Are liquid thermal-relief valves needed? Thermal stresses, or pressures from hydrogen evolution due to corrosion, can rupture a pipe or tube. Here is how to find such forces to see whether a relief valve is needed. ‘Sudhir R. Brahmbhatt, MG Industries D1 tm protecting process pipelines, engincers seldom perform calculations to see whether thermal stresses or pressure buildups (as a result of H, evolution from corrosion) exist. Such neglect could lead to rupture, especially if relief valves have not been employed, Here, we present a calculation method that will deter- mine whether or not a relief valve is required. An example illustrates the method. ‘Thermal expansion and corrosion In the case of thermal expansion, when pipes, tubes or process equipment are full of liquid and are blocked in, rupture can result from heat from several sources: Solar radiation. 1 Heat-tracing coils. Heat transfer by’ ra nearby process equipment. ‘Atypical example would be a heat exchanger blocked- im on the cold side, with flow continuing on the hot side, Such a situation could occur during normal operation, ‘e.g, when a hot product-stream was being pumped through an exchanger to a flash drum and the stream was being used to preheat the feed to a reactor. If a level controller that operated a control valve between the exchanger and flash drum were to close the control valve, the feed would be blocked in. ‘Then, of course, the system can be subject to thermal expansion, Stresses result from the difference in coeffi- Gents of thermal expansion between the liquid and the metal, (On the other hand, corrosion, which generates hydro- gen, can also give rise to severe stresses caused by gas pressure. Such a case may occur when, for example, the flow of sulfuric acid is stopped in a steel pipeline and it remains full. Afier some time, enough hydrogen may be generated to create pressures that will burst the pipe, To see whether a relief valve is needed, the stresses due to thermal expansion and corrosion must first be found. Here is a method to do this: Determining thermal stresses The net volume of liquid that expands is found by subtracting the pipe expansion due to both temperature yn_and conduction from GADACAL ENGINEERING WAY 14, TRH rise and pressure rise from the liquid volume expansion due to temperature rise: AV = (V,— Vp) — AVq ~ MV, @ ‘The volumetric expansion of the liquid at temperature ¢ above a reference temperature is given by: Vm Vall + at + b+ a) ® ‘The reference temperature tris 0°C. Values of , b, and ¢ are given for some liquids in Table 1 When a liquid expands from temperature to to tem perature fits volume at ts: Vs m Vig + Vnlatt — to) + b(t? — tot) + e( — 1e4)] (8) ‘The pipe expansion due to temperature is given by: Ary = T/AL(D + CD)AL + CL) — DEL] 4) In Eq. @), Lis the total pipe length including tings, i, it must account for the total restricted fluid volume. ‘Typical values of C appear in Table I. ‘The increase in pressure of the liquid—due either to heat or to gas buildup—will expand the pipe further (1). Such an inerease is usually minimal when compared wi the effects of heat alone, and can be ignored in making calculations. However, an equation for this effect (pipe ‘expansion due to pressure) is presented: AV, = fw (AR)YL + 1 R2 [AL] wet [EAP om pte] Poisson's ratio, 7, is 0.3 for steel and Alloy 20, a given in the American Nad. Standards Institute (aNSi), New York, ANSt Standard $1.3. Liquid compressibility is defined as Final volume — Inia volume) A~— (eitiprewut Stitalpesae) X © 1 diac soee pi eeeaaa ee a--(t ¥, 4) ® 69QUID THERNAL-REFIEY VALVES Coefficients of cubical expansion for some typical liquids Table | —————— Liguie Range,*C 2%, 10-9 b,10-8 9, 10-8 Benzene 1% 8 1.47625 127765 O.80eH “Tolvene 0100 1078 17790 IMethy!ateoho! 38-470 1.18857 1.56493 0.91113 ‘Butyl alcohol 6-108 083751 295% 0.12415 so Prepy!aleohol 0-83 1.04945 0.44303 2.7274 Chloroform 068 1.10715 4.65479 1.74920 carbon tersentoriae 0-76 118388 ORBHS! 1.35105 Ethyl acetate -96+72 12888 2.95088 0.14922 Hydrovhloriezcid, 33.2% 0-33 04460 0215 | — Sulture ac, cone. 0-60 05758 -oasd | nPentane 190430 1.50697 3435 0.975 “The coeiiont re for tr=0°C ‘For example, for benzene: VV [114.17628 10-9 2+ 1.2775 x 10°92 0.90645 x 10-8 3] From Ret, (2. Coefficients of linear thermal expansion for a few typical elloys Table It SN Temperature, Carbon 188 Wroushe = eel pele steel zee 20M iron om oz) ae oe 70 ° ° 0 ° 100 0.23 06 oz 026 125 a2 ose os: ome 200 099 148 tar an 250 140 2.09 170180 300 182 21 218206 400 270 280 am ann 500 82 501 4m 390 700 563 750 oa eos 900 7102 am 8m From Re. (6) Compressibilities of some solocted liquids Table ‘Temparasre,"C Pressure atm g,10~6, stm 20 102 20 030086 ° 1500 maa 14 @ 0 179 8 9 ° 15008 ‘20-Propyl alcohol 55 a 95 1786 8 103 Chloroform 2 087 ot. 100 oy a xy acotace 132 a1s74 i048 m8 8.139715 250 Benzene 20 12 953, 2 071974 684 avons 10 182578 100 1525 150 Sulfuric weld, 70%, wt. 60.2 wide range) 80-100 War 0 128 525 100 100200 asa From Ret. 12,41. 70 — Nomenclature ahe Coefficients for Eq. @) 4 Surface area of pipe in contact with Tiguid, £8 Ap Pipe cross-sectional area, f® Amual Cross-sectional arca of pipe metal (of the “ring” of a section of pipe), ft a Coefficient of linear thermal expansion ‘of pipe material, Ge Corrosion rate, mils/yr D Pipe inside dia, & E Modulus of elasticity, Ib/in? H Henry's law constant, atm L Pipe length between block valves, fe Ly Gas evolved, moles Hy/wk My Hydrogen equivalent weight of pipe ‘material, moles Pe Pressure, psi or atm AP Pressure change due to thermal stresses. AP R si or atm Pressure change due to corrosion, psi or atm, Pipe radius, ft T, Pipe thickness, t ‘Temperature, "F or °C jeg Average temperature, F or °C 5 Reference temperature, here O°C ye Volume of liquid at ¢, f° Vy Volume of liquid at t, Yi, Volume of liquid attr, AV Net volume change, fit Vp Pipe volume change due otemperanure My Pipe volume change duc to pressure ‘AVitmmat Liquid volume expansion due to temperature rise, f X_ —_ Amount of liquid in pipe, moles Greek letters 8 Liquid compressibility, aam—1 Y Poisson's ratio Pp Pipe material density, Ib/ft3 Eq. (7) can be rearranged and expressed in terms of the coefficients of liquid volume expansion to yield the following expressio apa (f) (seamed uh tc) gy Tatra Usually, (Vj — Vi) is much greater than AV, and AVp,. ‘Thus, Eq. (7) is generally sufficient for calculating the pressure rise due to thermal stresses. Determining stresses due to corrosion In an aqueous medium, the corrosion reaction of a metal may be represented by: Metal + H,0- H, + Metal oxide One mole of hydrogen is released for every mole ofbivalent metal that reacts. If Ly is the moles of hydrogen svolved/wk, then: Ci) ee is TN (6nd, (Geascre) (SSE). moterruk 10) ‘The number of moles of Hy evolved will vary if the valence of the metal is different. Such an effect must be stecounted for in calculations. Using Henry's law (ie., the solubility of a gas in a liquid—its mole fraction—is directly proportional to the pressure ofthe gas above the liquid), the pressure rise is: Ly aoe) © HY, Henry's law constant, is available in the literature. Eq, (11) is based on the following assumptions: (1) Hix nota function of pressure; (2) the hydrogen gas-phase is ideal; () the pipe is full of liquid and the liquid is incompressible; and (4) the pipe is rigid. Eq. (11) gives an approximate pressure rise for one ‘week with no flow in the pipe. Example A 4-in, Alloy 20, Sch. 10 pipeline is used to transport 70% H,SOy. The pipe's pressure rating is 500 psi and its 4D. is 426 in. The temperature is expected to rise occasionally to 130°F (548°C) from its normal value of 100F ($8.1°C). The pipeline could be out of service for up to one week. The distance between block valves is 9,900 f. Isa thermal-relief valve needed? Gonsider the worst case—130°F and 1 wk, From Table 1, for 70% H,SO,, use the volume for concentrated sulfuric acid, which is expressed as: V= Vig + Vol0.5788 x 10-3 (t= to) — 0.864 x 10-5 — 0%] (12) Eq, (12) is written in °C. The coefficient of linear thermal expansion for Alloy 20 (25Cr, 20Ni) is, from ‘Table 1, 0.556 in,/100 f, or 46.8 X 105 fe/100 ft Calculate the liquid volume expansion due to the temperature rise. In Eq, (12), subsdtuting the following: 1 — 9 = 16.7°C, and to = 38.1°C and rearranging, yields: Vim Ve ( Tas ) (og2s8x0-218.9 0.868 10 54a"—96.19) _ T+0.5758X10-* @B.1)—0.864% 10-* GBI)? 0.008975 Toseeey — 0.008107 (13) The initial volume of acid in the pipe is: Vig = (@/A)DL = (77/4)(A.26/12)%(9,000) = 979.9 (14) ‘And the change in volume is: AV, = 979.9 x 0.008107 = 7.94 (15) Galeulate the pressure rise due to the liquid volume ‘GHEICAT ENGINEERING MAY TSE ‘expansion. Rewriting Eq. (7) and substituting values from Eq. (13) into - (52) ()- - (= psaame) (4) @ ongoe2) ap a6) From Table II, for 70% H,50, is: 50 x 108 < A < 100 x 10, Thus, substituting into Eq. (16) yields: 80 atm < AP < 160 atm. Calculations for AVp, and AV, are omitted, since they are assumed to be much smaller than the above-calculated pressure rise. Now, the pressure rise due to corrosion is calculated, ‘The corrosion rate for Alloy 20 in H,SQ, at 54.8°C is about 5 mils/yr. Assume that this value is accurate enough. The density of Alloy 20 is 499 Ib/fi3, and M, is 50.8. M, is calculated by multiplying the moles x va- Tence/2for cach clement in an alloy and adding up the total of such terms. Substituting into Eq. (10): ) ( (4.26/12) 9,900 48) 1 b= (seco 308 0.87 moles of He generated/wk ‘The moles of H,80, in the pipe are: 979.9 £8 115.19 Ib/f® x (1/98) mole = 1,152 moles; where 115.19 Ib/B? is the density of sulfuric acid and 98 is its molecular weight. Henry's law constant for I in water at 20°C is 6.88 10 atm. Thus: = (6.88 X 109(0.87/(1,152 + 0.87) = 51.5 atm, ‘or about 760 psi in one week. A relif valve is needed, since the pressure calculated dduc to cither heat or corrosion (or certainly from both) ‘exceeds the design pressure of the piping. ‘Richard Greene, Eder an References 1. Roark RJ, "Formule or Sree and Stn Bont Ga New Yoo, p28, NAc “Handbook of Gheminay” 1th ed, 1901, MeGraw= HERBSOL G3 “Ney Yon fos Maker A. How to Sie Rei Valves, Chem Bg. june 2, 196, Vol Bhs. ie ‘ G edy"Handbook of Chemistry nd Physi,” $d ed, 1950 Cin aber Bohing Ca Cen pi 1 5 Woes Proc Pg Desig” Vl I Gul Pub Co, Hoan, rey 1084, McCrae ‘The author ee soi else eee fe reir press cgicar wa hr Eiotienom rah ES ‘Til din SM dena Beg eaaeie ae Ca an om Faitegh Best Univesity. He ea emis of ACE, n