Design of Allyl Chloride Distillation Tower

M. O. Talaat - Cairo University - Faculty of Engineering

Abstract
The main target of the present research is to study the details of the design of allyl chloride distillation tower comprising the basic design and economic study. This tower receives its feed from the bottom of 2 chloropropene distillation tower where the feed contains mainly allyl chloride ,mixed dichloropropene and very small traces of 2 chloropropene (mole fraction of allyl chloride in feed is 0.87) . The main function of this tower is to separate allyl chloride as a top product with minimum purity of 99 % .

1. Introduction
Allyl chloride is an extremely useful chemical intermediate since it can react both as an organic halide and as an olefin. Most derivatives of allyl chloride do not reach on end-use market themselves, but are part of further syntheses. The most important derivative of allyl chloride is epichlorohydrin, which is produced captively. Other chemicals made from allyl chloride include a variety of allylamines, silane derivatives, and various intermediates in the production of agrochemicals and pharmaceuticals (1). Efficient and economical synthesis of allyl chloride or 3-chloropropene was made possible by the discovery in the late 1930s of a direct high temperature (300500C) chlorination reaction by the Shell Development Co (24). This synthesis allows good yields and use of common inexpensive raw materials such as propylene and chlorine (5). The direct high temperature chlorination of propylene continues to be the primary route for the commercial production of allyl chloride. The reaction results in allyl chloride selectivities of 7580% from propylene and about 75% from chlorine. Additionally, a significant by-product of this reaction, 1,3-dichloropropene, finds commercial use as an effective nematocide when used in soil fumigation. Overall efficiency of propylene and chlorine use thus is significantly increased. A second method for synthesis of allyl chloride is thermal dehydrochlorination, i.e. cracking, of 1,2-dichloropropane, but this method is generally less satisfactory because of low allyl chloride selectivity (5060%) and operating temperatures of 500600C (4, 710). Packed and plate towers are most commonly used in distillation processes, but there are some constraints which restrict the use of each one of them. Packed columns are not preferred in case of very low liquid rates and withdrawal of side streams is difficult. Plate columns are able to handle wider range of flow rates

than packed ones, but they have higher hold up which is not safe in case of toxic or corrosive fluids (11). In this system (allyl chloride - mixed dichloropropene) as flow rate
of gas is not very high that refers that it will require lower diameter so assumption is made that it will be a packed tower and if diameter is found to be >.8 meter so the design will be changed to be plate tower (12). The main aim of the present work is to study the details of the design of allyl chloride tower and perform associated economic study.

2. Methodology 2.1. Determining number of theoretical stages (Mc-Cabe Thiele Method)

Mc-Cabe Thiele is the graphical representation of Lewis method. Lewis stated that :

1. Mechanism of mass transfer between liquid and vapour is Equimolar, i.e. The molar flow rates of liquid and vapour in each section is constant. 2. Heat of mixing = ZERO (ideal system) 3. Heat losses = ZERO 4. Molar latent heats of vaporization of both components is nearly equal. To obtain the number of theoretical stages using the McCabe-Thiele method, we shall divide the column into 3 sections: rectifying, feed and stripping sections. As these sections are then represented on the (x-y) equilibrium curve for the binary mixture in question and recombined to make a complete design, as shown in Figure (1)

Figure(1) : column is divided into three sections

For Top Section for any stage n :

y n 1

x R xn D R 1 R 1

Operating line of top section is of slope R/(1+R) and intercept of xD/(1+R)

Figure(2) : operating line of top section

For Bottom Section for any stage m :

y'm

L' W x' m1 x W V' V'

Operating line of top section is of slope L'/V' and intercept of -WXw/V'

Figure(3) : operating line of bottom section

In order to draw the bottom section operating line, two points are needed. One is known (xW,xW) and the other is got from q-line. q-line is the locus of intersection of top and bottom sections operating lines. So intersection of top section operating line and the q-line is the second point on the bottom section line(13). As feed to the Tower is saturated liquid i.e. q=1 therefore slope of q-line equals infinity and hence q-line will be vertical.

2.2. Packing selection criteria

The principal characteristics which must be obtainable in any type of packing are:

1. Providing a large surface area which means a high interfacial area between the gas and liquid. 2. Having an open structure which means low resistance to gas flow. 3. Promoting uniform liquid distribution on the packing surface. 4. Promoting uniform vapor gas flow across the column cross-section. 5. Mechanically strong and chemically inert. In this system it is preferred to use 38mm pall ring as a packing, to ensure more efficient operation and thats because the relatively high value of relative volatility so it is not required using expensive packing such as Super intalox or structured packing.

2.3. Installing packing 2.3.1 First method

Ceramic and metal packing are normally dumped into the column "wet", to ensure a truly random distribution and prevent damage to the packing, where the column is partially filled with water and the packing dumped into the water.

2.3.2 Second method

If the columns must be packed dry, just to avoid contamination of process fluids with water, the packing can be lowered into the column in buckets or other containers. Ceramic packing should not be dropped from a height of more than half a meter. In this system it is preferred to use the second method to avoid any contamination of the product.

3. Design calculations
3.1 Determination of diameter of column Top section

Where VW: Gas flow rate per unit cross section area Lw: Liquid flow rate per unit cross section area v: vapor density l: liquid density Kg/m3 Kg/m3 Kg/m2.s Kg/m2.s

LW= V W= V= L= L=

16.33 48.98 4.384 888 .0002425

Kmol/h Kmol/h Kg/m3 Kg/m3 N.s/m2

Hence Flv = .023 From generalized pressure-drop correlation shown in the following figure and for pressure drop = 42mm water per m packing therefore K4 = 1.9

Figure(4) : K4 chart,(14)

Hence V*w = 3.76 Kg/m2 s A= V/ V*w = .28 m2 D = [(4*A)/].5 = .6 m bottom section Applying the same procedures but substituting with the flow rates in the bottom section the following results were obtained : Flv = .08 K4 = 1.4 V*w = 4.3 Kg/m2 s A= .24 m2 D = .56 m Therefore the column Diameter will be .60 m 3.2 check on wettability of packing It is recommended that minimum wetting rate for packing ranging from 25-75mm is 2 and this value ensures that this packing has a good wettability. Wetting rate = For top section using volumetric liquid flow rate in the top section Wetting rate = For bottom section using volumetric liquid flow rate in the top section Wetting rate = since the wetting rate in both top and bottom section is larger than minimum wetting rate therefore the packing has a good wettability . (14)

3.3 check on cross channeling

It means bad contact between gas and liquid which occurs in large column diameters(14). In this system, since the diameter is small enough to prevent channeling so there is no afraid of channeling.

3.4 Determination of height of column

For the design of packed distillation columns it is simpler to treat the separation as a staged process, and use the concept of the height of an equivalent equilibrium stage to convert the number of ideal stages required to a height of packing. The height of an equivalent equilibrium stage, usually called the height of a theoretical plate (HETP), is the height of packing that will give the same separation as an equilibrium stage. It has been shown by Eckert (1975) that in distillation the HETP for a given type and size of packing is essentially constant, and independent of the system physical properties; providing good liquid distribution is maintained and the pressure drop is at least above 17 mm water per metre of packing height. The following values for Pall rings can be used to make an approximate estimate of the bed height required. Size, mm HETP, m

25 (1 in.) 0.4-0.5 38 (l.5 in.) 50 (2 in.) 0.6-0.75 0.75-1.0

For small-diameter columns, the rules of thumb presented by Frank , Ludwig and Vital et al are identical. They stated that for small columns HETP = 18DP HETP > DT for DT < 0.67 m where DP and DT are the packing and tower diameters, m, respectively, and the HETP is in meters. The above rules of thumb were based on experience with Pall rings. Therefore HETP = 18 38 = 684 mm = 0.68 m (Within specified range) HETP

Height of packing = Number of ideal stages NTS = 15.47 Hence height of packing = 15.47

.68= 10.5 m

hence the total height of the column will be 14 m due to top allowance : 1.5 m bottom allowance : 2 m

4. Results and Discussion

The number of theoretical stages required for a given separation is then the number of triangles that can be drawn between these operating lines and the equilibrium curve. The last triangle on the diagram represents the reboiler. Using Mc-Cabe Thiele method figure(5) was drawn and one can get that: -Number of theoretical stages (NTS) = 15.47 -Feed stage = 8

Figure(5) : Mc-Cabe Thiele Diagram - one should note that the number of theoretical stages is not very large as relative volatility of the system is high which means that the separation is easy and hence gives moderate NTS. Final results of design D = .6m = 1.5ft H = 14m = 57.4ft Packing : Pall Rings (Ceramic, 1.5'') - The column diameter is within specified range of packed columns ( D < .8 m) As the gas flow rate is small. - The material of packing was chosen to be ceramic material to overcome corrosion problems which affects the operation of the tower.

5. Economic study
5.1 Vessel cost

Figure 6 vertical pressure vessel. Time base mid-1998

Note Since column diameter is 0.6m, which is not present in the figure, hence calculate column diameter at 0.5m, then by using SIXTH-TENGTH FACTOR rule, calculate cost at diameter = 0.6m. From figure get cost at vessel height = 14m & diameter = 0.5m get purchased cost

Then get cost at D =0.6m by using SIXTH-TENGTH FACTOR law

5.2 Packing cost Cost of packing per m3 =CSn From a standard table Get C= 8750 S = 38mm

Total cost of column at1998 = vessel cost + packing cost = 11705 + Notes This cost is at 1998, hence now the cost at 2012 must be got now. The 1st step is to get the cost index at 1998 & 2012 Cost index at 1998 = 436 Cost index at 2012 = 707.5 = $ 12395

6. Conclusions
1. Allyl chloride is an extremely useful chemical intermediate since it can react both as an organic halide and as an olefin and has wide range of applications. 2. Number of theoretical stages (NTS) has been determined using Mc-Cabe Thiele method. 3. Choice of Packing is done according to Packing selection criteria and it is found that 38mm ceramic pall ring as a packing suits the system under consideration . 4. Column diameter is determined and it is within the range of Packed column diameters 5. Column height is determined using NTS and HETP

7. References 1. Ullmanns Encyclopedia of Industrial Chemistry, 5th Compl. rev. ed., vol.A1, VGH publishers, Deer field Beach, Fla., 1985 2. E. C. Williams, Ind. Eng. Chem. 16, 630632 (Dec. 10, 1938). 3. U.S. Pat. 2,130,084 (Sept. 13, 1938), H. P. A. Groll, G. Hearne, J. Burgin, and D. S. LaFrance (to Shell Development Co.). 4. H. P. A. Groll and G. Hearne, Ind. Eng. Chem. 31(12), 15301537 (Dec. 1939). 5. E. C. Williams, Trans. AIChE 37, 157207 (1941); Chem. Met. Eng. 47, 834838 (Dec. 1940). 6. U.S. Pat. 2,207,193 (July 9, 1940), H. P. A. Groll (to Shell Development Co.). 7. D. H. R. Barton and A. J. Head, Trans. Faraday Soc. 46, 114124 (1950). 8. K. A. Holbrook and J. S. Palmer, Trans. Faraday Soc. 67(1), 8087 (1971). 9. U.S. Pat. 4,319,062 (Mar. 9, 1982), T. S. Boozalis, J. B. Ivy, and G. G. Willis (to The Dow Chemical Company). 10. U.S. Pat. 2,966,525 (Dec. 27, 1960), D. E. Steen (to Monsanto Chemical Co.). 11. Perry, R.H. and Green, D.W: Perrys Chemical Engineers Handbook, McGrawHill, New York (1997). 12. Prof. Dr. Hamdi Abl el Aziz, Lecturer at chemical engineering department Cairo University, Mass Transfer lectures, (2012). 13. Robert E. Treybal, Mass Transfer operations, Third edition, McGraw-Hill, Singapore (1981). 14. Coulson & Richardsons: Chemical Engineering Design, HandBook, McGraw- Hill,
Volume 6, Third edition, Oxford (1999).