Introduction at 1,400-1,600°F and are rapidly quenched in
the transfer line exchangers (TLE) that generate An Ethylene Plant is a process for the produc- high pressure steam for use in other parts of the tion of polymer grade ethylene (99.9 vol %). It plant. The pyrolysis/quench systems are de- also produces major byproducts such as propyl- signed to handle the full range of gaseous and ene (chemical or polymer-grade), a butadiene liquid feedstocks from the light ethane to heavy rich C4 stream and C6-C8 aromatics rich pyroly- naphtha. sis gasoline. The Ethylene Plant is the major supplier of feedstock to the polyethylene plants The furnace effluent, after quenching, flows to for the creation of polyethylene plastics. the gasoline fractionator where the heavy oil fraction is removed from the gasoline and lighter The first section of the Ethylene Plant is the Py- fraction (liquids cracking only). rolysis Unit (see Fig. 1) that cracks the feedstock into ethylene. The hydrocarbon feedstock is Final cooling of furnace effluents is accompa- preheated and cracked in the presence of steam nied by a direct water quench in the quench in tubular SRT (Short Residence Time) pyrolysis tower. furnaces. The resultant products exit the furnace s The raw gas from the quench tower is com- 3. Analyses that are required for accounting pressed in a multistage centrifugal compressor purposes and data logging to greater than 500 pounds of pressure. Hydro- Analysis Used for Computer Control carbons condensed in the first charge compres- sion stages are returned to the quench tower For the purposes of control, the analyses are while those condensed in the later stages are divided into two groups as follows: removed and sent to the depropanizer. 1. Analyses that are required for closed-loop The compressed gas is then dried and sent to control of product specifications. the demethanizer. The bottoms go to the 2. Analyses that are required for closed-loop Deethanizer. control and optimization of criteria other than product specifications. Acetylene in the Deethanizer Overhead is hy- drogenated or, the acetylene can be removed by The above two groups are divided according to solvent extraction and recovered. The ethyl- relative importance. Certainly, continuous pro- ene/ethane stream is fractionated and ethane duction of product according to specification is leaving the bottom of the Ethylene fractionator is an extremely important function. recycled. Analysis of Product Purity The deethanizer bottoms and stripper bottoms from the charge compression system are depro- The principle product of an Ethylene Plant de- manding continual monitoring for product impuri- panized. The depropanizer bottoms is separated into mixed C4 and light gasoline streams. Poly- ties are ethylene and sometimes propylene mer-grade propylene can be produced by further product streams. Product specification analyses are among the more important of the analyses purification of the depropranizer overhead. Yield data for various feedstocks including ethane since off-specification product normally cannot (fresh feedstock or recycle) are shown below: be sent to the product pipeline and must be dis- posed of otherwise - usually to a flare system. Feedstock Ethane Propane Butane Naphtha Therefore, reliable analyzers for measuring Ethylene, 84.0 45.0 44.4 34.4 product specifications must be provided. Al- Wt% though product specifications can vary widely Propylene, 1.4 14.0 17.3 14.4 from plant to plant, they are typically: Wt% Butadiene, 1.4 2.0 3.0 4.9 CH4 + C2H6 < 0.15% C2H2 < 5 ppm Wt% Aromatics, 0.4 3.5 3.4 14.0 CO2 < 10 ppm Wt% The sample for these analyzers should be taken from the Ethylene Product line. The product The above yield data present typical high- severity operation to maximize ethylene produc- specification for propylene (if applicable) is typi- tion. If desired, byproducts may be increased or cally: decreased by altering cracking conditions. C2H6(MA) + C3H8(PD) < 2.0% To summarize, an Ethylene Plant consists of Ethylene Product Specification Control several parallel pyrolysis furnaces followed by a cracked gas compressor, an acetylene con- To be able to successfully control product purity, verter, a Demethanizer, a Deethanizer, a C2 it is necessary to be able to measure both the Splitter, a Depropranizer, a C3 Splitter and a De- methane and the ethane concentration in the butanizer. Ethylene Product. The methane impurity in the Ethylene Product is lighter than the light key The analyses to be made in an Ethylene Plant compound in the C2 Splitter Overhead Stream. will vary slightly from one plant to another; how- The control point for the methane impurity in the ever, the analyses can be divided into three ba- Ethylene Product is the Demethanizer Bottoms sic groups depending upon their intended use. Stream. Specifying the methane-to-ethane ratio The three groups are: (CH4/C2H6) in the Demethanizer Bottoms Stream 1. Analyses that are used in closed-loop con- will specify the concentration of the methane trol and optimization relative to ethylene in the C2 Splitter Overhead and subsequently in the Ethylene Product. A 2. Analyses that are required for monitoring and alarms s typical full scale range for this analysis ratio on Specifying the ethane/propylene ratio in the the Demethanizer Bottoms Stream would be Deethanizer Bottoms will specify the concentra- tion of ethane relative to propylene in the C3 CH4/C2H6 0.0 -> 0.002 Splitter Overhead and eventually the Propylene The ethane impurity in the Ethylene Product is Product. the heavy key in the C2 Splitter Overhead The propane impurity is the heavy key in the Stream. Once the methane concentration in the Propylene Product. The control point for the C2 Splitter overhead is determined from the De- propane impurity is therefore the C3 Splitter methanizer Bottoms Stream, the ethane concen- Overhead. Once the ethane concentration in the tration in the C2 Splitter Overhead can be ad- C3 Splitter Overhead is determined, the concen- justed or controlled to meet the CH4 + C2H6 tration of the propane in the C3 Splitter Over- specification in the Ethylene Product. A typical head can be adjusted to give the required C2 + full scale range for the ethane analysis is C3 product specification. Typical ranges for C2H6 0.0 -> 0.2 Vol. % these analysis are: The acetylene concentration in the Ethylene C2H6/C3H6 0.0 -> 0.02 Product is determined at the effluent of the last C3H8 0.0 -> 2.0 Vol % stage of the Acetylene Convertors (hydrogena- In the C3 Splitter, there is sometimes an im- tion reactors). Therefore, the objective of con- ported Propane - Propylene (P-P) stream. This trolling these reactors is to control the acetylene means, it will be necessary to also analyze this concentration in the effluent of the last stage of stream and the Depropanizer Overhead stream these reactors. The recommended analyses of to control the ethane in the Propylene Product. these reactors for control are as follows: Analysis Used for Additional Control & Op- Stream Component Range timization Reactor Feed C2H2 0.0 -> 5000 ppm CO 0.0 -> 5000 ppm Additional control and plant optimization func- Interstage C2H2 0.0 -> 500 ppm tions, requiring reliable on-line composition CO 0.0 -> 500 ppm analysis, exist in the furnace area and in the Reactor C2H2 0.0 -> 10 ppm fractionation area. Before specifying the analysis Effluent to be used for the additional control and optimi- zation functions, one must first specify the func- Additionally, the above analyses for Acetylene tions to be implemented. Reactors are used for computer optimization; i.e. minimize the amount of ethylene inadvertently Furnace Control and Optimization converted to ethane through the hydrogenation Normally the Cracking Furnace control and op- process in the reactors. timization functions that require on-line analysis Also, some Acetylene Reactors are difficult to are: operate; i.e. it is easy to have a reactor “run- 1. BTU Firing Rate Control away”. The above analysis allows supervisory 2. Velocity Control control of the Acetylene Reactors to prevent this 3. Conversion Control from happening. BTU Firing Control: For this control, the Fuel The analysis of the CO2 concentration in the Gas is normally analyzed for the following com- Ethylene Product is not usually tied into a com- ponents N2, H2, CH4, C2H4 and CO. From the puter control scheme. Violation of the CO2 speci- component analysis, the BTU content of the gas fication signifies CO2 break-through from the can be calculated and used to control the BTU caustic wash. This CO2 analysis is used primar- firing rate. ily for monitoring and alarm. Velocity Control (or Residence Time): For this Propylene Product Specification Control control, an analysis is made of the cracked gas Again, successful control of the sum of the two for the purpose of determining the molecular primary impurities in the Propylene Product re- weight. The sample point for this analysis is lo- quires control of the concentration of each of the cated on the effluent of the Secondary Transfer two individual impurities. The ethane impurity is Line Exchanger (TLE). Since speed of analysis the lighter than light key compound in the Pro- is critical for proper control, each sample point is pylene Product. Therefore, the control of this monitored by two analyzers. The first analyzer impurity is the Deethanizer Bottoms Stream. measures only a few compounds to provide the s control system with the information to calculate Additional process streams for possible control and estimate molecular weight for the velocity in the fractionation area are: control. The second analyzer provides a slower 1. Deethanizer Overhead but more complete analysis of the cracked gas. 2. Demethanizer Overhead The analysis from the second chromatograph is 3. C2 Splitter bottoms used to trim (or update) the estimated molecular 4. C3 Splitter Bottoms weight obtained from the first analyzer. 5. Depropanizer Overhead It is not always practical to have two analyzers 6. Depropanizer Bottoms on every furnace. What is frequently done is 7. Debutanizer Overhead have a dedicated analyzer for each furnace to 8. Debutanizer Bottoms perform the short analysis and to have a couple The control of the additional sample points are of chromatographs that are configured to pro- meant to optimize the recovery of the ethylene vide the complete analysis for a number of fur- and the recovery of the propylene, the reduction naces each. Furthermore, since the data form of fractionator utility costs and increased the short analysis is so critical for the proper throughput where appropriate. control of the velocity rates, the short analysis analyzers are typically set up to provide back-up Control of Ethylene Recovery: Ethylene is lost capability between each other in the event of in the Demethanizer Overhead stream and the analyzer failure. C2 Splitter Bottoms. Optimizing ethylene recov- ery involves control of these two streams. The Conversion Control: Conversion control re- chromatographic analyses required are the eth- quires the analysis of the Hydrocarbon Feed to ylene concentration in the Demethanizer over- the furnace and the Furnace Effluent or Cracked head and the ethylene concentration in the C2 Gas Stream. The cracked gas analysis used for Splitter Bottoms. Typical ranges for these analy- velocity control is also used to calculate conver- sis are: sion. Again, the partial analysis is used to esti- mate conversion, with the more complete analy- C2H4 (Demethanizer Overhead) 0.0 -> 1.0 Vol. % sis being used to trim or update the estimated C2H4 (C2 Splitter Bottoms) 0.0 -> 2.0 Vol. % conversion. Control of Propylene Recovery: Propylene is Cracked Gas Cracked Gas lost in the C2 Splitter Bottoms (Recycle Ethane) Mixed Feed Partial Detailed and in the C3 Splitter Bottoms stream. As pro- Stream Analysis Analysis pylene lost in the C2 Splitter Bottoms is heavier CH4 C2H4 H2 than the heavy key, the control point for the pro- C2H4 C2H6 CH4 pylene in the C2 Splitter Bottoms is the Deetha- C2H6 C3H6 C2H4 nizer Overhead. Control of propylene recovery, C3H8 C3H8 C2H6 therefore involves control of the Deethanizer C4+ C3H6 Overhead and the C3 Splitter Bottoms. The C3H8 analyses required for control of propylene re- C4’s covery are the propylene to ethane ratio in the C5+ Deethanizer Overhead stream and the propyl- Fractionator Control and Optimization ene in the C3 Splitter Bottoms stream. Typical ranges for these analyses are: In order to control the process to insure that the product streams meet specification as discussed C3H6 (C3 Splitter Bottoms) 0.0 -> 5.0 Vol. % earlier, the analyses of fractionator streams are C3H6/C2H6 (Deethanizer Overhead) 0.0 -> 0.2 C3H6 (C2 Splitter Bottoms) 0.0 -> 2.0 Vol. % made of the following: Additional Control of the C3 Splitter: Improved 1. Deethanizer Bottoms control of this column could be obtained by the 2. Demethanizer Bottoms analysis of the C3 Splitter Feed Stream. The 3. C2 Splitter Overhead feeds to this column are the Depropanizer Over- 4. C3 Splitter Overhead head Stream and Alkyl Import Stream (if appli- cable). In both streams, the compounds for analysis are propylene and propane. s Depropanizer Control: Control of the Depro- high limit in acetylene concentration in the efflu- panizer is limited frequently to the control of the ent of the Acetylene Convertor. total C4’s in the Depropanizer Overhead. The Analysis For Accounting Purposes chromatographic analysis required for this is the total C4’s in the Depropanizer Overhead stream. Chromatographs are also used to provide the compositional information needed for accounting Debutanizer Control: Control of the Debutan- purposes. Typical streams monitored for ac- izer tower is to the separation of the C4’s from counting purposes include: the C5’s and to keep the C4’s out of the Debutan- ized Gasoline stream. 1. Cracking Furnace Fresh Feed 2. Demethanizer H2 Rich Tail Gas All of these chromatographic analyses dis- 3. Demethanizer CH4 Rich Tail Gas cussed so far were made for the purpose of 4. C4 Content of the Import Alkyl Stream executing closed-loop control. Even if closed- 5. Import Refinery Gas loop control is not the objective of the plant, these analyses should be made to provide the The ethylene rich Import Refinery Gas is intro- plant operators with the information they need duced into the Cracked Gas Compressor ahead for proper operation. of the fractionation train. Analyses for Monitoring and Alarm Overall Benefits of Using Process GC’s In addition to the benefits listed throughout this Some chromatographic analyses are for moni- paper, using process GC’s as part of an overall toring and alarm purposes only. These analyses advanced control scheme can lead to very im- are the acetylene and carbon dioxide in the C2 pressive benefits. These additional benefits in- Splitter Overhead and the methyl acetylene and clude: propadiene (MA/PD) in the C3 Splitter Bottoms. 1. Increase the total pounds of ethylene or ole- Acetylene and carbon dioxide concentration are fins produced by 5 percent or more when included in the ethylene production specification. demand and feed supply are not limited. When either exceeds product specification, the product must be flared or otherwise disposed of. 2. Increase yield of ethylene or olefins per It is necessary to detect off-specification product pound of feed by 2-4 percent when feed ahead of the C2 Splitter Overhead accumulator supply or product demands are limited. since this accumulator supplies the ethylene refrigeration system. By detecting the off- 3. Reduce energy consumption per pound of product regardless of feed supply and mar- specification product ahead of the C2 Splitter Overhead Accumulator, contamination (requiring ket conditions. additional flaring) of the ethylene refrigeration 4. Achieve smoother operation with continuous system can be avoided. Conversely, as soon as and automatic coordination of plant-wide on-specification ethylene is produced, the ethyl- changes. ene can be delivered immediately as product minimizing the amount of ethylene flared. 5. Increase process on-stream time by auto- matically detecting and correcting conditions The analysis for methyl acetylene and propadi- that could lead to costly shutdowns. ene in the C3 Splitter Bottoms is a safety meas- ure. MA/PD tend to accumulate in the C3 Splitter 6. Produce a more consistent quality product Bottoms. Furthermore, MA/PD tend to explode if that assures customer satisfaction. their concentrations reach a certain value. The Furthermore, if process analyzers are coupled analysis of MA/PD provides the information for a with both advanced control and plant-wide opti- high limit alarm in the C3 Splitter Bottoms. mization schemes, overall plant profitability can Many of the analyses used for control are also improve an additional 5% above those already used for alarm purposes. These analyses are (a) given. high limit on all product specifications and (b) s
Table I: Chromatographic Analyses For An Ethylene Plant
International Thermodynamic Tables of the Fluid State, Argon, 1971: Division of Physical Chemistry, Commission on Thermodynamics and Thermochemistry, Thermodynamic Tables Project