Вы находитесь на странице: 1из 10
Chemical Engineering Journal 240 (2014) 45–54 Contents lists available at ScienceDirect Chemical Engineering Journal

Contents lists available at ScienceDirect

Chemical Engineering Journal

journal homepage: www.else vier.com/locate/cej

Journal journal homepage: www.else vier.com/locate/cej Techno-economic performance of the coal-to-olefins process

Techno-economic performance of the coal-to-olefins process with CCS

Dong Xiang 1 , Siyu Yang 1 , Xia Liu, Zihao Mai, Yu Qian

School of Chemical Engineering, South China University of Technology, Guangzhou 510640, PR China

China University of Technology, Guangzhou 510640, PR China highlights Conduct a techno-economic analysis of the

highlights

Conduct a techno-economic analysis of the coal-to-olefins (CTO) with CCS. Analyze effects of key factors on the CTO with appropriate capture rate 80%. Present strengths and weaknesses of the CTO compared to the methanol-to-olefins.

article info

Article history:

Received 5 September 2013 Received in revised form 21 November 2013 Accepted 23 November 2013 Available online 28 November 2013

Keywords:

Energy efficiency

Cost

Coal-to-olefins

CCS

Methanol-to-olefins

abstract

Coal-to-olefins (CTO) has been attracting more attention of the chemical process industry, in the light of the scarcity of oil resources and richness of coal in China. However, it is inherently accompanied with the problem of severe greenhouse gas emissions. CTO processes therefore face increasing challenges from other alternative processes, especially methanol-to-olefins (MTO) process. This paper conducts a detailed techno-economic analysis of the CTO process with CCS. The effect of carbon capture is studied. The CTO process with 80% carbon capture is slightly less thermodynamically efficient than the conventional CTO process. The corresponding mitigation cost of the process is 150 RMB/t, which is roughly equivalent to the current carbon price. Thus, the effect of energetic and economic penalties on this carbon capture con- figuration is negligible. In comparison to the MTO process, the CTO process with CCS is competitive in product cost even considering carbon tax and it is capable of resisting to market risk. CTO processes with appropriate CO 2 reduction are more applicable to olefins industry in China. 2013 Elsevier B.V. All rights reserved.

1. Introduction

As the backbone of the petrochemical industry, olefins produc- tion scale is critical to development of national economy. As more and more oil-to-olefins projects launched in China, the production grows quickly, and the self-sufficient rate of ethylene and propyl- ene will increases up to 53% and 74% by 2015 [1] . However, there is still a big gap between the domestic supply and demand, which is in urgently needed to be filled by olefins based on alternative re- sources. From 2005 to 2011, coal accounted for 75.1% of the total energy production of China, oil for 15.2%, and natural gas for 2.8%, as shown in Fig. 1 . The oil import dependence was ap- proached to 57% in 2012. Thus, development of the coal-based ole- fins industry is favorable in the context of increasingly severe oil supply shortage. There are now three coal-to-olefins (CTO) projects

Corresponding author. Address: Center for Process Systems Engineering, School of Chemical Engineering, South China University of Technology, Guangzhou 510640, PR China. Tel.: +86 20 87113046, +86 13802902300. E-mail address: ceyuqian@scut.edu.cn (Y. Qian). URL: http://www2.scut.edu.cn/ce/pse/qianyuen.htm (Y. Qian). 1 Dong Xiang and Siyu Yang contributed equally to this paper.

1385-8947/$ - see front matter 2013 Elsevier B.V. All rights reserved.

under operation and other two CTO projects in plan in the next there years in China. These installations are going to approach a capacity of 3 Mt/y [3] . However, CTO is facing the problem of high CO 2 emissions. There have been a number of techniques of CO 2 mitigation devel- oped from chemical and physical methods [4] . For chemical meth- ods, CO 2 is reused mostly as feedstock to produce valued chemical products. Although these methods enable us to exploit CO 2 as a valuable feedstock in many different applications such as the pro- duction of urea and methanol, their contribution to CO 2 mitigation is finite. Physical methods are generally regarded as geologically storing CO 2 underneath. In recent years, carbon capture and stor- age (CCS) technology has received increasing attention because of its large capacity of reducing CO 2 emissions. It is a more eco- nomical and efficient method compared to developing renewable energy, retrofitting major equipments, and improving energy inte- gration for resource and energy saving [5] . A CCS process in general involves three stages: separating CO 2 from flue gas, compressing CO 2 for pipeline transport, and inject- ing CO 2 into geologic reservoirs. For carbon capture, there are mainly three technologies developed, including post-combustion capture, oxy-fuel combustion capture, and pre-combustion

46

D. Xiang et al. / Chemical Engineering Journal 240 (2014) 45–54

Nomenclature

Abbreviations

AGR

acid gas removal

ASU

air separation unit

CCS

carbon capture and storage

CG

coal gasification

CTO

coal-to-olefins

LHV

lower heating value

MS

methanol synthesis

MTO

methanol-to-olefins

RMB

ren min bi

WGS

water gas shift

Notations in formulation

h

domestic-made factor administrative cost (RMB/t) cumulative cash flow (RMB) carbon capture rate (%) depreciation cost (RMB/t) distribution and selling cost (RMB/t) cash flow of year i (RMB) operating & maintenance cost (RMB/t)

C AC

CCF

CCR

C D

C DSC

CF i

C O & M

C POC plant overhead cost (RMB/t) C R raw material cost (RMB/t) C TS&M cost of CO 2 transportation, sequestration and monitor- ing (RMB/t) C U utilities cost (RMB/t)

EI equipment investment (RMB)

EI

r reference equipment investment of unit j (RMB)

J

E wCCS quantity of CO 2 emitted from the CTO plant with CCS (Mt/y)

E w / oCCS quantity of CO 2 emitted from the CTO plant without CCS (Mt/y)

MC

mitigation cost (RMB/t)

OP

olefins price (RMB/t)

OY i olefins yield (Mt/y)

PC product cost (RMB/t)

PC w CCS product cost of the CTO plant with CCS (RMB/t) PC w / o CCS product cost of the CTO plant without CCS (RMB/t) RF i ratio factor of component i (%) S j practical scale of unit j

r

S J

reference scale of unit j

sf

scale factor

TCI

total capital investment (RMB/t/y)

capture [6] . These technologies are usually applied in pulverized- coal power plants and some chemical plants [7] . Introducing a CCS will bring penalties on both energetic and economic perfor- mance [8–10] . For example, in most coal-based power plants, the CO 2 avoidance cost is about 250–330 RMB/t, which is much higher than the current carbon price. The penalties brought by the CCS on chemical processes is, however, lower than those on power generation processes [11,12]. It demonstrates that it is necessary to assess the impact of CCS on the whole perfor- mance of CTO processes. Planning a sound development roadmap for alternative olefins production requires a broad and comprehensive assessment. Tech- no-economic analysis is an essential part of this process. More importantly, the role of CCS in CTO development is needed to be analyzed to find the trade-off among environmental protection, en- ergy penalty, and economic performance. There have been some studies on techno-economic analysis of CTO processes [13–18] . However, the literatures on analyzing CTO processes with CCS from techno-economic point of view could not be found. Besides, some views back up developing methanol-to-olefins (MTO) processes since they have the advantages of low capital investment and envi- ronmental impact. There are now 1 MTO project under operation and other 10 MTO projects in plan in the next three years in China, which will approach to a capacity of 6.8 Mt/y [3] . With the poten- tial challenge of the MTO process, how should people configure CCS on the CTO process? We answer this question by the techno- economic comparison of the CTO process with CCS and the MTO process in this paper.

2. Process modeling

As a base of techno-economic analysis, major units of a CTO process are modeled, including an air separation unit (ASU), a coal gasification unit (CG), an acid gas removal unit (AGR), a carbon capture and storage unit (CCS), a water gas shift unit (WGS), a methanol synthesis unit (MS), and a methanol-to-olefins unit (MTO). For a plant with given capacity and specified operating con- ditions, the model calculates all mass and energy flows. The details of the modeling are described in the following sections.

3500 3000 Hydro,Nuclear,Wind 2500 Natural gas Crude oil 2000 Coal 1500 1000 500 0 1990
3500
3000
Hydro,Nuclear,Wind
2500
Natural gas
Crude oil
2000
Coal
1500
1000
500
0
1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 2010
Year
Mt

Fig. 1. Profile of major energy production in China [2] .

2.1. Coal-to-olefins process

The flow diagram of the CTO process, including the MTO pro- cess, is shown in Fig. 2 . Coal and water are gasified with the oxygen agent from the ASU, to produce syngas in the CG. The hot syngas is quenched in a radiant cooler and a convection condenser, where heat is recovered to generate steam. The syngas is then fed into the WGS to increase the ratio of H 2 /CO for the methanol synthesis. Before methanol synthesis, the syngas is cleaned in the AGR to re- move H 2 S and CO 2 . The clean syngas is then sent to the MS to pro- duce methanol. The crude methanol solution is concentrated to 90% (moral fraction) before fed into the MTO. Prior to olefins sep- aration, there are a serial of steps: quenching, washing, drying, and compression. The front-end depropanization separation technique is applied to separate olefins into ethylene and propylene [18] .

2.1.1. Coal gasification unit In the CG, Texaco gasification technique was adopted. For mod- eling, coal is firstly divided into three kinds of nonconventional matter as coke, ash, and unburned carbon. Then nonconventional matter is decomposed in RYield model in Aspen Plus by element

D. Xiang et al. / Chemical Engineering Journal 240 (2014) 45–54

47

Water Coal H 2 S concentration WGS reactor Acid gas tower Tail gas absorber Water
Water
Coal
H 2 S concentration
WGS reactor
Acid gas
tower
Tail gas
absorber
Water
Mill
Tail gas
Screen
Oxygen
Water
Scrubber
from ASU
Raw syngas
H
2 S
Steam
Gasifier
Air
&
N
2
Cooler
Convective
Water
Radiant
Cooler
S
Methanol
Waste water
Regenerator
Water& slag
Steam
Clean syngas
Quenching
NaOH
tower
Water
Lurgi
DMTO
methanol
Dryer
Methanol
reactor
Alkaline
reactor
Water
tower
scrubber
Water
Waste water
Water
Purge gas
Unreacted
Fuel gas
Ethylene
Propylene
Methanol
gas
C 2 splitter
Crude methanol
Atmospheric
distillation
Pressure
C 3 splitter
column
distillation
column
=
Bottom liquid
C
4
Depropanizer
Demethanizer
Dethanizer
Ethane
Propane

Fig. 2. Process flow diagram of the CTO process.

analysis [19] . After this, decomposed components, O 2 , water, etc. are all fed into RGibbs reactor, which calculates chemical equilib- rium by Gibbs energy minimization. The composition of gaseous

mix was determined according to the property of the input coal

as shown in Table 1 . The simulation was verified by comparing the composition of the output syngas with that of Zheng and Furin- sky’s work [21] . The simulated composition is similar to the refer- ence composition with only a small relative error less than 1.5% [22] .

2.1.2. Methanol synthesis unit

For modeling of methanol synthesis, Lurgi synthesis reactor was

used

and modeled by using the Requil model in Aspen Plus. In gen-

eral,

there are several major reversible reactions in the methanol

synthesis reactor. Cu–Zn–Al catalyst was used for this reaction with its suitable temperature 513 K and pressure 8.2 MPa [22, 23] . The main reactions are shown in Eqs. (1 and 2):

CO þ 2H 2 ! CH 3 OH

ð 1Þ

Table 1 Properties of coal in Yanzhou, China [20] .

Proximate analysis (wt.%)

Ultimate analysis (wt.%, dry)

Moisture content

5.81

Ash

7.53

Fixed carbon

49.85

Carbon

73.64

Volatile matter

37.24

Hydrogen

5.24

Ash

7.10

Nitrogen

1.13

 

Sulfur

2.63

Oxygen

9.83

CO 2 þ 3H 2 ! CH 3 OH þ H 2 O

ð 2Þ

The raw syngas from the CG is cleaned in the AGR presented in the CCS and then shifted into syngas with the molar ratio between hydrogen and carbon monoxide of about 2 [24] . The clean syngas is put into the MS as the feedstock. Following the synthesis reaction, the unreacted syngas are separated out from the chemical products and recycled back to the MS to increase the methanol production [6] . RadFrac model was used to simulate the separation columns and Peng-Rob was selected as the thermodynamic method. Details of the simulation refer to the author’s previous work [22] .

2.1.3. Methanol-to-olefins unit Methanol with molar fraction 90% is converted into product gas in MTO reactor. The hot product gas is cooled in the quenching tower and cleaned in the alkaline tower with NaOH solution to re- move H 2 S and CO 2 . After then, ethylene and propylene are ex- tracted by the front-end depropanization seperation technique. DMTO technique was used to synthesize olefins. The main reac- tions in the synthesis reactor could be summarized as follow:

2CH 3 OH

!

C 2 H 4 þ

2H 2 O

3CH 3 OH

!

C 3 H 6 þ

3H 2 O

4CH 3 OH ! C 4 H 8 þ

4H 2 O

ð

ð

ð

3Þ

4Þ

5Þ

An attrition resistant SAPO-34 was employed as the catalyst. According to the specification of the catalyst, the temperature and pressure were fixed at 763 K and pressure 0.22 MPa. In this condition, the methanol conversion has reported to be close to

48

D. Xiang et al. / Chemical Engineering Journal 240 (2014) 45–54

100%. The olefins synthesis was modeled by Rstoic model in Aspen Plus. The composition of product gas was calculated according to the Ref. [25] . RadFrac model was used to simulate rectifying col- umns. The process compressors were modeled by assuming com- mon isentropic and mechanical efficiency. The NRTL, ELECNRTL, and RKS-BM were adopted as the thermodynamic methods of water scrubber, alkaline tower, and separation tower, respectively. Details of the simulation referred to the author’s previous work

[18,26].

2.2. Carbon capture and storage process

The CCS includes carbon capture, compression, transportation, and storage. The process flow diagram is shown in Fig. 3 . The crude syngas from the gasifer consists of impurities that are mainly ash and acid gases. It is necessary to remove these impurities before methanol synthesis. We employed Rectisol method in this paper. The syngas from the WGS is fed into the water scrubber to remove ammonia and fly ash. After flash dehydration, it is fed into the bot- tom of the acid gas absorber and absorbed by top-down low tem- perature methanol, which is obtained from the regeneration tower and cooled through multistage cooling to 223 K. The upper part of the absorber mainly removes CO 2 while the lower part removes sulfur containing compounds. Without CO 2 capture process, CO 2 is separated and exhausted to environment by using N 2 as the stripping gas. In this case, the exhausted gas is a mixture of N 2 and CO 2 . For CO 2 capture process, a desorber and a companying flash are introduced to purify CO 2 to the high concentration of about 98%. The capture rate of CO 2 could be increased by changing the temperature and pressure of the flash. The H 2 S separated from methanol regenerator is placed into CLAUS conversion process for sulfur recovery. For modeling, RadFrac model was used to simulate the acid gas absorber, the desorber, the H 2 S concentration tower, and the regenerator. Flash model and Compr model were adopted for sim- ulating flashes and compressors, respectively. PSRK was selected as the thermodynamic method. The described CCS referred to the CCS demonstration of coal-to-liquild process installed by Shenhua group in Ordos, China [27] . Different from this CCS, we use pipeline

to transport CO 2 in our model. Purified CO 2 is firstly compressed to 15 MPa and then transported to and injected into underground reservoirs. 20 km for transportation distance and the saline aquifer at 2 km deep as the geological position of the reservoirs was conducted.

3. Analysis methodology

In this section, we mainly analyze the CTO process with CCS from technical and economic points of view. A few indexes are se- lected involving energy efficiency, capital investment, product cost, and cumulative cash flow. The energy efficiency is defined as the product energy gener- ated by all input energy, as shown in Eq. (6). The energy of coal, methanol, and olefins is calculated based on their lower heating values. The all input energy involves both the energy of feedstock and utilities.

Energy efficiency ¼

Product energy ðMWÞ

All input energy ðMWÞ

ð

6Þ

Another technical factor is carbon capture rate (CCR) which is defined as the mass flow of captured CO 2 divided by CO 2 emissions, as shown in Eq. (7).

CCR ¼ Captured CO 2 mass flow ð Mt=yÞ

CO 2 emissions ðMt= yÞ

ð 7Þ

For economic indexes, the capital invested for manufacturing and plant facilities is defined as the fixed capital investment, while those for the plant operation is defined as the working capital. The sum of the fixed capital investment and the working capital is de- fined as the total capital investment. In order to evaluate these in- dexes of olefins production processes, it is necessary to know the capital investment of the basic equipments of the CTO process that could be calculated according to the benchmark case shown in Ta- ble 2 . The detailed calculation of these equipments follows Eq. (8) . While the equipment investment of CO 2 transportation and storage was calculated by the Ref. [30] . The other components of the total capital investment could be determined according to their ratios to

Clean syngas

Acid gas absorber H 2 S concentration tower Water Desorber Tail gas Water scrubber H
Acid gas
absorber
H 2 S concentration
tower
Water
Desorber
Tail gas
Water
scrubber
H 2 S
Crude syngas
Air
N 2
S
Waste water
Methanol
Regenerator
CO 2
CO 2 transport
(Pipeline)
CO 2 storage
(Saline acquifer)

Tail gas

Fig. 3. Process flow diagram of the CCS process.

D. Xiang et al. / Chemical Engineering Journal 240 (2014) 45–54

49

the equipment investment. The ratios are shown in Table 3 and the calculation follows Eq. (9) [31–33]. In this paper, the capital invest- ment was updated to 2012 prices by using the Chemical Engineer- ing Plant Cost Index [34,35]. The currency exchange rate between US$ and RMB was 6.2 in 2012 and the olefins price was set to be 10,000 RMB/t [36] .

EI ¼ X h EI

r

j

J

S

j

r

j

S

!

sf

ð

8Þ

TCI ¼ EI 1 þ X RF i !

i

ð 9Þ

where EI is the equipment investment, h is the domestic-made fac- tor, EI is the reference equipment investment of unit j, S j is the practical scale of unit j, S is the reference scale of unit j , sf is the scale factor, TCI is the total capital investment, RF i is the ratio factor of capital investment of component i . For calculation of the product cost, we made some assumptions as listed in Table 4 . The consumption of raw materials and utilities was determined according to simulation results. Their correspond- ing costs were calculated on the basis of the average prices of 2012 in China [18] . Operating labor cost was calculated referring to Han’s work [13] . A straight-line method was adopted to calculate the depreciation cost under the assumption of 20 years life time and 4% salvage value. CO 2 TS&M cost was calculated by Mantri- pragada and Rubin’s work [11] . The rest part of product cost was calculated according to the ratio to product cost [31,32]. The prod- uct cost is defined as the sum of the above components as shown in Eq. (10).

r

j

r

j

PC ¼ C R þ C U þ C O&M þ C D þ C POC þ C AC þ C DSC þ C TS&M

ð 10Þ

where PC is the product cost, C R is the raw material cost, C U is the utilities cost, C O&M is the operating & maintenance cost, C D is the depreciation cost, C POC is the plant overhead cost, C AC is the admin- istrative cost, C DSC is the distribution and selling cost, C TS&M is the cost of CO 2 transportation, sequestration, and monitoring. The cost related to CO 2 emissions reduction should also be con- sidered during product cost estimation. In this paper, we used mit- igation cost (MC) to evaluate the cost according to Refs. [37,38]. MC represents the difference of cost per ton of CO 2 emissions avoided between the plant without CCS and the plant with CCS expressed in Eq. (11).

MC ¼ PC wCCS PC w=oCCS

E w=oCCS E wCCS

ð11Þ

where PC is the product cost of the CTO plant, E is the quantity of CO 2 emitted from the CTO plant, the subscripts w CCS and w/o CCS are referred to the plant configurations with and without CCS. Besides the capital investment and the product cost, there is an- other important economic factor-plant cash flow. It is usually con- sidered as the cumulative flow over the life of the project.

Table 3 Ratio factors for capital investment.

Component

Ratio factor (RF, %)

(1) Direct investment (1.1) Equipment (1.2) Installation (1.3) Instruments and controls (1.4) Piping

100

48

24

57

(1.5) Electrical (1.6) Buildings(including services) (1.7) Land (2) Indirect investment (2.1) Engineering and supervision (2.2) Construction expenses (2.3) Contractor’s fee (2.4) Contingency (3) Fixed capital investment (4) Working capital (5) Total capital investment

29

71

5

48

43

19

33

477

80

557

Table 4 Assumptions for the estimation of product cost.

Component

Basis

(1) Coal

Coal price 620 RMB/t; methanol 2,400 RMB/

t

(2) Utilities Water 2 RMB/t, electricity 0.7 RMB/kWh,

(3) Operating & Maintenance (3.1) Operating labor

steam 42 RMB/GJ

CTO 300 labors, MTO 100 labors, 100,000

 

RMB/labor/year

(3.2) Direct supervisory and clerical labor (3.3) Maintenance and repairs (3.4) Operating supplies (3.5) Laboratory charge (4) Depreciation

20% of operating labor

2% of fixed capital investment 0.7% of fixed capital investment 15% of operating labor Life period 20y, salvage value 4%

(5)

Plant overhead cost

60% (3.1 + 3.2 + 3.3)

(6) Administrative cost (7) Distribution and selling cost

2% of product cost 2% of product cost

(8)

CO 2 TS&M

64 RMB/t CO 2

(9)

Product cost

(1) + (2) + (3) + (4) + (5) + (6) + (7) + (8)

Cumulative cash flow was calculated by adding all of the cash flows from the inception of projects, as shown in simplified Eq. (12). As project life, 23 years was used in this paper, of which 3 years for plant construction and 20 years for operation. Assump- tions were made for construction phase that the expenditure factor was 80% for the first 2 years and 20% for the last year [37] .

CCF ¼ X CF i ¼ X ð OP PC þ C D Þ i OY i

i

i

ð 12Þ

where CCF is the cumulative cash flow, CF i is the cash flow of year i , OP is the olefins price, PC is the product cost, C D is the depreciation cost, OY i is the olefins yield of year i.

Table 2 Summary of investment data for main equipment components.

Unit

Benchmark

r

Scale ( S )

J

Size factor ( sf )

Domestic-made factor ( h )

r

EI (M$)

J

Refs.

ASU

Oxygen supply Daily coal input Daily coal input Material caloric value Sulfur output

21.3 kg/s

0.50

0.50

45.70

[22]

Coal handing

27.4 kg/s

0.67

0.65

29.10

[22]

CG

39.2 kg/s

0.67

0.80

78.00

[22]

WGS

1377 MW

0.67

0.65

39.80

[28]

AGR

29.3 mol/s

0.67

0.65

67.30

[28]

Pure CO 2 captured 2064.4 mol/s Syngas input 10,810 mol/s

0.67

0.65

32.80

[28]

MS

0.67

0.65

20.40

[22]

MTO

Methanol input

62.5 kg/s

0.60

1.00

223.06

[29]

50

D. Xiang et al. / Chemical Engineering Journal 240 (2014) 45–54

4. Results and discussion

This section reports the mass and energy data as well as com- pares the different cases of CTO processes with CCR ranging from 60% to 95%. A MTO process is also involved in this comparison, aiming to get which alternative olefins production should be devel- oped in large-scale. In the end of this section, we analyze three important parameters, plant scale, carbon tax, feedstock price to find their effects on economic performance.

4.1. Energy efficiency analysis

The CTO plant with CCS and the MTO plant producing the same 0.7 Mt/y olefins were simulated in Aspen Plus, which produce all process data needed to assess the techno-economic and environ- mental performance of cases studied. As an illustrative example for mass and energy balance, Table 5 presents the main stream properties in key points of the CTO plant diagram, and Table 6 pre- sents properties of N 2 stream, CO 2 stream, and tail gas stream of CCS at CCR 60%, 80%, and 95%. The properties of shift syngas stream and clean syngas stream of CCS can be found in Table 5 . The total material and energy consumption of MTO and CTO plants at different CCRs is shown in Table 7 . The energy consump- tions or generations of ASU, CG, WGS, CCS, MS, and MTO are also placed in this table. Producing 0.7 Mt/y of olefins needs about 1.8 Mt/y methanol for the MTO plant and 2.87 Mt/y coal for the CTO plant. The resulting CO 2 emissions of the CTO plant are close to 4.05 Mt/y. The energy efficiency to olefins product in Table 5 is calculated according to Eq. (6). With shorter conversion route, the energy efficiency of the MTO plant is around 80.98%, much higher than that of the CTO plant which is only 36.16%. CTO processes with CCS have two scenarios divided by CCR 80%. In the first scenario, the CTO process has a low CCR between 60%

and 80%. The corresponding energy efficiency ranges from 35.86% to 35.69% since the electricity consumption changes from 172.54 MW to 187.58 MW. In the second scenario, the CTO process has a high CCR between 80% and 95%. The corresponding energy efficiency ranges from 35.69% to 35.38% since the electricity con- sumption changes from 187.58 MW to 215.93 MW. It is clear that the increasing rate of electricity consumption of CCS in the second scenario is about 2 times larger than that in the first scenario shown in Fig. 4 . The decrease of energy efficiency is caused by the increase of electricity consumption of the CCS. On the one hand, we should raise the flash temperature and reduce the flash pressure in order to increase CCR and cool the methanol out of the flash to 223 K for recycling use. Correspondingly, the increas- ingly temperature difference leads to bigger ammonia cold energy consumption when CCR changing from 60% to 95%. On the other hand, with increasing CCR, CO 2 processing capacity and the com- pression energy consumption increase linearly, as shown in Fig. 4 .

4.2. Economic analysis

4.2.1. Capital investment, product cost, and cumulative cash flow The breakdown of total capital investment of CTO plants is shown in Fig. 5 . The MTO takes 45.6% of the total capital invest- ment, followed by the ASU and CG (about 37.3%). It is seen that additional investment for CCS makes the total capital investment increase from 2.52 10 4 RMB/t/y to 2.71 10 4 RMB/t/y when CCR is as high as 95%. On the other hand, the product cost of MTO and CTO plants are calculated and shown in Fig. 6 . For the CTO plant, most of capital is expended on purchasing coal, accounting for 39.5% of the product cost. The second largest is the cost for utilities, about 24.8% of the product cost. The total capital investment is involved in the prod- uct cost as the form of depreciation, amounting to 16.8% of the

Table 5 Simulation results of main streams in the CTO process.

Stream a

Coal (1)

Water

Oxygen

Syngas

Shift

N 2 (6)

Tail gas

Clean

Methanol

Product

C

4 =

Ethylene

Propylene

(2)

(3)

(4)

syngas

(7)

syngas

(9)

gas (10)

(11)

(12)

(13)

 

(5)

(8)

Molar fraction (%) N O

AR

2

2

1.39

95.00

3.61

0.87

1.03

0.85

0.98

100.00

30.21

0.99

1.00

0.81

0.11

H 2 O

100.00

19.07

01.61

10.18

69.59

CO

40.47

18.71

0.66

27.29

CO 2

11.67

31.56

67.10

3.46

0.01

0.06

H 2 S H 2

0.34

0.32

26.55

45.97

1.02

67.44

0.44

C

3.16

CH 4 CH 3 OH

1.11

0.02

89.70

0.12

C 2 H C 2 H C 3 H C 3 H C 4 H

6

4

8

6

10

0.25

0.18

13.75

99.82

0.57

0.74

0.38

8.90

3.50

99.62

0.04

2.56

C 4 H C 4 H C 5 H Molar flow

8

6

12

1.63

92.61

0.21

0.38

0.38

10,708

10,358

36,359

37,676

4893

16,410

25,433

8017

11,002

148

1499

883

(kmol/hr)

Mass flow

358,295

192,926

333,886 771,303

794,423

137,070 633,439

283,069

245,440

245,440

8253

42,064

37,184

(kg/hr)

Temperature

314

314

383

425

363

293

302

302

318

763

326

182

315

(K)

Pressure

0.1

0.1

4.1

2.76

5.00

0.2

0.2

2.78

0.40

0.22

0.55

0.20

1.73

(Mpa)

Enthalpy

1128.52 842.74 6.58

1347.27 1535.44 0.22

1206.44 308.34 542.73

463.06 0.30

19.74

4.68

(MW)

a In order to simplify the table, some minor streams are not included, such as water & slag stream in CG unit, S stream in AGR unit, and purge gas stream in MS u nit.

D. Xiang et al. / Chemical Engineering Journal 240 (2014) 45–54

Table 6 Simulation results of CCS at CCR 60%, 80%, and 95%.

51

Stream

CCR 60%

CCR 80%

CCR 95%

 

N 2

CO 2

Tail gas

N 2

CO 2

Tail gas

N 2

CO 2

Tail gas

Molar fraction (%)

N 2

100.00

0.04

34.93

100.00

0.03

32.12

100.00

0.03

48.98

AR

0.02

2.34

0.02

4.98

0.02

17.39

CO

0.75

0.82

0.59

1.66

0.54

5.31

CO 2

98.50

60.18

98.90

57.30

99.00

14.73

H 2 CH 3 OH Mole flow (kmol/hr) Mass flow (kg/hr) Temperature (K) Pressure (Mpa) Enthalpy (MW)

0.69

1.73

0.43

3.94

0.38

13.59

0.03

0.03

0.03

2350

6958

6909

1478

9255

3240

391

10,984

925

65,832

303,295

258,877

27,397

404,681

119,068

10,953

480,601

26,715

293

293

302

293

293

302

293

293

302

0.2

15

0.2

0.2

15

0.2

0.2

15

0.2

0.10

773.01

436.40

0.04

976.51

195.44

0.02

1226.38

14.29

Table 7 Mass and energy performance results from the techno-economic model for MTO and CTO plants at different CCRs.

 

Item

MTO plant

CTO plant with CCS

 
 

CCR 0%

CCR 60%

CCR 70%

CCR 80%

 

CCR 90%

CCR 95%

Input Coal (Mt/y)/(MW LHV) a Methanol (Mt/y)/(MW LHV) b Net Electricity input (MW e ) c Net Steam input (MW th ) c ASU (MW e /MW th ) CG (MW e /MW th ) WGS (MW e /MW th ) AGR or CCS (MW e /MW th ) MS (MW e /MW th ) MTO (MW e /MW th ) Total energy input (MW)

 

2.87/2800.24

2.87/2800.24

2.87/2800.24

2.87/2800.24

2.87/2800.24

2.87/2800.24

1.80/1250

––––––

36.61

146.21

172.54

179.10

187.58

 

204.14

215.93

123.98

212.75

212.75

212.75

212.75

212.75

212.75

144.57/–

144.57/–

144.57/–

144.57/–

144.57/–

144.57/–

70.74/– – / 15.10

 

70.74/– –/ 15.10

70.74/– –/ 15.10

70.74/– –/ 15.10

70.74/– –/ 15.10

70.74/– –/ 15.10

9.86/26.59

36.19/26.59

42.75/26.59

51.23/26.59

67.79/26.59

79.58/26.59

25.91/77.28

25.91/77.28

25.91/77.28

25.91/77.28

25.91/77.28

25.91/77.28

36.61/123.98

36.61/123.98

36.61/123.98

36.61/123.98

36.61/123.98

36.61/123.98

36.61/123.98

1410.59

3159.20

3185.53

3192.09

3200.57

 

3217.13

3228.92

Output Ethylene (Mt/y)/(MW LHV) b Propylene (Mt/y)/(MW LHV) b C 4 =(Mt/y)/(MW LHV) b Product energy (MW LHV) CO 2 emissions (Mt/y)

0.33/538.54

0.33/538.54

0.33/538.54

0.33/538.54

0.33/538.54

0.33/538.54

0.33/538.54

0.30/489.57

0.30/489.57

0.30/489.57

0.30/489.57

0.30/489.57

0.30/489.57

0.30/489.57

0.07/114.24

0.07/114.24

0.07/114.24

0.07/114.24

0.07/114.24

0.07/114.24

0.07/114.24

1142.35

1142.35

1142.35

1142.35

1142.35

 

1142.35

1142.35

Negligible

4.05

1.39

1.04

0.69

0.35

0.17

Energy efficiency (%, LHV basis) 80.98

36.16

35.86

35.79

35.69

35.50

35.38

a The LHV is based on Ref. [39] .

b The LHV is based on Ref. [16] .

c MW e represents the energy of electricity and MW th represents the energy of steam. The symbol of ‘‘ ’’ are used to make a distinction between generated and consumed energy.

90 2 Electricity consumption for ammonia cold 80 1.8 Electricity consumption for compression CCS electricity
90
2
Electricity consumption for ammonia cold
80
1.8
Electricity consumption for compression
CCS electricity consumption
1.6
70
CO 2 emissions
1.4
60
1.2
50
1
40
0.8
30
0.6
20
0.4
10
0.2
0
0
60
65
70
75
80
85
90
95
Energy consumption (MW)
CO 2 emissions (Mt/y)

CCR (%)

Fig. 4. The relationship between CCR and electricity consumption.

product cost, which is the next major contributor to product cost. By introducing the CCS process, a large amount of CO 2 is mitigated, ranging from 7360 t/d to 11,660 t/d. However, there is additional cost required for CCS energy use, geological sequestration, and monitoring. For the scenario with

40 Increase of CCS MTO MS 35 WGS ASU AGR CG 30 25 20 15
40
Increase of CCS
MTO
MS
35
WGS
ASU
AGR
CG
30
25
20
15
10
5
0
Total capital investment (1000 RMB/t/y)

0

60

70

80

CCR (%)

90

95

Fig. 5. Distribution of total capital investment for CTO plants at different CCRs.

low CCR, the product cost increases from 6911 RMB/t to 7131 RMB/t, leading to an increase of 3.2%. For the scenario with high CCR, the product cost increases to 7437 RMB/t, leading to an increase of 7.6%. It is obvious that the big change happens at the

52

D. Xiang et al. / Chemical Engineering Journal 240 (2014) 45–54

9000 CO2 TS&M Distribution and selling cost Administrative cost 8000 Depreciation Plant overhead cost Operating
9000
CO2 TS&M
Distribution and selling cost
Administrative cost
8000
Depreciation
Plant overhead cost
Operating & Maintenance
7000
6000
5000
4000
3000
2000
1000
0
Product cost (RMB/t)

MTO

CCR 0%

CCR 60% CCR 70% CCR 80% CCR 90% CCR 95%

Fig. 6. Distribution of product cost for MTO and CTO plants at different CCRs.

6000 5000 CTO without CCS CTO with CCR 80% 4000 CTO with CCR 95% 3000
6000
5000
CTO without CCS
CTO with CCR 80%
4000
CTO with CCR 95%
3000
MTO
2000
1000
0
5
10
15
20
23
-1000
Year
-2000
Cumulative cash flow (million RMB)

Fig. 8. Cumulative cash flow of MTO and CTO plants at different CCRs.

CCR 80%, which divides CTO plants with CCS into low capture con- figuration and high capture configuration. The big change could also be found in the mitigation cost and energy consumption of CCS, as shown in Figs. 7 and 4 . Thus, CTO with this carbon capture configuration is appropriate choice for olefins production consider- ing energy penalties, economic performance, and environmental protection. The product cost of the MTO plant is about 7896 RMB/t, which is much higher than that of the CTO plant with CCS. The methanol cost is the biggest part, amounting to 78.1%, fol- lowed by the utilities cost of 6.7% and depreciation cost of 6.0%. As shown in Fig. 8 , the plant with the highest cumulative cash flow is the CTO plant without CCS, followed by the ones with CCS and the MTO plant. The cumulative cash flow decreases from 5.0 10 9 RMB to 3.5 10 9 RMB as CCR increasing from 0% to 95%. While the cash flow of the MTO plant is only 2.9 10 9 RMB. Although the capital investments of CTO plants are about 2 times larger than that of MTO plant, the ratio of cumulative cash flow to the MTO plant is 1.2–1.7. In Fig. 8 , we could also find the break-even point and the payback period. The payback period is about 8 y for the plant without CCS, about 9 y for the plant with CCS, and about 7 y for the MTO plant.

4.2.2. Effects of plant scale, carbon tax, and feedstock price As discussed above, we select an appropriate CCR equal to 80% for case study of the effect of production scale, carbon tax, and feedstock price on its economic performance.

190 180 170 160 150 140 130 120 60 65 70 75 80 85 90
190
180
170
160
150
140
130
120
60
65
70
75
80
85
90
95
Mitigation cost (RMB/t CO 2 )

CCR (%)

Fig. 7. Relationship between CCR and mitigation cost.

As production scale is one of the most important factor for eco- nomic performance, we therefore study the effect of this factor on the capital investment and the product cost of the CTO plant with CCS. According to the results, it is clear to find that the capital investment will decrease as the plant capacity varies from 0.3 Mt/y to 2.0 Mt/y, as shown in Fig. 9 . The total capital invest- ment of a 2.0 Mt/y plant is about 46.8% of a 0.3 Mt/y plant. Since depreciation is a important factor, the product cost also decreases with increasing plant capacity. However, the production scale shows less effect on product cost. For example, the product cost of a 2.0 Mt/y plant is about 19.3% less than a 0.3 Mt/y plant, as shown in Fig. 10 . For the MTO plant, the effect of economies of scale is relatively small since the capital investment of the MTO plant is less than half of the CTO plant. As the largest developing country, China is facing increasing criticism for the largest greenhouse gas emissions. China’s 12th five-year plan clearly promised that a carbon trading market would be gradually established and CO 2 emissions intensity be reduced at the same time. The city of Shenzhen launched a carbon trading scheme on 18 June 2013, China’s first market for compulsory car- bon trading. The scheme covers 635 industrial companies and some public buildings accounting for about 40% of the city’s emis- sions [40] . This means that there will be an explicit cost associated with CO 2 emissions in the near future in China. The effect of increasing carbon tax on the product cost is shown in Fig. 11 . It is obvious that when carbon tax exceeds 250 RMB/t the product cost of the CTO plant without CCS is higher than that of the MTO plant, while the product cost of the CTO plant with

40 35 Incremental investment of CCS CTO without CCS 30 25 20 15 10 5
40
35
Incremental investment of CCS
CTO without CCS
30
25
20
15
10
5
0
0.3
0.5
0.7
0.9
1.1
1.3
1.5
1.7
2.0
Capacity (Mt/y)
Total capital investment (1000RMB/t/y)

Fig. 9. Total capital investment of the CTO plant with CCS varying with different capacities.

D. Xiang et al. / Chemical Engineering Journal 240 (2014) 45–54

53

9000 Incremental cost of CCS CTO without CCS 8000 7000 6000 5000 4000 3000 2000
9000
Incremental cost of CCS
CTO without CCS
8000
7000
6000
5000
4000
3000
2000
1000
0
0.3
0.5
0.7
0.9
1.1
1.3
1.5
1.7
2.0
Capacity (Mt/a)
Product cost (RMB/t)

Fig. 10. Product cost of the CTO plant with CCS varying with different capacities.

9000 8500 8000 7500 7000 6500 CTO without CCS CTO with CCS 6000 MTO 5500
9000
8500
8000
7500
7000
6500
CTO without CCS
CTO with CCS
6000
MTO
5500
5000
0
30
60
90
120
150
180 210
240
270 300
330 360 400
Carbon tax (RMB/t CO 2 )
Fig. 11. Effect of carbon tax on product cost.
15000
CTO without CCS
CTO with CCS
13000
MTO
11000
9000
7000
5000
3000
200/800
400/1600
600/2400
800/3200
1000/4000
1200/4800
Coal price/methanol price (RMB/t)
Product cost (RMB/t)
Product cost (RMB/t)

Fig. 12. Effect of prices of feedstock on product cost.

CCS is much lower than that of the MTO plant when carbon tax is as high as 400 RMB/t. For the CTO plant with CCS, the break-even carbon tax between CTO plants with and without CCS is about 150 RMB/t, roughly equivalent to the current carbon price. Thus, the CTO plant with CCS could be firstly built to demonstrate the potential application of CCS technologies from the aspects of envi- ronmental protection and overall economic performance. It is important to underline that, if the carbon price increases up to 300–400 RMB/t in the next few years, the application of CCS tech- nologies for large-scale CTO plants will become very profitable. The effect of feedstock price on product cost of the MTO plant is about 2 times that of the CTO plants with and without CCS, as

shown in Fig. 12 . This means that the product cost of the MTO plant is highly affected by feedstock price and that for CTO plants the influence is relatively small. Besides, coal price is more stable than methanol which is mostly determined by oil price in the past several years [18] . Although MTO plants have advantages of low capital investment and low environmental impact, their economic performances are easily intervened by methanol price. In other words, MTO plants have less anti-risk capability of market fluctu- ation than CTO plants in China. Expanding development of CTO plants with CCS should be encouraged since it could relieve the conflict between the supply and demand of olefins, meanwhile re- duce CO 2 emissions, and manifest a strong anti-risk capability to the raw material market.

5. Conclusions

Techno-economic performance of the CTO process with CCS was analyzed in this paper. The CTO process was also compared with the MTO process. The performance results indicate that the CTO plant with CCS is slightly less thermodynamic efficient than the conventional CTO plant without CCS. For the CTO plant with 80% carbon capture compared to the CTO plant, the total capital invest- ment increases by 6%, from 2.52 10 4 RMB/t/y to 2.69 10 4 RMB/ t/y, and the product cost rises nearly 11%, from 6442 RMB/t to 7131 RMB/t. The effects of economies of scale and carbon tax were also ana- lyzed. It was found that production scale has more effect on capital investment than product cost. If the scale of the CTO plant with CCS increases from 0.3 Mt/y to 2.0 Mt/y, the total capital investment and product cost will drop approximately 53.2% and 19.3%. The mitigation cost of CTO with CCS is about 150 RMB/t, roughly equiv- alent to the current carbon price. On the other hand, the product cost of the MTO plant is 7896 RMB/t, which is much higher that of the CTO plant with CCS even in the context of carbon tax as high as 400 RMB/t. Although the MTO plant has low capital investment and CO 2 emis- sions, its product cost ratio to the CTO plant with CCS is 0.9, its cumulative cash flow ratio is 0.7, and its economic performance is susceptible to fluctuation of market price. In contrast, the prod- uct cost of the CTO with CCS is lower and it could resist market risk. In a word, developing CTO processes with CCS is important to the sustainable development of olefins industry in China from the perspectives of resource reserve, economic performance, and envi- ronmental protection.

Acknowledgments

The authors are grateful for financial support from the China NSF Key Project (No. 21136003), the China NSF Project (No. 21306056), the National Basic Research Program (No. 2012CB720504; 2014CB744306), the Fundamental Research Funds for the Central Universities (No. 2013ZP0010), and Guangdong Province NSF Team Project (No. S2011030001366).

References

[1] Y. Qu, The prospect of China’s olefin market during the twelfth five-year plan, Petro. Petrochem. Today 20 (2012) 16–25 (in Chinese) . [2] National Bureau of Statistics, China energy statistics yearbook, China Stat. Press, Beijing, 2010 (in Chinese). [3] ICIS, China develops coal-to-olefins projects, which could lead to ethylene self- sufficiency, 2012 (assessed 25.08.2013), < http://www.icis.com/Articles/2012/

54

D. Xiang et al. / Chemical Engineering Journal 240 (2014) 45–54

[5] K.Z. House, C.F. Harvey, M.J. Aziz, D.P. Schrag, The energy penalty of post- combustion CO 2 capture & storage and its implications for retrofitting the U.S. installed base, Energy Environ. Sci. 2 (2009) 193–205 . [6] Z. Luo, M. Fang, M. Li, L. Gao, The Technology of CO 2 Capture, Storage and Usage, China Elec. Power Press, Beijing, 2012 (in Chinese) . [7] H. Lin, H. Jin, L. Gao, W. Han, Techno-economic evaluation of coal-based polygeneration systems of synthetic fuel and power with CO 2 recovery, Energy Convers. Manage. 52 (2011) 274–283 . [8] A. Pettinau, F. Ferrara, C. Amorino, Combustion vs. gasification for a demonstration CCS (carbon capture and storage) project in Italy: a techno- economic analysis, Energy 50 (2013) 160–169 . [9] Q. Yi, B. Lu, J. Feng, Y. Wu, W. Li, Evaluation of newly designed polygeneration system with CO 2 recycle, Energy Fuel 26 (2012) 1459–1469 . [10] K.S. Ng, Y. Lopez, G.M. Campbell, J. Sadhukhan, Heat integration and analysis of decarbonised IGCC sites, Chem. Eng. Res. Des. 88 (2010) 170–188 . [11] H.C. Mantripragada, E.S. Rubin, Techno-economic evaluation of coal-to-liquids (CTL) plants with carbon capture and sequestration, Energy Policy 39 (2011) 2808–2816 . [12] W. Zhou, B. Zhu, D. Chen, F. Zhao, W. Fei, Technoeconomic assessment of China’s indirect coal liquefaction projects with different CO 2 capture alternatives, Energy 36 (2011) 6559–6566 . [13] H. Han, Economic analysis of producing olefin from naphtha, coal and natural gas, Chem. Techno-Eco. 23 (2005) 14–18 (in Chinese) . [14] X. Yang, L. Dong, Technical progress and economic analysis on the direct production of light olefins from syngas, Chem. Ind. Eng. Progr. 31 (2012) 1726– 1731 (in Chinese) . [15] T. Ren, M.K. Patel, K. Blok, Steam cracking and methane to olefins: energy use, CO 2 emissions and production costs, Energy 33 (2008) 817–833 . [16] T. Ren, M.K. Patel, Basic petrochemicals from natural gas, coal and biomass:

[40] China Daily, China starts carbon trading in Shenzhen, 2013 (assessed