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Feedback of by-products to a formic acid plant

Design and evaluation of new process sections Perstorp AB Department of Chemical Engineering, LTH Sofia Rohlin
March 2011

From the formic acid plant in Perstorp two by-products, technical sodium sulphate and technical formic acid are obtained that are no longer desired. The aim of this master thesis is to investigate different methods to feed those products back to the process to obtain more of the desired products, formic acid and sodium sulphate. The chosen feedback processes were evaluated through lab-scale tests and simulations in Chemcad, designed and the fixed and variable costs were calculated. The best suggestion for the technical sulphate was to suspend the crystals in mother liquor from the process under stirring. This process will cost 626 400 SEK in equipment and installation and the variable costs were calculated to be 11 400 SEK per year. Those costs were considered reasonable and an investment in this solution is recommended. For the technical grade of formic acid a process containing a forced circulation evaporator followed by a filter was chosen. The overall cost of this process was almost 8,6 million SEK and the variable costs were calculated to be 214 000 SEK per year. Those costs were considered to be way to high for an application of this size and an investment in this process solution will not be made. Keywords: Formic acid, process design, fixed costs, variable costs, profitability

At Perstorp AB in Perstorp there is a plant manufacturing formic acid from sodium formate and sulphuric acid. Besides from formic acid it also produces sodium sulphate. [1] The sodium formate used contains organic impurities that accumulate throughout the process. At the end of the process these impurities are bled of together with some of the pure formic acid. This solution is sold as a technical formic acid. Small amounts of the impurities follow the sulphate, especially at the end of the process. The less pure sodium sulphate is sold as a technical grade of the sulphate. [2]

Perstorp wants to remove the technical grades of formic acid and sodium sulphate to obtain a greater yield of the purer products. [3] Another motivation behind the project is REACH, the European Union regulation of chemical substances. The by-products are not registered according to REACH and are therefore not allowed to be sold starting from 2012 if registrations are not made. [4]

The aim of this article is to investigate different methods of feeding the by-products back to the process. One solution for each by-product is to be chosen and evaluated through experiments

With those figures the total apparatus costs were determined and by multiplying with a factor the total cost of installation. The most promising alternatives were chosen to move forward with and evaluate. Suspension of technical sulphate The technical sulphate should be mixed with the pure to obtain only one quality. Mixing can be done with either dry or moist sulphate. pipelines. both the investment that needs to be made and the costs of running the new process sections. The aim of the trials was to find out how much of the sulphate powder the mother liquor can suspend. That was done by collecting as much information as possible about physical properties. . [3] Experimental work One feedback process was chosen for each byproduct and experiments were performed. The evaluations were made through experimental work on laboratory scale and simulations in the flow sheeting programme Chemcad. The variable costs were determined as well as the increase in profit more of the better products give. containing different amounts of formic acid. Experimental set-up for the suspension of technical sulphate. In these experiments the technical sulphate was suspended in two different mother liquors from the laboratory scale and simulations in Chemcad. pressures and other process data. This was done to see if the suggested methods were promising for the real process or not. vents and regulation equipment was also taken into consideration. The result was that the mother liquor containing the least amount of organic impurities was the most suitable suspension liquid. It is not desirable to bring back too much of the impurities because it deteriorates the crystallization of sodium sulphate throughout the process. Figure 1. The other objective was to find the most appropriate mother liquor to suspend the crystals in. Materials and method Through studies in internal and external literature different separation processes were suggested for the feedback processes. The data was then sent to companies distributing the needed equipment and they returned offerings with prices and sizes of the apparatus. flow rates. Another part of the assignment was to determine the sizes and costs of the process equipment needed. temperatures. That is because the suspended crystals and the liquid should be fed back to an earlier step in the process. Figure 1 shows the experimental set-up for these trials. organic impurities and sodium sulphate. With those factors the profitability of the new process sections could be determined. Another motive is to calculate the costs of the chosen process.

The feedback processes result in a raised level of impurities in the sodium sulphate. A new pump will have to be installed to pump the suspension from the tank Figure 2. but the levels are still very low. The next step was to design the new equipment in full scale. Simulations Mass and energy balance calculations were performed using the flow sheeting programme Chemcad. Experimental set-up for the separation of the components in technical formic acid. The filtration of the bottom product from the evaporation was performed under vacuum in a glass filter with an appropriate pore size. . In figure 2 the experimental set-up for these trials can be seen. that is because they are over saturated with particles. In most of the experiments about 10 % by weight was held back by the filter and the sodium sulphate concentration in that fraction was between 50 and 70 %. but then the stirrer would have to run faster and in the real process it will cause problems for pumps and pipes with too high concentration of particles.1 and 0. Process design Because of the positive indications from the experiments and simulations it was decided to move forward with the chosen processes. Evaporation and filtration of technical formic acid The separation method chosen for the technical formic acid was evaporation of the formic acid and water content followed by filtration of the concentrated organic/sodium sulphate solution to separate the solid particles. It was possible to suspend larger quantities.The crystals do not dissolve in the mother liquors. According to the simulations the existing quality of the sodium sulphate can be held even with the feedback. In both cases about 55 % by weight of the input solution was separated as water and formic acid vapour. The sulphate will fall down the tank from here and the mother liquor will be pumped using an existing pump. Therefore the test was to see how much sulphate can be put into motion in the liquid using a stirrer. It is also necessary to install an automatic control system to regulate the level in the tank. It was found that the limit was somewhere around 20-25 percent by weight of technical sulphate. The main objective was to keep track of the concentration of organic impurities in the good grade of sodium sulphate. 0.2 bars. and three experiments were performed at each pressure. Technical sulphate The full scale process requires a tank with a stirrer and a pump to be able to feedback the suspension to an earlier step in the process. The general idea is to elongate a conveyor transporting the technical sulphate to drying and allow transport in the opposite direction. The formic acid concentration of the evaporated and condensed liquid was about 80 % by weight. The technical formic acid was evaporated at two different pressures.

1 TT TE LS . Centrifug Technical formic acid is continuously pumped through the boiler with the pump belonging to the forced circulation evaporator system. The same pump is also used to transport the bottom product from the evaporator to the filter. The evaporator pressure is kept by having a pressure controller controlling a vacuum system. Filtrat Lagrings tank LIC . pipes and vents were determined for both of the process sections. Temperature regulation is done by regulating the inlet flow of steam to the boiler.1 Kondensor Vakuum pump Tank V för -4 drivvätska Katalytisk förbränning LS-2 LS-1 Tork Uppslamnings tank LS-3 FT PT TI .1 Indunstare TE TT TIC .to the first step in the original formic acid process. process. a vacuum system to keep the low pressure in the evaporator. The control system consists of liquid level switches in the upper and lower part of the tank. Equipment costs The costs of the required equipment including installation. The solution of technical formic acid will be pumped from its storage tank using the existing pump. Evaporated formic acid and water is condensed and cooled using cold water and then it falls free to a buffer tank for process formic acid. a filter and a storage tank. Figure 4 shows the intended 1 Polyol A till lagringstank Återföring till separationskärl Ventilation Förlängning av skruv Skruv EI-1 A -1 PIC . Flow sheet for the suggested process to feedback technical sulphate. First the costs of the equipment and pumps were summarized and then the sum was multiplied with a factor to include the other things mentioned.6 million SEK installed.3 Moderlut till förbränning Technical formic acid In the full scale process there will be a forced circulation evaporator unit. The mother liquor is then stored and burned while the sulphate crystals are transferred to the suspension tank in the technical sulphate feedback process. The biggest post in the .2 Pump FIC -1 FICQ -2 Pump FT Ånga 15 bara Från Centrifug Lagringstank Kokare ST-E-3 Lagringstank Recirkulation till tidigare lagringstank Pump FT / DT Kondensat till kondensattank Pump FIC / DIC . Flow sheet for the feedback process of technical formic acid. When the level in the tank reaches the top switch the inflow will be turned off while level below the switch in the bottom half will turn off the pump by the outflow. In figure 3 the scheme for the described process can be seen.3 Salt Till uppslamning Filter Figure 3. Suspension of technical sulphate was the least expensive of the two feedback processes costing 626 400 SEK installed. The filter separates the sodium sulphate crystals from the organic mother liquor. Figure 4. a steam trap. The steam is condensed in the boiler and then gathered in a steam trap. process control equipment.5 LS-4 LT LIC . [5] Evaporation and filtration of technical formic acid costs 8.

[7] Variable costs In the variable costs electricity to run pumps and stirrer and cost of steam for the boiler is included. [6] extra per year. The prices used in the calculations are 506 SEK per MWh of electricity (average price 2010) and 200 SEK per ton of steam. In this case the removal of the technical grade will mean lost income for this product while the higher yield of the other products gives a positive change in profit. The profit from this new process will be 1 788 000 SEK per year and it means that the pay off time for the investments will be four months. the suspension of technical sulphate is a relatively simple process and it will probably work about the same way as in the experiments.costs of this section is the evaporator at 1 776 000 SEK uninstalled. However. Profitability With today’s production rate and variable costs as mentioned above the profit for each side process can be determined. especially with the filtration. Using the feedback of technical sulphate there will be a greater yield of good quality sodium sulphate instead of the technical grade. With those prices the total variable cost was calculated as 11 400 SEK per year for the feedback of technical sulphate and 214 000 SEK per year for the process regarding the technical formic acid. They will accumulate in the process and deteriorate the crystallization of sodium sulphate throughout the process. but it will take about 15 years for the profit pay off the investment. This new process section will bring in 567 000 SEK Conclusions One conclusion that can be made from this work is that it will be expensive to invest in the evaporation unit for the feedback process for technical formic acid. With this new part of the process the yearly income from the formic acid plant will be 1. It is not economical to invest in a process that takes 15 years to start making money and not only be a cost. It is not certain that the particle sizes will be the same in the full scale process as in the laboratory trials. Costs of reparations are disregarded because they are difficult to estimate. That would mean a decrease in the better quality formic acid and therefore a decrease in income of that product. Also the costs of reparations have not been taken into consideration in the calculations.6 % higher than without it. In this article the existing bleed off has been used in the calculations because it is difficult to guess how much greater the new bleed off will have to be. because they are difficult to predict. Since there is no profit to be made on the technical grade today. [5&6] Discussion The problem with the new process sections is that they would not only feed sodium sulphate back. the new process will only contribute to a raise in income. . It is important to note that the suggested processes have only been tested on laboratory scale and therefore it is not 100 percent sure that it works in the real process. In the other process there can be problems. The problem can be solved by bleeding off more technical formic acid from the process. but also the organic impurities. [7] The feedback process of technical formic acid gives a greater yield of higher quality formic acid and it also gives some more sodium sulphate.

Perstorp AB. Ullmann’s Encyclopedia of Industrial Chemistry. . 2008 [3] Anders Johansson. 2011 [7] Production data and profit margins for the formic acid plant.It has been noted that it will be profitable to invest in the suggested process to feedback the technical sulphate. last saved November 2009 [5] Price on stirrer and pump. Another conclusion that can be made is that it will probably be necessary to bleed off more technical formic acid to decrease the accumulation of the organic impurities. E-mail correspondence with Pernilla Blackenfelt. internal document Perstorp AB. Wiley-VCH Verlag GmbH. Christian Berner AB. 201101-14 and technical offering from A-filter AB. The pure sodium sulphate has to be carefully analyzed to make sure that the quality can be kept as it is today. technical salesman. 2011-0223 Future work Since the evaporator was expensive the recommendation will be trying to find other options to eliminate technical formic acid as a product. Technical offerings from Bergius Trading and ChemoInvest special pumps. Another option that can be interesting to investigate is to be able to eliminate both of the by-products with one feedback process. References [1] Werner Reutemann och Heinz Kieczka. It is recommended to invest in the suspension process of technical sulphate and wait and evaluate other processes for the technical grade of formic acid. E-mail correspondence with Daniel Frosterud. Since it is necessary for the by-products to be either eliminated or REACH registered before 2012 this is something that can be investigated as a long term solution while the suspension can be a short term solution. 7th edition 2005 [2] Internal document Perstorp AB. Before putting the new process into practice it is important to try it first and see how much more technical formic acid has to be bled off or if it works with the amount bled off today. Product manager BU Performance Additives.6 % per year an investment seems to be a good choice. Another suggestion would be to compare the costs of new equipment with the cost of a REACH registration of the product to keep selling it after 2012. task description “återföring av techsulfat och tech50myrsyra”. With a payback time of four months and a raise in profit with 1. 2011 [6] Price on evaporation plant and filter. 2010 [4] Anna-Karin Hansen. Formic Acid. process description. formic acid plant. REACH – specific accounting and reporting rules. An investment in the suggested process is not recommended. approved by Mikael Elofsson. Perstorp AB. John Wiley and Sons Inc.

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