Chapter 8 Gas Absorption 1 Definition of Absorption: •Absorption is a (column-type) process that separates components of a gas mixture by their solubility differences in the added solvent. •In absorption, solute(s) is transferred from the gas phase to the liquid phase. •Desorption/stripping: the reverse of gas absorption: recover valuable solute from the absorbing solution and regenerate the solvents.In stripping, the transfer is from the liquid to the gas phase. 2 Illustrative figure of packed column Gas Gas Gas Liquid Liquid Gas Liquid Mist catcher Mist catcher Liquid Mist catcher Clamp plate Clamp plate Mist catcher Packing restrainer Clamp plateColumnar Columnar shell shell she Columnar Columnar shell Columnar shell Gas Packings Packings Packings Packings Packings Liquid Support Support plate Suppo Packing Packing Support plate plate Support Mist catcher Liquidredistribu redistribu torto Liquid Liquid redistri Liquid redistribu tor Liquid redistribu tor Columnar Columnar shell she Packing restrainer 4VS Packings Z Packings Packing u Packing Support Suppo Gas u (0.5Liquid ~ 04.V 85 )u F redistribu Liquid redistri to S DT Liquid u 1)U U min ;2) DT 8(避免壁流现 d 填料 Mist catcher Gas u (0.5 ~ 0.85)u F 3 Clamp plate Liquid [1.PACKINGS AND PACKED TOWER DESIGN] [Refer to Chapter 4 4.2 Packed Columns in Chinese textbook] Reading materials: pp. 546~557 4 2.PRINCIPLES OF ABSORPTION Column diameter: 4VS DT u u (0.5 ~ 0.85)u F VS-gas volume flow rate, m3/s, uF-velocity DT of liquid 1)U U min ;2) 4VSS flooding D d 填料 8(避免壁 u适宜 适宜(1) D should be rounded up; •Attention: T TT u(2)Checking: 85))uuFF 适宜 适宜 (0.5 ~ 0.85 DTT 1)U U min ; 2 ) min (Avoiding liquid 8(8避免壁流现象 ) flow dd packing 填料 along wall) 5 Tower height ZT (1)Calculation from HETP: ZT=HETP*NT. (2)Calculation from the number of transfer units: ZT=HOy*NOy; etc. •The height of the tower, and hence the total volume of packing, depends on the magnitude of the desired concentration changes and on the rate of mass transfer per unit of packed volume. •Calculations of the tower height, therefore, rest on material balances, enthalpy balances, and estimates of driving force and mass-transfer coefficients, and equilibrium relationship. 6 Va y a V (1)Material balances Vaa y a La V a •The types of equipment and designyyconcepts xa Laaused a in distillation are similar to those used for V L V y a a a L a L x a absorption and stripping. Here we choose packed a Va Vya Ly a x column(differential-contact plant Vxaaa )a asL the aV V y y example. a La xaLa L yLa a Vax Lower conc. end L LV y a a xa a Lx a V LVa a x y 稀端 L y x x a a a VaL x L xxa Vb y •Fig. 8.1-2 Material-balance x L L L a a V y V x Ly diagram for packed column. VLb yb V Vxxa yx V VVbb Lb y b Higher conc. end x xL V y yyb y Vb x x 浓端 L b b b 7 x V Ly y V 连续微分接触设备 Va y a Material balances for the portion V Vofaa the y a La column above an arbitrary section yy ax-y Va x, a a) a Total material: La V L Va (18L .2V L Laa Va xyaa aL (18.3) Component A: La xa Vy Lx VaVya V Vxxaaaa yaa LLyaVa V=molar flow rate of the gas V y y a La xaLa L yLa a Vax phase at x-y section y V L L a a xa Lax a V LVa a x y L= molar flow rate of the liquid L y x x a phase at x-y section a a VaL x L xxa yx Vb L LVLa xV a y Ly VLb yb V Vxxa yx V VVbb Lb y b V L x x xyybb y LVyb xb 8 b x V Ly y V (部分) (任意的) ( x-y 横截面) Va y a Overall material-balance equations, V Vaa y a La yy a (18.4)Va x Total material: La Vb Lb Va La a a V y ( 18 . 5 ) Component A: La xa Vb yb Lb xb VL V y a a a a a La xaa L Va Vya Ly a Operating-line equation x Vxaaa a L aV V y y Va ya La xa L a La xaLa L y x (18.6) yLa a Vax y V V V L L a a xa Lax a V LVa a x y L y x x a a a VaL x L xxa yx Vb L LVLa xV a y Ly VLb yb V Vxxa yx V VVbb Lb y b V L x x xyybb y LVyb xb 9 b x V Ly y V Operating-line equation: axa xxb b cu r ium y bb yya a yba aa ay a xxa a ay xyaa ibr tin bb a b uil ine gl yb bb byb bb bb yy b yb b yb b b yb b b y a ay b yb ya x ya a a x a b a x xaxb b byb byb by Eq •x and y represent the bulk compositions of the liquid and gas, respectively, in contact with each other at any given section through the column. yyb b era The operating-line must lies above the equilibrium line in order for absorption to take place, i.e., y y 0 (18.6) Op Va ya La xa L y x V V yb ve yb axb xxa b x10b 中溶质浓度较低时,气液流量的变化可以 忽略). axa xxb b ve cu r ium ay xyaa ibr y bb yya a yba aa ay a xxa a a b uil tin bb b yb b yb b b yb b b y a ay b yb ya x ya a a x a b a x xaxb b byb byb by Eq gl yb bb byb bb bb yy ine yyb b era •For dilute mixtures, containing less than 10% of soluble gas, the effect of changes in total flow is usually ignored and the design is based on the average flow rates(当混合气体 yb Op •Because of absorption, V decreases from bottom to top, and L increases from top to bottom. These changes make the operating line slightly curved. yb axb xxa b x11b Absorption Driving forces at an arbitrary section x-y: A Ay Driving y force y yx x x x A A yy yy xx xx A Equilibrium y curve y Driving force x x Absorption Driving forces: ( y y ) ( x x) 12 (2)Limiting (min) gas-liquid ratio •1)Influence of liquid flow rate L yb Assume that V, xa, ya, yb are held constant and yb L decreases. ibr uil Eq Op era tin ium gl cu ine rv e b b y y y b b b b L ( L / V ) Driving force Operating Cost yb y b b b b b y But, the column height yb( L / V )minb b byb bb b y y b b a •When L=Lmin(point b’), b b absorption driving force=0, b yyb b ayb b y a the column height=. ay b byb yya a xyaa yb ya yba aa x axb ya a a ay a xxa a x x 13 xa a b b •2)Minimum liquid-gas ratio (L/V)min (L/V)min corresponding to L=Lmin(point b’) with absorption driving force=0 and the column height=. •In any actual tower the liquid rate L must be greater than Lmin to achieve the specified change in gas composition. •3)Optimum liquid-gas ratio (L/V)opt L ( L / V ) Driving force Operating/ e e Operating/ energy Cost But, the column height •By balancing the operating costs against the fixed costs of the equipment, ( L / V )opt (1.1 ~ 1.5)(L / V )min 14 yb bb by yya a yba aa ay a xxa a axa xxb b xba xx bb e ine cu rv ium b tin gl yb ya L V min xb xa yb bb byb bb bb yy Op era •For normal curve, yyb b Eq u il ibr •Calculations of (L/V)min b b byb yb b b yb( L / V )minyb b b y y b b a b ayb b y a ay b xyaa yb ya x axb ya a a x x xba a b a x xb xaxb xb 15 x xb b •For abnormal curve, (L/V)min can be computed yb from the slope(倾斜) of the operating line ab’ that is yb tangent to the equilibrium curve. b Op era tin gl ine yybbL byb ya by b yb bbV min bxb xa b yb yb (L / V ) min b bb y b bya b yb b yyb ve y r a b b u a y c b b m u i r b i l yb yyaa i a u q xyaa y E b b y a aa xya axb yb a a xxaa xab xba ya 16 (3)Rate of absorption •Volumetric mass transfer coefficients (Kya, etc.) are used for most calculations, because it is more difficult to determine the coefficients per unit area and because the purpose of the design calculation is generally to determine the total absorber volume. •Kya=overall volumetric mass-transfer coefficient, kmol/(m3·h·unit mole fraction). •a=effective area of interface per unit packed volume, m2/m3 17 •Simplicity Treatment •The following treatment applies to lean gases低浓度气 体(up to 10% solute): •(a) Correction factors修正因子 for one-way diffusion are omitted for simplicity. •(b) Changes in gas and liquid flow rates (V and L) are neglected. •(c) kxa, kya, Kya, Kxa can be considered as constants. 18 •In chapters 6,7, the rate of mass transfer: 2·h·unit mole fraction)] r=N [kgmol/(m r ()A rN( A ) k y ( y A y Ai ) k x ( x Ai x A ) N K ( y y r ( A) y A A) A N A K x ( x xA ) 19 •Let r =rate of absorption per unit volume, kgmol/(m3·h) r k y a( y yi ) (18.7) r k x a( xi x) (18.8) r K y a( y y ) r K x a ( x x) (18.9) (18.10) •It is hard to measure or to predict a, but in most cases it is not necessary to know its actual value since design calculations can be based on the volumetric coefficients. α很难直接测定,一般不需要知道α具体值 20 •Determining the interface composition (yi, xi) •(yi, xi) is also hard to measure, but it can be obtained from the operating-line diagram using Eqs.(8.1-21) and (8.1-22): ( y yi ) kxa ( x xi ) kya (18.11) •Thus a line drawn from the operating line with a slope –kxa/kya will intersect the equilibrium line at (yi, xi). 21 ( y yi ) kxa ( x xi ) kya kxa ( 18 . 11 ) Slope kya y x curve k x a Equilibrium SlopeOperating kx a line kxa y a i Slope kkyxaSlope Slope ky a kya x k a i y y y y y xy kxa x x yxi Slope k a x y yi y kxa i xyi i Slope y xi xi kya x yi x y y y y Driving force : ( y yi ) ( xi x) (y y ) ( x x) 22 k y ( y A y Ai ) Ky k x ( x Ai x A ) •Determining the overall coefficients: Using the local slope y Aiofthe m xequilibrium xA , m, we have Ai , y A m curve A y y y y 11 A Ai Ai 1 m K k ( y y ) k ((x17.57x) ) y yk A k Ai x Ai A K y y x y Ai m xAi , y Therefore, (17.56) A m xA , y A y Ai y Ai y A 1 1 1 m K y k y( y A y Ai ) k x ( x Ai (18 x A.)12) K ya k ya kxa y Ai m xAi , y A m xA , Similarly, 1 1 1 K x a k x a m ky a (17.56) (18.13) 23 y Ai m xAi , y A m xA , 1 1 m K ya k ya kxa (18.12) 1 =overall resistance to mass transfer K yy a 1 k yy a = resistance to mass transfer in the gas film m =resistance to mass transfer in the liquid film k xx a 24 y y A Ai x Ai A “controls” Ai A y Aifilm m x , y mand xA , Liquid film “controls” •Gas 1 1 m (18.12) K ya k ya kxa 1 m 1 1 , Gas film " controls" When k y a kxa K y a k y a •Or, When the coefficients kya and kxa are of the same order of magnitude, and m is very much greater than 1.0, the liquid film resistance is said to be controlling. That is, 1 m 1 m , Liquid film " controls" kya kxa K y a kxa 25 •Liquid film controlling means that any change in kxa has a nearly proportional effect on both Kxa and Kya and on the rate of absorption, whereas a change in kya has little effect. •Examples of Liquid film controls: Absorption of CO2, H2,O2,Cl2 in water; •When the solubility of the gas is very high, m is very small and the gas-film resistance controls the rate of absorption. •Examples of gas-film controls: Absorption of HCl, NH3 in water; NH3 in acid solution; SO2, H2S in basic solvent. 26 •With gases of intermediate solubility both resistances are important, but the term controlling resistance is sometimes used for the larger resistance. •The absorption of NH3 in water is often cited as an example of gas-film control, since the gas film has about 80 to 90 percent of the total resistance. 27 •(4)Calculation of tower height •The following treatment applies to lean gases (up to 10% solute: (a) Correction factors for one-way diffusion are omitted for simplicity. (b) Changes in gas and liquid flow rates (V and L) are neglected. (c) kxa, kya, Kya, Kxa can be considered as constants. 28 VL, ,yxLa , xa V , ya a L , x , ,yxa a Z V , y a VL S=cross sectional area; V , yLa, xaaZ V , y a ZV , y dZ Z SdZ=differential volume in L, xa a V , y Z L , x dZ a adZ height dZ. Z ydZdZ VL ,,xy a Z Z y a, y V a dZ ydZ x y •The amount absorbed in VZ, y a y dZ x section dZ is Vdy. Z x y y Z ZxT xy dZ dZ Z T Vdy rSdZ ZT x dZ x V , yZb T y Z T x V , yb y Vdy K y a( y y ) SdZ y dy yZ T ZT x V , yb dx x y Z Z V , y x b T L , xb L , x x V dy V , yb V , by L , x b 0 dZ ZT K y aS y ( y y ) ZZLTT,ZxT L , xVb , ybb b L , x V , y b V ,V ybb, y L , xb b •Fig. Diagram of packed L,,xxbb L L , xb absorption tower 29 a T b a •(5)Number of transfer units传质单元数 •The equation for column height can be written as follows: V /S ZT K ya yb yb dy y ( y y ) a dy N oy (y y ) ya H oy V /S K ya (18 .16 ) =overall number of transfer units [NTU], based on gas phase.传质单 元数 [] =overall height of a transfer unit [HTU], based on gas phase,传质单元高 30 度 [m]. ZT Hoy Noy (18.17) (1)If the operating line and yb yb yb dydydy equilibrium line are straight and yb N NN oy oy oy parallel, ( y (y( y)y y) ) yb yb y3 yyb3 Operating line yyyb32 yb yyy3 y3y y2 2a 1 yyx2aa y 2y1 y y xyxaa1 ay1 1 xx xa y a y1 xa Equilibrium line x1 x2 x3 xb y3 ya ya ya yb ybyybayaya y2 (1. NN N (18(18 .18 oy oy oy y y y y y yb y1 y y y y y y b a b a b a xa N oyNN oy oy ya yayyaayaya x1 yb ybyybayaya x2 N oyNN oy oy yb ybyybbybyb x3 xb 31 yb dy N oyoperating •If the line and equilibrium line are (y y ) y a parallel, straight and yb y a N oy NTP (18.18) y y y yb dy dy y y Nplates a NTP=Number oy [结合第7章比较] NNoyoy b of theoretical ( y y ) y ( y y ) y Similarly, a a yy a b a xb xa NN ox ybNoyya NTP N ox x x NTP yb oy y y dy b by yb y a line (not straight and equilibrium yb operating N oy•(2) For a N oy N oy ( y y ) y y parallel), a a y a ya ya ybyy ( y ) ( y y ) a b b a a yb yay y N oy N oy N b (18a.19) y L y y b b oy y y b y L yb yb ln b y y a a yb y a 32 N oy •Derivation of Eq.(18.19) : •Assume y m xy b m x b yy y yy(mxyb()m x b) y y V ( y yVb )( y L(yxb )xbL)( x xb ) V V ym y y y ( ym yb )( y xbyb) b xb b L L y ~ straight y is straight line relationsh ip y ~ y is line relationsh ip yayb ya d (y ) d (yyb) dyyb ya yb ya dy dy1 ( y 1 ya()ydb (y )a )d (y ) dy N oy N oy 33 y y y yy yb yayb ya yb yb yb yb b y ~ y is straight line relationship d (y ) yb ya dy yb y a N oy yb yb ya dy 1 ( yb ya )d (y ) y y y yb ya ya yb dy ( y y ) y N oy N oy b a ln b ( y y ) yb ya ya ya yb y a N oy y L yb y a N oy ya ya N yb y a (18.19) b a (18.19) y ( yb y ) ( ya y ) L yb yb ln ya ya 34 yb dy •(3) When the line is straight but steeper N oyoperating yb than the equilibrium (y y ) y a line, as in Fig.18.13b, xb y a N oy NTP NTP=Number of theoretical plates b yb ya N oy ya ya ya •Why? y yb ya yb yb ya yya y a N oy b yb ya y L y y yb b Operating line b y yb y a x b b N oy NTU 1 NTP y L ya xybb y y yxba a b a aa Equilibrium line yb yb yb yy yyb b yb ya y35a xa xb •Similarly, for straight operating and equilibrium yb line (not parallel), dy N oy ( y y ) H Nox yZ T ox a xb xa N ox (18.20) x L y b y a ( xb xb) ( xa xa ) N oy x L y yby a ax dy xb b N oyx ln xa(xy yx ) b N oy ya a a yb yb L/S H ox [ m] K xa 36 •The overall height of a transfer unit [Hoy OR Hox] can be defined yb as the height of a packed section dy required to accomplish a change in concentration N oy ( y y )driving force in that section. equal to theyaaverage yb ya ( y y ) m Z T H oy yb y a N oy ya ya •Common equations for calculations of height of yb y a packedNsection: oy yb yb height of packed section=height of a transfer unit number of transfer units •There are four kinds of transfer units: 37 •Four kinds of transfer units: ZT H y N y H x N x H oy N oy H ox N ox Gas film: H y V /S kya L/S Liquid film: H x kxa V /S Overall gas: H oy K ya Overall liquid: H ox L/S K ya yb dy y yi (18.21) dx Nx x x xa i (18.22) Ny ya xb yb dy y y (18.23) dx N ox x x xa (18.24) N oy ya xb 38 (6)Alternate forms of transfer coefficients The gas-film coefficients reported in the literature are often based on a partial –pressure driving force instead of a mole-fraction differencedy and are written as kga or Kga. J A N A Dv M A •Similarly liquid-film coefficients may be given as kLa or db BT the driving force yA KLa, where dyA is a volumetric concentration JNAA db N LA=k Dv vMM dy difference. [k defined byAEq.(17.36)] cD 0 BT db y Ai yA k yaD K ya N db dy v M A kA ga ,K ga 0 y Ai P P k x aDv K xa N kA La JA , K(LcaAi c A ) M BT M (17.20) 39 Gy V Gx L , LM M S M S M M x Let GM GM GM Hy and H oy k g aP K g aP (18.25) Gx / x Gx / x Hx and H ox (18.26) kLa KLa G y V Gx L Where, GM =molal mass , velocity, kgmol/m2 h M S M S =mass velocity of gas stream based on G G V L y x M M x GM , cross section, kg/m2 h total tower M S GM S Gstream G y V Gx =mass L based on M velocity of liquid M H and H ( 18 . 25 ) M,M y x oy M 2 aP cross section, K g aP kg/m h M S M total Sk gtower GM GM 40 M M H and H ( 18 . 25 ) Gx / x Gx / x x y oy •The terms HG, HL, NG AND NL often appear in the literature instead of Hy, Hx, Ny AND Nx, as well as the corresponding terms for overall values, but here the y A y Ai do not ysignify 1 different subscripts difference in Ai yany A ( 17 . 56 ) either K units k ( yor magnitude. y ) k (x x ) y y A Ai x Ai A •Relationships among different kinds of height of a my AxAi, y AiA m xA ,y Ai y A 1y Ai unit: transfer K y 1 k y ( y1A y Aim) k x ( x Ai x A ) (18.12) k a K a k a y y m xy , y x m x , Ai Ai A (17.56) A GM GM m GM LM (18.27) K y a k y a k x a LM 41 Ai Ai db A A GM GM y m GM LM ( 18 . 27 ) N A db Dv M dy A K a k a k x a LM y y y 0 BT A G yG y V VGxG Ai L L GMGM k a , , x K a y S M y M S M S M S kg a , Kga P MMM M P x x Dv G GMGM (17.20) G M M N J ( c c ) 1 H and H . 25 ) y y A yH A Ai A y Ai y A(18 and H ( 18 . 25 ) oy A Ai y oy B k g aP K gKaP (17.56) T k g aP g aP K y G k/y( y A y Ai ) kGx (/xAi x A ) H xHx xLM x and andHHoxoxGx x/ x x (18 .26 (18 .26 )) aa y kkLxmx , y mx KK ,L aL a Ai Ai A A mGM H oy H y H x (18.27) LM 42 A 1y Ai myfrom Similarly, xAi, y m xA ,y Ai y A K y 1 k y ( y1A y Ai 1) k x ( x Ai x A ) (18.13) m k a K a k a 1 y Aix m y xA ,y Ai y A y AxxAi, yyAiA m K y LkMy ( y ALM y Ai ) LMk x (GxMAi x A ) mk a G K a k a x x y mx , y mxy , M Ai A Ai Ai A (17.56) (17.56) A LM H ox H x H y (18.29) mGM EXAMPLE 18.3. 43