2nd Term Capstone

MAPUA INSTITUTE OF TECHNOLOGY AT LAGUNA

Academic Year 2015 2016

PRODUCTION OF METHYLENE DIPHENYL DIISOCYANATEFROM BENZENE VIA AMINE PHOSGENATION

Andrade, Ehmmarie L.Baluca, Maie H.Sabino, Jenny Rose B.

35

Engr. Ria Grace Abdon

A Plant Design Project submittedin partial fulfilment of the requirements for the degree ofBachelor of Science in Chemical EngineeringTable of ContentsCHAPTER 1. MARKET STUDY3

I. Introduction4

A. General Overview5

B. Objectives5

II. Situational Analysis6

A. Supply and Demand Analysis7

i. World Demand and Consumption

ii. Demand Based on Import

B. Philippine Laws and Regulations8

i. Department of Environment and Natural Resources (DENR) Policies

ii. 16th Congress Senate Bill No. 1336 (Isocyanates Regulatory Act)

C. Competitors10

III. Target Market12

IV. Availability of Raw Materials14

V. SWOT Analysis17

VI. Preliminary Economic Evaluation18

VII. Marketing Strategy20

VIII. Company Profile22

A. About Us22

B. Our Vision23

IX. Plant Location24

A. Categories in Choosing a Plant Location24

B. Possible Locations25

CHAPTER 2. TECHNICAL STUDY31

I. Process Selection32

II. Process Description36

A. Aspen Hysys Simulation36

B. Overall Mass Balance39

References40

CHAPTER 1MARKET STUDY

I. IntroductionA. General OverviewMethylene diphenyl diisocyanate (MDI) or 1-isocyanato-4-[(4-isocyanatophenyl)methyl]benzene is one of the aromatic diisocyanates which is used in polyurethane production. It is formed from the condensation of aniline and formaldehyde with phosgene. There are two forms of MDI: Pure MDI and Polymeric MDI (PMDI). Pure MDI is used in the production of products like elastomers, sealants, adhesives and coatings found in items such as paints, glues, and weather resistant materials while, PMDI is a highly useful product to produce a wide variety of rigid, flexible, semi-rigid and polyisocyanurate and thermoset foams. Some additional uses of MDI in polyurethanes include insulation, footwear,sports and leisure products, and some specialty flexible foams (American Chemistry Council, 2015). Physical properties of MDI are summarized in Table 1.

Table 1.1. Physical Properties of MDI (Ashida, 2007)In the market, MDI is classified as isocyanates. Isocyanates, which is widely used in polyurethane applications, includes aliphatic isocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) or 4,4 dicyclohexyl diisocyanate (HMDI), and aromatic isocyanates such as toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI). The aliphatic isocyanates are used to a much lesser extent, and only for special applications. On the other hand, aromatic isocyanates are highly commercialized in various forms and functionalities (Ionescu, 2005).According to Ceresana (2015), the global demand for polyurethane increase by 4.5% per year. Asia-pacific is the prime market for polyurethane that accounts for 44% of the global demand. Due to the rising demand of polyurethane, the demand of isocyanate increases. The global capacity of isocyanate is expected to increase by more than 3 million tonnes of the current 5 million tonnes until 2020 and over 81% of the new capacities will be found in the Asia Pacific. According to Transparency Market Research (2013), the global polyurethane market is expected to reach 66.4 billion dollars by 2018.B. ObjectivesGeneral Overview This study is primarily aimed at designing a Methylene Diphenyl Diisocyanate manufacturing plant in the Philippines.Specific OverviewThe feasibility of the plant will be determined in terms of the goals: To conduct a market study that will discuss the demand, plant capacity, market share and target market. To develop a plausible process design for MDI production. To provide design work such as process diagram and description, heat and material balance, instrumentation diagram and; To maximize the potentials of each equipment in the production.II. Situational AnalysisMethylene diphenyl diisocyanate (MDI) was developed due to toluene diisocyanate (TDI) toxicity problems. And, its chemistry provides greater opportunities to modify and optimize for difference polyurethane specifications. The non-distilled or crude MDI mixture, or polymeric MDI, consists mainly of 4,4'-diphenylmethane diisocyanate, 2,4'- and 2,2'- isomers, and condensation products with more than two aromatic rings (Vilar, 2004).A. Supply and Demand Analysisi. World Demand and ConsumptionMethylene Diphenyl Diisocyanate (MDI) is an aromatic diisocyanate widely used in construction, refrigeration, textiles, transport, furniture and bedding, footwear, industrial and others. The largest demand of MDI is in construction while the largest consumption of MDI is the rigid foam for construction. Rigid foams create one of the most known and energy efficient insulations. It can significantly can cost cut the energy while making commercial and residential properties more convenient and efficient. Figure 1.1. World MDI Demand (left) and MDI Consumption (right) (Davies, P., 2012)

ii. Demand based on Import The import data of isocyanate is used to provide the import data of MDI assuming that there is 49% of MDI in the global market of isocyanates (Reuters, 2015). There is a great demand for MDI in the Philippines which is evidently shown by the import data provided by the Department of Trade and Industry from years 2006 to 2014. Also, there is no export of any type of isocyanates such as MDI.YearTrade Value, $Quantity of Isocyanates, kgQuantity of MDI, kg

200613,076,3305,899,8922,890,947

200713,341,0335,020,7492,460,167

200816,504,0985,197,7102,546,878

200917,234,9487,118,9243,488,273

201018,606,9296,643,9663,255,543

201125,127,6238,310,7994,072,292

201230,815,95110,318,1415,055,889

201319,980,0457,501,8613,675,912

201428,589,51910,741,5345,263,352

Table 1.2. Import Data of Isocyanates and MDI in the Philippines (DTI, 2015)Figure 2 shows that the demand for MDI is increasing for the following years as the trend line for the graph of kg MDI per year is sloping upwards (positive slope). This indicates that the product has a high marketability today and for the following years to come in the Philippines.

Figure 1.2. Demand trend for MDI in the Philippines based on ImportB. Philippine Laws and Regulationsi. Department of Environment and Natural Resources (DENR) PoliciesThe Department of Environment and Natural Resources (DENR), through its Environmental Management Bureau (EMB), has created a compilation and inventory of chemicals and chemical substances that can be used throughout the country, as regards to the implementation of the Republic Act No. 6969 known as Toxic Substances and Hazardous and Nuclear Wastes Control Act of 1990. The national inventory is known as the Philippine Inventory of Chemicals and Chemical Substances (PICCS).Manufacturers, importers, distributors, and users of chemicals or chemical substances that are included in the PICCS need no longer secure clearance from the DENR, provided that their chemicals or chemical substances are not listed in the Philippine Priority Chemicals (PCL) and not subject to Chemical Control Order (CCO). The chemicals or chemical substances that are not included in the PICCS cannot be manufactured, imported, distributed, or used unless have undergone the Pre-Manufacture and Pre-Importation Notification (PMPIN) process. Methylene Diphenyl Diisocyanate with a CAS No. of 26447-40-5 can be searched and found on the PICCS, through the PICCS Online Database version 2011 (http://emb.gov.ph/internal/CasREgistry.aspx). Therefore, these chemicals can be manufactured and distributed throughout the country. PICCS is updated every five years containing around 44,000 chemical substances.

ii. 16th Congress Senate Bill No. 1336 (Isocyanates Regulatory Act)Entitled as An Act Regulating the use of Isocyanates in the Workplace, this is filed on August 22, 2013 by Defensor Santiago, Miriam. This bill seeks to address the health and safety concerns posed by isocyanates in the workplace.Section 3. Requirements for a Workplace Using Isocyanates - An employer must observe the following requirements if the employer uses isocyanates in the place of business(A) Obtain Material Safety Data Sheets (MSDSs) from the supplier to know exactly what type of isocyanates they are working with and what precautions to take;(B) Obtain technical bulletings that may provide additional health and safety information;(C) Use a system designed to generate a minimum amount of fluid mist. It is prohibited to use compresses air to blow clean parts covered with isocyanate as the air pressure causes the isocyanates to be airborne;(D) Install complete enclosures or splash guards, depending on the operation, to keep the isocyanates contained and away from the operator;(E) Use exhaust ventilation to prevent accumulation and recirculation of airborne contaminants is hereby required;(F) Workers must use a full-facepiece, supplied-air respirator and must wear personal protective clothing such as hooded coveralls, chemical-resistant gloves, and footwear to prevent dermal absorption during the spray application process; and(G) Such other requirements prescribed by the Secretary of Labor and Employment.

C. Competitors

Wanhua Chemical Group Co., Ltd.It is the largest manufacturer of MDI in Asia Pacific. They give importance to innovation, product quality and customer service. The two main goals of the company are to become a chemical producer and to become an international player in the market. For 2013, the total assets are 3,111,368 in ten thousand yuan and gross profit margin on sales of MDI is 36.33%. Wanhua Chemical Group announced a decrease in price of polymeric MDI by 2, 600 yuans/ton to 12,400 yuans/ton and a decrease also in the price of pure MDI by 2,900 yuans/ton to 18,500 yuans/ton for June 2015 (Wanhua, 2015).

Shanghai Liansheng Isocyanate Co., Ltd.It was set up in March 2003 by a joint venture of BASF Aktiengesellschaft, Huntsman China Investment and Shanghai Huayi Group and Shanghai Chloro-Soda Chemical. The companys capacity at that time was 240 kilo tonnes per annum. On July 2014, a ceremony was held to start the construction of a new plant at Shanghai Chemical Industry Park to double the production of the venture. The total investment amount is 740 million dollars (Sinopec Shanghai Gaoqiao Company, 2015).

BASF (South Korea) Co., Ltd. It is one of the Koreas top ten chemical companies. It was established in 1998 and had provided Korea with four business units: Chemicals, specialties, polyurethanes and thermoplastics. One of the strength of BASF companies is the Verbund system, where the heat released by production processes can be used as energy in other plants and their by-products can serve as a feedstock elsewhere. The strategies employed in the companies are adding value as one company, aligning innovation to customers needs and forms the best team. The total assets of the companies amounted to 71,359 million in 2014 (BASF Report, 2014).

Nippon Polyurethane Industry Co., Ltd. It is a professional manufacturer of polyurethane products and raw materials in Asia such as MDI, TDI and HDI. They offer the assurance of timely and stable supply, together with a total commitment to cost reduction via efficient production operations and raw materials process controls. They are known as a highly reliable urethanes supplier. The capital of the company is 11.5 billion yen and total assets are 55.5 billion yen (UTECH Asia, 2015).

Mitsui Chemicals Inc.A Japanese owned company that deals with performance materials, petro and basic chemicals and other functional polymeric materials. Chemistry, Innovation and Dreams are main the keywords the represents the targets and ambitions of the company. The mission of the company is to provide high-quality products and services to customers through innovations and creation of materials and products while keeping in harmony with global environment. The first quarter sales of 2015 reached 379.1 billion yen. The current assets of the company are 717.2 billion yen (Mitsui Chemicals Group, 2015).III. Target MarketThe Philippines is completely dependent to the supply of MDI from the importation of foreign countries. Since 80% of MDI is used in polyurethane production (Reuters, 2015), the target market of the plant is the polyurethane manufacturers. In Table 3, the target companies are shown.CompaniesAddressProducts

Betafoam CorporationDasmarinas Technopark, Governor's Drive, Paliparan I, Dasmarinas, CavitePolyurethane foams

EcoFoam Polyurethane InsulationSEA Olympus Building, AC Cortes Ave., Mandaue City, Cebu Philippines 6014Rigid plastic material for structural insulation system for commercial, residential and industrial application

Gloscore Philippines, Inc.378 Edang Street, Pasay City PhilippinesWaterproofing and installation of Sprayed Polyurethane Foam on roofing, chilled water pipes, a/c ducts and slabs

HB Fuller Philippines, Inc.10 Gyro Street, Light Industry & Science Park, Barangay Diezmo, Cabuyao, LagunaPolyurethane foams

Ikeba Enterprises308 Producer's Market Bldg.,FTI ComplexTaguigMetro ManilaPolyurethane insulation for building insulation encapsulation, roofing protection and many other applications both-on site and in-factory

Insulflex Industries, Inc.# 9 Gregorio Del Pilar St.Paltok,Quezon CityPolyurethane Insulation

Mandaue Foam Industries, Inc.H. Cortes Street Brgy. TipoloMandaueCity, CebuPolyurethane foam for beds, furniture, packaging, garments, insulation and automotive industry

INOAC Philippines CorporationRGC Compound, Brgy PittlandCabuyao City, LagunaPolyurethane foam for sealing, filtering, padding, medical and etc.

Uratex Philippines-Multiflex RNC Philippines, Inc.Km. 23 East Service Road, South Super Highway, Muntinlupa CityCommercial and automotive polyurethane foam products in the Philippines

Vemaval, Inc.Vemaval Compound, Langka Road, FTI Complex, TaguigTaguigMetro ManilaVemaprene polyurethane for unique design and construction material combining many of the advantages of rigid plastics, metals, and ceramics with the extensibility of rubber

Table 1.3. Polyurethane Manufacturers in the Philippines (Philippine Companies, 2015)Uses of MDI in polyurethanes include flexible moulded foam such as car seats, furniture; rigid foams such as white goods, insulation, building materials, construction; and for automotive such as dashboards, bumpers, steering wheel, door panels, bumpers/panels (Boustead, 2005). These companies are large polyurethane manufacturers in the Philippines which supplies for other companies which offers fabrication, construction and services.IV. Availability of Raw MaterialsFor the first stage of Methylene Diphenyl Diisocyanate (MDI) production, the raw materials needed are benzene, sulfuric acid and nitric acid. Based on the import and export data from 2010 to 2014, benzene and sulfuric acid is locally available and the supply is too much that the country can able to gain profit in other country. On the other hand, the export for nitric acid shows that there is not too much supply locally. Still, nitric acid can be acquired from local manufacturers. In the second stage, hydrogen has export data and so, it can be obtained locally. For the last stage of production, similar to the situation of nitric acid, phosgene and formaldehyde is being imported. But, there are local manufacturers which produced this as their by-product.YearBENZENE

Import (kg)Trade Value ($)Export (kg)Trade Value ($)

20101061,25819,453,90122,528,047

201166313,60124,209,04931,344,112

2012601,07729,232,20930,932,159

2013502,4991,058,11024,379,60631,538,598

20142753,20122,050,00027,933,725

YearSULFURIC ACID


2010504,684,256168,594,663428,932,6699,466,518

2011656,809,247218,828,336291,284,49312,124,096

2012710,033,448211,179,18746,673,7371,443,400

2013687,767,630203,762,73998,388,8513,192,807

2014521,287,589175,540,635321,152,15910,207,439

YearNITRIC ACID


20106,171,2562,852,477

20115,561,5722,802,297

20123,937,7931,993,977

20133,590,5851,620,611

20143,775,1141,784,429

Table 1.4. Raw Materials for Benzene to Nitrobenzene (1st Stage)

YearHYDROGEN


20101,828,4144,963,2455,666,74737,759,077

20112,230,96226,209,1155,784,56549,698,062

20123,646,07222,853,72626,328,03330,711,393

20135,117,0596,375,6641,029,21618,107,230

20146,512,3736,777,6741,672,53312,093,632

Table 1.5. Raw Materials for Nitrobenzene to Aniline (2nd Stage)

YearFORMALDEHYDE


20105,698,2041,650,715

20113,844,2421,217,173

20124,375,5361,399,615

20134,387,3001,458,755

20143,633,7881,366,554

YearPHOSGENE


201066,727318,293

201141,412221,854

201252,223179,566

201319,726176,784

2014117,138150,558

Table 1.6. Raw Materials for Aniline to Methylene Diphenyl Diisocyanate (3rd Stage)

The table below shows the list of companies that able to supply the raw materials for Methylene Diphenyl Diisocyanate (MDI). Raw MaterialsCompanies

BenzenePetron Bataan Refinery

Sulfuric AcidMarubeni Philippines Corporation

Nitric AcidDow Chemical Company

Hydrogen Air Liquide Philippines

FormaldehydePetron Bataan Refinery

PhosgenePetron Bataan Refinery

Sodium HydroxideMarubeni Philippines Corporation

Table 1.7. Company of the Supplier

V. SWOT AnalysisSWOT MATRIXStrengths

1. The first MDI producer the Philippines2. Lower price than similar imported product3. Decrease in trade deficit4. Cost effective process using benzene as the starting materialWeaknesses

1. New in the market and the name has not been established2. High start-up cost specifically for safety3. The plant capacity may not meet all the needs of potential clients

Opportunities

1. Large demand of MDI due to Polyurethane companies existing locally2. Locally Available Raw MaterialsS-O Analysis

1-1. Aim for expansion after 10-15 years of success1-2. Partnership with the local suppliers2-1. Price flexibility2-2. Affordable price3-1. Generate new jobs for Filipinos3-2. Less dependence in import4-1. Keep up effective production for higher profitability4-2. Meet product demand expectations

W-O Analysis

1-1. Low cost yet effective advertising campaign and marketing efforts, and maintain product quality1-2. Establish partnership with suppliers to have a production stability2-1.Product price during start-up is balanced to the start-up cost3-1.Strict following of the schedules3-2. Balanced production

Threats

1. Our competitors are large, multinational chemical manufacturersS-T Analysis

1-1. Established ties with local manufacturers2-1. Strengthen marketing strategies3-1. Focus on the local market4-1. Optimize production process

W-T Analysis

1-1. Improve the quality of products and decrease manufacturing processes costs2-1. Improve process design and ensure environmental safety3-1. Small expansion of plant capacity

Table 1.7. SWOT Matrix AnalysisVI. Preliminary Economic Evaluation (Class 5 Estimate)A. Estimated Plant Capacity and Market ShareIn 2014, the total quantity of MDI demand in the Philippines is 5,263,352 kg. Based from the projection for 2018, the total demand is 6,132,880.911 kg. A plant capacity of (4,293,016.638) kg will be used in this project, for market share of 70%. The market share is based on the target market and SWOT analysis.The ISBL (Inside Battery Limit) cost can be estimated using the following correlation (Towler & Sinnott, 2008):

WhereC2 = ISBL capital cost of the plant with capacity S2C1 = ISBL capital cost of the plant with capacity S1n = typically 0.6 for chemical industryThe reference plant used in this project is Nippon Polyurethane Industry Co., Ltd. The cost of MDI plant with capacity of 63 kilo tons per year was estimated as 11.5 billion yen / 4390700000 PHP (U-Tech Asia, 2014 & PU Daily, 2014). For a plant capacity of 4.3 kilo tons per year at year 2018, the ISBL capital cost was calculated as 876,167,173.2 PHP.The OSBL (Outside Battery Limit) cost can vary from 20% to 50 % of the ISBL cost depending on the complexity of the process and required support facilities (Towler & Sinnott, 2013). For this project, it is assumed that the OSBL cost is assumed to be 40% of ISBL costs considering no details of the site are known.Based on historical and forecasted price of the product, it is anticipated that the proposed plant will generate of revenue per year. This is based on a product price of 156.7 PHP per kg. Operating cost is based on the price of the raw materials. Benzene will be supplied by at a price of 35.6 PHP/kg. The hydrogen will be supplied by with a price of 56.396PHP/kg. Phosgene will be supplied by at a price of 60.816 PHP/kg. Formaldehyde will be supplied by with a price of 17.787 PHP/kg. Nitric acid will be supplied at a price of 21.075PHP/ kg. Molar masskmolCapacity, kgPrice, Million Pesos

Benzene78.1116383.621279724.2845.558

Nitric Acid63.0116383.621032331.6721.76

Hydrogen2.0249150.8699284.725.599

Formaldehyde30.0316383.624920008.75

Phosgene98.9149150.864861510.5295.658

MDI250.2516383.624300000673.81

Table 1.8. Capacity of plant and the prices (Stoichiometric ratio and proportion method)The total operating cost estimated as per year is 377.325M PHP. ISBL CAPEX876.167(876167173.2)M PHP

OSBL CAPEX350.467(350466869.3)M PHP

CONTINGENCY122.663(122663404.3)M PHP

TOTAL CAPEX1349.297(1349297447)M PHP

ANNUAL OPEX377.325 (377325000)M PHP

ANNUAL REVENUE673.81 (673810000)M PHP

ANNUAL NET INCOME296.485(296485000)M PHP

PAYBACK PERIOD at 100% Capacity4.55Years

Table 1.9. Preliminary Total Capacity Expenditures of the PlantTo estimate the Internal Rate of Return (IRR) for this project, it is anticipated that the plant will be installed within two years. Hence, capital expenditure is assumed to be equally distributed in two consecutive years. It is also assumed that the plant will be running at turndown capacity, e.g. 55% of the normal capacity, on the first year of operation, and 75% of normal capacity on the second year or operation. Normal capacity will only be attained on the following years. Minimum acceptable rate of return (MARR) is assumed to be 15%.YearMPHP

02016-616.078

12017-616.078

22018138.601

32019189.002

42020252.002

52021252.002

62022252.002

72023252.002

82024252.002

92025252.002

102026252.002

112027252.002

122028252.002

132029252.002

142030252.002

152031252.002

162032252.002

172033252.002

182034252.002

IRR25.14%

Table 1.10. Preliminary Project Cash Flow and IRRVII. Marketing StrategyThe target market of this MDI plant is mainly polyurethane industries in the Philippines. The growing demand of the MDI gives the plant more opportunities to grow in the market. A good marketing strategy is needed in order for a plant to be recognized in the market.Objectives and Goals: To increase sales To become recognized as a Trusted Methylene Diphenyl Diisocyanate Producing plant To become the pioneer producer of MDI in the Philippines To appeal to the customers need through innovation To expand the companys production to meet the total MDI demand in the Philippines To establish good partnership with the supplier to have a stable productionFocus Points: ProductThe plant will produce methylene diphenyl diisocyanate from Benzene. The company guarantees that the customers expectation will be satisfied and will give a good review through safe and high-quality outputs. PricingThe price of the product would depend on the standard price ceiling of the other manufacturers, but it can be lowered due to absence of freight cost and bulk order. Sales PromotionThe transaction will be business to business among its prospect clients which will provide the company with consumers response and a direct communication on the incentive available for them. Advertisement A company website would be developed showcasing the company profile, location, products and customer reviews. Aside from a company website, the company would also engage in community service led by the government to appeal to the media.

VIII. Company Profile

A. About UsKapnayan Philippines, Inc. (KPh) is a newly established and first ever MDI-producing plant in the Philippines using Benzene as feedstock. We cater local polyurethane industries and provides them high quality products.As an organization, KPh gives conscious effort to do its part in the nations path towards success. The innovative approach we used ensures us that we are equipped to provide the consumers high quality products. The plant operations will provide workers, a tremendous positive impact to the local community. We are also committed to each and every one of our customers because it is for them and through them that we are in this business.

B. Our Vision To engage with competence and responsibility in the industrial business while pursuing to meet up with the worlds growing demand for sustainability. To be recognized as a pioneer in the production MissionThe vision will be achieved by: Seeking to deliver sustainable products and services in accordance to proper assessment Developing strategic partnerships to increase development and opportunity Exercising integrity and professionalism Caring for the community and its people Building a global level information infrastructure Realizing harmonious coexistence between society and the environment

IX. Plant LocationA. Categories in Choosing a Plant Location1. Resources It is important that there are available resources and raw materials in the chosen location for chemical plant. Its biggest advantage is minimizing the cost of the plant such as transportation and other cost. 1. Infrastructural Facilities Power, water, communication, transportation and commercial establishments is included. 1. Accessibility Locating a plant near the supplier and consumer lessens the transportation cost. Being accessible attracts more local and foreign investors. 1. Incentives It is offered by the government which is to attract investors to build businesses in controlled environment promoting social responsibility and provides community benefits. Tax, cheaper cost of utilities and other factors are some of the benefits that can be obtained. 1. Availability of Manpower Skilled workers plays an important role in the growth of the company.1. Climatic Conditions Climatic conditions such as rainfall, drought, and temperature changes may sometimes affect the productivity and efficiency of the plant.(Your Article Library, 2015)Based on the above categories, there are three possible locations available which are the Hermosa Ecozone Industrial Park (HEIP), First Philippines Industrial Park (FPIP) and Laguna Technopark Industrial Park (LTI). These are all registered Special Economic Zone (ecozone) under manufacturing which is provided by the Philippine Economic Zone Authority (DTI-PEZA, 2015).

B. Possible Locations0. Hermosa Ecozone Industrial ParkHermosa Ecozone Industrial Park (HEIP) is located at Palihan Hermosa, Bataan with a 162-hectares land area. During April to November, the season was dry while rainy on May to October (hermosa.gov.ph, 2015). It is accessible through Subic Clark-Tarlac expressway (SCTEx). The distance of HEIP to Petron Bataan Refinery which will be the major supplier of MDIs raw material is about 40.2 km. FromDistance (km)Time of Travel (minutes)

Metro Manila98.2115

Subic International Airport29.435

Clark International Airport53.747

Subic Seaport Terminal Incorporated25.430

Petron Bataan Refinery40.261

Table 1.11. Accessibility of Hermosa Ecozone Industrial Park

Figure 1.3. Distance of HEIP fromPetron Bataan Refinery

HEIP is able to provide quality infrastructure such as power supply, water supply, centralized waste water treatment plant, communication systems, road network, storm drainage system and administration building. Electricity is supplied by Peninsula Electric Company (PENELCO) with a 10MVA substation which is expandable for future purposes. Water supply is obtained through deep wells and a water recycling facility through a dual piping system with 18,000 cubic meters per day total capacity. Centralized wastewater treatment facility with a 12,000 cubic meters per day capacity is also provided. Communication systems are provided by Digitel and PLDT which is capable for 1,000 international and domestic lines for voice, fax, data, video conferencing and internet services. Highway grade roads include 22 m main roads and 15 m service roads with pedestrian lanes and planting strips. Adequate drainage system ensures there will no floods. And, administration building which keeps that industrial park organize and in proper operation.Benefits can also be obtained in locating in HEIP. Available tax incentives includes exemption from corporate income tax for four to eight years, exemption from duties and taxes on imported capital equipment or materials, exemption from export taxes and exemption from value added tax. The power, sewer and water cost is lower compared outside. Logistic costs can be lowered because the place is located near the airport and seaport (Science Park of the Philippines, Inc., 2015).0. First Philippine Industrial ParkFirst Philippine Industrial Park (FPIP) is a 457-hectares land area located in Santo Tomas, Batangas. Dry season occurs from January to April while wet season occurs from May to December. Another possible supplier of MDIs raw materials is Pilipinas Shell Corporation Refinery having a distance of 54 km to FPIP. It is accessible through South Luzon Expressway (SLEX). FromDistance (in kilometers)Time (in minutes)

Metro Manila58.968

Ninoy Aquino International Airport (NAIA)49.649

Manila North Harbour Port61.481

Pilipinas Shell Corporation Refinery5464

Table 1.12. Accessibility of First Philippine Industrial Park

Figure 1.4. Distance from Pilipinas Shell Petroleum Corporation Refinery to First Philippine Industrial Park.

The infrastructure, facilities and services available in FPIP are power, telecommunications system, water supply, sewerage system, road networks, and general activity areas. Power is supplied by Manila Electric Company (MERALCO) with substation of 115KV with an ecozone rate of approximately lesser Php1/kwh. Communication uses fiber-optic technology and installed underground. Water supply is obtained from deep well for industrial use with a centralized water distribution system and standby generators. Sewerage facility is available. Roads are 40 m wide main roads and 23 m wide secondary roads with pedestrian, bicycle lanes and planting strips. With this, FPIP can be able to facilitate small scale to high scale operations. They boast manpower quality, labor cost and availability. They also offer end-to-end solution in the construction of different facility types that is suited for the business needs. Eco parks inside the FPIP shows the diversity and it implies the care for environment. In promoting the growth of investment in the country, the government offers incentives for the investors. The following incentives are: income tax for 4 to 8 years, exemption from national and local taxes, lieu thereof, special 5% tax rate on Gross Income, Tax credit substitution, exemption from wharfage dues, and additional deduction from training expenses are also included (First Philippine Industrial Park, 2015). 0. Laguna Technopark IncorporatedLaguna Technopark Incorporated is located at Bian, Laguna with a 460 hectares land area. Two types of season are available which the wet and dry seasons are. Wet season occurs from June to September while dry occurs from November to April. It is accessible via South Luzon Expressway or by National Road. Uratex Philippines is one of the largest manufacturers of polyurethane foams for automotive and furniture which uses methylene diphenyl diisocyanate (MDI) as raw material. Distance from Uratex Philippines located in Muntinlupa City is about 25.7 km.FromDistance (km)Travel Time (min)

Uratex Philippines25.733

Metro Manila44.663

Petron Bataan Refinery183.2202

Pilipinas Shell Petroleum Corporation Refinery76.788

Ninoy Aquino International Airport (NAIA)33.938

Batangas Port7155

Table 1.13. Accessibility of Laguna Technopark Incorporated

Figure 1.5. Distance of Uratex Philippines from Laguna Technopark Incorporated

Laguna Technopark Incorporated is owned by the two large names in businesses which are the Ayala Land and Mitsubishi Corporation. Compared other established cities, land cost is lower. Infrastructures available are the concrete highway roads, integrated landscapes and pockets of green space in design, communication systems, power substations, public transportation and shuttle services, domestic and industrial water supply, centralized sewerage systems, regulating ponds and commercial buildings.Incentives available are corporate income tax holiday from 4 to 6 years, all local and national special tax rate on 5% on gross income in lieu, exemption from duties and taxes on imported raw materials, supplies and equipment, exemption from wharfage dues and export tax imposed fees, deduction from taxable income of training expenses for labor and management and tax credit on locally purchased capital equipment and spare parts equivalent to 25% of the taxes and duties (Laguna Technopark Incorporated, 2014).

CHAPTER 2TECHNICAL STUDY

I. Process Selection

Figure 2.1. Schematic diagram showing the principal operations leading to the production of MDI (Boustead, 2005)

Methylene diphenyl diisocyanante (MDI) is simply produced by the condensation of aniline with formaldehyde followed by reaction with phosgene. This can be produced starting at different points in the process after oil refining which are from benzene, from nitrobenzene and from aniline. From the comparative study, it is economically effective to start from benzene.

Starting MaterialAdvantagesDisadvantagesPrices, Php/kg(2014)NFPA DiamondExplosive LimitIDLH, ppm

HealthFlammabilityInstabilityLowerUpper

Benzene Supply in the Philippines is abundant Less material and transportation costs Cost-effective More equipment costs61.03(Platts, 2014)2301.4%8%500

Nitrobenzene The stage of the process and equipment cost is lessened. No supply in the Philippines More material and transportation costs

61.24(Micro Market Monitor, 2015)3211.8%1.8%200

Aniline The stage of the process and equipment cost is greatly lessened. Supply in the Philippines is limited More material and transportation costs79.90(Chem Plan, 2014)3201.3%20-25 %100

Table 2.1.Raw Materials Prices and Properties (Cameo Chemicals, 2015).Starting from benzene, there are three parts of production: nitrobenzene production, aniline production and MDI production. For nitrobenzene production, the commercially used process is direct nitration of benzene with the use of nitric acid-sulphuric acid mixture. It is produced in continuous process which is more effective for large plants and has a yield of 95-96%. It also offers lower capital cost and more efficient labor usage which is good for starting-up plants (Maxwell, G. 2005). For aniline production, it has three common exothermic processes which are hydrogenation of nitrobenzene, nitrobenzene reduction with iron fillings and ammonolysis of phenol. Based on the comparative study, hydrogenation of nitrobenzene is most appropriate and most advantageous among the given methods (Maxwell, G., 2005).ParametersCatalytic HydrogenationNitrobenzene reduction with Iron fillingsAmmonolysis of Phenol

Raw MaterialsNitrobenzene and HydrogenNitrobenzene, Iron fillings and Hydrochloric acidPhenol and Ammonia

ProductsAnilineAnilineAniline

By - ProductsNoneColored iron oxide pigmentsDiphenylamine, Triphenylamine and Carbazole

CatalystCopper or PalladiumIron metalSilica-Alumina

Reactions

YieldMore than 99%90 95 %80% - 96%

Reaction Time-8 to 10 h-

Energy ConsumptionLowLowLow

Economic FeasibilityHighUneconomical surpassing the market for iron pigmentsFavorable using phenol route

Process SeparationSimpleSludge Separation-

Table 2.2. Aniline Process Comparative StudyFor methylene diphenyl diisocyanate (MDI) production,

II. Process DescriptionA. ASPEN HSYSY SIMULATION1st Stage: Benzene to NitrobenzeneWasherNaOH

Figure 2.3. ASPEN HYSYS Simulation (1st Stage)The process follows the chemical reaction between benzene and nitric acid in acidic media (using sulphuric acid).

Figure 2.4. Nitrobenzene ReactionBenzene together with acid mixture is fed into the nitrator with conversion rate of 97% (Albinali, A, Al-Kandari, H., Al-Farsi, E., and etc., 2013). The sulfuric acid is not being consumed during the reaction. Its role is to promote the formation of the nitronium ion and prevents it from binding with water. Then, it is fed into the separator to obtain the mixtures of crude nitrobenzene and used sulfuric acid. The crude nitrobenzene is fed to a washer which is reacted with sodium hydroxide to neutralize small amount of acid it contains. On the other hand, the used sulfuric acid is fed to acid stripper to re-concentrate the sulfuric acid and be recycled back to the nitration process. Lastly, the crude nitrobenzene has undergone distillation to produce desired nitrobenzene concentration (Maxwell, G., 2005).2nd Stage: Nitrobenzene to Aniline

Figure 2.5. ASPEN HYSYS Simulation (2nd Stage)Using the nitrobenzene from the first stage, it is heated to change its phase into gas so that, it can be reacted with hydrogen gas. The process follows the hydrogenation of nitrobenzene.

Figure 2.6. Aniline ReactionThe raw materials are fed into a fluidized-bed catalyst and its conversion is quantitative depending on the regeneration of the catalyst. Then, the hydrogen gas is allowed to be vent out. It is fed into a separator to separate water and obtain the desired concentration of the aniline (Maxwell, G., 2005).3rd Stage: Aniline to MDI

Figure 2.7. ASPEN HYSYS Simulation (3rd Stage)Using the aniline from the second stage, the process follows phosgenation process.

Figure 2.8. MDA and MDA ReactionSince ASPEN HYSYS Simulation has limitations, the two-step reaction is converted to one-step reaction which is applied as the reaction of the converter. In actual process, there will be two reactors. For the first reactor, it produces methylene dianiline (MDA). It will undergo distillation process to concentrate it. For the second reactor, it produces the final product, methylene diphenyl diisocyanate (MDI). Then, it will undergo stripping process in order to separate the hydrochloric acid from the final product. Lastly, it will undergo distillation process to produce the desire concentration (Sulzer, 2015).B. Overall Mass BalanceFrom the calculated preliminary production capacity of the plant which is 4.1 kilo tonnes/yr of MDI, the raw material benzene is computed to be 607.5 kg/h.For the 1st stage, benzene and mixed acid are the raw materials. The mixed acid ratio ranges from 32 to 39% nitric acid, 53 to 60% sulphuric acid, 8% water. Hence, the acid masses are 949.2 kg/h for 64% nitric acid and 1488 kg/h for 98% sulphuric acid. For the washer, the 97% sodium hydroxide needed is 76.35 kg/h. So the nitrobenzene produced is 956.9 kg/h.For the 2nd stage, hydrogen gas is reacted with nitrobenzene. The hydrogen gas needed is 8625 kg/h following the H2-Nitrobenzene ratio which is 9:1. This is followed in order to ensure that the hydrogen reacts with the nitrobenzene. So, the aniline produced is 722.1 kg/hFor the 3rd stage, the process is phosgenation which consists of two reactions. For the first reaction, the formaldehyde needed is 310.2 kg/h. For the second reaction, the phosgene needed is 1134 kg/h. Therefore, the preliminary production capacity was met. REFERENCES

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