Production of 1,3-Butadiene and Associated Coproducts Ethylene and

Article Cite This: Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

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Production of 1,3-Butadiene and Associated Coproducts Ethylene and Propylene from Lignin Namit Tripathi,† Srinivas Palanki,*,† Qiang Xu,† and Krishna D. P. Nigam‡ †

Dan F. Smith Department of Chemical Engineering, Lamar University, P.O. Box 10053 Beaumont, Texas 77710, United States Indian Institute of Technology, Delhi Hauz Khas, New Delhi, India

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‡

ABSTRACT: 1,3-Butadiene is used in the production of commercially important elastomers. However, the sustained production of 1,3-butadiene is facing challenges due to the reduction in availability of heavier cracker feedstock. In this article, three different routes that utilize biomass to produce 1,3-butadiene and associated coproducts ethylene and propylene from lignin are explored. Steady-state simulation models are developed, and it is shown that, while all three routes are feasible, the yield of 1,3-butadiene is low in all cases. For this reason, it is necessary to consider the production of other useful products, such as ethylene and propylene, in an integrated plant that is used to make up the shortfall of 1,3-butadiene. The simulation models provide an estimate of the amount of lignin needed to produce additional 1,3-butadiene to augment the shortfall from a traditional 1,3-butadiene plant. Furthermore, the simulation models can be used to calculate the emissions of carbon dioxide and carbon monoxide.

1. INTRODUCTION 1,3-Butadiene is an important raw material in the production of commercially important elastomers, such as styrene butadiene rubber, polybutadiene rubber, and styrene butadiene latex. Currently, most 1,3-butadiene is obtained by steam cracking in olefin plants, and the quantity of butadiene obtained depends on the feedstock used by crackers. Generally, heavier cracker feedstock produces more butadiene than the lighter ones. As the cracker feedstock around the globe is trending toward lighter feedstock (e.g., ethane from shale gas), the sustained production of 1,3-butadiene by existing butadiene facilities with olefin plants is facing challenges, and thus it is necessary to look for alternative feedstock sources of 1,3-butadiene.1 In addition, processes that produce 1,3-butadiene also frequently produce coproducts ethylene and propylene. Ethylene is extensively used in agriculture as a plant hormone to ripen fruits. It is also used in the chemical industry to produce ethylbenzene, ethylene dichloride, ethylene oxide, high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and petrochemical intermediates. According to the market trends and published reports, ethylene demand in the market is expected to grow.2 Propylene is the secondlargest-volume chemical produced globally. It is an important © XXXX American Chemical Society

raw material for the production of organic chemicals such as polypropylene, acrylonitrile, propylene oxide, and oxoalcohols as well as for a large variety of industrial products. Over the next few years, the demand for propylene is expected to grow at a constant pace.3 For this reason, it is also necessary to look at the production of coproducts ethylene and propylene while considering the production of 1,3-butadiene. There is increasing interest in exploring the use of biomass as a sustainable and renewable alternative to fossil-based chemistry.4 In particular, one such important research areas is focused on utilizing lignocellulosic biomass, which is more abundant and relatively cheaper than starchy biomass. Lignocellulosic biomass consists of approximately 50% cellulose, 30% hemicellulose, and 20% lignin on a weight basis.5 The U.S. Department of Energy has developed a list of 12 potential biobased platform chemicals.4 There is a considerable amount of literature on the development of thermochemical processes to convert Special Issue: Biorenewable Energy and Chemicals Received: Revised: Accepted: Published: A

February 1, 2019 June 11, 2019 June 14, 2019 June 14, 2019 DOI: 10.1021/acs.iecr.9b00664 Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

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Industrial & Engineering Chemistry Research

Figure 1. Process flow diagram for route 1.

biomass to fuels.6−9 Geilen et al.10 describe the use of a multifunctional catalyst to produce lactones, diols, or cyclic ethers from lignocellulosic biomass. De et al.11 describe recent developments in hydrodeoxygenation catalysts in the effective transformation of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Dutta and Pal12 survey sustainable one-pot conversion methods of cellulose into 5-hydroxymethylfurfural and isosorbide, which are then converted to commercially important products in an integrated biorefinery. Gollakota et al.13 and Fiorentino et al.14 provide a recent review on the conversion of biomass to chemicals. In parallel with experimental approaches for determining pathways to convert biomass to useful chemicals, there have also been simulation efforts to model these processes. For example, Huang et al. developed a detailed process model for a comprehensive integrated biorefinery.15 A comprehensive review of biomass gasification modeling was conducted by Baruah and Baruah.16 Although there is extensive literature in experimental research to convert biomass to useful chemicals, it is observed that most of these approaches utilize the cellulose found in biomass to convert to useful chemicals, and lignin is used as a low-grade fuel. Although lignin holds great potential as a renewable source of fuels and aromatic chemicals, lignin valorization technologies are substantially less developed than those for the polysaccharides.17 Lignin is an amorphous and highly branched polymer of phenyl propane units, and this chemical structure indicates that it may be a good source of valuable chemicals. Furthermore, most modeling efforts are geared toward the pyrolysis of biomass for the production of heat and electricity. Most studies in the biomass literature focus on the conversion of cellulose, and there is very little literature on the use of lignin as a starting material for making commodity chemicals. In this article, three different chemical processes to convert lignin to 1,3-butadiene and associated coproducts ethylene and propylene are developed by utilizing commercially available catalysts and unit operations. On the basis of the proposed new processes, simulation models are developed to conceptually demonstrate

their efficacies. This study bridges traditional petrochemical and biochemical processes together and lays a solid foundation for exploring biomass resources to make up the shortage of heavier petrochemical feedstocks in the current era of lighter feedstocks from shale gas. The organization of this article is as follows. In section 2, three processes are described to convert lignin to 1,3-butadiene and associated coproducts ethylene and propylene. A detailed process description is given for the three processes under consideration. Section 3 describes how the steady-state process models are developed in the Aspen Plus environment. Section 4 provides details of simulation results as well as a comparison of the 1,3-butadiene yield of the three processes. Finally, concluding remarks are made in section 5.

2. PROCESS DESCRIPTION The production of syngas from biomass has been investigated in the literature using various types of gasifiers.18−21 Syngas plays an important role as an intermediate in the production of Fischer−Tropsch liquids, and its production from biomass exhibits a promising prospective.22 Several biomass to syngas demonstration projects have been developed recently, such as the Hynol project in the United States, the BioMeet and BioFuels projects in Sweden, and the BGMSS project in Japan.23−25 In this article, lignin is first converted to syngas in a hightemperature, low-pressure gasifier. Then, three alternative routes are considered to convert the syngas to 1,3-butadiene and associated coproducts. Each of these routes involves multiple steps (reaction and separation), and the process conditions for each step are taken from the literature as described in the succeeding subsections. The first route converts lignin to 1,3-butadiene and associated coproducts via syngas, dimethyl ether (DME), and light oils (LO). The second route converts lignin to 1,3-butadiene and associated coproducts via syngas, methanol (MeOH), and light oils (LO). The third route converts lignin to 1,3-butadiene and associated coproducts via syngas and light oils (LO). In particular, we have focused on the use of the commercially available and most commonly used B

DOI: 10.1021/acs.iecr.9b00664 Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

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C3H6 + CH3OH → C4 H8 + H 2O

SAPO-34 catalyst for the conversion to 1,3 butadiene, ethylene, and propylene. A brief description of each process is given below. 2.1. Gasification. In the present study, syngas with high CO and H2 content is obtained via a gasification step. The gasification unit is based on the thermoselect process for producing syngas from waste biomass.21 A mixture of lignin and water is utilized as the feedstock for the reactor operating at 1500 K and 0.1 MPa. The following reaction occurs:26 lignin + 8.7H 2O → 9CO + 14.5H 2

The product leaving the reactor is pressurized to 2.1 MPa and cooled to 223.15 K and then fed into the first distillation tower. It is necessary to utilize cryogenic distillation conditions because of the low boiling points of propylene and butenes. The distillate, which is predominantly propylene, is collected as the top product in the tower. The bottom product of the first distillation consists mainly of butenes and water and is fed into the second distillation tower. The bottoms product of this column is mainly water. The distillate, which is predominantly butenes, is collected as the top product in the second distillation tower and is supplied to the iso/dehyd unit, which is used for the production of 1,3-butadiene. The details of this unit are described later in section 2.5. 2.3. Route 2. Figure 2 shows a process flow diagram of route 2. In the H2/CO/CO2 adjustment unit, the syngas is mixed with H2 to achieve a H2/CO ratio of 5:1 before it is supplied to the reactor.28 The following reaction occurs:

(1)

The syngas produced in the gasification unit is cooled, and CO2 in the cleaned syngas is separated in an absorption tower. This gasification step is common to all three routes considered in this research. The remaining steps of the three routes are described below in sections 2.2−2.5. 2.2. Route 1. Figure 1 shows a process flow diagram of route 1. The dimethyl ether (DME) synthesis unit is based on the process described by Holdings.27 The following reactions occur: CO + 2H 2 → CH3OH (methanol synthesis)

(2)

CO + H 2O → CO2 + H 2 (water−gas shift)

(3)

CO + CO2 + 5H 2 → 2CH3OH + H 2O

(4)

The synthesis of DME from syngas is favored at higher pressures. The syngas stream is pressurized to 3.3 MPa and cooled to 553.15 K and then fed into a reactor.26 The CO conversion28 is 36%. The product mixture leaving the reactor is cooled to 223.15 K and then separated into gas and liquid phases. The liquid mixture is supplied to the DME-to-LOs reactor, which is based on a report by Park et al.29 The following reaction occurs at 553.15 K: (5)

CH3CH 2OCH3 → CH3OH + C2H4

(6)

C2H4 + CH3OH → C3H6 + H 2O

(7)

(9)

The MeOH synthesis unit is designed on the basis of the operation conditions for a commercial plant.30 The syngas is pressurized to 5.1 MPa and cooled to 573.15 K before being fed into the reactor. The product mixture leaving the reactor is cooled to 273.15 K, and the excess hydrogen is separated as the gas phase. The liquid phase, which consists mainly of methanol, is supplied to the MeOH-to-LOs unit. The following reactions occur in the MeOH-to-LOs reactor:

2CH3OH → CH3OCH3 + H 2O (methanol dehydration)

CH3OH + CH3OCH3 → CH3CH 2OCH3 + H 2O

(8)

2CH3OH → C2H4 + 2H 2O

(10)

3CH3OH → C3H6 + 3H 2O

(11)

4CH3OH → C4 H8 + 4H 2O

(12)

The MeOH-to-LOs unit is designed on the basis of a report by Kumita et al.31 The feed mixture is supplied to the reactor at 0.1 MPa and 273.15 K. The product stream is pressurized to 2.1 MPa and cooled to 223.15 K and then fed into the first distillation tower. The distillate, containing predominantly C


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2.5. Iso/Dehyd. For all three routes, the iso/dehyd unit is based on a Mitsubishi patent.33 This process is used to supply 1,3-butadiene commercially from n-butene obtained through the steam cracking of naphtha. The hydrocarbon mixture containing n-C4H8 is mixed with air and steam and then heated to the desired temperature and supplied to the reactor. The composition of the air/steam/hydrocarbon mixture used as a feed gas is 13.1:11.2:3.6.28 The product mixture leaving the reactor is supplied to the distillation towers, which in turn provide 1,3-butadiene as the final product.

propylene, is collected as a top product in the tower. The bottom product of the first distillation consists mainly of butenes, and water and is fed into the second distillation tower. The bottom product of this column is mainly water. The distillate, which is predominantly butenes, is collected as the top product in the second distillation tower and is supplied to the iso/dehyd unit, which is used for the production of 1,3-butadiene. The details of this unit are the same as that used for route 1 and are described later in section 2.5. 2.4. Route 3. Figure 3 shows a process flow diagram for route 3. The unit for the direct synthesis of LOs from syngas is designed on the basis of a report by Schulte et al.32 The syngas is pressurized to 2.2 MPa and cooled to 613.15 K and then supplied to the reactor. The following reaction occurs:

3. PROCESS MODELING AND SIMULATION Steady-state models for each process are developed in Aspen Plus V1034 based on the plant process flow diagram and operating conditions acquired from the literature.26,28 Radfrac is used to model the distillation columns. A Gibbs reactor is used to model the syngas reactor in all of the processes under the assumption that the syngas reactions reach equilibrium conversion. Kinetic models for the DME synthesis and MeOH synthesis reactions are not available; however, because experimental values of conversion are available for these reactors, these are modeled as stoichiometric reactors with fixed conversion. The NRTL model is used for the distillation process because of the presence of polar compounds in the organic mixture.34 Thermodynamic properties of lignin are not directly available in the standard ASPEN PLUS properties database. A methodology to compute the properties of lignin in ASPEN PLUS was recently developed and verified experimentally by the National Renewable Energy Laboratory,35 and this methodology is used in this research. Lignin is modeled as a mixture of p-hydroxyphenylpropane, guaiacylpropane, and syringylpropane.26,35 The molecular structure of these lignin

11CO + 20H 2 → CH4 + C2H4 + C3H6 + C4 H8 + CO2 + 9H 2O

(13)

The product leaving the reactor is cooled to 223.15 K and the pressure is reduced to 2.1 MPa. The liquid phase, which consists of propylene, butenes, and water, is fed into the first distillation tower, and the gas phase, which contains primarily ethylene, is collected for further processing of ethylene. The distillate, containing predominantly propylene, is collected as a top product in the tower. The bottoms stream, which consists of butenes and water, is fed into the second distillation tower. Water is removed as the bottom product. The distillate, which is predominantly butenes, is collected as the top product in the second distillation tower and is supplied to the iso/dehyd unit, which is used for the production of 1,3-butadiene. The details of this unit are the same as that used for routes 1 and 2 and are described below. D


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adjusted to the stoichiometric ratio shown in eq 1. The total amount of ethylene, propylene, and 1,3 butadiene produced in each of the three routes was computed via these simulations. It is observed from Figures 4−6 that as the lignin flow rate increases, a greater amount of ethylene, propylene, and 1,3 butadiene is produced in each of the three routes.

components is drawn, and ASPEN PLUS is utilized to calculate the required component properties using the NIST thermodynamic engine. The composition of lignin and feed is taken from existing data,26,35 which is shown in Tables 1 and 2, respectively. Table 1. Lignin Composition component

mass fraction (%)

p-hydroxyphenylpropane guaiacylpropane syringylpropane

0.34 0.33 0.33

Table 2. Feed Composition component

mass fraction (%)

p-hydroxyphenylpropane guaiacylpropane syringylpropane water

18.19 17.65 17.65 46.51

Equipment configurations and operating parameters for each piece of equipment are based on the information available in the literature.28 The theoretical number of stages, operating pressures, reflux ratio, and feed trays of each column and operating parameters for reactors for all three processes are provided in Tables 3, 4, and 5.

Figure 4. Ethylene production.

Table 3. Equipment Configurations for Route 1 gasifier no. of trays reflux ratio feed tray temperature (K) pressure (MPa)

DME reactor

LO reactor

butadiene reactor

columns 50 1 25

1500

553.15

553.15

608.15

0.1

3.3

0.1

0.1

2.1


methanol reactor

LO reactor

butadiene reactor

Figure 5. Propylene production. columns 50 1 25

1500

573.15

273.15

608.15

0.1

5.1

0.1

0.1

Table 6 shows a comparison of the yields of ethylene, propylene, and 1,3-butadiene in each route in terms of the weight of useful product per unit weight of lignin used when the lignin feed is 647 655 kg/h. It is observed that the yield of 1,3butadiene is low in all three routes. This is mainly because commercial catalyst SAPO-34 used in the conversion of syngas

2.1


LO reactor

butadiene reactor

columns 50 1 25

1500 0.1

613.15 2.4

608.15 0.1

2.1

4. RESULTS AND DISCUSSION ASPEN PLUS simulations were run using the same equipment specifications for lignin flow rates ranging from 480 000 to 720 000 kg/h of lignin feed. For each case, the water feed was

Figure 6. 1,3-Butadiene production. E


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Industrial & Engineering Chemistry Research Table 6. 1,3-Butadiene, Ethylene, and Propylene Yield Results method

1,3-butadiene yield (wt % lignin basis)

ethylene yield (wt % lignin basis)

propylene yield (wt % lignin basis)

route 1 route 2 route 3

3.4 1.0 1.6

0.4 0 10.4

3.1 0 10.2

Table 8. Comparison of the Butadiene Stream from a Conventional Naphtha Cracker and from Lignin Processes

component propene n-butane i-butane 1-butene i-butene trans-2butene cis-2butene 1,3butadiene 1-pentene hydrogen

conventional feed (kg/h) (turndown capacity)

feed from route 1 (kg/h) (@ lignin flow of 408 064 kg/ h)

feed from route 3 (kg/h) (@ lignin flow of 790 625 kg/ h)

2.52 1917.72 892.08 1592.64 5896.8 824.04

4487.78

41 594.1

488.414

29 316.3

650.16

687.514

12 751.2

12650

12 650

497.328 381.5

4397.17

products to alkenes in the last reaction step is not tuned to high yields of 1,3-butadiene.29 Route 1 gives the highest yield of 3.4 wt %. For this reason, it is necessary to look for other valuable products, such as propylene and ethylene, produced via the three routes for the economic viability of using lignin as a feed source. With this additional consideration, it is observed that route 3, which produces 1.6 wt % 1,3-butadiene in addition to 10.4 wt % ethylene and 10.2 wt % propylene, can prove to be economical in an integrated plant that utilizes not only 1,3-butadiene but also ethylene and propylene to make valuable products. In a previous publication,36 we had considered the production of 1,3-butadiene from a conventional naphtha cracker feed. Normal and turndown throughputs of 1,3-butadiene in the naphtha feed were 25 050 and 12 625 kg/h, respectively, based on values from BASF.37 If we assume that such a plant is operating at a turndown throughput of 12 625 kg/h due to a shortage of naphtha cracker feed and we would like to produce an additional 12 625 kg/h of 1,3-butadiene from a lignin source, then Figure 7 can be utilized to calculate the necessary lignin

conventional naphtha cracker streams and is the subject of a future publication. CO2 and CO conversion and utilization are gaining significant attention worldwide because of their impact on global climate change. All of the proposed processes emit CO and CO2, which can be captured and converted to syngas from a tri-reforming process.38 The emission of CO and CO2 into the atmosphere as an exhaust from all three routes is shown in Figures 7 and 8. It is

Figure 7. CO2 emission.

Figure 8. CO emission.

feed to produce this additional 1,3-butadiene, and this result is shown in Table 7. It is observed that we need a lignin feed of

observed that route 1 has the highest emission of CO and CO2, so route 3 is preferred if we want to minimize CO and CO2 in addition to getting the best yield of useful products (i.e., 1,3butadiene, ethylene, and propylene).

Table 7. Lignin Required to Produce the Required Additional 1,3-Butadiene in Routes 1 and 3 method

lignin flow (kg/h)

1,3-butadiene flow (kg/h)

route 1 route 3

408 064 790 625

12 625 12 625

1139.04

5. CONCLUSIONS Currently, several 1,3-butadiene plants are being run at turndown capacities due to the reduction in availability of heavier cracker feedstock, which is the traditional route to 1,3butadiene. In this article, three different routes that utilize biomass to produce 1,3-butadiene and associated coproducts ethylene and propylene from lignin are explored. Steady-state simulation models are developed, and the yield of useful products from these routes is studied. It is found that the highest yield of 3.4 wt % of 1,3-butadiene is produced in a process that converts lignin to 1,3-butadiene via syngas, dimethyl ether, and light olefins. However, if we consider the production of ethylene and propylene as additional useful products, then the process

408 064 kg/h if we use route 1 and a lignin feed of 790 625 kg/h if we use route 3. It can be seen from Table 8 that the composition of a conventional naphtha cracker feed, which is used to recover 1,3-butadiene, is substantially different from the product stream of the lignin processes (routes 1 and 3). Routes 1 and 3 have significant amounts of ethylene and propylene that need to be integrated in other parts of the plant to make other high-value products. Furthermore, the separation equipment for these product streams will not be the same as the one used for F


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(14) Fiorentino, G.; Ripa, M.; Ulgiati, S. Chemicals from biomass: technological versus environmental feasibility. A review. Biofuels, Bioprod. Biorefin. 2017, 11 (1), 195−214. (15) Huang, H. J.; Lin, W.; Ramaswamy, S.; Tschirner, U. Process Modeling of Comprehensive Integrated Forest BiorefineryAn Integrated Approach. Appl. Biochem. Biotechnol. 2009, 154, 26−37. (16) Baruah, D.; Baruah, D. C. Modeling of biomass gasification: A review. Renewable Sustainable Energy Rev. 2014, 39, 806−815. (17) Azadi, P.; Inderwildi, O. R.; Farnood, R.; King, D. A. Liquid fuels, hydrogen and chemicals from lignin: A critical review. Renewable Sustainable Energy Rev. 2013, 21, 506−523. (18) Lv, P.; Yuan, Z.; Wu, C.; Ma, L.; Chen, Y.; Tsubaki, N. Bio-syngas production from biomass catalytic gasification. Energy Convers. Manage. 2007, 48, 1132−1139. (19) Richardson, Y.; Blin, J.; Julbe, A. A short review on purification and conditioning of syngas produced by biomass gasification: Catalytic strategies, process intensification and new concepts. Prog. Energy Combust. Sci. 2012, 38, 765−781. (20) Couto, N.; Rouboa, A.; Silva, V.; Monteiro, E.; Bouziane, K. Influence of biomass gasification process on the final composition of syngas. Energy Procedia 2013, 36, 596−606. (21) Yamada, S.; Shimizu, M.; Miyoshi, F. JFE Technical Report, 2004, No. 3, pp 21−26. http://www.jfe-steel.co.jp/en/research/ report/003/pdf/003-05.pdf (Accessed on December 17, 2018). (22) Dong, Y.; Hynol, S. M. an economic process for methanol production from biomass and natural gas with reduced CO2 emission. Int. J. Hydrogen Energy 1997, 22 (10−11), 971−977. (23) Norbeck, J. M.; Johnson, K. https://nepis.epa.gov/Exe/ZyPDF. cgi/P100ULLF.PDF?Dockey=P100ULLF.PDF. (Accessed on April 22, 2019). (24) Brandberg, A.; Hjortsberg, H.; Savbark, B.; Ekbom, T.; Hjerpe, C. J.; Landalv, I. https://www.osti.gov/etdeweb/servlets/purl/ 20086721 (Accessed on April 22, 2019). (25) Mitsubishi Heavy Industries. Biomass gasification methanol synthesis system. http://www.mhi.co.jp/power/e_power/techno/ biomass/, April 2006 (Accessed on April 22, 2019). (26) Palanki, S.; Balzaretti, D. Design of Forest Products Process Plants for Production of Platform Chemicals. Journal of Bioprocess Engineering and Biorefinery 2012, 1, 233. (27) JFE Holdings, Inc. U.S. Patent 2006/0052647, March 9, 2006. (28) Hanaoka, T.; Fujimoto, S.; Yoshida, M. Efficiency estimation and improvement of the 1,3-butadiene production process from lignin via syngas through process simulation. Energy Fuels 2017, 31, 12965− 12976. (29) Park, S.; Watanabe, Y.; Nishita, Y.; Fukuoka, T.; Inagaki, S.; Kubota, Y. Catalytic conversion of dimethyl ether into propylene over MCM-68 zeolite. J. Catal. 2014, 319, 265−273. (30) New Zealand Institute of Chemistry. Chemical processes. http://nzic.org.nz/ChemProcesses/energy/7D.pdf (Accessed on December 17, 2018). (31) Kumita, Y.; Gascon, J.; Stavitski, E.; Moulijn, J. A.; Kapteijn, F. Shape selective methanol to olefins over highly thermostable DDR catalysts. Appl. Catal., A 2011, 391, 234−243. (32) Schulte, H. J.; Graf, B.; Xia, W.; Muhler, M. Nitrogen and oxygenfunctionalized multiwalled carbon nanotubes used as support in ironcatalyzed, high temperature Fischer−Tropsch synthesis. ChemCatChem 2012, 4, 350−355. (33) Mitsubishi Chemical Corporation. Method for producing conjugated diene, Jpn. Patent No. PCT/JP2010/058842. (34) Aspen Tech, Inc. Aspen Physical Property System; Aspen Plus V10, 2018. (35) Wooley, W. R.; Putsche, V. Development of an ASPEN PLUS Physical Property Database for Biofuels Components; NREL/TP-42520685, UC Category 1503, DE96007902. (36) Tripathi, N.; Xu, Q.; Palanki, S., Modeling and Simulation of 1,3 Butadiene Extraction Process at Turndown Capacity, Chem. Eng. Technol., 2019, submitted. (37) BASF management’s report on segments of investment in chemical products, https://report.basf.com/2017/en/managements-

that converts lignin to 1,3-butadiene via syngas and light olefins has better economic potential. Furthermore, this process that directly converts syngas to light olefins has lower emissions of carbon monoxide and carbon dioxide. Finally, the amount of lignin needed to produce additional 1,3-butadiene to augment the shortfall from a traditional 1,3-butadiene plant is calculated.

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AUTHOR INFORMATION

Corresponding Author

*Phone: 409-880-8741. Fax: 409-880-8121. E-mail: spalanki@ lamar.edu. ORCID

Srinivas Palanki: 0000-0002-6016-4619 Qiang Xu: 0000-0002-2252-0838 Notes

The authors declare no competing financial interest.

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REFERENCES

(1) Plotkin, J. S. The Continuing Quest for Butadiene, 2016, https:// www.acs.org/content/acs/en/pressroom/cutting-edge-chemistry/thecontinuing-quest-for-butadiene.html (Accessed on December 23, 2018). (2) Ethylene market forecast by application (HDPE, LDPE, LLDPE, Petrochemical intermediates), geography, global market size, share, growth, development and demand. https://www.psmarketresearch. com/market-analysis/ethylene-market (Accessed on November 26, 2018). (3) Chemical Engineering Handbook: Propylene, https://ihsmarkit. com/products/propylene-chemical-economics-handbook.html (Accessed on December 12, 2018). (4) Kamm, B. Production of platform chemicals and synthesis gas from biomass. Angew. Chem., Int. Ed. 2007, 46, 5056−5058. (5) Okuda, K.; Ohara, S.; Umetsu, M.; Takami, S.; Adschiri, T. Disassembly of lignin and chemical recovery in supercritical water and p-cresol mixture: Studies on lignin model compounds. Bioresour. Technol. 2008, 99, 1846−1852. (6) Robbins, M. P.; Evans, G.; Valentine, J.; Donnison, I. S.; Allison, G. G. New opportunities for the exploitation of energy crops by thermochemical conversion in northern Europe and the UK. Prog. Energy Combust. Sci. 2012, 38, 138−55. (7) Pedersen, T. H.; Grigoras, I. F.; Hoffmann, J.; Toor, S. S.; Daraban, I. M.; Jensen, C. U. Continuous hydrothermal co-liquefaction of aspen wood and glycerol with water phase recirculation. Appl. Energy 2016, 162, 1034−1041. (8) Toor, S. S.; Rosendahl, L.; Rudolf, A. Hydrothermal liquefaction of biomass: a review of subcritical water technologies. Energy 2011, 36, 2328−2342. (9) Jindal, M. K.; Jha, M. K. Hydrothermal liquefaction of wood: a critical review. Rev. Chem. Eng. 2016, 32, 459−488. (10) Geilen, F. M. A.; Engendahl, B.; Harwardt, A.; Marquardt, W.; Klankermayer, J. Selective and Flexible Transformation of BiomassDerived Platform Chemicals by a Multifunctional Catalytic System. Angew. Chem. Int. Ed 2010, 49 (32), 5510−5514. (11) De, S.; Saha, B.; Luque, R. Hydrodeoxygenation processes: Advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels. Bioresour. Technol. 2015, 178, 108− 118. (12) Dutta, S.; Pal, S. Promises in direct conversion of cellulose and lignocellulosic biomass to chemicals and fuels: Combined solvent− nanocatalysis approach for biorefinery. Biomass Bioenergy 2014, 62, 182−197. (13) Gollakota, A. R. K.; Kishore, N.; Gu, S. A review on hydrothermal liquefaction of biomass. Renewable Sustainable Energy Rev. 2018, 81, 1378−1392. G


Article

Industrial & Engineering Chemistry Research report/segments/chemicals/products-and-investments.html (Accessed on December 8, 2018). (38) Zhang, Y.; Cruz, J.; Zhang, S.; Lou, H.; Benson, T. Process simulation and optimization of methanol production coupled to trireforming process. Int. J. Hydrogen Energy 2013, 38, 13617−13630.

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Production of 1,3-Butadiene and Associated Coproducts Ethylene and

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