AIChE Paper Number Fouling Mitigation of Quench Tower System

Holger Schmigalle General Process Manager Olefins Linde LE

Christer Tolergard Technical Support Manager Borouge

Prepared for Presentation at the 2010 Spring National Meeting San Antonio, Texas, March 25th 2010

AIChE and EPC shall not be responsible for statements or opinions contained in papers or printed in its publications

Fouling Mitigation of Quench Tower System

Abstract: Especially gas cracking plants are sensitive to fouling in the quench water section. One main fouling mechanism in the quench tower and in the related equipment is the accumulation of material with a high pour point. Fouling can be avoided or at least significantly reduced if the pour point of the hydrocarbon phase can be lowered below process temperatures of the system. To mitigate fouling for the Borouge Plant in Ruwais Abu Dhabi Linde Engineering has built a redistillation unit. In this unit the heavy hydrocarbon product of the plant is fractionated and a hydrocarbon fraction is routed back to the quench tower for pour point adjustment. Compared to the former performance of the quench tower measured process parameters indicate that an increased run length of the quench tower can be achieved.

Introduction Borouge is operating an ethane cracker with a capacity of 600000 t/a of ethylene in Ruwais, Abu Dhabi. The plant was very successfully started up in the year 2001. The feed for the cracking process is ethane only. Even C3+ byproducts produced by the cracking process are not sent back to the furnaces after separation. The plant is typically operating with an ethane conversion of 68%. However, ethane conversions in the range of 65% to 70% are covered by the design and operated time by time. After cooling down in the secondary quench exchangers the cracked gas is entering the quench water section.

Figure 1: 2 cycle quench water section for gas cracking plant

In the quench water section the cracked gas is cooled down in a 2 cycle quench water column. In the bottom cycle cooling of the gas is achieved by saturation with water. Coke particles and a liquid oil fraction, if existing, are separated from the gas stream and drained from the system. The gas stream is further cooled down in the upper section by circulation of quench water. The column internals of this section consists of angle trays in the bottom and of a random packing in the upper section. Some of the heat taken out of the gas stream by the quench water is used for process heating while most of the heat is absorbed by cooling water. The cooling water coolers are plate & frame heat exchanger consisting of 4 parallel blocks designed with one block as spare exchanger. The Problem Directly after startup a constant increase of pressure drop could be recognized. After operation of about 18 month the increase of pressure drop over the quench water tower was so significant that the quench water tower became a capacity bottleneck limiting operation of the plant. In the beginning root cause of the pressure drop increase was not clear. The water quality in the upper quench water cycle was all time very clean. The water didnt show any turbidity and also coke particles could not be detected. By analysis of the water of the upper quench water cycle it was not possible to detect a hydrocarbon phase. Only the fact that the quench water coolers showed fouling gave the indication that fouling could be involved. Heat exchanger where opened and material from the fouling layer was analyzed. The material was of tarry consistency. It could be fully dissolved in aromatics. The pour point was between 40 and 50 C. When scanning the column the picture became clearer. The scan in figure 2 shows that the column was flooding in the upper section. In the random packing having a height of 11 m the upper 4 meter where causing the main increase of pressure drop.

Figure 2: Scan of upper column section To overcome the problem pyrolysis gasoline produced in the cracker was injected via column reflux. Even with an increased rate of gasoline injection which was finally limited by the size of the separation section the problem could not be solved. When coming in contact with the gas stream the gasoline was instantly vaporizing before it came to the location where accumulated material was plugging the packing. As alternative an injection with washoil consisting mainly of C10+ components was performed. Already with an injection rate of 1.5 t/h the column could be washed very efficiently. Significant amounts of heavies could be removed from the quench tower packing and the pressure drop in this section of the column could be lowered. Disadvantage was that the tarry components getting liquefied where causing massive contamination of the entire wash water section leading to instrumentation failures, pump trips and emulsion problems in the process water train.

Even by further optimization of the online washing procedure the online washing was a significant operational effort which had to be well planned in advance. The load of the plant had to be reduced and an increased oil load in the blow down to the waste water treatment had to be accepted. Even when the procedure of cleaning was optimized a risk of tripping the plant by uncontrolled distribution of tarry components was all time existent. The Root Cause Especially in gas cracking plants fouling of the quench water and cracked gas compressor section is often experienced. One of the main reasons for this increased fouling tendency is the different composition of a cracked gas in gas cracking plants compared to liquid crackers. In figure 3 the distribution of C5 and heavier components in the cracked gas is compared for ethane, propane and naphtha cracking.
0.0020 Fraction of cracked gas [molfrac] 0.0018 0.0016 0.0014 0.0012 0.0010 0.0008 0.0006 0.0004 0.0002 0.0000 C5 C6 C7 C8 Naphtha Propane Ethane C10 Oil

C9

Figure 3: Typical distribution for C5+components It is obvious that in naphtha cracking the content of the C5 plus components is much higher then in the both gas cracking cases. Especially from C7 upwards the content of heavies in plants with gas cracking service is very low. This fact is reflected in the design of gas cracking plants as an oil quench system typically is not foreseen. Usually the gas from the furnaces is routed directly to the water quench column. Compared to propane cracking the content of the C5 and heavier components is once more significantly reduced in ethane cracking service. Especially component concentrations in the range C8 to C10 are very low.

With this information the increased fouling risk in plants with gas cracking service is better to understand. As gas crackers do not have an oil wash column oily components can pass to process sections like wash water section or cracked gas compression. The drastically reduced content in the C8-C10 component range results in heavy hydrocarbon liquids containing an increased amount of tar and oil with an increased pour point. Due to the low partial pressure of the heavy components in the cracked gas the heavy end is fed also to process parts with lower process temperatures where then fouling due to pour point violation is very likely. The Approach To overcome the fouling problems in the quench water column the approach was to avoid process temperatures which are below pour point temperatures. As process temperatures are determined by other process requirements measures were defined which allow reducing the pour point temperature thus far below process temperature that accumulation of solidifying components can be avoided. Pour point temperatures of the hydrocarbon fraction which accumulates in the quench water tower packing can significantly be reduced by enrichment of C8-C10 components. For this reason a redistillation tower was introduced into the process. Taking the hydrocarbon fraction from the gasoline/water separator of the quench section heavies are split from the overhead product. While the bottom product is sent to the existing facilities for incineration the overhead product is partially recycled to the quench water tower. By continuous injection of the redistillation overhead product to the quench tower the equilibrium of C8-C10 components is influenced in that way that lighter components move into the liquid phase and reduce the pour point of the liquid hydrocarbon fraction. The use of a redistillation column is not new for adjustment of a gasoline product specification. It is used in many plants. The new idea in this concept is to integrate the redistillation column in this way into the process that the aimed process conditions to avoid or reduce fouling are met. How effective the redistillation tower works can be visualized in figure 4 by comparing process and pour point temperatures in the upper quench water column.

90.000

Process temperature
80.000

Pour Point Temperature

70.000

Temperature [C]

60.000

With redistillaton
50.000

Without redistillaton

40.000

Without redistillaton

30.000

20.000

10.000

With redistillaton
0.000 Stage1 Stage2 Stage3 Stage4 Stage5 Stage6

Figure 4: Influence on pour point temperature of hydrocarbon fraction in

quench tower

It is assumed to have a quench tower design with 6 theoretical trays. The diagram shows the process temperature and the pour point temperature over each stage for ethane cracking. The process temperature in the top of the column is very near to the pour point and the risk of fouling is significant. By continuous injection of some redistillation overhead product the pour point especially in the upper area of the column can be reduced drastically.

The Result The use of the redistillation column showed various positive effects for the operation of the quench water section. When operating the redistillation column efficiency of pour point reduction of the modified process could directly be detected by the quench water which leaves the column from the chimney tray of the upper section. Before the redistillation tower was operated the quench water was very clean. A hydrocarbon phase could never be detected. That at least some hydrocarbons have been in the water could only be reasoned as equipment with quench water service showed fouling. With the redistillation tower in operation a small hydrocarbon flow is leaving the column with the quench water flow. As viscosity of this hydrocarbon phase is quite high separation from the water phase is relatively easy. The material of the hydrocarbon phase has the same properties compared to the material which was taken out of the column by online washing. With operation of the redistillation column the pressure drop in the column did not increase significantly. However, actual run length which can be achieved without washing of the quench tower will be experienced in the next years. A positive side effect is the operation of all equipment being in quench water service. While is was required to flush the equipment time by time with gasoline fouling of heat exchangers and pumps is now requiring less additional washing efforts. Summary It can be said that theories described herein are proven by the operational results of the quench section of the Borouge plant. Beside of the fact that fouling of the quench water tower could be mitigated also fouling of other equipments in the quench water system could be significantly reduced. Especially for existing quench systems where fouling mitigation has to be achieved the revamp by adding of a redistillation tower is a promising option.