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Continuous stirred-tank reactor

From Wikipedia, the free encyclopedia
Type of chemical reactor
Diagram showing the setup of a continuous stirred-tank reactor

Thecontinuous stirred-tank reactor (CSTR), also known asvat- orbackmix reactor,mixed flow reactor (MFR), or acontinuous-flow stirred-tank reactor (CFSTR), is a common model for achemical reactor inchemical engineering andenvironmental engineering. A CSTR often refers to a model used to estimate the key unit operation variables when using a continuous agitated-tank reactor to reach a specified output. The mathematical model works for all fluids: liquids, gases, andslurries.

The behavior of a CSTR is often approximated or modeled by that of an ideal CSTR, which assumesperfect mixing. In a perfectly mixed reactor, reagent is instantaneously and uniformly mixed throughout the reactor upon entry. Consequently, the output composition is identical to composition of the material inside the reactor, which is a function of residence time and reaction rate. The CSTR is the ideal limit of complete mixing in reactor design, which is the complete opposite of aplug flow reactor (PFR). In practice, no reactors behave ideally but instead fall somewhere in between the mixing limits of an ideal CSTR and PFR.

Ideal CSTR

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Cross-sectional diagram of a CSTR

Modeling

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A continuous fluid flow containing non-conservative chemical reactantA enters an ideal CSTR of volumeV.

Assumptions

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  • perfect or ideal mixing
  • steady state(dNAdt=0){\displaystyle {\Bigl (}{\frac {dN_{A}}{dt}}=0{\Bigr )}}, whereNA is the number of moles of speciesA
  • closed boundaries
  • constant fluiddensity (valid for most liquids; valid for gases only if there is no net change in the number of moles or drastic temperature change)
  • nth-order reaction (r =kCAn), wherek is the reaction rate constant,CA is the concentration of speciesA, andn is the order of the reaction
  • isothermal conditions, or constant temperature (k is constant)
  • single, irreversiblereaction (νA = −1)
  • All reactantA is converted to products via chemical reaction
  • NA =CAV

Governing equations

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Integral mass balance on number of molesNA of speciesA in a reactor of volumeV:

1.[Net accumulation of A]=[A in][A out]+[Net generation of A]{\displaystyle [{\text{Net accumulation of}}~A]=[A~{\text{in}}]-[A~{\text{out}}]+[{\text{Net generation of}}~A]}

2.dNAdt=FAoFA+VνArA{\displaystyle {\frac {dN_{A}}{dt}}=F_{Ao}-F_{A}+V\nu _{A}r_{A}}[1]

where

  • FAo is the molar flow rate inlet of speciesA
  • FA is the molar flow rate outlet of speciesA
  • vA is thestoichiometric coefficient
  • rA is the reaction rate

Applying the assumptions of steady state andνA = −1, Equation 2 simplifies to:

3.0=FAoFAVrA{\displaystyle 0=F_{Ao}-F_{A}-Vr_{A}}

The molar flow rates of speciesA can then be rewritten in terms of the concentration ofA and the fluid flow rate (Q):

4.0=QCAoQCAVrA{\displaystyle 0=QC_{Ao}-QC_{A}-Vr_{A}}[2]

Equation 4 can then be rearranged to isolaterA and simplified:

5.rA=QV(CAoCA){\displaystyle r_{A}={\frac {Q}{V}}(C_{Ao}-C_{A})}[2]

6.rA=1τ(CAoCA){\displaystyle r_{A}={\frac {1}{\tau }}(C_{Ao}-C_{A})}

where

Residence time is the total amount of time a discrete quantity of reagent spends inside the reactor. For an ideal reactor, the theoretical residence time,τ{\displaystyle \tau }, is always equal to the reactor volume divided by the fluid flow rate.[2] See the next section for a more in-depth discussion on the residence time distribution of a CSTR.

Depending on theorder of the reaction, the reaction rate,rA, is generally dependent on the concentration of speciesA in the reactor and the rate constant. A key assumption when modeling a CSTR is that any reactant in the fluid is perfectly (i.e. uniformly) mixed in the reactor, implying that the concentration within the reactor is the same in the outlet stream.[3] The rate constant can be determined using a known empirical reaction rate that is adjusted for temperature using theArrhenius temperature dependence.[2] Generally, as the temperature increases so does the rate at which the reaction occurs.

Equation 6 can be solved by integration after substituting the proper rate expression. The table below summarizes the outlet concentration of speciesA for an ideal CSTR. The values of the outlet concentration and residence time are major design criteria in the design of CSTRs for industrial applications.

Outlet Concentration for an Ideal CSTR
Reaction OrderCA
n=0CA=CAokτ{\displaystyle C_{A}={C_{Ao}}-{k\tau }}
n=1CA=CAo1+kτ{\displaystyle C_{A}={\frac {C_{Ao}}{1+k\tau }}}[1]
n=2CA=1+1+4kτCAo2kτ{\displaystyle C_{A}={\frac {-1+{\sqrt {1+4k\tau C_{Ao}}}}{2k\tau }}}
Other nNumerical solution required

Residence time distribution

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Exit age distribution E(t) and cumulative age distribution F(t) functions for an ideal CSTR

An ideal CSTR will exhibit well-defined flow behavior that can be characterized by the reactor'sresidence time distribution, or exit age distribution.[4] Not all fluid particles will spend the same amount of time within the reactor. The exit age distribution (E(t)) defines the probability that a given fluid particle will spend time t in the reactor. Similarly, the cumulative age distribution (F(t)) gives the probability that a given fluid particle has an exit age less than time t.[3] One of the key takeaways from the exit age distribution is that a very small number of fluid particles will never exit the CSTR.[5] Depending on the application of the reactor, this may either be an asset or a drawback.

Non-ideal CSTR

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While the ideal CSTR model is useful for predicting the fate of constituents during a chemical or biological process, CSTRs rarely exhibit ideal behavior in reality.[2] More commonly, the reactor hydraulics do not behave ideally or the system conditions do not obey the initial assumptions. Perfect mixing is a theoretical concept that is not achievable in practice.[6] For engineering purposes, however, if the residence time is 5–10 times the mixing time, the perfect mixing assumption generally holds true.

Exit age distribution E(t) and cumulative age distribution F(t) functions for a CSTR with dead space

Non-ideal hydraulic behavior is commonly classified by either dead space or short-circuiting. These phenomena occur when some fluid spends less time in the reactor than the theoretical residence time,τ{\displaystyle \tau }. The presence of corners or baffles in a reactor often results in some dead space where the fluid is poorly mixed.[6] Similarly, a jet of fluid in the reactor can cause short-circuiting, in which a portion of the flow exits the reactor much quicker than the bulk fluid. If dead space or short-circuiting occur in a CSTR, the relevant chemical or biological reactions may not finish before the fluid exits the reactor.[2] Any deviation from ideal flow will result in a residence time distribution different from the ideal distribution, as seen at right.

Modeling non-ideal flow

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Although ideal flow reactors are seldom found in practice, they are useful tools for modeling non-ideal flow reactors. Any flow regime can be achieved by modeling a reactor as a combination of ideal CSTRs andplug flow reactors (PFRs) either in series or in parallel.[6] For examples, an infinite series of ideal CSTRs is hydraulically equivalent to an ideal PFR.[2] Reactor models combining a number of CSTRs in series are often termed tanks-in-series (TIS) models.[7]

To model systems that do not obey the assumptions of constant temperature and a single reaction, additional dependent variables must be considered. If the system is considered to be in unsteady-state, a differential equation or a system of coupled differential equations must be solved. Deviations of the CSTR behavior can be considered by the dispersion model. CSTRs are known to be one of the systems which exhibit complex behavior such as steady-state multiplicity, limit cycles, and chaos.

Cascades of CSTRs

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A series of three CSTRs

Cascades of CSTRs, also known as a series of CSTRs, are used to decrease the volume of a system.[8]

Minimizing volume

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As the number of CSTRs in series increases, the total reactor volume decreases.

As seen in the graph with one CSTR, where the inverse rate is plotted as a function offractional conversion, the area in the box is equal toVFAo{\displaystyle {\frac {V}{F_{Ao}}}} where V is the total reactor volume andFAo{\displaystyle F_{Ao}} is the molar flow rate of the feed. When the same process is applied to a cascade of CSTRs as seen in the graph with three CSTRs, the volume of each reactor is calculated from each inlet and outlet fractional conversion, therefore resulting in a decrease in total reactor volume. Optimum size is achieved when the area above the rectangles from the CSTRs in series that was previously covered by a single CSTR is maximized. For afirst order reaction with two CSTRs, equal volumes should be used. As the number of ideal CSTRs (n) approaches infinity, the total reactor volume approaches that of an idealPFR for the same reaction and fractional conversion.

Ideal cascade of CSTRs

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From the design equation of a single CSTR whereτ=CAoCArA{\displaystyle \tau ={\frac {C_{Ao}-C_{A}}{-r_{A}}}}, we can determine that for a single CSTR in series thatτi=CA(i1)CAirAi{\displaystyle \tau _{i}={\frac {C_{A(i-1)}-C_{Ai}}{-r_{Ai}}}}, whereτ{\displaystyle \tau } is thespace time of the reactor,CAo{\displaystyle C_{Ao}} is the feed concentration of A,CA{\displaystyle C_{A}} is the outlet concentration of A, andrA{\displaystyle -r_{A}} is therate of reaction of A.

First order

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For anisothermal first order, constant density reaction in a cascade of identical CSTRs operating atsteady state

For one CSTR:CA1=CAo1+kτ{\displaystyle C_{A1}={\frac {C_{Ao}}{1+k\tau }}}, where k is therate constant andCA1{\displaystyle C_{A1}} is the outlet concentration of A from the first CSTR

Two CSTRs:CA1=CAo1+kτ{\displaystyle C_{A1}={\frac {C_{Ao}}{1+k\tau }}} andCA2=CA11+kτ{\displaystyle C_{A2}={\frac {C_{A1}}{1+k\tau }}}

Plugging in the first CSTR equation to the second:CA2=CAo(1+kτ)2{\displaystyle C_{A2}={\frac {C_{Ao}}{(1+k\tau )^{2}}}}

Therefore for m identical CSTRs in series:CAm=CAo(1+kτ)m{\displaystyle C_{Am}={\frac {C_{Ao}}{(1+k\tau )^{m}}}}

When the volumes of the individual CSTRs in series vary, the order of the CSTRs does not change the overall conversion for a first order reaction as long as the CSTRs are run at the same temperature.

Zeroth order

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At steady state, the general equation for an isothermalzeroth order reaction at in a cascade of CSTRs is given byCAm=CAoi=1mkiτi{\displaystyle C_{Am}=C_{Ao}-\sum _{i=1}^{m}k_{i}\tau _{i}}

When the cascade of CSTRs is isothermal with identical reactors, the concentration is given byCAm=CAomkiτi{\displaystyle C_{Am}=C_{Ao}-mk_{i}\tau _{i}}

Second order

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For an isothermalsecond order reaction at steady state in a cascade of CSTRs, the general design equation isCAi=1+1+4kiτiCA(i1)2kiτi{\displaystyle C_{Ai}={\frac {-1+{\sqrt {1+4k_{i}\tau _{i}C_{A(i-1)}}}}{2k_{i}\tau _{i}}}}

Non-ideal cascade of CSTRs

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With non-ideal reactors,residence time distributions can be calculated. At the concentration at the jth reactor in series is given by

CjCo=1entt¯[1+ntt¯+12!(ntt¯)2+...+1(j1)!(ntt¯)j1]{\displaystyle {\frac {C_{j}}{C_{o}}}=1-e^{-{\frac {nt}{\bar {t}}}}[1+{\frac {nt}{\bar {t}}}+{\frac {1}{2!}}({\frac {nt}{\bar {t}}})^{2}+...+{\frac {1}{(j-1)!}}({\frac {nt}{\bar {t}}})^{j-1}]}

where n is the total number of CSTRs in series, andt¯{\displaystyle {\bar {t}}} is the average residence time of the cascade given byt¯=VQ{\displaystyle {\bar {t}}={\frac {V}{Q}}} where Q is thevolumetric flow rate.

From this, the cumulative residence time distribution (F(t)) can be calculated as

F(t)=CnCo=1entt¯[1+ntt¯+12!(ntt¯)2+...+1(n1)!(ntt¯)n1]{\displaystyle F(t)={\frac {C_{n}}{C_{o}}}=1-e^{-{\frac {nt}{\bar {t}}}}[1+{\frac {nt}{\bar {t}}}+{\frac {1}{2!}}({\frac {nt}{\bar {t}}})^{2}+...+{\frac {1}{(n-1)!}}({\frac {nt}{\bar {t}}})^{n-1}]}

As n → ∞, F(t) approaches the ideal PFR response. Thevariance associated with F(t) for apulse stimulus into a cascade of CSTRs isσt2=t¯2n{\displaystyle \sigma _{t}^{2}={\frac {{\bar {t}}^{2}}{n}}}.

Cost

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Cost initially decreases with the number of CSTRs as volume decreases but as operational costs increase, the total cost eventually begins to increase.

When determining the cost of a series of CSTRs,capital andoperating costs must be taken into account. As seen above, an increase in the number of CSTRs in series will decrease the total reactor volume. Since cost scales with volume, capital costs are lowered by increasing the number of CSTRs. The largest decrease in cost, and therefore volume, occurs between a single CSTR and having two CSTRs in series. When considering operating cost, operating cost scales with the number ofpumps and controls, construction, installation, and maintenance that accompany larger cascades. Therefore as the number of CSTRs increases, the operating cost increases. Therefore, there is a minimum cost associated with a cascade of CSTRs.

Zeroth order reactions

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From a rearrangement of the equation given for identical isothermal CSTRs running azeroth order reaction:τ=CAoCAmmk{\displaystyle \tau ={\frac {C_{Ao}-C_{Am}}{mk}}}, the volume of each individual CSTR will scale by1m{\displaystyle {\frac {1}{m}}}. Therefore the total reactor volume is independent of the number of CSTRs for a zeroth order reaction. Therefore, cost is not a function of the number of reactors for a zeroth order reaction and does not decrease as the number of CSTRs increases.

Selectivity of parallel reactions

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When consideringparallel reactions, utilizing a cascade of CSTRs can achieve greaterselectivity for a desired product.

For a given parallel reactionAB{\displaystyle {\ce {A -> B}}} andAC{\displaystyle {\ce {A -> C}}} with constantsk1{\displaystyle k_{1}} andk2{\displaystyle k_{2}} and rate equationsd[B]dt=k1[A]n1{\displaystyle {\frac {d[{\ce {B}}]}{dt}}=k_{1}[{\ce {A}}]^{n_{1}}} andd[C]dt=k2[A]n2{\displaystyle {\frac {d[{\ce {C}}]}{dt}}=k_{2}[{\ce {A}}]^{n_{2}}}, respectively, we can obtain a relationship between the two by dividingd[B]dt{\displaystyle {\frac {d[{\ce {B}}]}{dt}}} byd[C]dt{\displaystyle {\frac {d[{\ce {C}}]}{dt}}}. Therefored[B]d[C]=k1k2[A]n1n2{\displaystyle {\frac {d[{\ce {B}}]}{d[{\ce {C}}]}}={\frac {k_{1}}{k_{2}}}[{\ce {A}}]^{n_{1}-n_{2}}}. In the case wheren1>n2{\displaystyle n_{1}>n_{2}} and B is the desired product, the cascade of CSTRs is favored with a fresh secondary feed ofA{\displaystyle {\ce {A}}} in order to maximize the concentration ofA{\displaystyle {\ce {A}}}.

For a parallel reaction with two or more reactants such asA+DB{\displaystyle {\ce {A + D -> B}}} andA+DC{\displaystyle {\ce {A + D -> C}}} with constantsk1{\displaystyle k_{1}} andk2{\displaystyle k_{2}} and rate equationsd[B]dt=k1[A]n1[D]m1{\displaystyle {\frac {d[{\ce {B}}]}{dt}}=k_{1}[{\ce {A}}]^{n_{1}}[{\ce {D}}]^{m_{1}}} andd[C]dt=k2[A]n2[D]m12{\displaystyle {\frac {d[{\ce {C}}]}{dt}}=k_{2}[{\ce {A}}]^{n_{2}}[{\ce {D}}]^{m_{1}2}}, respectively, we can obtain a relationship between the two by dividingd[B]dt{\displaystyle {\frac {d[{\ce {B}}]}{dt}}} byd[C]dt{\displaystyle {\frac {d[{\ce {C}}]}{dt}}}. Therefored[B]d[C]=k1k2[A]n1n2[D]m1m2{\displaystyle {\frac {d[{\ce {B}}]}{d[{\ce {C}}]}}={\frac {k_{1}}{k_{2}}}[{\ce {A}}]^{n_{1}-n_{2}}[{\ce {D}}]^{m_{1}-m_{2}}}. In the case wheren1>n2{\displaystyle n_{1}>n_{2}} andm1>m2{\displaystyle m_{1}>m_{2}} and B is the desired product, a cascade of CSTRs with an inlet stream of high[A]{\displaystyle {\ce {[A]}}} and[D]{\displaystyle {\ce {[D]}}} is favored. In the case wheren1>n2{\displaystyle n_{1}>n_{2}} andm1<m2{\displaystyle m_{1}<m_{2}} and B is the desired product, a cascade of CSTRs with a high concentration ofA{\displaystyle {\ce {A}}} in the feed and small secondary streams ofD{\displaystyle {\ce {D}}} is favored.[9]

Series reactions such asABC{\displaystyle {\ce {A -> B -> C}}} also have selectivity betweenB{\displaystyle {\ce {B}}} andC{\displaystyle {\ce {C}}} but CSTRs in general are typically not chosen when the desired product isB{\displaystyle {\ce {B}}} as the back mixing from the CSTR favorsC{\displaystyle {\ce {C}}}. Typically abatch reactor orPFR is chosen for these reactions.

Applications

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CSTRs facilitate rapid dilution of reagents through mixing. Therefore, for non-zero-order reactions, the low concentration of reagent in the reactor means a CSTR will be less efficient at removing the reagent compared to a PFR with the same residence time.[3] Therefore, CSTRs are typically larger than PFRs, which may be a challenge in applications where space is limited. However, one of the added benefits of dilution in CSTRs is the ability to neutralize shocks to the system. As opposed to PFRs, the performance of CSTRs is less susceptible to changes in the influent composition, which makes it ideal for a variety of industrial applications:

Anaerobic digesters atNewtown Creek Wastewater Treatment Plant in Greenpoint, Brooklyn

Environmental engineering

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Chemical engineering

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  • Loop reactor for production of pharmaceuticals[12]

See also

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Notes

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References

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  1. ^abSchmidt, Lanny D. (1998).The Engineering of Chemical Reactions. New York: Oxford University Press.ISBN 0-19-510588-5.
  2. ^abcdefghiMetcalf & Eddy (2013-09-03).Wastewater engineering : treatment and resource recovery. Tchobanoglous, George,, Stensel, H. David,, Tsuchihashi, Ryujiro,, Burton, Franklin L. (Franklin Louis), 1927-, Abu-Orf, Mohammad,, Bowden, Gregory (Fifth ed.). New York, NY.ISBN 978-0-07-340118-8.OCLC 858915999.{{cite book}}: CS1 maint: location missing publisher (link)
  3. ^abcBenjamin, Mark M. (2013-06-13).Water quality engineering : physical/chemical treatment processes. Lawler, Desmond F. Hoboken, New Jersey.ISBN 978-1-118-63227-7.OCLC 856567226.{{cite book}}: CS1 maint: location missing publisher (link)
  4. ^Bolin, Bert; Rodhe, Henning (January 1973)."A note on the concepts of age distribution and transit time in natural reservoirs".Tellus.25 (1):58–62.Bibcode:1973Tell...25...58B.doi:10.3402/tellusa.v25i1.9644.ISSN 0040-2826.
  5. ^Monsen, Nancy E.; Cloern, James E.; Lucas, Lisa V.; Monismith, Stephen G. (September 2002)."A comment on the use of flushing time, residence time, and age as transport time scales".Limnology and Oceanography.47 (5):1545–1553.Bibcode:2002LimOc..47.1545M.doi:10.4319/lo.2002.47.5.1545.S2CID 11505988.
  6. ^abcDavis, Mark E. (2003).Fundamentals of chemical reaction engineering. Davis, Robert J. (International ed.). Boston: McGraw-Hill.ISBN 978-1-62870-437-2.OCLC 880604539.
  7. ^Stokes, R. L.; Nauman, E. Bruce (1970). "Residence Time Distribution Functions for Stirred Tanks in Series".Canadian Journal of Chemical Engineering.48 (6):723–725.Bibcode:1970CJChE..48..723S.doi:10.1002/cjce.5450480612.
  8. ^Hill, Charles G.; Root, Thatcher W. (2014).Introduction to Chemical Engineering Kinetics and Reactor Design, Second Edition. Hoboken, new Jersey: Wiley. pp. 241–253,349–358.ISBN 9781118368251.
  9. ^Levenspiel, Octave (1998).Chemical Reaction Engineering, 3rd Edition. Wiley.ISBN 978-0-471-25424-9.
  10. ^Hurtado, F.J.; Kaiser, A.S.; Zamora, B. (March 2015). "Fluid dynamic analysis of a continuous stirred tank reactor for technical optimization of wastewater digestion".Water Research.71:282–293.Bibcode:2015WatRe..71..282H.doi:10.1016/j.watres.2014.11.053.ISSN 0043-1354.PMID 25635665.
  11. ^Kadlec, Robert H.; Wallace, Scott D. (2009).Treatment Wetlands (second ed.). Boca Raton, FL, USA: CRC Press. p. 181.ISBN 978-1-56670-526-4.
  12. ^ab"Visual Encyclopedia of Chemical Engineering".encyclopedia.che.engin.umich.edu. Archived fromthe original on 2013-12-14. Retrieved2020-04-30.
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