Market Demand and Production Capacity Expansion of Hydrogen Peroxide in Bangladesh

Corresponding Author: Mohammad Rafiqul Islam Department of Environmental Science, Independent University, Bangladesh (IUB), Dhaka, Bangladesh Email: sad.safwan@yahoo.com Abstract: The work on production capacity expansion of hydrogen peroxide plants is part of an extensive research. In this research, the expansion of hydrogen peroxide plant, including the local current production and market demands of hydrogen peroxide has been highlighted. Hydrogen peroxide (H2O2) is one of the basic chemicals. The market size of hydrogen peroxide in Bangladesh has been ever bigger than caustic soda. Textile, Dyeing, Medicine, Pharmaceuticals, Water Treatment, Soap, Pulp and Paper Industries are using hydrogen peroxide (H2O2) as huge quantity. Recently new application is developed for hydrogen peroxide in the effluent treatment of various organic wastes of refineries and other chemical industries. In Bangladesh, there are only four plants which are producing various grades and qualities of hydrogen peroxide. Among these, three plants are producing the 50.00% (w/w) and one plant is producing the 35.00% (w/w) concentration of hydrogen peroxide. But locally, the consumption of 50.00% (w/w) is higher than 35.00% (w/w) concentration of hydrogen peroxide. The current production capacity of hydrogen peroxide in Bangladesh is not adequate to meet the country’s requirement. In Bangladesh, production of hydrogen peroxide is about 190 Ton Per Day (TPD) but demand is 350 Ton per Day (TPD) which is higher than the local production. In that case, some quantity of 50.00% (w/w) concentrates of hydrogen peroxide is being imported from foreign countries like as India, China, Korea and Thailand. To avoid imports the hydrogen peroxide and to meet the requirement of local consumers, either needs to install a new production plant or increase the capacity of the existing plant. Chemical Engineers recommend that the expansion of local plants is better than newly installed the plant and it will more competence. The main purpose of the study to introduce the answer regarding the basic question, “how will we expand the capacity of an existing H2O2 plant?” In this study, a complete expansion and operation data of the H2O2 manufacturing plant have been shown so that the plant can be run efficiently. Beside this, the properties, manufacturing procedures, applications and local demanding of hydrogen peroxide are briefly discussed in this study. Finally, this invention will be helpful for the engineering team, operation team and marketing team so that they can implement their own jobs in the expansion project.


Introduction
A chemical plant is an industrial process plant. The general objective of the chemical plant is to create new materials via the chemical transformation or separation. The chemical plant uses specialized raw materials, equipments, unites and technologies in the manufacturing process. Generally, the products of the chemical industry can divide into three categories: Basic chemicals, specialty chemicals and consumer chemicals. Hydrogen peroxide is a basic chemical which is being produced by the hydrogenation, oxidization, extraction and purification system in the manufacturing process (http://nzic.org.nz/ChemProcesses/production/1E.pdf). Firstly, the concentration of hydrogen peroxide makes 35.00% and concentrated it to 50.00% by a concentrated section. The H 2 O 2 manufacturing plant runs through the continuous system and supplies the product through the batch process.
There are only four hydrogen peroxide industries in Bangladesh namely, HP Chemicals Industries Ltd, ASM Chemical Industries Ltd, TK Group Industries Ltd. (Samuda) and Tasnim Chemical Industries Ltd. Among them, 35.00% (w/v) concentrate of hydrogen peroxide is being produced by only HP Chemicals Industries Ltd. and 50.00% (w/w) concentrate of hydrogen peroxide is being produced by the remaining industries (Salahuddin, 2011). The design of a factory is made by a team including chemists, plant designers and chemical engineers for suitable construction. Just like the above sentences, need to make a team where will include engineers, chemists and operators for the expanding of existing production capacity. During the designing and planning of the expanding plant, they will study on a few factors such as technology, solution process, costing and typically as an initial screening to eliminate unprofitable designs. If the process appears profitable, then other factors will be considered, such as safety, environmental constraints, controllability etc. Suppose, if we want to increase the production capacity from 35 to 60 TPD as 50.00% concentrate. H 2 O 2 at an investment of limited cost, we will think about the changing utilities, the designed parameters, calculating the consumption of raw materials, quality of raw materials and finished product etc. We investigated and visited the ASM Chemical Industries Ltd. A few months ago, they expanded their existing production capacity from 35 TPD to 60 TPD that means, it expanded from existing capacity 35 Ton day −1 (50.00% conc. of H 2 O 2 ) = 57.7 Ton day −1 (35.00% conce. of H 2 O 2 ) to 60 Ton day −1 (50.00% conce. of H 2 O 2 ) = 88.5 Ton day −1 (50.00% conce. of H 2 O 2 ) (https://asmchemical.com).

Current Demand and Consumption
Presently the apparent consumption data of Hydrogen Peroxide production and market demand in Bangladesh are shown in Table 1 and 2 (Salahuddin, 2011).
It was shown in (Fig. 1), the local demand of hydrogen peroxide had been doubled in the last twenty years, which was a matter of surprising.

Characteristics of Hydrogen Peroxide
Hydrogen Peroxide is a chemical substance with the formula H 2 O 2 . In its pure form, it is a colorless liquid slightly more viscous than water. However, for safety reasons it is normally used as an aqua solution. Hydrogen peroxide is the simplest peroxide (a compound with an oxygen-oxygen single-bond) and finds use as a strong oxidizer, bleaching agent and disinfection. The concentrated hydrogen peroxide, or "high test peroxide", is a reactive oxygen species and has been used as a propellant in rocketry. Hydrogen peroxide is often described as being "water" but with one more oxygen atom", a description that can give the incorrect impression of significant chemical similarity between the two compounds. While they have a similar melting point and appearance, pure hydrogen peroxide will explode if heated to boiling, will cause serious contact burns to the skin and can set materials alight on contact. For these reasons it is usually handled as a dilute solution (household grades are typically 3-6% in the U.S. and somewhat higher in Europe) (https://en.wikipedia.org/wiki/). Its chemistry is dominated by the nature of its most unstable peroxide bond.

Properties
Hydrogen peroxide (H 2 O 2 ) is a weak acidic, colorless liquid, miscible with water in all proportions, was discovered by Thenard in 1818 and has been used industrially since the mid-19th century (https://www.diyspaceexploration.com/preparingmanufacture-hydrogen-peroxide). It is the simplest peroxide (molecules containing two oxygen atoms covalently bonded to one another) and is commercially available in aqueous solution over a wide concentration range. The main uses of hydrogen peroxide are in the preparation of other peroxides and as an oxidizing agent. The boiling point of H 2 O 2 has been extrapolated as being 150.2°C, approximately 50°C higher than water (http://nzic.org.nz/ChemProcesses/production/1E.pdf). Practically, hydrogen peroxide will undergo potentially explosive thermal decomposition if heated to this temperature. It may be safely distilled at lower temperatures under reduced pressure. In aqueous solutions hydrogen peroxide differs from the pure material due to the effects of hydrogen bonding between water and hydrogen peroxide molecules. Hydrogen peroxide and water form a eutectic mixture, exhibiting freezing-point depression; pure water has a melting point of 0°C and pure hydrogen peroxide of -0.43°C, but a 50% (by volume) solution of the two freezes at -51°C. The boiling point of the same mixtures is also depressed in relation with the mean of both boiling points (125.1°C). It occurred at 114°C. This boiling point is 14°C greater than that of pure water and 36.2°C less than that of pure hydrogen peroxide (https://en.wikipedia.org/wiki/). Density of an aqua solution of hydrogen peroxide is different as per the concentration of hydrogen peroxide which was given in the Table 3 (http://www.h2o2.com/technicallibrary/physical-chemical-properties). It is noted that the density of hydrogen peroxide increased with the temperature increasing which was shown in Fig. 2

Specification of Hydrogen Peroxide
Different grades of hydrogen peroxide produced different functions and different usage such as food grade, drug grade, industrial grade (technical and chemical grade). Basically, maximum hydrogen peroxide produced for industrial usages in Bangladesh. The specification of industrial grade hydrogen peroxide was shown in Table 4. Typically; these grades also contain proprietary formula stabilizers which were designed to address specific needs of industry. Food Grade" means that it was approved by the United States Department of Agriculture for use in food processing.  Specifically, it means that the United States Department of Agriculture has tested samples of a production run to certify that it is not contaminated, that its concentration level is the level stated and that it does not contain harmful stabilizers. Industrial grade of hydrogen peroxide is also manufactured in concentrations ranging from 20 to 70% for use in industrial, chemical and manufacturing applications which are not fit for use in food preparation or for agricultural or domestic home uses (http://www.h2o2.com/technicallibrary/physical-chemical-properties). Drug store/grocery store grade hydrogen peroxide, available in a 3.00% solution is always stabilized to increase the shelf life of the product. Total fifteen grades of hydrogen peroxide are found in the world based on their applications (https://en.wikipedia.org/wiki/; http://h2o2uses.com/hydrogen-peroxide-grades-andstabilizers). Product grade(s):

Methodology
The first record of commercial production of hydrogen peroxide appeared in the 1865 to 1875 period. The first commercial production in the United States was by the Oakland Chemical Company, Brooklyn, New York, in 1881. Laporte Chemicals Ltd. established a factory in Yorkshire, England in 1888 (https://www.diyspaceexploration.com/preparingmanufacture-hydrogen-peroxide). With the exception of the substitution of Fluoro-silicic acid in the hydrochloric acid, Thenard's process was used essentially unchanged for the manufacture of hydrogen peroxide until nearly 1900. The formation of hydrogen peroxide in the electrolysis of sulfuric acid was first reported in 1853; later developments made the manufacture of hydrogen peroxide by an electrolytic process possible in 1908. By 1939, only 10% of the world's production was by the barium peroxide process (http://www.idconline.com/technical_references/pdfs/ch emical_engineering/Preparing_to_Manufacture_Hydroge n_Peroxide.pdf). Currently, hydrogen peroxide is commercially manufactured either by an electrolytic (inorganic) method or one of two organic processes. The electrolytic process involves the electrochemical formation of peroxydisulfuric acid or peroxydisulfate (from an ammonium bisulfate solution), their subsequent hydrolysis and separation hydrogen peroxide (https://www.diyspaceexploration.com/preparingmanufacture-hydrogen-peroxide; http://www.idconline.com/technical_references/pdfs/che mical_engineering/Preparing_to_Manufacture_Hydroge n_Peroxide.pdf).
One of the organic processes used commercially for the manufacture of hydrogen peroxide involves the catalytic reduction of a substituted anthraquinone and subsequent oxidation back to the quinone structure with the production of H 2 O 2 . Detail explanation of anthraquinone method which dissolves in an appropriate organic solvent, are used as reaction media. The organic solvent is usually a mixture of several organic solvents. The solution obtained by dissolving the anthraquinone in the organic solvent is called "Working Solution" The anthraquinone in the working solution are subjected to reduction with hydrogen in presences of a Paladium(Pd) catalyst to produce anthrahydroquinones (http://www.cncec.com.cn; Kato et al., (n.d.)). In Bangladesh, hydrogen is generally obtained from natural gas.
The anthrahydroquinones are oxidized with air. In this step one mole of hydrogen peroxide is formed per one mole of oxidized anthrahydroquinone. Hydrogen peroxide produced in working solution after the above mentioned steps. It is separated from the working solution by extraction with water. The working solution from which hydrogen peroxide has been separated is returned to the reduction step again, thereby forming a cyclic process (http://www.cncec.com.cn).
Produced hydrogen peroxide is concentrated in another concentration unite by distillation, condensation and vacuum system.The section includes the principles of different segments of the manufacturing process which include working solution preparation, hydrogenation, oxidation, extraction and purifications

Working Solution Preparation
2-Ethyle Anthra Quinone (2-EAQ) is dissolved in two solvents. One is non polar and another is polar (http://www.cncec.com.cn; Kosydar et al., 2010). Collectively the anthraquinone and solvents are called the working solution. Large amount of Heavy Aromatics (AH) and Tri Octyle Phosphate (TOP) needs to prepare working solution. Both solvents require distilling for removing the colloidal matter, impurities etc.
Chemical reactions are given as follow (Fig. 3).

Fig. 3. Chemical reaction for producing hydrogen peroxide
Preparation of one cubic meter of working solution needs 136 kg of 2-EAQ with the ratio of Heavy Aromatics to Tri Octyle Phosphate:: 75:25 (http://www.cncec.com.cn). This working solution is recycled.

Hydrogenation
During production, working solution with heated hydrogen combined sent to the hydrogenation tower and (Raw heated hydrogen comes to the hydrogenation tower from the hydrogen generation plant). Hydrogenation system is three sections series and operation individually at the same time; each section is filled with 4.0 Ton palladium catalyst. After reaction in each section, working will go tom the separator where separate the hydrogen tail gas and hydrogenated working solution (http://www.cncec.com.cn): •

Working Solution Regeneration
Hydrogenation generates not only peroxideproducing anthrahydroquinones but also some byproducts. These by-products include anthraquinone species that can be converted back to useful quinones by regeneration. During the regeneration process, a sidestream of working solution is fed through a bed of dehydrogenation catalyst. The regeneration converts deoxidized anthraquinones and tetrahydroanthraquinones to their corresponding anthraquinones. Specific gravity of K 2 CO 3 : 1.4 at 25°C. Block flow diagram of H 2 O 2 producing plant is shown in Fig. 4.

Requirement Utilities and Raw Materials
This plant processes natural gas through a steam reforming stage and subsequent high temperature shift catalytic stage to produce high purity hydrogen gas. The gas is finally purified in a pressure swing absorber before being used by the hydrogenation. Beside this, High purity water is used to feed the extractor, concentrator as well as the package boiler. Conventional degassing followed by cation and anion exchange beds is used to purify town water for use in the peroxide production (https://asmchemical.com; http://www.cncec.com.cn): • The facility of utilities must be ensured before setting the hydrogen peroxide plant. The design basis for the utilities and raw material are as follows (https://asmchemical.com; http://www.cncec.com.cn).

Required Equipments
According to the production capacity of Hydrogen Peroxide, The followings mechanical and electrical equipments, instruments, towers and tanks to be required. To increase the existing plant capacity from 35 TPD to 60 TPD, the new items will be added to this list which is given in the Table  7 (http://www.cncec.com.cn).

Results and Discussion
Predominantly, hydrogen peroxide produced from the working solution in the presence of aluminum, palladium, oxygen and hydrogen gas through hydrogenation and oxidation. This is called auto oxidation process.
If the amount and purity of raw materials and their dosing rate and ratio are not present in the processing section sufficiently, the production will be slow down and hampered equally, product's quality will not get correctly. Therefore, the amount of raw materials plays an important role in the direct synthesis of hydrogen peroxide. Here has been shown that the raw materials consuming data, equipment's data and operation's data of new an expansion plant. It is generated by our study which is in Table 5 to 7. Beside this, another report of the study has been shown that user's needs more hydrogen peroxide in Bangladesh for their industrial usage. However, Bangladeshi manufacturers could not meet the local user's demand. So, we saw the great gaps between production capacity and the user's needs which have been shown in Table 1 and 2. To fill this gap, a current production capacity of hydrogen peroxide should be increased as well as the growth of the industry in the development of Bangladesh. Current plant capacity expansion is essential for long term economic growth and economic resilience of Bangladesh.
Investment cost is needed to consider when to take the planning for installing or expanding the factory. raw materials, equipments, land area, manpower and other utilities are considered in the expanding project. Working sol n preheater As Usual 59 H2ed tail gas condenser As Usual 60 H2edsol n filter Newly Required 61 Oxidation middle Tower As Usual 62 O2nd tail gas condenser As Usual

Use of Hydrogen Peroxide (H 2 O 2 )
Hydrogen peroxide is commonly used as bleaching, sanitizing, cleaning agent in the textile industries, pulp and paper industries, leather industries, pharmaceuticals, water and effluent treatment plants. It can also kill micro-organisms. Hydrogen peroxide (in very low concentrations, typically around 5%) to bleach human hair, hence the phrases "peroxide blonde" and "bottle blonde". It burns the skin upon contact in sufficient concentration. In lower concentrations (3%), it is used medically for cleaning wounds and removing dead tissue. Combined with urea as carbamide peroxide, it is used for whitening teeth (http://www.americanenergyindependence.com/peroxide .aspx). Hydrogen peroxide usage specifically in the following areas:

Laboratory for Quality Control
The purpose of the laboratory is to provide information in the process performance and to carry out quality control testing of hydrogen peroxide. Proprietary equipment is to be used to measure the synthesis loop operation at each stage of the process. To check the products quality and performance of the process operation, A few sophisticated laboratory equipments will require in the laboratory such as gas chromatography, polarography and spectrophotometer etc. Utility testing can be carried out in support of on-line process instrumentation. The laboratory test information is used by operations personnel to control the loop.

Packaging and Transportation
Hydrogen peroxide is shipped in polyethylene drums of 30 kg, 240 kg and 1 MT, IBCs. These drums are fitted with specially designed vented caps to ensure safe storage and transportation.
For bulk quantity customers within Bangladesh, deliver hydrogen peroxide through their dedicated tank-trucks of 12 MT capacities. Services are offered to provide bulk storage of 1, 8 and 12 MT in polyethylene construction. For deliveries outside Bangladesh, supply in 30/240 kg polyethylene drums loaded on shipping containers or in isotainers of 20 MT capacities for bulk users (http://www.adityabirlachemicals.com/products/peroxide s/hydrogen_peroxide.html).

Required Manpower
Minimum quantity of manpower to require for the plant operation is given in the Table 8 (Hydrogen peroxide plant, concentration unites, de-mineralized water plant, gas reforming plant). Generally, operation team, all type of engineering team, technical team, quality team and other expertise works are required during the commissioning period.

Financial Analysis
The financial analysis of the new hydrogen peroxide project is based on the data presented in the previous chapters and the following assumptions (https://www.academia.edu/13116964/Items_Raw_ma terial_and_Inputs_Utilities_Maintenance_and_repair_ Labour_direct_Factory_over): • Construction period = 1 year • Source of finance = 30% equity 70% loan • Tax holidays = 5 years • Bank interest = 10-12% • Discount cash flow = 8.5% • Accounts receivable = 30 days • Raw material local = 30 days • Work in progress = 2 days • Finished products = 30 days • Cash in hand = 5 days • Accounts payable = 30 day

Total Initiative Investment Cost
The total investment cost of the hydrogen peroxide project including working capital is estimated at USD5, 00, 00, 00.00. The major breakdown of the total initial investment cost is shown in Table 7  Pre-production expenditure includes interest during construction, commissioning training, costs of registration, licensing and formation of the company including legal fees, commissioning expenses, etc.

Conclusion
In this article the limitation is that the detailed areas of the plant did not explain which was important in the operation and expansion of the existing hydrogen peroxide plant. Activation of alumina, regeneration working solution, normal shutdown procedures, hydrogen generation unit, concentration unite, cooling water system, de-mineralized water system and waste management are not discussed in the study. In our study, we sort out the lack of knowledge regarding the market demand, plant expansion, production procedure, chemical's calculation, operation method and costing with investment. It can be helpful or beneficial to manufacturer, users, business planners and operation people in this area. On the other hand, in view of the huge prospect in the textile, agriculture, tannery, pharmaceuticals and wastewater treatment is the demand for H 2 O 2 going to increase in the near future. With the overall industrialization trends in Bangladesh, new hydrogen peroxide plants are required to install in Bangladesh or, the existing plants are required to increase the production capacity. Besides this, we have to present us with a unique opportunity for service and gain huge profit while adding to the country's GDP (Gross Domestic Product).