8.

SIMULATION OF DMF PROCESS PLANT USING ASPEN

8.1 Simulation :
This chapter includes the study of comparison of handmade calculations and
computer simulated results using Aspen V9 design software.Now a day, each and every
industry is using advanced simulation software in order to observe the process without
being actually running the real plant so that they can know the faults of designs in real
process equipment and adjustment of flow rates of process streams in the plant. DMF
manufacturing from HMF is simulated in order to check the correctness of hand calculation
and how the parameters like pressure and temperature effects the operations.Process Flow
sheet drawn in aspen in Figure 8.1.

First the required components are added from simulation basis manager. If the
component is not present in Aspen, have an option to define them Aspen hypotheticals tab
and providing with the information like molecular eight, mass density and normal boiling
point. ”Fluid Package” is Aspen terminology for a collection of data that includes all the
thermodynamic, component, and reaction parameters required to run the model. Select
Peng Robinson as this method provides maximum data to the chemicals. Report will be
submitted in Appendix Column.

Figure 8.1 Process Flow sheet of DMF manufacturing in Aspen

49
 9. INSTRUMENTATION AND PROCESS CONTROL

Instruments are providing to monitor the key process variables during plant
operation. They may be incorporated in automatic control loops or used for the manual
monitoring of the process operation. They may also be part of an automatic computer
data logging system.Instruments monitoring critical process variables will be fitted with
automatic alarms to alert the operators to critical and hazardous situations.

9.1. INSTRUMENTATION & CONTROL OBJECTIVES

The primary objective of the designer when specifying instrumentation and control
schemes are:
i. Safer Plant Operation:
a) To keep the process variables within known safe operating limits.
b) To detect dangerous situations and to provide alarms & automatic shut-down systems.
c) To provide inter locks and alarms to prevent dangerous operating procedures.
ii. Production rate: To achieve the design product output.
iii. Product Quality: To maintain the product composition within specific quality
standards.
iv. Cost: To operate at the lowest production cost, commensurate with the other
objectives.

9.2. COMPONENTS OF THE CONTROL SYSTEM

Process: Any operation or series of operations that produces a desired final result
is a process. Measuring Means: Measuring means of all the parts of the control system,
the measuring element is perhaps the most important. If measurements are not made
properly the remainder of the system cannot operate satisfactorily.
Analysis of Measurement:
 Variables to be :
a) Pressure Measurements

b) Temperature Measurements
c) Flow Rate Measurements
d) Level Measurements


50
 Variables to be Recorded:
a) Indicated temperature

b) Composition
c) Pressure
Controller
The controller is the mechanism that responds to any error indicated by the error
detecting mechanism. The output of the controller is some predetermined function of
the error. In the controller there is also an error-detecting mechanism which compares
the measured variables with the desired value of the measured variable, the difference
being the error.
Final Control Element
The final control element receives the signal from the controller and by some
predetermined relationships changes the energy input to the process.
9.3. ALARMS AND SAFETY TRIPS
Alarms are used to alert operators of serious, and potentially hazardous, deviations in
process conditions. Key instruments are fitted with switches and relays to operate
audible and visual alarms on the control panels.
The basic components of automatic trip systems are:
a. A sensor to monitor the control variable and provide an output signal when a preset
valve is exceeded (the instrument).
b. A link to transfer the signal to the actuator usually consisting of a system of
pneumatic or electric relays.
c. An actuator to carry out the required action, close or open a valve, switch off a motor.

9.4. TEMPERATURE CONTROLLER

Thermocouples are the most commonly used temperature sensing devices. The two
dissimilar wires produce a milli volt emf that varies with the „‟hot junction‟‟ temperature.
Iron constricted thermocouples are commonly used over the 0 to 13000F temperature
range.

9.5. PRESSURE CONTROLLER

Bourdon tubes, bellows, and diaphragms are used to sense pressure and differential
pressure. For example, in a mechanical system the process pressure force is balanced by
the movement of a spring. The spring position can be related to process pressure.
51
9.6. FLOW CONTROLLERS
These are used to control feed rate into a process unit. Orifice plates are by far the most
common type of flow rate sensor. Normally, orifice plates are designed to give pressure
drops in the range of 20 to 200 inch of water. Venture tubes and turbine meters are also
used.

9.7. LEVEL CONTROLLER

Liquid levels are detected in a variety of ways. The three most common are:
1.Following the position of a float that is lighter than the fluid.

2. Measuring the apparent weight of a heavy cylinder as it buoyed up more or less by the
liquid.

3. Measuring the difference in static pressure between two fixed elevations, one in the
vapor above the liquid and the other under the liquid surface. The differential pressure
between the two liquid level taps is directly related to the liquid level in the vessel.

9.8. CONTROL VALVES:

The interface with the process at the other end of the control loop is made by the final
control element is an automatic control valve with throttles the flow of a stem that open or
closes an orifice opening as the stem is raised or lowered. The stem is attached to a
diaphragm that is driven by changing air pressure above the diaphragm. The force of the
air pressure is opposed by a spring.

9.9. DISTILLATION COLUMN CONTROL

The process control set up of the distillation columns is presented in this section. The
primary objective of distillation column control is to maintain the specified composition
of the top and bottom products, and any side streams; correcting for the effects of
disturbances in: Controls are shown in Figure 9.1.
a. Feed flow-rate, composition and temperature.
b. Steam supply pressure.
c. Cooling water pressure and header temperature.
d. Ambient conditions, which cause changes in internal reflux.

52
Figure. 9.1 Controllers and valves for distillation column

53
 10. MATERIALS OF CONSTRUCTION

10.1. IMPORTANT MATERIALS AVAILABLE:

10.1.1 Iron and Steel:
Although many materials have greater corrosion resistance than iron and steel, cost
aspects favor the use of iron and steel. As a result they are often used as a material of
construction when it is known that some corrosion will occur. They are not suitable for
use with dilute acids, but can be used with many strong acids, since a protective coating
composed of corrosion products forms on the metal surface.
10.1.2 Stainless Steel:
There are more than 100 different types of stainless steels. The main reason for the
existence of stainless steels is in their resistance to corrosion. Chromium is the main
alloying element, and the steel should contain at least 11%. Chromium is a reactive
element but it and its alloys passivity exhibit excellent resistance to many environments.
So stainless steel contains chromium, nickel, iron, and also containing small amount of
other essentials properties. They have excellent corrosion resistance and heat-resistance
properties.
10.1.3 Nickel and its Alloy:
Nickel exhibits high corrosion resistance to most alkalies. The strength and hardness of
nickel is almost as great as carbon steel. In general, oxidizing conditions promote the
corrosion of nickel, and reducing conditions retard it. Monel, an alloy of nickel
containing 67% nickel and 30% copper is often used in food industry. This alloy is
stronger than nickel and has better corrosion resistance properties than nickel or copper.
10.1.4 Copper:
Copper and Copper base alloys are used in the formation of heat exchanger tubing,
piping, fittings, etc. although corrosion rates are comparatively small.

10.1.5 Aluminum:
The lightness and relative ease of fabrication of Aluminum and its alloys are factors
favoring the use of these materials.
Grades of carbon steel:
i. Low Carbon steel – Composition of 0.05% - 0.25% carbon and up to 0.4%
manganese. Also known as mild steel, it is a low cost material that is easy to shape.
ii. Medium Carbon steel – Composition of 0.29% - 0.54% carbon with 0.60% - 1.65%
manganese. Medium Carbon steel is ductile and strong with good wear properties.
iii. High Carbon steel – Composition of 0.55% - 0.95 % carbon with 0.30% - 0.90%
manganese. It is very strong and holds shape well, making it ideal for springs and wire.

54
iv. Very High Carbon steel – Composition of 0.96% - 2.1% carbon. Its high carbon
content makes it an extremely strong material, though it is brittle and requires special
handling.

10.2. RECOMMENDED MATERIALS OF CONSTRUCTION:

Properties of S.S-304:
i. Have combination of desirable mechanical properties corrosion resistance with ease
of fabrication for industrial application.
ii. They are shock resistant.
iii. Strength about 750 MN/m2.
iv. Yield strength about 270 MN/m2.
v. Elongation varies between 30-75% depending upon carbon constant.
Reason for the Selection of S.S.304
Materials used for construction of different equipment’s are shown in Table 10.1.
Table 10.1 Materials used for construction of different equipment’s

Equipment Material Significance

Reactor Stainless steel 304 Good strength,
Corrosive resistance

Mixer Stainless steel 304 Good strength,

Corrosive resistance

Decanter Carbon steel Better Corrosive

base,SS 316 resistence at
wielded parts elevated
temperatures.

Separator Stainless steel 304 Good strength,

Corrosive resistance

Stainless steel 304 Good strength,

Plug Flow Reactor Corrosive resistance

55
11. HEALTH, SAFETY AND ENVIRONMENTAL ASPECTS
11.1. HUMAN HEALTH AND ENVIRONMENT:

In our process the methanol involved is the most dangerous for fire hazards.
Since it is used in liquid form above atmospheric boiling point under pressure it has an
explosion risk in case of a fire. The methanol also releases a lot of heat when burned
(ΔHc = 710 kJ/mol) and the flash point is very low at 12˚C . DMC has about the same
flash point at 17˚C . The same goes for the dehydrating agents. The flash point of 2-
cyanopyridine is 89.0˚C and while the flash point of 2-picolinamide is expected to be
higher than that of 2-cyanopyridine . It is stated in the MSDS’s of 2-cyanopyridine and
phenol that skin contact with either of these compounds should be avoided at all costs
and that they are very poisonous .
Methanol and DMC are also dangerous compounds if ingested due to methanol
poisoning. The dimethyl carbonate is broken down to CO2 and methanol in the body
so it has the same effect if ingested.
The carbon dioxide can cause unconsciousness or death at concentration of 10%
or more in the air . Because of the high amounts of carbon dioxide used it is possible
that in case of a leak this concentration will be reached close to the ground up to a
certain height. This probability increases in case of a dike around the unit or in an
enclosed compartment. Carbon dioxide is heavier than air in high concentrations and
thus will stay close to the ground. This concentration is not possible to see for humans
and thus is very dangerous.
11.2. MANAGEMENT’S RESPONSIBILITY FOR SAFETY:

Although top management cannot personally assume the role of safety engineer
or safety director for the entire plant, it can through executive action make clear to all
levels of supervision that top management is actively behind a consorted effort to
reduce accidents and make the plant a better and safer place for employees to earn their
livelihood. In addition, top management should make sure that each supervisor
understands that he is responsible for the success of the safety program in his
geographical area of the plant, and that he will have to answer for poor safety practices
in his area. To prevent misunderstanding these facts should be reduced to some written
form. Though directives, management should also make the necessary provisions to
provide safe tools and equipment‟s to install safety guards where feasible to discover and
correct safety hazards, to plan production processes with safety as a central theme, and in
general provide for an industrial climate that is conductive to general employee health and

56
safety. In addition management should organize safety activities and training on a
continuing basis under the direction of designated individuals and make sure that every
employee is provided with necessary training supervision to install in him a desire to work
safely.

11.3. PLANT MAINTENANCE:

Plant maintenance is another critical phase in plant safety. It is vital that plant
maintenance and repairs be conducted in a manner to preserve the integrity of the plant
and equipment. How often do we see machinery guards removed to affect a repair and
then left lying or worse yet, discarded? Every time this is done a trap to set for the
unwary or unthinking man who follow.
Maintenance practices in themselves offer many opportunities to improve
safety performance. Emphasis should be placed on the use of the correct tools, and
those should be kept in good condition. Care should be exercised to remove
mushroomed edges four tools such as hammers, chisels, slug wrenches, shields should
be in place and goggles worn by man using an abrasive wheel. Portable electrical tools
can be a hazard if not kept in good condition and periodically tested. Common problem
is found in the erection and use of scaffolds. How often is a means of safe access (a
ladder) provided? Handrails should be provided when the elevation is above 3.5 feet.
Wooden planks must be in good condition. Very often these simple requirements are
not met.

11.4. TRANSPORTATION AND SAFETY CONCERNS:

The proper training of plant personnel in safety procedures is not only

important, it is required by OSHA. The ethanol industry has an enviable safety record,
even though there are numerous safety hazards that can pose significant risk. While
state and federal laws set certain requirements, it is important for management to go
beyond these base regulations by placing a strong company emphasis on plant safety.
No matter what the size of the plant, a Safety Director, responsible for encouraging and
enforcing safety procedures, needs to be appointed. An important first step is to either
develop a safety manual internally or hire an experienced safety consultant to develop
one. This manual will serve as the guide to implementing an effective safety program
that will minimize on-the-job injuries. In addition, a well-developed safety manual will
also reduce the number of OSHA violations by pointing out problem areas in advance.
It is important to establish an environment of “safety first” right from the start.

57
11.5. SAFETY RECOMMENDATIONS:

The plant safety manual should cover basic safety expectations, enforcement
provisions and other critical operational procedures, including:
• Lockout/Tagout
• Confined space entry
• Use of personal protective equipment
• Emergency response
• Hazard communication (employee right-to-know)
• Hot works
• Respiratory protection
• Fall protection
• Other related management issues affecting the facility
Train employees at the time of initial employment about the safety program,
safety expectations and how employees will be held accountable for the
implementation of the plants safety program.

All personnel should have an understanding of hazardous materials present in

the plant. This includes training them on how to work with those hazardous materials
safely (prior to use) and the use of any appropriate personal protective equipment.

11.6. MATERIAL SAFETY DATA SHEETS

In this section the MSDS for Hydroxymethyl Frufural and Dimethyl Furan are
provided.
11.6.1 Hydroxymethyl Furfural:
Product Name: 5-(Hydroxymethyl)-2-furaldehyde
Chemical Name: 5-Hydroxymethyl fufural
Chemical Formula: C6H6O3
Fire and explosion data
Flammability of the Product: Flammable.
Flash Points: CLOSED CUP: 74°C (165.2°F). OPEN CUP: 79°C (174.2°F).
Flammable Limits: LOWER: 6% UPPER: 36.5%
Products of Combustion: These products are carbon oxides (CO, CO2)
Handling and storage
Precautions: Keep locked up. Keep away from heat. Keep away from sources of
ignition. Ground all equipment containing material. Do not ingest. Do not breathe

58
gas/fumes/ vapor/spray. Wear suitable protective clothing. In case of insufficient
ventilation, wear suitable respiratory equipment. If ingested, seek medical advice
immediately and show the container or the label. Avoid contact with skin and eyes.
Keep away from incompatibles such as oxidizing agents, metals, acids.
Storage: Store in a segregated and approved area. Keep container in a cool, well-
ventilated area. Keep container tightly closed and sealed until ready for use. Avoid all
possible sources of ignition (spark or flame).

11.6.2 Dimethyl Furan:

Chemical Name: 2,5-dimethylfuran
Chemical Formula: C6H8O
Fire and explosion data
Flammability of the Product: Flammable.
Flash Points: CLOSED CUP: 7°C (44.6°F).
Vapor Pressure: 155 mm Hg @ 25 °C (77 °F)
Flammable Limits: LOWER: 1.6% UPPER: 8.7%
Handling and storage
Precautions; Obtain special instructions before use. Do not handle until all
safety precautions have been read and understood. Wear protective gloves. Wear eye
or face protection. Wear protective clothing. Keep away from heat, hot surfaces, sparks,
open flames and other ignition sources. No smoking. Use explosion-proof electrical,
ventilating, lighting and all material-handling equipment. Use only non-sparking tools.
Take precautionary measures against static discharge. Keep container tightly closed.
Use only outdoors or in a well-ventilated area. Avoid release to the environment. Avoid
breathing vapor. Wash hands thoroughly after handling.
Storage: Store and handle in accordance with all current regulations and standards.
Grounding and bonding required.

59
 12. PLANT LOCATION AND LAYOUT

The location of the plant can have a crucial effect on the profitability of a
project, and the scope for future expansion. Many factors must be considered when
selecting a suitable site, and only a brief review of the principal factors will be given in
this section.The desired location for HMF and DMF plant is Kakinada, Andhra
Pradesh, India.
The principal factors to be considered are:
 Location, with respect to the marketing area.

 Raw material supply.

 Transport facilities.

 Availability of labour.

 Availability of utilities: water, fuel, power.

 Availability of suitable land.

 Environmental impact and effluent disposal.

 Local community considerations.

 Climate.

 Political strategic considerations.

12.1.1. Marketing Area:
For materials that are produced in bulk quantities such as cement, mineral acids
and fertilizers, where the cost of the product per ton is relatively low and for the cost
of transport of a significant fraction of the sales price, the plant should be located close
to the primary market. This consideration will be less important for low volume
production and high-priced products such as pharmaceuticals. In an International
market, there may be an advantage to be gained by locating the plant within an area
with preferential tariff.
12.1.2. Raw Materials:
The availability and price of suitable raw materials will often determine the site
location. Plants producing bulk chemicals are best located close to the source of the
major raw material and also close to the marketing area.
12.1.3. Transport:
The transport of materials and products to and from plant will be an overriding
consideration in site selection. If practicable, a site should be selected that is close to at

60
least two major forms of transport: road, rail, waterway or a seaport. Road transport is
being increasingly used, and is suitable for local distribution from a central warehouse.
Rail transport will be cheaper for the long- distance transport of bulk chemicals. Air
transport is convenient and efficient for the movement of personnel and essential
equipment and supplies, and the proximity of the site to a major airport should be
considered.

12.1.4. Availability of Labor:

Labor will be needed for construction of the plant and its operation. Skilled
construction workers will usually be brought in from outside the site, but there should
be an adequate pool of unskilled labour available locally; and labour suitable for
training to operate the plant. Skilled tradesmen will be needed for plant maintenance.
Local trade union customs and restrictive practices will have to be considered when
assessing the availability and suitability of the labour for recruitment and training.

12.2. Plant Layout

Because the process requires only one tanker truck per hour of both product and feed,
the plant does not necessarily need to have a rail connection, although it would increase
efficiency. The only requirement for plant layout is that Distillation column needs to
not be covered by the factory roof since there will be a hydrogen flame coming off the
condenser. Aside from that, this layout was chosen to reduce pipeline length and to
ensure that utilities are in proximity of process equipment that requires them (i.e.
electricity connection near mixer, ethyl acetate near the reactor, and heating and cooling
utilities near the distillation columns). Plant layout for HMF and DMF Process is
shown in Figure 12.1 .

61
Figure 12.1 . Plant layout for HMF and DMF Process Plant

62
 13. PRELIMINARY COST ESTIMATION
Plant capacity = 11,000 tonnes per annum of DMF
13.1. Cost of major Equipments:
The costs of major equipments as per 2018 evaluated using cost indices are given in table.
13.1.
Table 13.1. Costs of Major Equipments
S. No. Equipment No’s Total Price in Rs.
1. Pumps 3 1,517,850
2. Mixers 1 1,381,550
3 Heat Exchangers 3 10,603,750
4 Heaters 1 11,142,000
5 Compressor 1 12,930,100
6 Reactors 2 39,832,100
7 Flash Vessels 2 11,594,850
8 Coolers 2 8,052,150
9 Distillation Columns 2 182,197,150

Total equipment cost 827,435,350

13.2. Fixed Capital Investment:

1. Total purchased equipment cost (TPEC) = 1.25×cost of major equipments
= 1034294188 Rs.
2. Cost of installation = 40% of TPEC
= 413717675 Rs.
3. Insulation cost = 2% of TPEC
= 20685883.75 Rs.
4. Cost of instruments and controls = 30% of TPEC
=310288256.3 Rs.
5. Cost of piping = 30% of TPEC
= 310288256.3 Rs.
6. Cost of electrical insulation = 20% of TPEC
= 206858837.5 Rs

63
7. Building including service and land (BSL) = 20000000 Rs.
8. (i) Roads and walls = 8000000 Rs.
(ii) Fences = 30% of BSL
= 902500 Rs.
9. Account, construction and engineering = 20% of TPEC
= 206858837.5 Rs.
10. Fixed capital = sum of (1) to (9)
= 2532394434 Rs.
11. Contingency = 10% of fixed costs
= 253239443.4 Rs
Total fixed costs = Fixed capital + Contingency
= 2785633877 Rs.
13.3. Manufacturing Cost:
12.3.1 Direct manufacturing cost:
(a) Cost of Raw material = 1498200000 Rs.
(b) Operating Direct Supervision Electrical Labour:
The pay scale for each designation is given under table 13.2.
Table 13.2. Pay Scale for Each Designation
S.No. Designation No’s Pay/month Rs.
1 Head of Department 1 100000
2 Production manager 3 75000
3 Asst. Manager 6 40000
4 Shift engineer 4 25000
5 Shift operator 6 15000
6 Chemist 3 `10000
7 Unskilled operator 8 8000
8 Maintenance engineer 3 15000
9 Boiler attendants 3 5000
10 Maintenance staff 3 5000
11 Clerical staff 6 5000

Total salary = 954000 Rs. /month

= 11448000 Rs. /annum

91
64
 (1) Utilities 10% of raw materials = 1498200000 Rs.
(2) Maintenance & repairs 6% of fixed capital investment = 151943666 Rs
(3) Operating supplies 20% of maintenance cost = 30388733.21 Rs.
(4) Laboratory charges 20% of operating supplies = 6077746.642 Rs.
Direct Manufacturing Cost = 3196258146 Rs.
12.3.2 Fixed charges:
1. Depreciation:
a.10% of fixed capital for machinery and
equipments = 253239443.4 Rs
b.3% of initial cost of building = 600000 Rs.
Total sum = 253839443.4 Rs.
2. Local Taxes = 2% of fixed capital = 50647888.68 Rs.
3. Insurances = 1% of fixed capital = 25323944.34 Rs.
4. Fixed Manufacturing
cost = sum of (1) to (3) =5836500719.8 Rs
12.3.3 Plant Overhead:

Total manufacturing cost = 1498200000+3196258146+21879887.91

= 9054638753 Rs.
General Expenses:
=175095021.6 Rs
Total general expenses = 471920057.6 Rs.
Total production cost = manufacturing cost + general expenses
= 9708246701 Rs

13.4 Working capital Investment:

25% of fixed capital investment = 633098608.5
Total Capital investment = total fixed capital + working capital
= 3418732486 Rs
13.5 Profit: = 47,93,61,247 Rs

Payout time: = 252394434/363888748

= 6.99 years

65
 14. CONCLUSION
This project lays emphasis on Manufacturing of Hydoxymethyl Furfural and
Dimethyl Furan which are produced from dehydration and hydrogenolysis of sugars, here
we use Fructose as our feed, with annual production capacity of 15,000 TPA of HMF and
11,000 TPA of DMF . Overall material and energy balances are done and found to be in
accordance with theoretical results.

In specific equipment design, first a distillation column was designed , we got 12

trays column with a diameter of 5.47 m and 0.012 bar for each tray , feed tray location is 5
Apart a mixer was designed. The volume of the mixer was found to be 1.415 m3 by using
the residence time of one and half hour. The height and diameter of mixer was found to be
1.594 m and 1.063 m respectively. Coming to agitator design of mixer, Impeller Diameter
was found to be 0.3543 m, length and width of the blade are 0.088 m and 0.07 m. The
power required was also calculated. By comparing results, we can see how process
intensification can affect the sizing of the equipment, thereby reducing overall costs and
improving the mass transfer efficiency.

Materials of construction, specific to each equipment are listed. Health, safety and
environmental aspects with regard to handling and use of HMF and DMF are discussed.a
desired plant location and a model plant layout is shown. An appropriate cost estimate is
also made for the entire plant

66
 15. BIBLIOGRAPHY
1. G.W. Huber, S. Iborra, A. Corma, Synthesis of transportation fuels from biomass:
chemistry, catalysts, and engineering, Chem. Rev. 106 (9) (2006)

2. Y. Roman-Leshkov, C.J. Barrett, Z.Y. Liu, J.A. Dumesic, Production of

dimethylfuran for liquid fuels from biomass-derived carbohydrates, Nature
447 (2007) .

3. Y. Roman-Leshkov, J.N. Chheda, J.A. Dumesic, Phase modifiers promote

efficient production of hydroxymethylfurfural from fructose, Science 312 (2006)

4. F.K. Kazi, J. Fortman, R. Anex, G. Kothandaraman, D. Hsu, A. Aden, A.

Dutta,Techno-economic Analysis of Biochemical Scenarios for Production of
Cellulosic Ethanol, NREL, Golden, CO, June 2010 (NREL/TP-6A2-46588).

5. Y. Yang, C.W. Hu, M.M. Abu-Omar, Green Chemistry 14 (2012) .

6. G. Yong, Y. Zhang, J.Y. Ying, Angewandte Chemie International Edition 47

(2008)

7. M. Chidambaram, A. T. Bell, Green Chemistry. 2010, 12, 1253–1262. (1988).

8. Juanjuan Shi, Yingyu Wang, Xini Yu, Weichen Du, Zhaoyin Hou, Key Lab of
Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang
University, Hangzhou 310028, PR China.(2000)

9. Mitra J, Zhou XY, Rauchfuss T. Pd/C-catalyzed reactions of

HMF:decarbonylation, hydrogenation, and hydrogenolysis. Green Chem (2015);

10. Rao, R. S., Baker, R. T. & Vannice, M. A. Furfural hydrogenation over

carbonsupported copper. Catal. Lett. (1999).

11. Szmant, H. H. & Chundury, D. D. The preparation of

Hydroxymethylfurfuraldehyde from high fructose corn syrup and other
carbohydrates. J. Chem. Technol. Biotechnol. (1981).

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 APPENDIX
Simulation Report:

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 TO BE "UNPUBLISHED" AND LICENSED WITH DISCLOSURE
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TABLE OF CONTENTS

RUN CONTROL SECTION.................................... 1

RUN CONTROL INFORMATION........................... 1

FLOWSHEET SECTION...................................... 2
FLOWSHEET CONNECTIVITY BY STREAMS................. 2
FLOWSHEET CONNECTIVITY BY BLOCKS.................. 2
COMPUTATIONAL SEQUENCE............................ 2
OVERALL FLOWSHEET BALANCE......................... 2

PHYSICAL PROPERTIES SECTION............................ 3

COMPONENTS........................................ 3

U-O-S BLOCK SECTION.................................... 4

BLOCK: B1 MODEL: RYIELD.................... 4
BLOCK: B3 MODEL: FLASH2.................... 5
BLOCK: B5 MODEL: DSTWU..................... 6

STREAM SECTION......................................... 8
S1 S10 S11 S2 S4.................................. 8
S9................................................ 9

PROBLEM STATUS SECTION................................. 10

BLOCK STATUS...................................... 10

69
ASPEN PLUS PLAT: WINDOWS VER: 35.0 05/05/2018 PAGE 1

RUN CONTROL SECTION

RUN CONTROL INFORMATION

-----------------------

THIS COPY OF ASPEN PLUS LICENSED TO

TYPE OF RUN: NEW

INPUT FILE NAME: _1443lxp.inm

OUTPUT PROBLEM DATA FILE NAME: _1443lxp

LOCATED IN:

PDF SIZE USED FOR INPUT TRANSLATION:

NUMBER OF FILE RECORDS (PSIZE) = 0
NUMBER OF IN-CORE RECORDS = 256
PSIZE NEEDED FOR SIMULATION = 256

CALLING PROGRAM NAME: apmain

LOCATED IN: C:\Program Files (x86)\AspenTech\Aspen Plus V9.0\Engine\\xeq

SIMULATION REQUESTED FOR ENTIRE FLOWSHEET

ASPEN PLUS PLAT: WINDOWS VER: 35.0 05/05/2018 PAGE 2

FLOWSHEET SECTION

FLOWSHEET CONNECTIVITY BY STREAMS

---------------------------------

STREAM SOURCE DEST STREAM SOURCE DEST

S1 ---- B1 S2 B1 B3
S4 B3 ---- S9 B3 B5
S10 B5 ---- S11 B5 ----

FLOWSHEET CONNECTIVITY BY BLOCKS

--------------------------------

BLOCK INLETS OUTLETS

B1 S1 S2
B3 S2 S4 S9

70
B5 S9 S10 S11

COMPUTATIONAL SEQUENCE
----------------------

SEQUENCE USED WAS:

*B1 B3 *B5

OVERALL FLOWSHEET BALANCE

-------------------------

*** MASS AND ENERGY BALANCE ***

IN OUT GENERATION RELATIVE DIFF.
CONVENTIONAL COMPONENTS
(KMOL/HR )
WATER 0.00000 31.7186 31.7186 0.224014E-15
HYDROGEN 70.8375 23.6092 -47.2283 0.501530E-16
HMF 15.8589 0.00000 -15.8589 0.00000
2:5-D-01 0.00000 15.8515 15.8515 0.00000
TOTAL BALANCE
MOLE(KMOL/HR ) 86.6965 71.1793 -15.5172 0.163915E-15
MASS(KG/HR ) 2142.80 2142.80 0.00000
ENTHALPY(CAL/SEC ) -424473. -753556. 0.436707

*** CO2 EQUIVALENT SUMMARY ***

FEED STREAMS CO2E 0.00000 KG/HR
PRODUCT STREAMS CO2E 0.00000 KG/HR
NET STREAMS CO2E PRODUCTION 0.00000 KG/HR
UTILITIES CO2E PRODUCTION 0.00000 KG/HR
TOTAL CO2E PRODUCTION 0.00000 KG/HR

ASPEN PLUS PLAT: WINDOWS VER: 35.0 05/05/2018 PAGE 3

PHYSICAL PROPERTIES SECTION

COMPONENTS
----------

ID TYPE ALIAS NAME

WATER C H2O WATER
HYDROGEN C H2 HYDROGEN
HMF C C6H6O3-N5 5-HYDROXYMETHYLFURFURAL
2:5-D-01 C C6H8O-N1 2,5-DIMETHYLOXOLE

71
ASPEN PLUS PLAT: WINDOWS VER: 35.0 05/05/2018 PAGE 4

U-O-S BLOCK SECTION

BLOCK: B1 MODEL: RYIELD

------------------------------
INLET STREAM: S1
OUTLET STREAM: S2
PROPERTY OPTION SET: PENG-ROB STANDARD PR EQUATION OF
STATE

******************************************************************
*****
* *
* SPECIFIED YIELDS HAVE BEEN NORMALIZED TO MAINTAIN
MASS BALANCE *
* *

******************************************************************
*****

*** MASS AND ENERGY BALANCE ***

IN OUT GENERATION RELATIVE DIFF.
TOTAL BALANCE
MOLE(KMOL/HR ) 86.6965 71.1793 -15.5172 0.00000
MASS(KG/HR ) 2142.80 2142.80 0.00000
ENTHALPY(CAL/SEC ) -424473. -589110. 0.279468

*** CO2 EQUIVALENT SUMMARY ***

FEED STREAMS CO2E 0.00000 KG/HR
PRODUCT STREAMS CO2E 0.00000 KG/HR
NET STREAMS CO2E PRODUCTION 0.00000 KG/HR
UTILITIES CO2E PRODUCTION 0.00000 KG/HR
TOTAL CO2E PRODUCTION 0.00000 KG/HR

ASPEN PLUS PLAT: WINDOWS VER: 35.0 05/05/2018 PAGE 5

U-O-S BLOCK SECTION

BLOCK: B1 MODEL: RYIELD (CONTINUED)

*** INPUT DATA ***

TWO PHASE TP FLASH

72
 SPECIFIED TEMPERATURE C 220.000
SPECIFIED PRESSURE BAR 17.2000
MAXIMUM NO. ITERATIONS 30
CONVERGENCE TOLERANCE 0.000100000

MASS-YIELD
SUBSTREAM MIXED :
WATER 572. HYDROGEN 47.6 2:5-D-01 0.152E+04

*** RESULTS ***

OUTLET TEMPERATURE C 220.00
OUTLET PRESSURE BAR 17.200
HEAT DUTY CAL/SEC -0.16464E+06
VAPOR FRACTION 1.0000

V-L PHASE EQUILIBRIUM :

COMP F(I) X(I) Y(I) K(I)

WATER 0.44562 0.45895 0.44562 2.1854
HYDROGEN 0.33169 0.61596E-02 0.33169 121.20
2:5-D-01 0.22270 0.53489 0.22270 0.93712

BLOCK: B3 MODEL: FLASH2

------------------------------
INLET STREAM: S2
OUTLET VAPOR STREAM: S4
OUTLET LIQUID STREAM: S9
PROPERTY OPTION SET: PENG-ROB STANDARD PR EQUATION OF
STATE

ASPEN PLUS PLAT: WINDOWS VER: 35.0 05/05/2018

PAGE 6

U-O-S BLOCK SECTION

BLOCK: B3 MODEL: FLASH2 (CONTINUED)

*** MASS AND ENERGY BALANCE ***

IN OUT RELATIVE DIFF.
TOTAL BALANCE
MOLE(KMOL/HR ) 71.1793 71.1793 0.199649E-15
MASS(KG/HR ) 2142.80 2142.80 0.00000
ENTHALPY(CAL/SEC ) -589110. -753556. 0.218227

73
 *** CO2 EQUIVALENT SUMMARY ***
FEED STREAMS CO2E 0.00000 KG/HR
PRODUCT STREAMS CO2E 0.00000 KG/HR
NET STREAMS CO2E PRODUCTION 0.00000 KG/HR
UTILITIES CO2E PRODUCTION 0.00000 KG/HR
TOTAL CO2E PRODUCTION 0.00000 KG/HR

*** INPUT DATA ***

TWO PHASE TP FLASH
SPECIFIED TEMPERATURE C 25.0000
SPECIFIED PRESSURE BAR 17.2252
MAXIMUM NO. ITERATIONS 30
CONVERGENCE TOLERANCE 0.000100000

*** RESULTS ***

OUTLET TEMPERATURE C 25.000
OUTLET PRESSURE BAR 17.225
HEAT DUTY CAL/SEC -0.16445E+06
VAPOR FRACTION 0.33434

V-L PHASE EQUILIBRIUM :

COMP F(I) X(I) Y(I) K(I)

WATER 0.44562 0.66759 0.36792E-02 0.55111E-02
HYDROGEN 0.33169 0.41675E-03 0.99122 2378.5
2:5-D-01 0.22270 0.33199 0.50977E-02 0.15355E-01

BLOCK: B5 MODEL: DSTWU

-----------------------------
INLET STREAM: S9
CONDENSER OUTLET: S10
REBOILER OUTLET: S11
PROPERTY OPTION SET: PENG-ROB STANDARD PR EQUATION OF
STATE
ASPEN PLUS PLAT: WINDOWS VER: 35.0 05/05/2018 PAGE
7

U-O-S BLOCK SECTION

BLOCK: B5 MODEL: DSTWU (CONTINUED)

74
******************************************************************
*****
* *
* ERRORS IN BLOCK CALCULATIONS *
* *
* ERROR IN BUBBLE POINT CALCULATION OF BOTTOMS
*
* *

******************************************************************
*****

*** MASS AND ENERGY BALANCE ***

IN OUT RELATIVE DIFF.
TOTAL BALANCE
MOLE(KMOL/HR ) 47.3810 47.3810 0.00000
MASS(KG/HR ) 2082.01 2082.01 0.218418E-15
ENTHALPY(CAL/SEC ) -751171. -751171. 0.00000

*** CO2 EQUIVALENT SUMMARY ***

FEED STREAMS CO2E 0.00000 KG/HR
PRODUCT STREAMS CO2E 0.00000 KG/HR
NET STREAMS CO2E PRODUCTION 0.00000 KG/HR
UTILITIES CO2E PRODUCTION 0.00000 KG/HR
TOTAL CO2E PRODUCTION 0.00000 KG/HR

*** INPUT DATA ***

HEAVY KEY COMPONENT WATER
RECOVERY FOR HEAVY KEY 0.000100000
LIGHT KEY COMPONENT 2:5-D-01
RECOVERY FOR LIGHT KEY 0.99000
TOP STAGE PRESSURE (BAR ) 16.0000
BOTTOM STAGE PRESSURE (BAR ) 17.0000
NO. OF EQUILIBRIUM STAGES 25.0000
DISTILLATE VAPOR FRACTION 0.0

*** RESULTS ***

DISTILLATE TEMP. (C ) 262.15 K
BOTTOM TEMP. (C ) 391.15K
MINIMUM REFLUX RATIO 2.6
ACTUAL REFLUX RATIO 4.1
MINIMUM STAGES 8
ACTUAL EQUILIBRIUM STAGES 13
NUMBER OF ACTUAL STAGES ABOVE FEED 6

75
 DIST. VS FEED MISSING
CONDENSER COOLING REQUIRED (CAL/SEC ) MISSING
NET CONDENSER DUTY (CAL/SEC ) MISSING
REBOILER HEATING REQUIRED (CAL/SEC ) MISSING
NET REBOILER DUTY (CAL/SEC ) MISSING

ASPEN PLUS PLAT: WINDOWS VER: 35.0 05/05/2018

PAGE 8

STREAM SECTION

S1 S10 S11 S2 S4
----------------

STREAM ID S1 S10 S11 S2 S4

FROM : ---- B5 B5 B1 B3
TO : B1 ---- ---- B3 ----

SUBSTREAM: MIXED
PHASE: MIXED MIXED MIXED VAPOR VAPOR
COMPONENTS: KMOL/HR
WATER 0.0 15.8155 15.8155 31.7186 8.7558-02
HYDROGEN 70.8375 9.8730-03 9.8730-03 23.6092 23.5895
HMF 15.8589 0.0 0.0 0.0 0.0
2:5-D-01 0.0 7.8651 7.8651 15.8515 0.1213
TOTAL FLOW:
KMOL/HR 86.6965 23.6905 23.6905 71.1793 23.7983
KG/HR 2142.8000 1041.0035 1041.0035 2142.8000 60.7931
L/MIN 2.9308+04 17.9996 17.9996 2710.4240 575.4231
STATE VARIABLES:
TEMP C 25.0000 25.0239 25.0239 220.0000 25.0000
PRES BAR 1.0000 16.5000 16.5000 17.2000 17.2253
VFRAC 0.8171 1.7601-05 1.7601-05 1.0000 1.0000
LFRAC 0.1829 1.0000 1.0000 0.0 0.0
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
CAL/MOL -1.7626+04 -5.7074+04 -5.7074+04 -2.9795+04 -360.8374
CAL/GM -713.1329 -1298.8502 -1298.8502 -989.7311 -141.2551
CAL/SEC -4.2447+05 -3.7559+05 -3.7559+05 -5.8911+05 -2385.3702
ENTROPY:
CAL/MOL-K -24.0207 -56.6058 -56.6058 -18.8442 -5.9560
CAL/GM-K -0.9719 -1.2882 -1.2882 -0.6260 -2.3316
DENSITY:
MOL/CC 4.9302-05 2.1936-02 2.1936-02 4.3769-04 6.8930-04
GM/CC 1.2185-03 0.9639 0.9639 1.3176-02 1.7608-03

76
AVG MW 24.7161 43.9418 43.9418 30.1042 2.5545

ASPEN PLUS PLAT: WINDOWS VER: 35.0 05/05/2018 PAGE 9

STREAM SECTION

S9
--

STREAM ID S9
FROM : B3
TO : B5

SUBSTREAM: MIXED
PHASE: LIQUID
COMPONENTS: KMOL/HR
WATER 31.6311
HYDROGEN 1.9746-02
HMF 0.0
2:5-D-01 15.7302
TOTAL FLOW:
KMOL/HR 47.3810
KG/HR 2082.0069
L/MIN 35.9778
STATE VARIABLES:
TEMP C 25.0000
PRES BAR 17.2253
VFRAC 0.0
LFRAC 1.0000
SFRAC 0.0
ENTHALPY:
CAL/MOL -5.7074+04
CAL/GM -1298.8502
CAL/SEC -7.5117+05
ENTROPY:
CAL/MOL-K -56.6082
CAL/GM-K -1.2883
DENSITY:
MOL/CC 2.1949-02
GM/CC 0.9645
AVG MW 43.9418

77
 ASPEN PLUS PLAT: WINDOWS VER: 35.0 05/05/2018 PAGE
10

PROBLEM STATUS SECTION

BLOCK STATUS
------------

******************************************************************
**********
* *
* Calculations were completed with errors *
* *
* The following Unit Operation blocks were *
* completed with warnings: *
* B1 *
* *
* The following Unit Operation blocks were *
* completed with errors: *
* B5 *
* *
* All streams were flashed normally *
* *
*********************************************************************

78