Production of Hydroxy-Propylated

Starches
Modeling and Evaluation with
SuperPro Designer®

INTELLIGEN, INC.
Simulation, Design, and Scheduling Tools
For the Process Manufacturing Industries
www.intelligen.com

Intelligen, Inc. Page 1

Introduction
This example analyzes a starch modification process that produces hydroxyl-propylated starches (HP
starches). The main market for modified starches is the food and beverage industry. Other non-food
markets include paper making, pharmaceuticals, textiles, and the chemical industries. Figure 1 shows the
global modified starch production in recent years and a projection of the expected future growth (Grand
View Research, 2018).

Figure 1: Modified starch market volume (kilotons)

Starch is the most abundant carbohydrate reserve in plants. This is because plants produce glucose units
via photosynthesis and then store them by polymerizing glucose into polysaccharides called amylose and
amylopectin. These polysaccharides are the primary components of starch granules, and both of them co-
exist in most plants. Amylose consists only of linear chains, while amylopectin also includes branched
chains. Starch granules also contain a small concentration of protein, lipids, and minerals.

Starch is the basis of the nutrition pyramid for humans, and it provides about 70-80% of the calories
consumed. In addition to being a primary energy source for humans, starch has characteristics which
have allowed it to become an abundant and cheap additive within the food industry and other industries.
For instance, in the food industry native starches are frequently used as thickening and gelling agents.
However, under certain processing or storage conditions, native starches can show undesirable
properties such as low resistance to high shear rates, thermal decomposition, high retrogradation
(molecular rearrangement and recrystallization), syneresis (expulsion of water), etc. This limits their
applications somewhat.

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New processing techniques and the increasing demand for biodegradable and renewable resources have
opened new markets to starch beyond the food industry. However, the disadvantages listed above also
apply to the use of native starches in certain industrial applications. For this reason, starches frequently
must be modified chemically or physically to enhance their positive attributes or to minimize their negative
attributes in order to meet the unique requirements of each application.

A common category of modified starches are the cross-linked starches. Crosslinking of starch occurs
when linear or branched chains are covalently interconnected. The reagents used, such as phosphoryl
chloride (commonly called phosphorus oxychloride or POCl3) form ether or ester bonds with hydroxyl
groups in the starch molecules. This modification increases the degree of polymerization, thereby
increasing the polymer’s rigidity. In the food industry, cross-linked starches are frequently used in
formulations of frozen products due to their stabilizing, thickening, and retrogradation resistance
properties. Crosslinked starches are more resistant to low pH, rupture, and high temperature, and they
have high capacity for holding water. These properties also allow cross-linked starches to be used in
other industries such as plastics (Alcázar-Alay and Meireles, 2015).

Another category of modified starches is hydroxyl-propylated (HP) starches. To produce these, starch is
etherified with propylene oxide (PO). This chemical modification provides improved stability and film-
forming properties to starches used in paper, surface sizing or coating, textile warp sizing, and adhesives.
HP starches also improve the shelf life, freeze-thaw stability, cold storage stability, clarity, and texture
properties of starch paste in food applications. Waxy starches (high in amylopectin) are used for these
modifications. Because of the slow retrogradation of amylopectin, it is very effective in retarding bread
staleness and improving bread crumb texture, thereby enhancing bread shelf life and quality (Bertolini,
2009). HP starches are also used as thickening and stabilizing agents in low-fat or low-calorie dairy
products, due to their compatibility with milk proteins. They are used in a variety of sauces, dressings, and
frozen foods as well.

Multiple chemical modifications are sometimes combined in order to achieve the desired starch
properties. For instance, this SuperPro example simulates the production of a dual-modified HP starch
crosslinked with phosphoryl chloride. These dual modifications of crosslinking and hydroxyl-propylation
are used together widely, and the resulting product combines the merits of both modifications. In general,
the food industry is allowed to use only lightly modified starches, while other industrial applications may
use heavier modifications. The extent of modification is defined by the amount of chemicals used or by
the extent of the reaction.

The starch modifications in this model take place under alkaline conditions using large amounts of sodium
hydroxide (NaOH). The high pH during processing can cause unwanted starch solubilization. In order to
prevent the starch granules from solubilizing at this stage, large amounts of sodium sulfate (Na2SO4) are
used. The crosslinking reaction is fast, while the hydroxypropylation is much slower. The operating
temperature, starch concentration (Baume), amount of NaOH and Na2SO4, and amount of POCl3 and PO

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dosed all influence the reaction kinetics and efficiency, and ultimately the product quality, properties, and
specifications. The PO is near or above its boiling point at atmospheric pressure, and it is handled with
caution since it is extremely flammable. As a result, nitrogen gas is added to the reactor in order to ensure
that the concentration of oxygen there is low.

Detailed Process Description

A conceptual process for starch modification was modeled in SuperPro Designer in an effort to capture
the expected stream flowrates, process equipment requirements, utilities consumption, and production
costs.

For reporting and analysis purposes, the process has been divided into three sections:

 Starch modification
 PO Neutralization
 Washing and Drying
Flowsheet sections in SuperPro are simply sets of related unit procedures (processing steps). For
information on how to specify flowsheet sections and edit their properties, please consult Chapter 8.1 of
the SuperPro manual. The contents of each of this example’s flowsheet sections are described in greater
detail below. The process will be easier to follow if you open this example within SuperPro and view the
flowsheet while reading about the process.

Starch Modification

The purpose of this section is to perform the chemical reactions required to modify the starch and to
subsequently remove the excess PO from the starch slurry. The starch slurry is assumed to come directly
from the corn refinery (refer to the Corn Refinery example in SuperPro’s Examples\ Food Processing
folder; the starch input stream composition is roughly equivalent to stream S-116 in that example, which is
just before the Belt Filtration in the Starch Separation section of that model).

The process in this flowsheet begins with the modification reactor (P-1 / R-101), which operates in batch
mode. The reactor procedure includes the following operations:
- Pull-In Starch Slurry
- Pull-In Sodium Sulfate
- Pull-In Sodium Hydroxide
- Nitrogen Sweep-1
- Pull-In Phosphorus Oxychloride
- Starch Cross-Linking Reaction
- Pull-In PO

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 - Starch Hydroxy-Propylation Reaction
- Nitrogen Sweep-2
- Transfer out
- CIP (Clean-In-Place)

Initially, starch slurry is pulled into the reactor from the Starch Separation section of the Corn Refinery,
with a solids concentration of about 40%. Then sodium sulfate is pulled in to the desired composition (a
10:1 ratio of starch:sodium sulfate). Sodium hydroxide is added to increase the pH of the slurry, and a
nitrogen sweep is performed in order to reduce the amount of oxygen in the headspace of the reactor.
Next, Phosphorus Oxychloride (POCl3) is added to the desired concentration. As soon POCl3 is added,
the crosslinking reaction starts. The mass stoichiometry of the reaction is the following:

0.05 POCl3 + 99.95 Starch  100 cross-linked starch

The extent of the reaction was set to 100%.

Next, Propylene Oxide (PO) is added. The addition of PO initiates the starch hydroxypropylation, which
was modeled with two reactions that proceed in parallel with the following mass stoichiometries:

Starch etherification: 96 Cross-linked starch + 4 PO  100 HP starch

Starch solubilization: 100 Cross-linked starch  100 Solubilized starch

The extent of hydroxypropylation was set at 96%, while the remaining 4% of starch was simply
solubilized. The duration of the reaction was set at 17 hours, during which the temperature is controlled at
40 °C using cooling water. At the end of the reaction, another nitrogen sweep is performed in order to
remove most of the unreacted PO from the headspace of the reactor. The contents of the reactor are then
transferred out, and a CIP operation cleans the reactor prior to the next batch. In this flowsheet,
Procedure P-1 actually represents 4 identical equipment units operating in “staggered mode” (please see
section 6.1.c of the SuperPro manual for information about equipment in “staggered mode”.) These 4
units each have a 32-hour batch-to-batch cycle time, and an 8-h Transfer-Out duration. Therefore, one of
them is always in Transfer-Out mode, providing a continuous outlet flow to the downstream equipment.

The outlet stream from the reactors is passed through a stripper column (P-2), which removes the
remaining PO from the slurry. It is important to remove the excess PO from the slurry rapidly in order to
avoid formation of toxic by-products such as chlorohydrins. The slurry then goes into a buffer tank (P-10 /
V-102), which continuously feeds the downstream section.

PO Neutralization

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As mentioned above, some of the excess PO is removed using a nitrogen sweep through the reactor,
while the remainder is removed by mixing the slurry with air in a stripper column. Since PO is toxic and
flammable, the two air streams containing PO cannot be vented to the atmosphere. Instead, they are
mixed in a mixer (P-3) and sent to a scrubber column (P-4 / C-102), in which an aqueous sulfuric acid
solution absorbs the gaseous PO. The solution is sent to a reactor (P-5 / R-102), where PO is hydrolyzed
into propylene glycol in the acidic environment. This reaction is actually initiated in the scrubber column
and is completed in the reactor. The reaction has the following molar stoichiometry:

1 Propylene Oxide + 1 Water  1 Propylene glycol

The reaction has a conversion of 20% in the scrubber and 100% (of the remaining PO) in the reactor. The
residence time in the reactor is 1 hour. A small fraction of the acidic solution is then split off as waste (in
P-6; this is the “loop bleed”). The rest of the solution is pumped (using P-7) through a flow adjusting unit
(P-8) which adds fresh sulfuric acid solution, then through a cooler (P-9) which drops the temperature to
about 32 °C, and finally back to the scrubber.

Washing and Drying

The PO-free starch slurry is mixed with other recycling streams (in P-11) and sent to a set of
hydrocyclones in order to purify the starch. In reality, multiple sets of hydrocyclones are used in series.
For the sake of simplicity, only three were included in this example. A pump (P-12) sends the slurry to the
first hydrocyclone (P-13). The underflow stream of this hydrocyclone (S-109) is mixed with water (in P-15)
which has been pre-heated to 42 °C. The diluted slurry then passes through a second hydrocyclone (P-
17). The overflow is recycled back to mixer P-11. The underflow is sent to a storage tank (P-21) which
feeds the screw belt (P-22) where the slurry is concentrated to about 60% dry solids (DS). The filtrate (S-
104), which contains a small amount of starch, is recycled back to mixer P-11. A flash dryer (P-23 / SRD-
101) is used to dry the starch to a final moisture content of about 10%. The overflow of the first
hydrocyclone (P-13) is pumped to another hydrocyclone (P-19) which concentrates the stream’s starch
and recycles it back to mixer P-11. The overflow of P-19, which contains almost all the impurities, is
cooled (in P-20) and sent to the wastewater treatment plant.

Economic Evaluation
This plant processes about 100,000 metrics tons of starch per year in the form of slurry (about 250,000
tons of slurry per year), with an assumed uptime of about 8000 hours per year. Various assumptions were
made for the costs of raw materials, heat transfer agents, wastewater treatment, equipment purchase
costs, labor, etc. In addition to the mass and energy balances, SuperPro Designer calculates the capital

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and operating expenses (CAPEX and OPEX), the production cost, and the profitability of the project. The
financial results can be found in SuperPro’s Economic Evaluation (EER), Cash Flow Analysis (CRF),
Itemized Cost (ICR), and Excel Custom reports.

Table 1, which was extracted from the EER and is shown below, provides information on equipment sizes
and purchase costs. The SuperPro built-in cost models were used for estimating the purchase cost of all
equipment, apart from the stripper which was manually set to $1,000,000. Table 2, which was also
extracted from the EER, provides an estimate of the Fixed Capital Estimate Summary, which is around
$86.5 million for a plant of this capacity.

1. MAJOR EQUIPMENT SPECIFICATION AND FOB COST (2017 prices)

Quantity/
Standby/ Name Description Unit Cost ($) Cost ($)
Staggered
1/0/3 R-101 Stirred Reactor 1,930,000 7,720,000
Vessel Volume = 282.29 m3
1/0/0 V-102 Blending Tank 669,000 669,000
Vessel Volume = 247.64 m3
1/0/0 CY-101 Hydrocyclone 2,000 2,000
Rated Throughput = 86256.62 L/h
1/0/0 PM-101 Centrifugal Pump 66,000 66,000
Pump Power = 20.54 kW
1/0/0 PM-102 Centrifugal Pump 62,000 62,000
Pump Power = 17.63 kW
1/0/0 CY-102 Hydrocyclone 2,000 2,000
Rated Throughput = 74048.78 L/h
1/0/0 V-101 Blending Tank 307,000 307,000
Vessel Volume = 29.98 m3
2/0/0 BF-101 Belt Filter 269,000 538,000
Belt Width = 6.29 m
1/0/0 SDR-101 Spray Dryer 248,000 248,000
Dryer Volume = 68.79 m3
1/0/0 HX-101 Heat Exchanger 18,000 18,000
Heat Exchange Area = 4.28 m2
1/0/0 PM-103 Centrifugal Pump 53,000 53,000
Pump Power = 12.18 kW
1/0/0 CY-103 Hydrocyclone 2,000 2,000
Rated Throughput = 51151.37 L/h
1/0/0 HX-102 Heat Exchanger 23,000 23,000
Heat Exchange Area = 6.60 m2
1/0/0 C-101 Stripper 1,000,000 1,000,000
Absorber Volume = 9.79 m3
1/0/0 C-102 Absorber 16,000 16,000
Absorber Volume = 4.11 m3
1/0/0 R-102 Stirred Reactor 777,000 777,000
Vessel Volume = 22.04 m3
1/0/0 HX-103 Heat Exchanger 47,000 47,000

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 Heat Exchange Area = 21.80 m2
1/0/0 PM-104 Centrifugal Pump 25,000 25,000
Pump Power = 2.35 kW
Unlisted Equipment 2,894,000

2. FIXED CAPITAL ESTIMATE SUMMARY (2017 prices in $)

3A. Total Plant Direct Cost (TPDC) (physical cost)

1. Equipment Purchase Cost 14,469,000
2. Installation 5,340,000
3. Process Piping 5,064,000
4. Instrumentation 5,788,000
5. Insulation 434,000
6. Electrical 1,447,000
7. Buildings 6,511,000
8. Yard Improvement 2,170,000
9. Auxiliary Facilities 5,788,000
TPDC 47,010,000

3B. Total Plant Indirect Cost (TPIC)

10. Engineering 11,752,000
11. Construction 16,453,000
TPIC 28,206,000

3C. Total Plant Cost (TPC = TPDC+TPIC)

TPC 75,216,000

3D. Contractor's Fee & Contingency (CFC)

12. Contractor's Fee 3,761,000
13. Contingency 7,522,000
CFC = 12+13 11,282,000

3E. Direct Fixed Capital Cost (DFC = TPC+CFC)

DFC 86,498,000

Tables 3a,b,c provide information on the assumed unit costs and the calculated annual amounts and
costs for raw materials, labor, and utilities, respectively. The total annual cost of raw materials was
calculated to be around $31 million. The cost of starch ($25 million) is the most important raw material
cost (80% of the total), followed by water (7.6%) and propylene oxide (6.9%).

3a. MATERIALS COST - PROCESS SUMMARY

Bulk Material Unit Cost ($) Amount Annual Cost ($) %

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Air 0.00 1,124,614,816 kg 0 0.00
Ash 0.00 50,000 kg 0 0.00
NaOH (50% w/w) 0.00 2,400,000 kg 0 0.00
Nitrogen 0.00 114,501 kg 0 0.00
POCl3 2.00 50,000 kg 100,000 0.32
Propylene Oxide 0.50 4,250,000 kg 2,125,000 6.86
Sodium Sulfate 0.15 10,000,000 kg 1,500,000 4.84
Soluble Protein 0.00 250,000 kg 0 0.00
Solubles 0.00 125,000 kg 0 0.00
Starch 0.25 99,575,000 kg 24,893,750 80.40
Sulfuric Acid 0.07 53,510 kg 3,746 0.01
Water 0.01 467,833,710 kg 2,339,169 7.56
TOTAL 30,961,664 100.00
NOTE: Bulk material consumption amount includes material used as:
- Raw Materials
- Cleaning Agents

The cost of labor was estimated to be around $4.1 million per year (Table 3b). Although only operator
labor is listed in this table, the $69/hr Unit Cost for each operator labor hour is a “factored” estimate which
includes costs for various other personnel (supervision, administration, etc).

3b. LABOR COST - PROCESS SUMMARY

Labor Type Unit Cost (S) Annual Amount Annual Cost ($) %
Operator ($/h) 69.00 (h) 58,738 ($) 4,052,929 100.00
TOTAL 58,738 4,052,929 100.00

Table 3c displays the utilities costs ($3.3 million per year). Steam is the most important utility cost item
(90% of the total). A unit cost of $30/MT was assumed for steam. The dryer is the main user of this utility.

3c. UTILITIES COST (2017 prices) - PROCESS SUMMARY

Utility Unit Cost ($) Annual Amount Ref. Annual Cost ($) %
Std Power ($) 0.10 Amount2,554,072 Units
kW-h ($) 255,407 7.80
Steam 30.00 97,720 MT 2,931,601 89.58
Cooling Water 0.05 1,713,613 MT 85,681 2.62
TOTAL 3,272,688 100.00

Figure 2 provides a breakdown of the total annual operating costs. Clearly, raw materials and facility-
dependent costs (annualized fixed capital investment, maintenance, etc.) contribute the most to the total

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annual operating costs. Raw materials in particular account for 53% of the total operating cost, while
facility dependent costs account for 28% of the total.

Figure 2: Annual Operating Cost Breakdown (%)

Finally, Table 5 provides an executive summary of the process. The total CAPEX required was estimated
to be around $94.6 million. If the selling price of HP starch is set at $0.75/kg then the expected annual
revenues are around $83 million, and the expected payback time is around 4 years.

5. EXECUTIVE SUMMARY (2016 prices)

Total Capital Investment 94,564,000 $
Capital Investment Charged to This Project 94,564,000 $
Operating Cost 58,469,000 $/yr
Revenues 83,206,000 $/yr
Cost Basis Annual Rate 110,940,770 kg MP/yr
Unit Production Cost 0.53 $/kg MP
Net Unit Production Cost 0.53 $/kg MP
Unit Production Revenue 0.75 $/kg MP
Gross Margin 29.73 %
Return On Investment 24.38 %
Payback Time 4.10 years
IRR (After Taxes) 17.73 %
NPV (at 7.0% Interest) 70,752,000 $
Total Capital Investment 83,206,000 $
MP = Total Flow of Stream 'HP_Starch'

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Summary
Our objective with this example was to present a simple starch modification plant model in SuperPro
Designer that is easy to understand and follow. As indicated in the preceding analysis, a starch
modification plant with a capacity of about 100,000 metric tons of starch per year requires a total CAPEX
of around $95 million and annual operating expenditures (including depreciation) of around $58 million.
The predominant cost is the cost of the starch raw material, followed by the cost of depreciation for a new
facility. Depreciated facilities would have a considerably lower production cost. Assuming a selling price of
$0.75/kg for HP starch, the payback time of this investment was estimated to be about 4 years, making it
an attractive and profitable investment.

References
1) Grand View Research, 2018, https://www.grandviewresearch.com/industry-analysis/modified-starch-
market.
2) Sylvia Carolina Alcázar-Alay and Maria Angela Almeida Meireles, 2015, Physicochemical properties,
modifications and applications of starches from different botanical sources, Food Sci. Technol
(Campinas) vol.35 no.2.
3) Andrea Bertolini, 2009, Chapter 1 Trends in starch applications in Starches: Characterization,
Properties, and Applications, Taylor & Francis Group, CRC Press, USA.

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