Author:

Alfi Soemardji, MSc, Process Engineer

January 2012 Stamicarbon B.V., the Netherlands

HOW GREEN IS THE STAMICARBON UREA PROCESS?

Table of contents

Page

1. 2. 3. 4. 5. 5.1. 5.2. 5.3. 5.4. 5.5. 5.6. 6. 7. 8.

Abstract ................................................................................................................. 1 Preface .................................................................................................................. 1 Introduction ............................................................................................................ 2 Emission sources in the urea plant ........................................................................ 2 Emission reduction in the urea plant ...................................................................... 3 In-line solution .................................................................................................... 3 End-of-pipe solution ........................................................................................... 3 Absorber ............................................................................................................ 3 Acidic Scrubber .................................................................................................. 7 Flare................................................................................................................... 9 Emergency Absorber ....................................................................................... 13 Green Stamicarbon urea process ........................................................................ 14 Conclusions ......................................................................................................... 14 References .......................................................................................................... 15

All technical and other information contained herein is based on general Stamicarbon experience and within this limit is accurate to the best of our knowledge. However, no liability is accepted therefore and no warranty or guarantee is to be inferred. Copyright Stamicarbon BV. All rights reserved. No part of this publication may be reproduced in any form or by any means without the permission of Stamicarbon BV. You will access its contents solely for your own private use and will comply with all applicable laws and regulatory requirements relating to your use of this information.

1. Abstract
The Stamicarbon urea process, like other processes, unfortunately emits gaseous (ammonia) emissions due to the fact that the urea reaction is an equilibrium reaction. In principle, emission problems can be solved in two different ways, either with an inline and/or with an end-of-pipe solution. The combination of the equilibrium reaction and the presence of inerts make an in-line solution not feasible. Therefore end-of-pipe solutions to eliminate ammonia emissions in both urea melt and finishing plants are still needed to obtain a green and environmentally sustainable process. This paper covers the different available end-of-pipe solutions such as absorbers (including emergency absorber), acidic scrubbers and flares. These options have a wide range of operating windows for further optimization and achieving optimum environmental performance. Flaring reduces the ammonia emission by converting the ammonia into carbon dioxide and nitrogen oxides (NOx). Therefore, the environmental impact evaluation - after implementation of the new end-of-pipe solution - needs to be reviewed, especially when applying continuous emission flare because the environmental impact of these new type emissions are not more tolerable than ammonia emission. Stamicarbon believes that a green urea process combines optimum process conditions with a good choice of end-of-pipe solutions. The available alternatives for end-of-pipe solutions target an optimum Triple P balan ce, i.e. the balancing between financial-economical achievements (profit), environmental impact (planet) and public acceptance (people).

2. Preface
Stamicarbon, the innovative, experienced and reliable licensor
Stamicarbon, founded in 1947, is the global market leader in the development and licensing of patented urea technology. It sells proprietary know-how and delivers services to existing and prospective urea producers. It has licensed over 250 urea plants located in over fifty countries. Furthermore it has completed over 90 revamp projects in Stamicarbon and nonStamicarbon plants. Stamicarbon grants licenses for new urea plants, providing the urea producer with all the knowledge and resources to build a reliable, state-of-the-art, low cost and profitable urea plant. Besides new plants we also take care of revamping existing plants, increasing capacity and improving efficiency with several debottlenecking services and tools. Stamicarbons is committed to Full Lifecycle Support, helping the urea producer to get maximum return on investment for 30 years and more. Full lifecycle support comprises from planned inspections and maintenance, troubleshooting, to round-the-clock emergency support. Reliable and durable equipment is integral to the success of urea production. Thats why Stamicarbon supplies critical high-pressure equipment for an optimum performance for a maximum lifespan. Innovations Innovation drives performance in the fertilizer industry. Stamicarbon maintains its leading position by its continuous high-quality innovations in close cooperation with research institutes, suppliers and customers. This has lead to developing breakthrough innovations, amongst others contributing to investment cost reduction and operating costs reductions: AVANCORE urea process (savings on plant height and equipment) Mega Plant Technology (economy of scale) Urea 2000plus Technology (integrated condenser / reactor and savings on plant height and piping) Urea Granulation Technology (formaldehyde just 0.3 wt% and run times >100 days) Safurex stainless-steel material (savings on materials, equipment and maintenance)

Stamicarbon BV
Mercator 2, 6135 KW SITTARD P.O. Box 53, 6160 AB GELEEN The Netherlands Telephone +31 46 4237000 Fax : +31 46 4237001 info@stamicarbon.com www.stamicarbon.com

3. Introduction
Environmental issues have been high on the agenda in global discussions for some time, and it is becoming more and more important especially for production facilities. Urea production facilities are no exception in this respect and operating companies will have to respond more actively to environmental issues, either as a result of local or global regulations or as a result of pressure from the commercial or public domain. As one of the leading licensors, Stamicarbon is continuously working on these subjects by making its process greener and to create a sustainable green urea process as the ultimate goal. Stamicarbon urea process, as any other processes, unfortunately emits small amounts of reactants and dust. In particular ammonia is subjected to more and more environmental concerns. For the urea process, we offer the best available technology for ammonia emission reduction, the optimal solution differing from project to project. The final design for a specific project depends on the applicable requirements from local authorities, the philosophy of the operating company and of course the economical feasibility. The ammonia emission reduction in urea plants and compliance with environmental standards are becoming an important qualifier for technology licensors, but also represent our own responsibility to strive for a sustainable future. This paper shows a framework on gaseous emissions in urea plants and its prevention, in both melt and finishing plants.

4. Emission sources in the urea plant

The gaseous emissions can be distinguished into two different types, discontinuous and continuous emissions. Discontinuous emissions usually originate from process safety valves, rupture discs, breathing vents and drain valves. Continuous emissions originate from the fact that inerts are introduced in a urea plant with the raw materials and by using air. Such inerts include nitrogen, hydrogen and methane. The fact that inerts need to be purged makes emissions (incl. ammonia) inevitable unless these emissions are subjected to treatment.

5. Emission reduction in the urea plant

In principle, there are two types of solution that can be applied here; in-line and end-of-pipe solutions.

5.1. In-line solution

Urea is commonly made by applying the following reactions path. 2 NH3 + CO2 NH2COONH4 2 NH3 + CO2 NH2COONH4 CO(NH2)2 + H2O CO(NH2)2 + H2O

It is an equilibrium reaction, which means that this reaction is reversible and will not reach 100% completion. Therefore, in a urea plant, all components from the chemical reactions above are present, that is reactants, product and intermediate. Part of the un-reacted (remaining) reactant, especially ammonia, if not subjected to further treatment, would be purged with the inerts. It is this combination of the equilibrium reaction and the presence of inerts (at least from the raw materials) that makes an in-line solution not feasible.

5.2. End-of-pipe solution

Some alternative end of-pipe solutions are available, depending on the type of the emission, as shown in Table 1.
Type of emission Continuous Discontinuous Melt Plant Absorber Acidic Scrubber Flare Flare Emergency Absorber Finishing Section Acidic Scrubber -

Table 1. Possibilities of End-of-Pipe Solution in a Urea Plant

5.3. Absorber
In the Stamicarbon melt plant; there are two types of absorbers, the Low Pressure (LP) Absorber and the Atmospheric Absorber. The main difference between these two absorbers is the operating pressure. Both absorbers are used for bringing the ammonia from the gas phase to the liquid phase by washing it with water (liquid).

LP Absorber The LP absorber operates at a low pressure of about 4 bar; it absorbs the ammonia that still remains in the vent gas from the high pressure scrubber. The column has two packed beds, top and bottom beds, as can be seen in Figure 1. The vent gas will enter at the bottom of the column and be washed directly with cold ammoniawater while passing through the bottom bed. The remaining gas will go further to the top bed where it will be washed with cold steam condensate. The remaining vent gas, which exists mainly of inerts, will be then released into the atmosphere. The liquid that comes out from this absorber contains some ammonia, but it still lean enough to be used as wash water for the atmospheric absorber.

Figure 1. LP Absorber According to Stamicarbons experience, operating this absorber at 4 bar is the optimum condition when comparing the investment cost of the equipment and the improvement on the ammonia emission that can be achieved. The maximum pressure of this absorber will be slightly higher than 4 bar, being about 6 bar. In case it is needed, operating it at 6 bar will give some further reduction of the ammonia emission by approximately 50%. Increasing pressure will result in a reduction of ammonia emission until a maximum is reached. However Figure 2 shows that beyond a certain pressure emission level is hardly reduced further.

Ammonia Emission Level

Column Pressure

Figure 2. Effect of Column Pressure on the Ammonia Emission from the LP Absorber

The flow and temperature of the steam condensate are two other parameters that could be used for further reduction of the ammonia emission, as shown in Figure 3. The steam condensate temperature that we chose is around 40 oC, since usually there is no possibility to cool this condensate to a lower temperature. When there is a refrigeration facility available (usually in the ammonia plant), extra cooling will bring down the ammonia emission further. A higher flow of steam condensate will of course result in better washing of the ammonia into the liquid phase. On the other hand, this extra condensate flow means an extra load going to the waste water treatment section. 15 25 35 45 55

Ammonia Emission Level

Flow Temperature

1200 1700 2200 2700 Figure 3. Effect of Steam Condensate Condition on the Ammonia Emission from the LP Absorber The main emission from this absorber is the inerts. Reducing the inert concentration in the system will therefore reduce the emission. The inert concentration can be reduced by using purer raw materials and by reducing the amount of passivation air. The amount of passivation air can be reduced by using a better corrosion-resistant material, for example Safurex. Atmospheric Absorber This absorber is designed to absorb ammonia from the off gases from the low pressure section using the effluent from the LP absorber. The low pressure of these gases determines the pressure of this absorber; therefore pressure is not a parameter anymore to reduce the emissions. As in the LP absorber, this column also has a top and a bottom bed. The gas feed enters at the bottom of the column and is washed by the re-circulated and cooled bottom effluent of the same column. The remaining gas is then washed in the top bed with the effluent from the LP absorber, before being released into the atmosphere. The bottom effluent of this absorber contains absorbed ammonia and is sent to the waste water section, where the ammonia will be recovered for recirculation to the synthesis section. The temperature and the flow of the bottom effluent circulation are adjustable parameters for this absorber. There is a limit to the improvement these adjustments can bring though. A way to reduce the emission further is using a more efficient absorbent, for example steam condensate to the top bed. The different schemes for this absorber can be seen in Figure 4.
5

a. Without Steam Condensate

b. With Steam Condensate

Figure 4. Atmospheric Absorber Additional steam condensate, as shown in scheme b, can result in a significant reduction of the ammonia emission from this absorber. Figure 5 Shows that a lower temperature (< 40oC) of the condensate, in contrary, barely reduces the ammonia emission from this absorber compared to the steam condensate flow. However, also here, additional steam condensate flow means an extra load going to the waste water treatment section. 15 0,07 Ammonia Emission Level 0,06 0,05 0,04 0,03 0,02 0,01 0,00 0 500 1000 1500 2000 Flow Temperature 25 35 45 55

Figure 5. Effect of Steam Condensate Condition on the Ammonia Emission from the Atmospheric Absorber

5.4. Acidic Scrubber

When very low concentrations of ammonia emission are required, acidic scrubbing can be applied. By adding an acid to the absorbent, usually nitric acid or sulphuric acid, ammonia is extracted from the vapor phase by chemical reaction to an ammonium salt and overhead vapor concentrations of < 30 mg ammonia/Nm3 can be reached. However, acidic scrubbing produces an aqueous solution of ammonium salt as a by-product. Acidic Scrubber for Melt Plant Figure 6 shows an acidic scrubber as applied by Stamicarbon in a melt plant, scrubbing the overhead vapor of the LP absorber and the atmospheric absorber. Acidic scrubbing takes place in the bottom bed. In the top bed clean water removes acid from the vapor from the bottom bed (if any). A recycle stream is applied here to reduce the liquid make-up and the purge of the aqueous solution of ammonium salt. This type of scrubbing is very convenient when there is a UAN- or ammonium sulphate facility on site to discharge the ammonium salt solution to.
Cleaned off-gas
Steam condensate

Acid solution Off gas from absorbers

Ammonium salt solution

Figure 6. Acidic Scrubbing for Melt Plant Acidic Scrubber for Finishing Section In the finishing section there are several configurations in which acidic scrubbing can be applied. Here two examples are given applying sulphuric acid. This acid is easy to obtain and ammonium sulphate is widely used as a fertilizer, either as a liquid fertilizer or as a solid mixture with urea. In the examples urea dust scrubbing and acidic scrubbing is combined. Other configurations are also possible (like separating urea dust scrubbing and acidic scrubbing and using nitric acid) and the choice of the client is also determined by the opportunities already available on site (like whether or not having a UAN- or ammonium sulphate facility to discharge the ammonium salt solution to).

Figure 7 shows a Stamicarbon design for acidic scrubbing integrated with urea ammonium sulphate (UAS) production.

Cleaned off-gas Stack

Condenser Steam

Ejector Acidic scrubber Cooling water Sulphuric acid Off-gas from finishing section Steam Cond. Ammonium sulphate

Evaporator Pelletizer UAS product

Cooling water

Mixing tank

Figure 7. Integrated Acidic Scrubbing and UAS Production The off-gas from the finishing section is washed in the acidic scrubber using sulphuric acid. The acid concentration can be varied; lowering the pH of the recycle solution increases the ammonia reduction efficiency, but at the same time increases the hydrolysis of urea. Clean gas goes to the atmosphere via the stack. Depending on the concentration of the solution from the scrubber, some solid ammonium sulphate might need to be added to the mixing tank to obtain a final UAS melt with a sulphur content of about 5%-w. This solution, with a typical composition of 38%-w urea and 10%-w ammonium sulphate, is concentrated in a vacuum evaporator to form a melt with water content of about 0.3%-w. This melt is then shaped in a pelletizer to yield solid UAS pastilles. The vapor from the evaporator is condensed. The off-gas from the condenser is sent to the granulation stack and the condensate from the condenser is returned to the scrubber. The subatmospheric pressure in the evaporation section is maintained by an ejector.

Figure 8 shows a design where in a granulation process, instead of making UAS, the melt from the evaporator is recycled back to the granulator, resulting in sulphur enriched urea granules.

Figure 8. Integrated Acidic Scrubbing and Sulphur Enriched Urea Production Plant

5.5. Flare
When flaring is applied in the melt plant distinction is made between continuous and discontinuous flaring. Continuous Flaring A continuous flare can be used for all process and breathing vents, for example from the absorbers. The gas streams coming from these vents are collected in a blow-off separator to separate the gas phase from the liquid phase (if any). The gas is then incinerated in the flare and the liquid is recycled back to the ammonia-water tank. Figure 9 shows a scheme for this type of flaring. During normal operation the continuous emission source will only contain at maximum about 1%-m ammonia, the rest being mainly nitrogen, oxygen and water. Due to this oxygen content, a nitrogen stream is added, not only to prevent extra oxygen ingress, but also to avoid the occurrence of an explosive mixture in the system. Therefore quite some support gas is required to incinerate the gas stream coming from this source.
9

Nitrogen From process & breathing vents

Support gas

Ammonia water

To ammonia water tank

Figure 9. Continuous Flaring System in the Urea Plant Discontinuous Flaring Discontinuous flaring can be distinguished by emission source: discontinuous ammonia flaring and the discontinuous flaring of other vapors. The discontinuous ammonia flare is dedicated for pure ammonia emission sources (e.g. from the ammonia pump). The liquid ammonia coming from the pump is collected and sent to a blow-off separator/evaporator, as can be seen in Figure 10. The bottom part of the separator is heated with steam to release other gases that are trapped in the liquid and nitrogen is added to the tank to prevent oxygen ingress to the system. The gases coming from this separator/evaporator are then incinerated in the flare and the liquid ammonia can be returned to battery limit.

Support gas Ammonia Nitrogen

Pure ammonia Steam to B.L.

Cond.

Figure 10. Discontinuous Ammonia Flaring System in Urea Plant

10

Discontinuous flaring of other vapors is intended for all other discontinuous sources in the melt plant, such as PSVs. These sources are collected in a large blow -off separator via a collecting header. This collecting header is equipped with a steam inlet in order to keep the line open. The gas from the separator is incinerated in the flare and the liquid is recovered in a separate drain tank. From this drain tank, the liquid is circulated into the system by means of a circulation pump. The scheme of this flaring system can be seen in Figure 11. The nitrogen line to the separator, as mentioned before, is to prevent oxygen ingress to the system.

Figure 11. Discontinuous emergency Flaring System in Urea Plant In general discontinuous emission contains more ammonia than continuous emission. As indication, depending on the source of the emergency blow-off, it can contain about 30%-m ammonia. Therefore a discontinuous emission has typically a higher heating value than a continuous emission. This heating value will affect the amount of support gas needed to incinerate the gas, as can be seen in Table 2. Table 2. Typical required Mass Ratios of Support Gas and Nitrogen to Ammonia for Flaring Emission Sources in a Urea Plant2
Source Support gas to Ammonia Nitrogen to Ammonia Discontinuous Emission 1:10 Very little, only for purge Continuous Emission 140:1 600:1

According to Table 2, flaring of a continuous emission will typically require 140 kg of support gas for burning 1 kg of emitted ammonia. This ratio is tremendously high compared to a discontinuous emission. This justifies reconsideration of flaring of continuous emissions, because flaring produces nitrogen oxides (NO x) and extra carbon dioxide from the complete burning of ammonia, whereas venting will emit mainly ammonia.
11

Table 3 gives the environmental benchmark indicators used to compare the impact of different kind of emissions.
Environmental Benchmark Indicator Troposphere Acidification Ozone Forming Potential (TOPF) 1 0 1 1.22

Source/ type of gas Venting/ ammonia Flaring/ nitrogen dioxide (NOx)

Global Warming Potential (GWP) 0 30

Ozone Depletion Potential (ODP) 0 0.017

Table 3. Environmental Benchmark Indicators for Venting and Flaring of Ammonia2 Global Warming Potential (GWP)4 indicates the contribution of a specified gas mass to global warming by comparison with reference gas carbon dioxide. The GWP has been defined as the ratio of the time integrated warming effect from the instantaneous release of a kilogram of a specified gas, compared to that of a kilogram of reference gas carbon dioxide. The GWP value represents the global warming potential of the gas over one hundred years. Acidification is used to describe the loss of nutrient bases in ground or water through the process of leaching and their replacement by acidic elements. The acidification is indicated by the acid equivalent. The acid equivalent is a measure to determine the environmental impact of the acidifying substances, which are mainly caused by sulfur and nitrogen based molecules. The equivalent determines the degree of acidity of a substance per mole. Troposphere Ozone Forming Potential (TOFP)7 equivalent indicates the formation of ozone in the troposphere, causing radiative forcing. The troposphere is defined as the lowest part of the atmosphere from the surface to about ten kilometer in altitude in mid-latitudes where clouds and weather phenomena occur. Ozone is formed by two preceding pollutants in the presence of ultraviolet sunlight: volatile organic compounds and nitrogen oxides. TOFP uses ratios to convert emission masses to masses of the TOFP equivalent. Ozone Depletion Potential (ODP)3 equivalent indicates the ability of a specified gas to destroy stratospheric ozone by reaction with the ozone to oxygen. The ODP has been defined as the ratio of the total amount of ozone destroyed due to a kilogram of specified gas and the amount of ozone destroyed by a kilogram of reference refrigerant gas CFC-11 (CCL3F).

Table 3 clearly tells us that flaring of ammonia has a more negative effect on the environment than direct venting. Flaring contributes to global warming, troposphere ozone formation and ozone depletion, while venting does not. Flaring of ammonia introduces a new type of emission for urea melt plants in the form of nitrogen oxides. The only advantage of flaring is that it can be a suitable solution to avoid ammonia nuisance to the surrounding area of the plant during upset or emergency situations.

12

5.6. Emergency Absorber

The emergency absorber is designed to reduce emissions resulting from a tube rupture in the synthesis. The schematic plot of this absorber is shown in Figure 6. At the discharge of a PSV/rupture disc safeguarding against the consequences of tube rupture in the synthesis, a vapor/liquid separator is installed to separate the liquid from the vapor phase. The remaining vapor will go through an absorber bed, before being vented into the atmosphere. A large amount of water (approximately 1400 m3 in 3 hours), is applied counter-currently through the bed. This reduces the ammonia emission after tube rupture from about 100 ton to about 10 ton (for a 3000 MTPD urea plant).

Figure 6. Emergency Absorber In spite of the large amount of stand-by (cooling) water needed for this system, the collected liquid from the absorber cannot be sent to the sewer directly and since the resulting liquid is very diluted, a large collecting tank is required. From that tank the solution can (gradually) be sent to a biological waste water treatment or can (gradually) be reprocessed to the urea plant. An emergency absorber system like this probably will never be used throughout the life-time of the plant, which is the main reason why this option is rarely installed.

13

6. Green Stamicarbon urea process

Research shows that the biggest ammonia emission contributor is livestock. Livestock is responsible for about 70% of the total ammonia emission to the atmosphere (data from 2002, measured in mid-Atlantic Northeast), which is about 5 times higher than the ammonia emission coming from urea plants. So, urea plants are not the main contributor of ammonia emission. It is our responsibility to reduce this smaller contribution and so to strive for an environmental sustainable future. At the end it is about balancing the feasibility between the Triple P sustainability pillars: the financial-economical achievements (profit), environmental results (planet) and public acceptance (people). In all cases, there is always a solution available which we can propose to fulfill the customers requirement.

7. Conclusions
1. The fact that inerts are introduced in urea production and the fact that ammonia is always present in a urea solution/melt makes that the inert purge contains ammonia, usually requiring end-of-pipe type treatment to keep the ammonia emission within acceptable limits. Absorption and acidic scrubbing of ammonia are effective treatment methods for reducing ammonia emission. Both options are easy to apply and have a certain design window within which investment can be balanced with required environmental performance. Flaring is an alternative end-of-pipe solution. It reduces the ammonia emission, but generates nitrogen oxides (NOx) emission, which is worse from an environmental point of view compared to the ammonia emission.

2.

3.

14

8. References
1. 2. 3. 4. 5. 6. 7. 8. Gevers, Bart, Implementation of Stamicarbons Key technology Developments in Recent Urea Grass Roots Projects, 2nd GPCA Fertilizer Conference, Doha, 2011 Dobre, Joey, MSc., Stamicarbons Approach in Mitigating the Environmental Impact of a Urea Plant, 2010 IFA Technical Symposium, Sun City, South Africa, 2010 Ravishankara, A. R., et al., Nitrous Oxide (N2O): The dominant OzoneDepleting Substance Emitted in the 21st Century), Science Vol. 326, p123, 2009 Forster, P., Ramaswamy V., et al., Intergovernmental Panel on Climate Change, Fourth Assessment Report, Changes in atmospheric constituents and in radiative forcing, Ch 2, 2007 Gevers, Bart, Emissions from Urea Plants: An Update, Uhde Fertilizer Symposium 2006, Dortmund, Germany, 2006 Emission Inventory Improvement Program, Estimating Ammonia Emissions from Anthropogenic Non Agricultural Sources, Draft Final Report, April 2004 Houghton, J.T., et al., Intergovernmental Panel on Climate Change, Climate Change 2001: The Scientific Basis, Ch 6, 2001 United nations Industrial Development Organization (UNIDO) & International Fertilizer development Centre (IFDC), Fertilizer Manual, Kluwer Academic Publishers, The Netherlands, 1998

15