Techno-Economic Analysis of The Production of Epichlorohydrin From Glycerol

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Article
Techno-economic analysis of the production of epichlorohydrin from glycerol.
Alberto Almena, and Mariano Martín
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.5b02555 • Publication Date (Web): 28 Oct 2015
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Page 1 of 44 Industrial & Engineering Chemistry Research
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Techno-economic analysis of the production
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11 of epichlorohydrin from glycerol.
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14 Alberto Almena, Mariano Martín1
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18 Department of Chemical Engineering. University of Salamanca, Pza. Caídos 1-5, 37008 Salamanca (Spain)
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20 Abstract
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25 In this work we evaluate the production of epichlorohydrin from glycerol, the main byproduct in the biodiesel
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27 industry. A process flowsheet is synthesized consisting of glycerol purification, reaction with HCl and final
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reaction with NaOH to produce epichlorohydrin. Both reactions are complex equilibriums and recovery of the
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30 reaction medium, hexanoic acid, and purification of the products is required. The process is selected based on
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32 the use of cheap and available secondary raw materials, namely HCl and NaOH, compared to other technical
33 alternatives. We couple MATLAB with CHEMCAD to simulate the mass and energy balances. Finally, the
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35 economic analysis of the process shows that the process is profitable due to the high selling cost of the
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37 epichlorohydrin. For the production of 26.5 kt/yr of epichlorohydrin 99.9%, 41.5 kt/yr of glycerol, 29 t/y of HCl
38 and 15.9 kt/yr of NaOH are need. The investment adds up to 63.7 M€ with a production cost of 1.28 €/kg.
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48 Keywords: Glycerol, epichlorohydrin, Techno-economic analysis, Process simulation.
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57 Corresponding author. Tel.: +34 923294479
58 Email address: mariano.m3@usal.es
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ACS Paragon Plus Environment
Industrial & Engineering Chemistry Research Page 2 of 44
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3 1.-Introduction.
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Along with biodiesel, in a ratio 10:1, glycerol is obtained as byproduct. Therefore, by increasing the
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9 amount of biodiesel produced, the availability of glycerol increases too. As a result, it is imperative to find
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11 alternative markets and uses for glycerol capable of processing the large amount produced within
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13 biorefineries, while providing an added value that helps with the biodiesel economy. There are two possible
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15 strategies to solve this problem, either to use glycerol as raw material for obtaining fuel additives or to produce
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17 higher value products and commodities. Over the last years different chemicals have been produced out of
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glycerol such as hydrogen and FT-liquids, 1 ethanol, to enhance up to 5% the production of biofuels from an
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22 algae based biorefinery, 2 methanol, to reduce by one half the fossil based raw materials in the production of
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24 biodiesel 3 or glycerol ethers, increasing the yield to biofuels by 20%. 4 However, the margin of benefits in
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26 biofuels production is tight. Alternatively, glycerol can be used in the production of polymers such as PHB or
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28 polyesters, 5 with more favourable economics.
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30 Epichlorohydrin is a high volume commodity chemical used largely for epoxy resins production,
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although smaller quantities have, until recently, been employed for the manufacture of synthetic glycerol.6 By
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35 looking at 2012 data, the worldwide production of epichlorohydrin raised to about 2.0 million Mg (near to 9 x
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37 106 kt). 7 In spite of the several routes known for epichlorohydrin manufacture, it is mostly obtained from
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39 propylene and chlorine in a multi-step process. This process consists of the allylic chlorination of propylene to
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41 allyl chloride followed by hypochlorination, resulting in a 3:1 mixture of 1,3-DCH and 2,3-DCH (dichlorohydrin:
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43 DCH). The product mixture is treated with an alkali to obtain epichlorohydrin. 8 Although this process is widely
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used at large scale, it suffers from some undesirable features, particularly the low yield in terms of chlorine
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48 usage. Only one out of the four chlorine atoms employed in the manufacture of epichlorohydrin using this route
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50 is retained in the product molecule, while the rest emerges as by-product hydrogen chloride or waste chloride
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52 anion. Additionally, inefficiencies in the chlorination and hypochlorination steps lead to the formation of
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54 unwanted chlorinated organics that, together with the large amount of waste water produced by the
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56 conventional production process, are expensive to dispose of.9 Such factors have prompted the search for
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60 2
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3 alternative routes to epichlorohydrin that are more atom-efficient and environment-friendly. The escalating cost
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of petrochemical raw materials such as propylene has also contributed to the accelerated search for processes
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8 that employ less expensive and renewable raw materials.8 Furthermore, the raw materials, propylene and
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10 chlorine, are flammable and toxic respectively. However, epichlorohydrin can be produced from glycerol in a
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12 two step process where first dichlorhydrin is produced in a gas-liquid contactor and later epichlorohydrin is
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14 produced in a packed bed one.
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16 In this paper we present the conceptual design of the production process to transform glycerin into
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epichlorohydrin using HCl and NaOH as reagents instead of other crude based sources of carbon. We use a
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21 simulation based approach for rigorous simulation of the process integrating MATLAB and CHEMCAD to
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23 design a process and evaluate its economics. The rest of the paper is divided as follows. Section two
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25 describes the process and presents the flowsheet. In section three, the models for the different units are
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27 presented. We used CHEMCAD for modelling the distillation towers and MATLAB-EXCEL for modelling the
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29 reactors. Next, we present the production cost and the investment for such a plant. Finally, a discussion on the
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process and its perspectives is presented.
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36 2.- Process description
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The process consists of four stages: feedstock preparation involving glycerol purification and
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42 reactants preparation, glycerol hydrochlorination and product recovery, epichlorohydrin production and product
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44 purification up to commercial composition.
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46 The crude glycerol is fed to the process at standard conditions, 293 K and 100 kPa. We assume that
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48 it does not contain any NaOH as residue from the biodiesel production process. We expect that the use of
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50 heterogeneous catalysts is employed in the near future and NaOH residues will no longer be an issue.
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Otherwise, a prior neutralization step would be required to remove this impurity. Next, glycerol has to be
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55 heated up to the boiling point before it is fed to the distillation column as saturated liquid. In this column, T-01,
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57 the glycerol is separated from the impurities, namely water and methanol. A packed distillation column is used,
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60 3
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3 with an upper bound for the bottoms temperature of 423 K, to avoid glycerol decomposition.10 Thus, the
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packed column operates under vacuum, at a pressure up to 10 kPa. Basically, all the water and methanol will
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8 be separated as distillate from the glycerol, which is fed to the next stage.
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10 The bottom stream containing the main reactant, glycerol, is mixed with the recirculation, comprising
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12 the recycled catalyst and the heavy intermediate products from the bottom of the column T-02. The mixture is
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14 cooled down to the reaction temperature (383 K) and loaded into the semibatch reactor, R-01. A semibatch
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16 reactor is chosen to minimize the side-reaction of glycerol to trichloropropane, which occurs in the presence of
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a high concentration of hydrogen chloride in the reaction mixture. Furthermore, a semibatch reactor allows the
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21 continuous addition of hydrogen chloride maintaining its concentration low.8
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23 The other main reactant introduced into reactor R-01 is the chlorinating agent, hydrogen chloride,
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25 which needs to be brought to the reaction conditions. A multistep compression system is used, consisting of
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27 two compressors and two interstage coolers. The hydrogen chloride is compressed up to 760 kPa, cooled
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29 down to 383 K and fed into the semibatch reactor. Intercooling aims at reducing the energy consumption. Next,
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the hydrogen chloride is bubbled into the reaction mixture.
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34 The reaction that occurs in the semibatch reactor is the hydrochlorination of glycerol, presented in
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36 Figure 1.
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52 Figure 1 – Hydrochlorination of glycerol reaction.
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3 The hydrochlorination is performed isothermally at 383 K and under hydrogen chloride pressure of
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760 kPa, in the presence of hexanoic acid (5 % mol) as catalyst. Working at high pressure the liquid-vapor
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8 contact is improved, and the existing equilibrium limit shown for the absorption of the HCl in glycerol at
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10 atmospheric pressure is overcome, 8 resulting in a better absorption of the gas in the liquid and consequently a
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12 more efficient production of DCH. Operating isothermally allows controlling the side reactions. 8 The reaction
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14 product mixture comprises dichlorohydrins, in a mole ratio of 30-50 to 1 of 1,3-DCH and 2,3-DCH respectively,
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16 monochlorohydrins (MCH), water and catalyst. This ratio represents a very important advantage over the
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current industrial process, showing a ratio only of 3 to 1. The improved 1,3-regioselectivity undergoes
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21 cyclization with a base to form epichlorohydrin about 300 times faster than from the 2,3-DCH. This translates
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23 into smaller equipment in the second reaction stage.
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25 The chlorinating agent is bubbled to the reaction mixture gradually, in an excess of 10 % by weight.
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27 Keeping its concentration in the reaction mixture at a low value, together with the choice of the optimal working
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29 catalyst, inhibits the side reaction of trichloropropane formation. 8 The hydrogen chloride not dissolved in the
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reaction mixture, together with the steam formed by the evaporation of the water in the mixture, is evacuated
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34 from the isothermal semibatch reactor when the internal pressure exceeds the upper bound.
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36 After 3 h of reaction, the mixture containing the dichlorohydrins is cooled and expanded to the
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38 pressure conditions of the product recovery column. At this stage, dichlorohydrins, hydrochloric acid and water
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40 formed in the reaction step are separated from the heavy components, namely monochlorohydrins, catalyst
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42 and unreacted glycerol. The recirculation comprises the heavy components, obtained at the bottom of the
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44 column. This stream is returned to the reaction step. To maintain low pressure drop, a packed column is
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47 usedAlmost sharp separation of the substances can be achieved by operating under vacuum, 5 kPa.11
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49 The distillate is sent to a liquid-liquid separator where the two phases, organic and aqueous, are
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51 separated. The purpose of this embodiment is to make use of the amount of water formed in the first reaction
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53 stage to prepare the sodium hydroxide solution, a reactant of the second reaction stage.
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55 The organic phase, comprising mostly of dichlorohydrins and a small amount of water dissolved, is
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57 heated up to the reaction temperature and sent to reactor R-02. On the other hand, the aqueous phase with
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60 5
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3 most of the water, and saturated with dichlorohydrins and other species such as hydrochloric acid and traces
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of catalyst, is mixed with a concentrated solution of sodium hydroxide in mixer M-03 to be first neutralized and
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8 later diluted to the appropriate concentration for the reaction: 20 w% aqueous solution. The original solution of
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10 NaOH is prepared in a stirred tank, M-02. The sodium hydroxide fed to the process represents an excess of 5
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12 mol % of the dichlorohydrins fed to the reactor R-02, plus the necessary amount to neutralize the hydrochloric
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14 acid. Both stirred tanks operate adiabatically, reducing the energy consumption in the subsequent heating of
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16 the solution to reaction temperature.
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The reactant streams are only mixed in the reactor, to prevent the formation of epichlorohydrin and its
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21 decomposition before the reaction stage. Reactants are fed to the top of the reactor tower R-02, a packed
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23 column where dehydrochlorination of dichlorohydrins occurs. It operates isothermally at 363 K to avoid an
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25 increase in the yield of the hydrolysis of epichlorohydrin and under vacuum conditions, 30 kPa, to make easier
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27 the azeotropic distillation12. Therefore, external refrigeration is needed. The main reaction is presented in
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29 Figure 2:
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39 Figure 2 – Dehydrochlorination of dichlorohydrins reaction.
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43 The advantage of a reactive distillation column is the short contact time between the water and the
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epichlorohydrin, minimizing the hydrolysis of the produced epichlorohydrin to glycerol, which represents the
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48 major yield losses. Steam is injected from the bottom of the column, stripping the undissolved epichlorohydrin
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50 produced by the reaction. The amount of steam used for the stripping of epichlorohydrin is such that the
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52 composition at the top has a water/epichlorohydrin ratio by weight of from about 1 to 2.5.12
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3 The bottoms of the column are mainly waste water, with all the substances dissolved in it, such as
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epichlorohydrin, sodium chloride, unreacted dichlorohydrins and sodium hydroxide excess. This stream is
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8 cooled to make use of its energy and disposed of as waste product.
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10 The top stream comprising the epichlorohydrin-water azeotrope, a mixture 24 w% of water at
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12 atmospheric pressure, 13 is cooled down and condensed. Next, it is sent to a decanter to separate the two
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14 phases, according to the identification of this azeotrope as heterogeneous. 14 The organic phase, with a water
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16 concentration of 1.48 w%, set by the solubility limit of water in epichlorohydrin, goes to an evaporator to follow
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the purification process, while the aqueous phase is treated as waste.15 Further studies of this process may
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21 found how to treat the wastewater so as to reuse it joining the stripping steam to the R-02. A previous
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23 treatment of this stream would be needed to remove the epichlorohydrin that accompany in a 6.58 w%,15
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25 according to the solubility of epichlorohydrin in water, which would affect the equilibra in the reactor.
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27 The next stage in the purification of the epichlorohydrin is a pressure swing absorption (PSA) system.
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29 The evaporated organic phase obtained in the decanter is compressed to 4.5 bar to improve the water
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absorption in the molecular sieve. The PSA unit consists of two parallel 4A zeolite beds, with an absorption
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34 capacity of at least 0.215 mg/g.16 When one of the molecular sieves is working, the other one is being
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36 regenerated using hot air. Thus, continuous operation is ensured and the purity of the epichlorohydrin is raised
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38 to 99.9%. Finally, the product is expanded to atmospheric pressure, recovering energy, and then it is
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40 condensed and stored.
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42 A schematic flow chart of the studied process is represented in Figure 3 as follows:
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26 Figure 3 – Process flow chart.
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30 3. - Modelling issues.
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3.1. - Distillation columns. Rigorous simulation using CHEMCAD.
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34 In the process there are two distillation columns that are modelled in CHEMCAD. The first one, T-01,
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36 is a packed distillation column that purifies the glycerol, from the composition obtained in a biodiesel plant, to
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38 the appropriate one for reaction. This column has as a constraint that the bottoms, consisting mainly on
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40 glycerol, must exit the column below 423 K to avoid decomposition. Therefore, it operates under vacuum, at 10
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42 kPa. 15 stages and total condenser are used to reach a 99.99 % recovery of glycerol. The thermodynamic
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model for this column is UNIFAC. Water and methanol exit as distillate.
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47 In the second tower, the packed distillation column T-02, heavy components comprising
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49 monochlorohydrins, catalyst and unreacted glycerol are recovered and recycled while the main product is sent
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51 to further reactions. CHEMCAD database has only one of the dichlorohydrins and one of the
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53 monochlorohydrins isomer defined, 1,3-DCH and 3-MCH respectively. The similar boiling points and
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55 characteristics of each pair of isomers, together with the fact that the defined ones are found in a much larger
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proportion, made us assume that the two monochlorohydrins will behave as 3-chloropropane-1,2-diol, while
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60 8
1
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3 both dichlorohydrins behave as 1,3-dichloropropan-2-ol. The thermodynamic model selected for this column is
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NRTL. The column is expected to recover 99.99 % of the dichlorohydrins in the distillate, accompanied by the
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8 water in the feed to the column, with a package height of 30.2 m and operating at 5 kPa. Total condenser is
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10 used. Nearly 100 % of the monochlorohydrins, catalyst and glycerol are obtained in the bottoms.
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14 3.2.-Synthesis reactor R-01.
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16 This reactor is responsible for the first reaction stage of the process. In this section, the mechanism
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18 and kinetic model for the production of monochlorohydrins and dichlorohydrins from glycerol are described.
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20 The hydrochlorination of glycerol, catalyzed by a carboxylic acid, can be considered to take place
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22 following a two step mechanism, see Figure 4. It starts with glycerol chlorination to monochlorohydrins, mainly
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24 to 3-MCH, which suffers a second chlorination to dichlorohydrin. For each of the five chlorinations, a hydroxyl
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27 group of the glycerol is substituted by a chlorine atom and, consequently, a water molecule is formed as
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29 byproduct. The 1,3-dichlorohydrin is the main product of this reaction and represents a great advantage over
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31 the current industrial process.
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Figure 4 – Dehydrochlorination of glycerol scheme.
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54 At this point, it is important to perform a detailed analysis of the first reaction step of the process,
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57 describing the assumptions within the mechanism of dehydrochlorination of glycerol. Based on experimental
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60 9
1
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3 observations, 17 it was found that the reaction that converts 2-MCH into 2,3-DCH is not possible because of the
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absence of vicinal OH groups, that inhibits the second hydroxyl mechanism substitution, and thus, it can be
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8 neglected. Furthermore, reactions 2 and 4 can be considered irreversible because 2-MCH is produced during
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10 the reaction and 2,3-DCH is always obtained in small quantities. Therefore, the scheme can be simplified into
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12 the one shown in Figure 5.
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24 Figure 5 – Dehydrochlorination of glycerol simplified scheme.
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The four reactions comprising the catalyzed glycerol hydrochlorination, which best explains the
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31 experimental data, can be represented by the following equations:
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33 K1
34
1) C3H8O3 + HCl + Catalyst 3-C3H7ClO2 + H2O + Catalyst
K-1
35
36
37 K2
2) C3H8O3 + HCl + Catalyst 2-C3H7ClO2 + H2O + Catalyst
38
39
40 K3
41 3) 3-C3H7ClO2 + HCl + Catalyst 1,3-C3H6ClO + H2O + Catalyst
42 K-3
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44 K4
45 4) 3-C3H7ClO2 + HCl + Catalyst 2,3-C3H6ClO + H2O + Catalyst
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49 Each of the reactions presented above are based on the substitution of a hydroxyl group with a
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51 chlorine one. The elementary steps are beyond the scope of this paper. There are two hypothesis, considering
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53 all the steps of the mechanism elementary (more complex) or assuming the ester formation as the rate
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56 determining step, which agrees with experimental evidence. To simplify the kinetic model for each substitution,
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58 where the ester formation is considered as the rate-determining step, a pseudo constant is introduced, that
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60 10
1
2
3 lumps all the elementary steps of the complex hydrochlorination mechanism. Thus, the kinetic model becomes
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5
as follows: 17
6
7
8 =
. . − . . (1)

9
10
11
= . . . (2)
12

13 =
. . − . , . (3)
14
15
16 = . . . (4)
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18 Values of the kinetic constants are listed in Table 1.17 They are obtained under atmospheric pressure
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20 and using malonic acid as carboxylic acid catalyst.
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23 Table 1. – Kinetic constant and Arrhenius parameters for catalyst glycerol hydrochlorination.
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25
26 T (ºC) K 1* K 2* K 3* K 4* KE1* KE3*
27 80 7 667 ± 940 450 ± 41 714 ± 227 8±3 3 846 194
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29
90 11 704 ± 1 272 764 ± 60 1 109 ± 307 13 ± 5 3 064 167
30 100 13 274 ± 1 692 1 089 ± 87 1 784 ± 407 26 ± 7 2 470 146
31 110 19 433 ± 2 216 1 465 ± 123 2 383 ± 532 32 ± 9 2 015 128
32 120 27 411 ± 2 861 2 215 ± 170 2 179 ± 685 31 ± 13 1 660 113
33 Reaction 1 Reaction 2 Reaction 3 Reaction 4
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35 Ea (kJ mol ) -1
35.2 ± 0.3 44.3 ± 0.2 34.9 ± 0.8 42.1 ± 1.0
36 ln A 20.9 ± 9 21.3 ± 0.7 18.6 ± 2.2 16.5 ± 2.8
37
38 *Kinetic constants are expressed in cm6/(mol2 min)
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40 Even under these pressure conditions, it is admitted that the equilibria represented by equations 1
41
42 and 3 are almost completely shifted towards products.17 Further studies show that by increasing the HCl
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44
pressure, the equilibrium limit is overcome.8, 18 Moreover, according to the results of Santacesaria, et al., 18 by
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47 increasing the HCl pressure, the yield to the main product increases by a factor by almost 3. Therefore, the
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49 kinetics of the production of 1,3-DCH under pressure is speeded up. Bell, et al.8 found that the optimal HCl
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51 pressure is 760 kPa.
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53 Finally, the use of a more active catalyst, selective to the main product and easy to recycle, is
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55 expected for industrial scale. Therefore, the carboxylic acid of choice is hexanoic acid. The reason to select it
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57
over acetic acid, the catalyst with the best performance studied so far, is the fact that hexanoic acid is as
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60 11
1
2
3 effective as acetic acid at the end of the reaction time but it is also less volatile, even heavier than
4
5
dichlorohydrins.8,19 Therefore, the recovery of the catalyst is easier, allowing its recycle.
6
7
8 The kinetic rates listed in Table 1 are obtained experimentally at atmospheric pressure using malonic
9
10 acid for catalyzing the glycerol hydrochlorination. Therefore, the kinetic data available in the literature are not
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12 obtained under the favorable conditions described above. To provide simulation results under these
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14 conditions, we have used the mechanisms described in the literature to come up with a modified kinetic model.
15
16 For this model to match the experimental results at high pressure and using a different catalyst, we use a
17
18
parameter estimation problem based on an adjustable parameter (θP). Typically the absorption of a gas in a
19
20
21 liquid is directly proportional to the pressure and thus, this parameter multiplies the kinetic rates of the
22
23 literature. The value of this parameter is calculated using an error function in Matlab, so that the model allows
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25 fitting the experimental results at the optimal pressure at 3 hours of reaction time, Bell, et al.,8 Santacesaria, et
26
27 al.18 and Herliati, et al.20
28
29
30
31
Thus, after the elimination of the equilibrium limitation by increasing the HCl pressure, and adjusting
32
33
34 the reaction rate, the following model becomes as given by equations (5) – (8):
35
36
37
38 = . "# . . . (5)
39
40 = . "# . . . (6)
41
42
43 = . "# . . . (7)
44
45 = . "# . . . (8)
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47
48
49 The optimal conditions to achieve a high yield to 1,3-DCH include an operating temperature of 383 K,
50
51 gradual feed of HCl to the reactor in 10 w% excess with respect to the stoichiometric mass and a pressure of
52
53
760 kPa. The catalyst ratio needed is 0.08 mol of hexanoic acid per mol of glycerol fed to reactor. 8
54
55
56 The most appropriate reactor to carry out the catalyzed glycerol hydrochlorination is a stirred
57
58 isothermal semibatch unit. The glycerol and the hexanoic acid are charged into the reactor at reaction
59
60 12
1
2
3 conditions. Then, the gaseous chlorinating agent is bubbled gradually as the reaction proceeds. Avoiding a
4
5
great excess of hydrogen chloride in the reaction mixture makes negligible a side reaction to trichloropropene,
6
7
8 while the operating conditions minimizes the glycerol and monochlorohydrins esterification.
9
10 Mass balances of components in the semicontinuous reactor, according to the reactions seen before,
11
12 are shown in equations (9) – (15):
13
14 .- Glycerol:
15
16 $%&'(
= −) + + . ,)-+ (9)
17 $
18
19 .- Hydrogen chloride:
20
21 $%./'
= 0 1 − 0 2 − ) + + + + . ,)-+ (10)
22 $
23
24 .- 3-chloropropane-1,2-diol:
25
$%34/.
26
$
= ) − − + . ,)-+ (11)
27
28
29
30
31 .- 2-chloropropane-1,3-diol:
32
33 $%34/.
$
= ) + . ,)-+ (12)
34
35
36 .- 1,3-dichloropropan-2-ol:
37
$%,35/.
38 = ) + . ,)-+ (13)
39 $
40
41 .- 2,3-diclhoropropan-1-ol:
42
$%,35/.
43 = ) + . ,)-+ (14)
44 $
45
46 .- Water:
47
$%.6
48 = ) + + + + . ,)-+ − 0 2 (15)
49 $
50
51
The gas phase exiting the semibatch has been computed using an offline simulation in CHEMCAD to
52
53
54 account for the gas-liquid equilibrium determining the amount of HCl and water vapor not dissolved in the
55
56 liquid phase. The main reaction takes place in the liquid phase so, although an amount of gas is added, the
57
58
59
60 13
1
2
3 density of the reaction mixture has a negligible variation. Thus, the reaction mixture volume has a linear
4
5
relationship with time:
6
7
8 ,)-+ = ,7 + 87 . - (16)
9
10
11 Finally, it is necessary to mention that we consider that the 2-MCH fed to the semibatch reactor by
12
13 the recirculation stream reacts to dichlorohydrin following the equations (7) and (8), just like the 3-MCH formed
14
15 inside the reactor does. This consideration is reasonable due to the small amount that is recycled, the heavy
16
17 key is the catalyst, and the fact that the time available for 2-MCH to react is 3 hours, which appears to be
18
19 sufficient for the substitution of the hydroxyl group occurs.8
20
21
Equations (5) – (16) comprise the synthesis reactor model, an ordinary differential equations system
22
23
24 that is solved using MATLAB R2013. The initial conditions for the Matlab model are the charged kilomoles of
25
26 stream 6 *, in one hour of reactor charging time, and the following parameters: T= 383 K; Vo= 4272 dm3; vo=
27
28 0.288 cm3/s; FHCle=9.2510-3 kmol/ s; FHCls=6.9310-4 kmol/ s; FH2Os=3.2910-4 kmol/ s.
29
30
31
32 3.3.-Reactive distillation column.
33
34 The second reaction stage is carried out in a reactive distillation column, where the
35
36 dehydrochlorination of dichlorohydrins takes place. The kinetics of the reaction and the modeling of the reactor
37
38 are depicted below.
39
40 The dehydrochlorination of dichlorohydrins is a one step reaction where a dichlorohydrin molecule
41
42
43
reacts with a sodium hydroxide molecule in aqueous medium, as follows:
44
45
C3H6Cl2O + NaOH C3H5ClO + NaCl + H2O
46
47
48
Both dichlorohydrins react to epichlorohydrin following the above expression, but the rate of the
49
50
51 transformation of 1,3-DCH is about 300 times faster than of 2,3-DCH.8
52
53 The presence of epichlorohydrin in an aqueous basic medium causes epichlorohydrin hydrolysis as a
54
55 side reaction, which represents an important yield loss: 21
56
57
58 C3H5ClO + NaOH + H2O C3H8O3 + NaCl
59
60 14
1
2
3
4 However, the use of a reactive distillation column makes possible a short contact time between water
5
6 and epichlorohydrin that, together with the optimal conditions, enhance the main reaction and minimize the
7
8 epichlorohydrin hydrolysis. The optimal reaction conditions are 363 K and 30 kPa.9,21 The basic aqueous
9
10
11 solution reactant must have a concentration of 20 w%, in an amount of sodium hydroxide that represents an
12
13 excess of 5 mol% related to the dichlorohydrins fed to the reactor.12 Furthermore, the column operates
14
15 isothermally at the optimal temperature, removing the heat of reaction that would enhance the main reaction,
16
17 but also the hydrolysis.
18
19 The kinetics of the dehydrochlorination and hydrolysis reactions has been studied experimentally. It
20
21 turns out that second order kinetic model provides the best fit in both cases.21 Thus, the kinetic equation for the
22
23
24
dehydrochlorination of dichlorohydrins can be expressed as given by eq. (17):
25
26 = 9 . [DCH] . [NaOH] (17)
27
28
29 The reaction rate follows the Arrhenius model. In the temperature range 313 K – 333 K, close to the
30
31 reaction temperature, the kinetic constant 9 is given as follows: 21
32
77K
33 9 = 8.97 x 107 . e I .J (l/mol s) (18)
34
35
36 The reaction temperature, 363 K, 9, 21 is above the upper limit, but it is assumed that the Arrhenius
37
38
39
model holds. Equation (17) was obtained for the 1,3-DCH. 2,3-DCH reacts to epichlorohydrin 300 times slower
40
41 than the isomer 1,3-DCH.8 Therefore, it is assumed that the kinetic constant of the 2,3-DCH (9 ∗ ) is 300
42
43 times smaller than 9 . The reaction rate for 2,3-DCH is named ∗ .
44
45 On the other hand, the experimental results for the hydrolysis of the epichlorohydrin can be
46
47 represented by assuming a second order kinetic model, such as given by eq. (19):
48
M = 9M . [NOP] . [QP ]
49
(19)
50
51
52
The reaction rate of the hydrolysis of epichlorohydrin follows an Arrhenius type of model too. The
53
54
55 kinetic constant 9M is computed using eq. (20): 21
56
T7TU7K
57 9M = 5.66 x 107 . e I .J (l/mol min) (20)
58
59
60 15
1
2
3
4 The main reaction rate is more than ten orders of magnitude larger than the side reaction. However,
5
6 the hydrolysis rate depends on the OH- anions, including those of the water, so that the yield of the side
7
8
reaction could be important because of the large amount of water available within the reaction mixture. To
9
10
11 minimize the hydrolysis loss, it is necessary to reduce the contact time between water and epichlorohydrin.
12
13 The reactor of choice is an isothermal reactive distillation column, as it was discussed in the process
14
15 description. The column packing consists of metal Pall rings of 50 mm diameter and disposed randomly,
16
17 according to the rules of thumb and the design specifications. At the bottom, steam is injected to strip the
18
19 undissolved epichlorohydrin produced by the reaction. The countercurrent vapor stream is not considered for
20
21 the global mass balance given by the set of differential equations, but the performance of its flow across the
22
23
24
package is studied and plotted later. External refrigeration is needed to remove a large part of the energy
25
26 produced during the reaction, which exceeds the needs to evaporate the epichlorohydrin generated, in order
27
28 to maintain an isothermal operation. The plug flow model is assumed to hold for the operation of the column
29
30 reactor. The countercurrent vapor stream is not considered in the reactor model, but the performance of its
31
32 flow across the package is studied and plotted later. Thus, a mass balance is performed to a differential
33
34 volume of the column (see Figure 6), where the reaction rate is considered invariable. The balance can be
35
36
37
expressed as given by eq. (21):
38
V X∆VW
39 )0 +VW − )0 +VWX∆VW − ZV W )[# + \, = 0 (21)
W
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57 Figure 6 – Mass balance in a differential volume of reactor R-02.
58
59
60 16
1
2
3 Since the cross section is constant along the column, the differential of volume can be expressed as
4
5
6
the product of transversal section (]), the porosity of the package (^), the liquid hold up, (εL) , where the
7
8 reaction actually takes place, and a differential of height (∆_). Applying the First Mean Value Theorem for
9
10 Integrals and the Mean Value Theorem for Derivatives, the eq. (22) is obtained:
11
$à
12 = ^c · ^ . ] . ) + (22)
13 $b
14
15
16 According to the developed model and considering the reactions that take place in the column
17
18 reactor, the mass balances for each component are shown in eqs. (23) – (29):
19
21
$`,35/.
22
= − ^c · ^ . ] . ) + (23)
23 $b
24
26
$`,35/.
27
$b
= − ^c · ^ . ] . ) ∗ + (24)
28
29
30 .- Sodium hydroxide:
31
$èf6.
32 = − ^c · ^ . ] . ) + ∗ + M + (25)
33 $b
34
35 .- Epichlorohydrin:
36
$`.
37 = ^c · ^ . ] . ) + ∗ − M + (26)
$b
38
39
40 .- Sodium chloride:
41
$èf/'
42 = ^c · ^ . ] . ) + ∗ + M + (27)
$b
43
44
45
.- Water:
46 $`.6
47
$b
= ^c · ^ . ] . ) + ∗ − M + (28)
48
49
. - Glycerol:
50
51 $`&'(
52 = ^c · ^ . ] . )M + (29)
$b
53
54
55 The water stream dissolves epichlorohydrin until it is saturated and takes on other species such as
56
57 NaOH, NaCl, glycerol and DCH’s that are below the solubility limit so that the stream exits the column through
58
59
60 17
1
2
3 bottoms as a waste. The ordinary differential equations system consists of eq. 17 – 20 and eq. 23 – 29 and it is
4
5
solved using MATLAB R2013, being the initial conditions the shown kinetics constants, the molar inflow of the
6
7
8 different components, the porosity of de packing (^ = 0.94),22 and the section of the column (] =
9
10 0.636 i ).23 The reaction takes place in the liquid phase and therefore it only considers a fraction of the void
11
12 volume of the packed column. However, for simplicity due to the unknown hydrodynamics of the column, we
13
14 assumed that the kinetic rates and the porosity already account for that effect in the parameters. Thus, the
15
16 liquid hold up is assumed to be one in the computations (^c = 1.)Further validation of the model is however
17
18
19 required, but the lack of data in the literature prevented this fact. Therefore, we oversize the column height by
20
21 10% to be on the safe side. Furthermore, we will compute the epichlorohydrin in vapor and dissolved to
22
23 determine the one that exits on top and from the bottoms, in which case takes the solubility limit of
24
25 epichlorohydrin in water with a value of 0.0658 kg/kg. 15
26
27 4.- Results
28
29
30 In this section, results on the simulation of an epichlorohydrin production plant using glycerol as raw
31
32 material are presented. The economics are performed assuming that the plant is allocated in Spain. Based on
33
34 the market for epichlorohydrin and the availability of glycerol, economic and financial viability studies are
35
36 carried out. It turns out that an economic plant size is 26,000 t/yr. 23
37
38
39
4.1.- Mass and energy balances
40
41
42 The simulation of the process provides the mass and energy balances, the needs of raw materials
43
44 and utilities. The raw materials fed to the production process comprise 41,500 t/yr of crude glycerol, 29,300 t/yr
45
46 of anhydrous hydrogen chloride and 15,200 t/yr of sodium hydroxide. Their prices, updated to 2014, are given
47
48 as Delivery Duty Paid (DDP), which represents the final price of the substance at the plant’s door. In this
49
50 regard, crude glycerol costs 20.69 €/t DDP, 24 with an estimated mean concentration of 80 w% of glycerol, 15
51
52
w% of methanol and 5 w% of water as impurities.25 On the other hand, anhydrous hydrogen chloride with a 99
53
54
55 w% of purity has a price of 261.34 €/t DDP, 26 while 99 w% pure sodium hydroxide costs 252.74 €/t.27
56
57
58
59
60 18
1
2
3 Furthermore, 56,400 t/yr of 4x106 Pa steam are needed, together with 15,900 t/yr of 6x106 Pa steam
4
5
and 5.3x106 t/yr of cooling water. These utilities are needed across the plant including heat exchangers,
6
7
8 condensers and reboilers of distillation columns and reactors cooling.
9
10 The results of the reactors simulation are shown below. The semibatch reactor for the production of
11
12 mono and dichlorohydrins is charged initially with glycerol, catalyst and other accompanying substances as
13
14 described before; loading the reactor takes one hour. On the other hand, the anhydrous hydrogen chloride is
15
16 added gradually, with a flow rate of 20 kg/min as required by the reaction conditions. As the reaction time last
17
18
three hours, four semibatch reactors are necessary to assure a continuous flow of products and good
19
20
21 temperature control.
22
23 According to the kinetic mechanism developed in section 3, the adjustable parameter ("# ) has a
24
25 value of (8.5 10-4)-1. Thus, the profile of the products in the semibatch during the three hours is shown in Figure
26
27 7. It can be seen the formation of 3-MCH peaking near 5500 s. Next, the second hydroxyl substitution begins
28
29 to be important and the 1,3-DCH is formed. The HCl concentration in the reaction mixture is kept at low values,
30
31
in order to avoid the formation of trichloropropane. It can be seen that a large amount of water is also obtained
32
33
34 as byproduct, while glycerol is totally converted and the other species, namely 2,3-DCH, 2-MCH and dissolved
35
36 HCl, are obtained at a low concentration. It is important to mention that there is no 2-MCH entering the reactor,
37
38 as we can see in figure 7. As it was explained in the reactor modelling section, 2-MCH inflow is included as 3-
39
40 MCH inlet.8
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 19
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34 Figure 7 – Evolution in time of the components moles in semibatch reactor.
35
36
37 The second reaction step of the process occurs in the reactive distillation column, where the
38
39 dichlorohydrin stream and the aqueous sodium hydroxide solution stream are fed separately at the top of the
40
41 column. Steam is injected at the bottoms as stripping agent to recover the undissolved epichlorohydrin,
42
43 forming an organic liquid phase, which is evaporated by a fraction of the heat of reaction. Optimal results were
44
45
obtained at a packing height of 14.8 m.
46
47
48 The solution of the reactive distillation column model, including water is shown in Figure 8. The
49
50 presence of so high flow of water is due to the NaOH solution that is needed for the reaction, accompanying as
51
52 solvent. It can be seen that there is not any distinction between liquid epichlorohydrin or countercurrent vapor
53
54 epichlorohydrin. Thus, the molar flow of the epichlorohydrin inside the reactor grows due to the reaction and
55
56 decrease of the reactants NaOH and both dichlorohydrins.
57
58
59
60 20
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33 Figure 8 – Evolution of the reactive distillation column model.
34
35
36
37 The evolution of the concentration of the aqueous liquid phase and the countercurrent vapor phase,
38
39 inside the column packing, is shown in Figure 9.
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 21
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29 Figure 9 – Evolution of the components molar flows along the reactive distillation column.
30
31
32 In Figure 9, it can be seen the formation of epichlorohydrin and its dissolution into the aqueous phase
33
34
until the solubility limit is reached. The dissolved epichlorohydrin achieves the solubility limit quickly, due to the
35
36
37 high reaction rate, and then it remains almost constant, only increasing proportionally to the water production
38
39 by the reaction. At this moment, the organic phase is formed and starts to evaporate, becoming part of the
40
41 countercurrent stripping gas stream. The vapor phase is free of epichlorohydrin at the moment of its injection
42
43 at the end of the package. The concentration of the epichlorohydrin in the countercurrent stream increases
44
45 along the packing, while the epichlorohydrin in the organic phase is evaporated and stripped, getting the
46
47
saturation at the top of the column. Thus, the epichlorohydrin-water azeotrope is obtained at the top of the
48
49
50 column that at the vacuum operation conditions achieves a 22.8 w% of water. The heat generated in the main
51
52 reaction, according to the energy balance, takes a value of 55.5 MJ/kg of epichlorohydrin produced. Out of it
53
54 410 kJ are consumed per kg of epichlorohydrin evaporated. Thus the energy to be removed from the system is
55
56 2.17 x 105 MJ/h, so the 2% of the reaction heat will evaporate the undissolved epichlorohydrin and join the
57
58
59
60 22
1
2
3 countercurrent vapor stream. The excess will be indirectly refrigerated. The other substances, such as NaOH,
4
5
NaCl, glycerol and DCHs do not reach their solubility limit along the reactor, so they remain in the aqueous
6
7
8 phase and constitute the waste stream at the bottoms. The high amount of liquid water that flows inside the
9
10 reactive column is not plotted in Figure 9, for clarity.
11
12
13
14 Following this process, with the quantity of the components fed indicated at the beginning of this
15
16 section, we produce 26,540 t/yr of epichlorohydrin with at least 99.9 w% of purity, the commercial
17
18 concentration of this product. The process yield reaches 80 %, related to the mass of pure glycerol fed to the
19
20 plant, higher than the yield of the current industrial process set at 73 % related to the pure propylene fed, 28
21
22 and using a sustainable raw material. See the stream compositions in the supplementary material.
23
24
25
26 4.2.- Economic evaluation
27
28 In this section, we estimate the investment costs of the designed plant, the payout time, the
29
30 production costs, the total invested capital and the sales revenue.
31
32
The epichlorohydrin production cost comprises the manufacturing costs and the management costs:
33
34
35 -- The manufacturing costs are the expenses involved in the stages that process the raw materials
36
37 into the main product. They include the raw materials cost, direct and indirect labor, utilities, supplies,
38
39 maintenance, laboratory, equipment depreciation, insurance and taxes. Silla’s method 29 is used to compute
40
41 the cost of utilities, supplies, maintenance, laboratory, insurance and taxes cost items. In the case of labor
42
43 costs, the salaries of the various employees are taken from the XVII Spanish Labor of Chemical Engineering
44
45
Agreement (2013) and updated to 2014.30 The equipment depreciation is computed assuming straight-line
46
47
48 depreciation 31 and the raw material cost is the sum of the products of each substance quantity and its price
49
50 (DDP). The manufacturing costs add up to 24 M€/yr.
51
52 --On the other hand, management costs are also estimated by Silla’s 29 method and add up to 10
53
54 M€/yr.
55
56
57
58
59
60 23
1
2
3 Therefore, the epichlorohydrin production cost is estimated to be 36 M€/yr, and its breakdown is
4
5
shown in Figure 10. This cost, according to the capacity of production of the plant, results in an
6
7
8 epichlorohydrin production unit cost of 1,282 €/t. The current epichlorohydrin selling price in 2014 prices is
9
10 1,976.22 €/t, 32 at the exit of the plant (ExW).
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31 Figure 10 – Production cost breakdown
32
33
34 The total invested capital is also computed comprising the investment necessary to the construction
35
36 of the plant and its start up, including equipment purchase and installation, ground acquisition and its
37
38 adjustment and all related to the project development. The total invested capital includes tied-up capital and
39
40 working capital:
41
42
--The tied-up capital comprises the direct capital, building expenses, research, start up and other expenses
43
44
45 items. As part of the direct capital, the equipment purchase, see Table 2 for the complete list, and installation
46
47 cost are shown in Table 3. The design of the various units across the flowsheet such as tanks or heat
48
49 exchangers is based on typical design rules in Walas 33 and Sinnot 34. The compressors are designed based
50
51 on the power and the reactors based on the kinetics and/or residence times in the literature or a combination
52
53 of both. For further details of the equipment units see Almena. 23 The equipment purchase is mainly obtained
54
55
from Matche, 35 or else in Peters, Timmerhaus and West’s tool, 36 in which case the price is updated to 2014
56
57
58
59
60 24
1
2
3 values. The installation factor used for each unit is fixed by Madrigal et al.37 In addition, the correlations used
4
5
for estimating the cost of most of the units are presented in the supplementary material.
6
7
8 Table 2. – Equipment design variables.
9
10
11
12 3
Unit Type Material Volume (m )
13 Crude Glycerol Tank Large Vertical API Carbon steel &API 4367
14 Epichlorohydrin Tank Large Vertical API Carbon steel & API 2655
15
Wastes Tank Large Vertical API Carbon steel & API 8896
16
17 M-01 Static inline mixer Stainless steel AISI 316 -
18 M-02 Stirred Tank Stainless steel AISI 304 4.35
19 M-03 Stirred Tank Stainless steel AISI 304 4.35
20 M-04 Static inline mixer Stainless steel AISI 316 -
21 R-01 Semibatch (x4) Stainless steel AISI 304 12.25 (x4)
22
23 Unit Type Material Diameter (m) Height (m)
24 T-01 Packed column Carbon steel 0.90 10.0
25 T-02 Packed column Stainless steel 2.70 33.2
26 R-02 Packed column Stainless steel 0.90 16.0
27
28 Unit Type Material Diameter (m) Length (m)
29 Dec-01 Horizontal cylinder Stainless steel AISI 304 0.762 13.1
30 Dec-02 Vertical tank Carbon steel 0.90 2.70
31 2
32 Unit Type Material Heat exchange area (m )
33 I-01 Shell and tubes Carbon steel 12.7
35 I-03 Shell and tubes Stainless steel AISI 316 (only tubes) 25.8
36 I-04 Double pipe Stainless steel AISI 316 3.9
38 I-06 Double pipe Carbon steel 5.3
40
I-08 Shell and tubes Carbon steel 72.7
41
45 CD-01 Shell and tubes Carbon steel 25.4
46 EV-01 Shell and tubes Carbon steel 46.0
47 CD-02 Shell and tubes Stainless steel AISI 316 (only tubes) 264.1
48 EV-02 Shell and tubes Stainless steel AISI 316 108.0
49
50 Unit Type Material Power (kW)
51 C-01 Centrifugal Stainless steel AISI 316 141.56
52 C-02 Centrifugal Stainless steel AISI 316 97.52
53 C-03 Centrifugal Carbon steel 70.15
54 Exp-01 Radial expander Carbon steel 52.61 (Produced)
55
56
57 Unit Bed Type Package weight (kg) Material Diameter (m) Height (m)
58 S-01 4 A Zeolite 220 (x2) Carbon steel 0.60 2.40
59
60 25
1
2
3
4
5
Meanwhile, piping (including valves and pumps) represents 45 % of equipment cost, instrumentation
6
7
8 accounts for 20 %, isolation 7%, electric installation adds up to 15 % and utilities installation represent 40 % of
9
10 equipment cost based on typical values.29, 33 In addition, the cost of the ground needed for the allocation of the
11
12 project ascends to 7.25 M€. The sum of it corresponds to fixed capital. Besides, the honoraries must be
13
14 considered, which represents 20 % of fixed capital. Direct capital is computed as the sum between the fixed
15
16 capital and the honoraries. Other expenses and building expenses represent 20 % and 7 % of the direct
17
18
capital respectively. Furthermore, fixed investments also include research, representing 12 % of them, and
19
20
21 start up expenses, which suppose the 8 % of the fixed investment. As a result, the tied-up capital adds up to
22
23 55.6 M€.
24
25
26 Table 3. – Equipment purchase and installation cost.
27
28
29 Installation Installation
Equipment set Purchase Cost Total Cost
30 Factor Cost
31 Storage Tanks 972,000 € 1.7 680,000 € 1,652,000 €
32
33 Mixers 822,000 € 1.8 657,000 € 1,479,000 €
34 Semibatch reactors 1,337,000 € 1.8 1,069,000 € 2,406,000 €
35 Columns (distillation and
36 2,352,000 € 2.1 2,587,000 € 4,939,000 €
reaction)
37
38 Liquid-liquid separators 43,000 € 1.7 30,000 € 73,000 €
39 Heat exchangers 909,000 € 1.9 801,000 € 1,727,000 €
40 Compressors 578,000 € 1.2 116,000 € 694,000 €
41
Molecular Sieves 18,000 2.1 20,000 38.000
42
43 FINAL COST 7,031,000 € - 5,977,000 € 13,008,000 €
44
45
46 --The working capital is the second kind of investment and makes it possible to operate the plant. It is
47
48 calculated for an only one cycle of production, fixing one month as time base, and it includes the following
49
50
items: raw materials, manufacturing materials, stored products, sales outstanding one month ahead and
51
52
53 liquidity. The sum of all this items reaches 7.2 M€, as working capital needed.
54
55 The total invested capital adds up to 63.7 M€. The breakdown for the invested capital is shown in
56
57 Figure 11.
58
59
60 26
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22 Figure 11 – Total invested capital breakdown
23
24
25 Next, we compute the sales revenue obtained by the operation of the plant. According to the plant
26
27
28
production capacity of 26,540 t/yr of epichlorohydrin and the product selling price fixed in 1,976.22 €/t ExW, 32
29
30 the sales revenue ascends to 52.9 M€.
31
32 In order to check the profitability of the epichlorohydrin plant, the economic evaluation results in a
33
34 gross profit of nearly 18.5 M€, which represents a gross profit percentage of 29 %. Once deducted the
35
36 corporate income tax, set at 30 % for the chemist industry in Spain, the net profit takes a value of 12.9 M€ (20
37
38 %). It means that the plant, expected to be working for an average life or 20 years, is profitable, with an
39
40
41
invested capital recovery period of 5 years.
42
43 The price of raw materials is volatile, above all of them that of glycerol. Therefore, it is interesting to
44
45 see the effect of the variation of the prices of glycerol, HCl and NaOH in the production cost of epichlorohydrin.
46
47 Figure 12 shows a parametric figure of the sensitivity analysis of the prices of the main raw materials on the
48
49 production cost of epichlorohydrin. We cover a rage of 0.75-1.25 times the cost of each one. As expected,
50
51 there is a linear relationship between the product costs and that of the raw materials from 1.16€/kg to 1.4€/kg.
52
53
The unit cost of the product is more sensitive to the price of NaOH and HCl than to the price of crude glycerol.
54
55
56
57
58
59
60 27
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
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34 Figure 12.-Sensitivity analysis of the effect of the raw material prices on the production cost.
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36
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38 5.- Discussion and Conclusions
39
40
41 In this work a novel process for the production of epichlorohydrin has been proposed using glycerol
42
43 as a sustainable raw material. The aim is to provide further added value to the main byproduct of the biodiesel
44
45
46 industry by providing an alternative market for it.
47
48 The process consists of four stages, glycerol purification, its reaction to mono and dichlorohydrins
49
50 and their separation, epichlorohydrin production and final product purification. We use a hybrid modular-
51
52 equation based modeling approach to simulate the operation of such process integrating MATLAB and
53
54 CHEMCAD.
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60 28
1
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3 It was found that the proposed process has yield 10% higher than the current industrial process
4
5
(80.5% vs. 73 % related to the mass of pure glycerol fed to the plant) using a sustainable raw material.
6
7
8 The process consumes 41.5 kt/yr of glycerol, 29 t/yr of HCl and 15.9 kt/yr of NaOH to produce 26.5
9
10 kt/y of epichlorohydrin at 99.9 w%. The investment cost adds up to 63.7 M€ with a production cost of 1.28
11
12 €/kg. As a result the payout time is 5 years, while the plant is projected to operate continuously during an
13
14 average life of 20 years.
15
16
17
18
Nomenclature
19
20
21
22 A: Cross sectional area (m2).
23 C: Concentration (mol/cm3).
24 Ea: Activation energy (kJ/mol).
25 F: Molar flow (kmol/s).
26 Fe: Molar inflow (kmol/s)
27 Fs: Molar outflow (kmol/s)
28 k: Arrhenius constant.
29 K: Velocity constant. Units dependant on the reaction
30 N: Number of moles in reactor (kmol).
31
r: reaction rate.
32
V: Liquid volume (dm3).
33
34 ε: Porosity.
35 εL: Liquid hold up parameter.
36 θP: Parameter (Dimensionless).
37
38 Subscripts:
39
40 MCH: Monochlorohydrin.
41 DCH: Dichlorohydrin.
42
Gly: Glycerol.
43
44
EH: Epichlorohydrin.
45 e: Inlet
46 M€: Millions of Euros.
47 s: Outlet
48 o: Initial
49
50
51 *S Supporting Information
52 Detailed correlations for units cost estimation and the stream tables for the entire flowsheet are also provided.
53 This material is available free of charge via the Internet at http://pubs.acs.org.
54
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60 29
1
2
3 References
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5
6
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11 biodiesel from algae oil via glycerol fermentation. Applied Energy. 2014, 135, 108–114.
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14 Recycling of Methanol Produced from Glycerol. Environmental Progress & Sustainable Energy. 2013, 32 (4),
15 791–801.
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12 Epichlorohydrin via Glycerol Chlorination. Ind. Eng. Chem. Res. 2010, 49, 964–970.
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15 Technical Aspects of the Synthesis of Chlorohydrins from Glycerol Ind. Eng. Chem. Res. 2014, 53, 8939–
16 8962.
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20 Dichloro-2-Propanol Using Aspen Plus. International Journal of Chemistry. 2011, 3 (1), 196–201.
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25 (22) RASCHIG. Ring Division, Porosity of a random packing of 3.5 inches metal pall rings. 2014. Last
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1-800-t-fd-nwe/.
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13 7199-0.
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23 Spanish. Ingeniería Química. 1991, 23 (271), 229-240.
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21 Figure 1.- Hydrochlorination of glycerol reaction.
22 90x35mm (300 x 300 DPI)
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12 Figure 2.- Dehydrochlorination of dichlorohydrins reaction.
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26 Figure 3 – Process flow chart.
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Figure 4 – Dehydrochlorination of glycerol scheme.
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Figure 5 – Dehydrochlorination of glycerol simplified scheme.
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35 Figure 6 – Mass balance in a differential volume of reactor R-02.
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34 Figure 7 – Evolution in time of the composition in semibatch reactor.
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29 Figure 9 – Evolution of the components molar flows along the reactive distillation column.
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35 Figure 10 – Production cost breakdown
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36 Figure 11 – Total invested capital breakdown
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34 Figure 12.-Sensitivity analysis of the effect of the raw material prices on the production cost.
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Techno-Economic Analysis of The Production of Epichlorohydrin From Glycerol

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