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Design and Control of An Improved Acrylic Acid Process
Design and Control of An Improved Acrylic Acid Process
Xiaomeng Suo, Hao Zhang, Qing Ye ∗ , Xin Dai, Hao Yu, Rui Li
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Institute of Petrochemical Engineering,
Changzhou University, Changzhou, Jiangsu 213164, China
a r t i c l e i n f o a b s t r a c t
Article history: The acrylic acid (AA) process involves the partial oxidation of a flammable and explosive gas
Received 17 May 2015 medium (propylene), so considerable attention is paid to the concentration of the reactants.
Received in revised form 16 August Water and air is added to dilute the reactant and enhance the thermal stability of the reac-
2015 tion. Different compositions of water and air can lead to different methods to separate AA
Accepted 24 August 2015 product. A modified AA process is developed based on the AA process proposed by Turton,
Available online 1 September 2015 and consists of a tubular reactor, an absorber and only two distillation columns, one of which
is an azeotropic distillation column. This process is characterized by shortening and simpli-
Keywords: fying AA refining process so that equipment investment cost can be reduced. A plantwide
Acrylic acid control structure featured with cascade control provides effective control for the multiunit
Improved process process and insures safe operation of the two distillation columns. Dynamic results also
Dynamic control reveal that it is useful to apply temperature/temperature cascade control and composi-
tion/temperature cascade control to the distillation columns with maximum temperature
limitations.
© 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
1. Introduction There are two safety concerns about the AA process based
on the reactions above. Firstly, the reactions involve par-
Acrylic acid (AA) is widely used as an intermediate of chem- tial oxidation of a flammable and explosive gas medium
icals and polymer in textile industry (Xu et al., 2006). There (propylene), so considerable attention must be paid to the
are several alternative processes to produce it, but the most compositions of propylene and oxygen in the feed stream to
common way nowadays is the partial oxidation of propylene the reactor.
(Lin, 2001). The mechanism of producing AA is that propylene The second safety concern is associated with the highly
is oxidized to acrolein first and then the acrolein is oxidized exothermic polymerization of AA (Cutie et al., 1997). AA of
to AA. However, several side reactions occur, resulting in the high concentration is dimerized at temperatures higher than
oxidation of reactants and products. The main reaction and 110 ◦ C, therefore the separation sequence must be operated
the typical side reactions are as follows: under vacuum to keep the bottom temperature in the distilla-
Main reaction: tion columns below this temperature.
[o] [o]
In Turton’s design (2008) (Fig. 1), a fluidized-bed reactor is
C3 H6 −→CH2 CHCHO−→CH2 CHCOOH used, which is operated at isothermal condition and ensures
safety and stability of the reaction with the addition of large
Side reactions:
amounts of water and air. The water inlet concentration of
[o]
C3 H6 −→CO2 + H2 O the reactor is quite large. As a result, liquid–liquid extraction
is a proper way to separate water from the product stream.
[o]
CH2 CHCHO−→CH3 COOH + CO2 AA and acetic acid (ACE) are extracted into the organic phase.
∗
Corresponding author. Tel.: +86 519 86330355; fax: +86 519 86330355.
E-mail address: huagonglou508@126.com (Q. Ye).
http://dx.doi.org/10.1016/j.cherd.2015.08.022
0263-8762/© 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 346–356 347
9 Values
C3 H6 + O2 → 3CO2 + 3H2 O (3)
a
are calculated as follows:
n n
2 ji Gji xj n x Gij xk kj Gkj
ln i = j=1
n + j=1
nj ij − k=1
n
G x G x G x
k=1 ki k j=1 kj k k=1 kj k
E Where
Aij −Aji
i
−ri = ko,i exp − p(C3 H6 )p(O2 ) ij = RT , Gij = exp(−˛ij ij ), Aij (J/mol).
RT
chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 346–356 349
Fig. 3 – The ternary diagram for (a) AA–water–toluene and (b) ACE–water–toluene at 0.265 bar.
by the residue curve maps and the LLE of this system. a pressure of 0.1 bar generated by Aspen plus. Because of a
The azeotropic compositions of toluene are better because small amount of light component (ACE) entering in the feed,
this mixture contains much more water, which means that the distillate rate of the De-ACE column is small. As a result,
toluene, as the entrainer, is more capable of carrying water a high reflux ratio is required. A small amount of impurities
to the top of the column. Thus, less entrainer of toluene is (ACE, in this work) can be removed by distillation, however all
needed to be inside of the column. The distance in Fig. 3 for these distillation columns exhibit high reflux ratios.
the points between organic phase composition and azeotropic
composition can be better and further apart. So toluene is a 4. Effect of important design variables
good choice as the entrainer for this system.
The phase equilibrium in the AA process is quite nonlinear 4.1. Reactor
with a heterogeneous azeotrope formed in the binary system
of toluene and water, as is shown in the T–xy diagram given The feed vapor stream is feed to a tubular reactor contain-
in Fig. 4. The valid phases in azeotrope column are VLL. The ing 16,000 tubes, 0.026 m in diameter and 10 m in length. The
pressure is 0.265 bar, which gives a heterogeneous azeotrope exothermic heat is removed by heat conduction oil cooling at
temperature of 38.8 ◦ C closed to the decanter temperature. The 290 ◦ C. The cooling duty is 24.98 MW. The void fraction of the
bottom stream from the column contains 0.14 wt% water. The catalyst in the tubular reactor is 0.8, and the solid density is
composition of the vapor from the top of the column is close 2000 kg/m3 . The heat-transfer coefficient in the tubular reactor
to the composition of the toluene/water azeotrope. is 1 kW m−2 K−1 (Guan et al., 2002).
The separation of ACE and AA in the De-ACE column is not Fig. 6 shows the effect of the tube numbers (Ntubes) and
easy. Fig. 5 gives the T–xy diagram of the AA/ACE system at coolant temperature on the production of AA and ACE. The
production of AA and ACE increase as more tubes are used but is withdrawn from the overhead. The composition of water in
the increase is at an increasing smaller rate. Here, 16,000 tubes the bottom stream is specified below 0.14 wt%, which can be
are used to realize the same convention in Turton’s process. achieved by increasing the number of theoretical plates (Ns1).
The coolant temperature is set at 290 ◦ C, where there exists However, the bottom temperature increases at the same time.
a peak value of the production of AA. The production of ACE Fig. 8 shows the effects of Ns1 bottom temperature and the
increases as coolant temperature increases. So, the reaction total annual cost (TAC) of this column (Douglas, 1998). TAC
temperature should be well controlled to ensure the largest decreases as more trays are added while the bottom tem-
production of AA. Fig. 7 gives the temperature profile of the perature increases. So Ns1 is set at 14 so that the bottom
tubular reactor. The maximum temperature is 300.7 ◦ C and temperature doesn’t exceed 110 ◦ C, and the cost of azeotrope
located at about 0.33 m down the 10-m reactor, which should column is minimized at the same time.
be controlled when the reactor is in operation.
4.3. De-ACE column
4.2. Azeotrope column
The function of column is to separate AA and ACE. It is a
The function of this column is to separate water from the AA conventional distillation column, but it has maximum tem-
and ACE by the formation of water–toluene azeotrope which perature limitation in its bottom too. Fig. 9 shows the effects
5. Plantwide control
composition controller. However, according to the simula- stream leaving HX (direct acting). This feed forward con-
tion we have run, AA composition cannot be held when trol structure works well to control temperature changes
the temperature of the trays is held near the bottom or of the flow leaving HX caused by fresh feed flow rate
the bottom temperature is held constant by manipulating disturbances, and it performs better than the direct tem-
reboiler duty. So composition control is considered, and perature control.
composition–temperature cascade control structure is used in (5) The pressure in the flash tank is controlled by manip-
the bottom of De-ACE column. This control structure com- ulating the gas leaving the top of the vessel (direct
bines the advantages of composition control strategy with acting).
temperature control strategy and avoids the defects of both (6) The liquid level of the flash tank is controlled by manip-
strategies. Temperature control is fast but it may not hold ulating the stream leaving the bottom (direct acting).
purity specifications. Composition control is slow but it can (7) The base levels of the absorber and two distillation
drive AA purity to the set point. The composition controller columns are controlled by manipulating the flow rate of
(reserve acting) is used to determine AA composition and the stream leaving the bottom (direct acting).
generates set point signals for bottom temperature controller (8) The pressure in the absorber is controlled by manipulat-
(reserve acting). The set point ranges from 106 ◦ C to 110 ◦ C, so ing the flow rate of the off-gas (direct acting).
maximum temperature limitation is not violated. (9) The flow rate of the wash stream to the absorber is
The other various control loops are listed as follows: rationed to the gas feed coming from the flash tank.
(10) The pressure in the azeotrope column is controlled by
manipulating the flowrate of the vapor stream from the
(1) Fresh feed of the mixture of propylene, water and air is
top (direct acting).
flow controlled (reverse acting).
(11) Organic reflux from the decanter is rationed to the
(2) Peak temperature of the tubular reactor is controlled
azeotrope column feed.
by manipulating the temperature of heat conduction oil
(12) The bottom temperatures of the azeotrope column and
(reverse acting).
De-ACE column are controlled by manipulating the
(3) The pressure of the reactor is controlled by manipulating
reboiler heat inputs of the two columns, respectively
the discharge valve of the reactor (direct acting).
(reverse acting).
(4) The condenser duty of HX is ratioed to the feed flow
(13) The temperature of the decanter is controlled by manip-
rate of HX, and the ratio (condenser duty/mass feed flow
ulating the condenser duty (reverse acting).
rate of HX) is manipulated by the temperature of the
354 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 346–356
Fig. 14 – Dynamic response of the control structure to 20% feed flowrate disturbances.
(14) The decanter pressure is controlled by manipulating the (19) The top pressure of De-ACE column is controlled by
flow rate of the vent stream (direct acting). manipulating the condenser duty (reverse acting).
(15) Aqueous level is controlled by manipulating the flow rate (20) A deadtime of 1 min is inserted to all temperature control
of the aqueous stream (direct acting). loops to fit measurement lags while a deadtime of 3 min
(16) Organic level is controlled by manipulating the flow rate is necessary for composition control loops.
of toluene makeup (reverse acting).
(17) Liquid level in the reflux drum of De-ACE column is con- Conventional proportional and integral (PI) settings are
trolled by manipulating reflux flowrate because the reflux used in all control loops (Luyben, 1996, 2000). The level controls
ratio is quite large (direct acting) (Luyben, 2009). are only proportional with gain (Kc ) = 2. The pressure controls
(18) Distillate flowrate of De-ACE column is rationed to reflux of flash tank, decanter and two distillation columns are PI with
flowrate. Kc = 20 and I = 12 min, which is the Aspen default turning. The
chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 346–356 355
Fig. 15 – Dynamic response of the control structure to 10% feed composition disturbances.
flow control is PI with Kc = 0.5 and 1 = 0.3 min. The tempera- composition disturbances. Fig. 14 gives the dynamic results
ture and composition control loops, which consist of deadtime for 20% step changes in set point of the fresh feed flow con-
and PI parameters, are obtained by running relay-feedback troller with orange lines for the increase and green lines for
tests and using Tyreus-Luyben tuning rules. PI parameters of the decrease. Fig. 15 shows the response of the control struc-
temperature controllers are listed in Table 3. The composition ture to 10% feed composition disturbances with varying of
controller is PI with Kc = 1.52 and I = 50.16. air/propylene feed ratio, in which orange lines for the increase
The plantwide control structure we proposed is shown in and green lines for the decrease. Both of disturbances are
Fig. 13. Now, dynamic performance of this control structure is introduced at 0.5 h, and the whole process reaches a new
evaluated by introducing feed flowrate disturbances and feed steady-state within 8 h. The peak temperature of the reactor is
356 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 346–356
well controlled. Temperature transient deviations of the flow staff at the Institute of Petrochemical Technology (Changzhou
leaving HX are controlled within 1 ◦ C. Bottom temperatures University).
of the two distillation columns are controlled below 110 ◦ C by
using cascade control structure, and the purities of AA and References
ACE are held close to the set points.
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pared with that of Turton’s design, the modified process is Guan, T., Liu, X.Y., Pen, Z.G., 2002. Calculation for convective heat
much more simplified so that equipment investment cost can transfer coefficient of organic heat transfer material forced
be reduced. flowing in tube. Ind. Boiler Mag. 6, 9–10.
Lin, M.M., 2001. Selective oxidation of propane to acrylic acid
The effective dynamic control of the multiunit process
with molecular oxygen. Appl. Catal. A: Gen. 207, 1–16.
has been achieved by adding various PI controllers. Close
Luyben, W.L., 1996. Tuning proportional-integral-derivative
control of the high-purity AA product is insured by using tem- controllers for integrator/deadtime processes. Ind. Eng. Chem.
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Conflict of interest Luyben, W.L., 2009. Unusual control structure for high reflux ratio
distillation columns. Ind. Eng. Chem. Res. 48, 11048–11059.
The authors declare no financial interest. Turton, R., Bailie, R.C., Whiting, W.B., Shaeiwitz, J.A., 2008.
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We are thankful for support from the project fund of the China
Chem. Eng. 14, 419–427.
Petroleum & Chemical Corp. (411024) and assistance from the