaminants (DW1+DW2+DW3 refers to water separated from DCU separation column products) In conclusion, the economies obtained for the case calculated with ATCA with a single contaminant were of 85.24 % for the fresh water and, respectively, 73.98 % for the waste water discharged from the processes. Due to the fact that the identified economies were not reliable, by considering a single contaminant, the problem rises to verify the method with another method that can use two or more contaminants. The savings achieved for the case calculated with WATER, were of 54.43% for the fresh water and, respectively, 26.32 % for the waste water discharged from the processes. Based on these objectives we synthesized a water network common to the three processes considered. The solution of the joint reuse between the three fabrication processes analyzed from an industrial crude oil refinery site is realistic, because the waste water issued both from the fluid catalytic cracking unit and from the delayed coking unit is reused inside the cracking process and in the crude distillation unit, having no incompatibilities between the chemical species recycled in the process and the existing ones. The practical implementation of the integration solution leads to an improvement of the process performances measured by the diminishing of fresh water consumption and waste water discharge in the environment. The new topology with new technological relations between the site processes does not affect their good functioning and this creates the conditions of feasibility from the economic point of view. In this paper we did not use operating costs or capital costs because this paper has not as an objective to determine some economic indicators.

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