Life Cycle Assessment of Environmental Damages Caused by Nitrate Fertilizers Production in Bulgaria

Copyright © IFAC IFAC DECOM-TT SYSTEMS 2004 AUTOMATIC FOR BUILDING THE INFRASTRUCTURE IN DEVELOPING COUNTRIES Automatic Systems for Building the Infrastructure in Developing Bansko, Bulgaria,Countries 2004 October 3 - 5, 2004 Bansko, Bulgaria

LIFE CYCLE ASSESSMENT OF ENVIRONMENTAL DAMAGES CAUSED BY NITRATE FERTILIZERS PRODUCTION IN BULGARIA

A. Lekova, D. Boiadjiev, S. Kostova, A. Gràncharova Institute of Control and Systems Research, Bulgarian Academy of Sciences P.O.B. 79, 1113 Sofia, Bulgaria E-mail: alecova (boiadjiev, skostova, alexandra)@icsr.bas.bg,

Abstract: The objectives of this study were to assess the production of nitrate fertilizers taking into account all the stages in its life cycle from “cradle-to-grave” via Life Cycle Impact Assessment methodology. Archived data of two artificial fertilizer plants “Neohim” and “Agropolihim” has been utilized. Definition of the boundaries of the analysis and the stages of the nitrogen fertilizer life cycle, as identification of burdens, chemical and other environmental impacts, have been performed during the production of two types of nitrate fertilizers: stabilized ammonium nitrate and NEOFERT ®. Data analysis is conducted by using LCA software - “TRACI” of USEPA. Stressors that may have potential effects on the following impact categories: global changing of nitrogen cycle, acidification, eutrophication, global warming, human health criteria, land and water use, have been characterized. Copyright © 2004 IFAC Keywords: environmental engineering, environmental monitoring, ecology.

1.

GOALS AND SCOPE DEFINITION

LCA is a tool that has been widely used for environmental analysis. A general methodological framework for performing LCA’s according to the state of the art, and taking into account the latest scientific developments within the SETAC-society, is defined in the international standard ISO-14040 (ISO, 1997). The key idea of LCA is to take into account all the stages in the life cycle of the process or product. This is generally done by compiling an inventory of relevant inputs and outputs, and evaluating and interpreting the potential environmental impacts of these inputs and outputs. Policy decisions must act on which source of pollutant causes how much damage. This requires an Impact Pathway Analysis (IPA), tracing the passage of the pollutant from where it is emitted to the affected receptors (populations, crops, waters, forests, materials, etc). The Life Cycle Impact Assessment (LCIA) phase of an LCA is the evaluation of potential human health, environmental,

and resource depletion impacts identified during the inventory analysis. According to ExternE methodology (Rabl, 2001): life cycle impact assessment attempts to establish a relation between the product or process and its potential environmental impacts. We have adapted that framework to the conditions for fertilizers production in Bulgaria, which is shown in Table1. Definition of the boundaries of the analysis and the stages of the nitrogen fertilizer life cycle, as identification of burdens, chemical and other environmental impacts, have been performed during the production of two types of nitrate fertilizers: stabilized ammonium nitrate in “Agropolihim”, placed in the North-Eastern part of Bulgaria (InkoApostol Marinchev, 1999) and NEOFERT ®ammonium nitrate for fertilizing in “Neohim” in the Southern part of Bulgaria (Grancharov at al., 2000). Data analysis is performed by using LCA software “TRACI” of USEPA (TRACI).

2. DEFINING THE BOUNDARIES OF THE LCA AND UPSTREAM EMISSIONS The system is centered on the artificial fertilizers plant itself. One of the distinguishing features of the study is the inclusion of site dependence. For each stage of each nitrogen fertilizer chain we have therefore identified specific locations for the artificial fertilizers plant and all of the other activities drawn within the system boundaries, e.g. to identify routes for the transport of nitrogen fertilizer to farms and the “nitrogen cycle” set up in the soil and water. The location is important in determining the size of impacts and climate dependencies. There are several factors to this, the most important of which are: ƒ

ƒ ƒ ƒ ƒ

Variation in technology arising from differing legal requirements (e.g. concerning the use of pollution abatement techniques, occupational safety standards, etc.); Variation in nitrogen fertilizer quality (Bulgarian Data Standard); Variations in atmospheric dispersion; Variation in local agriculture practice for using nitrogen fertilizer, season, climate, soil and plant profile; Differences in the sensitivity of the human and natural environment upon which nitrogen fertilizer chain burdens impact.

The assessment of the nitrogen fertilizer cycle includes evaluation of the stages associated with the information shown in the first column in Table1. The EU technology of the production process (EFMA, 2003) is close to the technology used in Bulgaria (Grancharov at al., 2000). The main raw materials, which are used in the fertilizer plant, are: electricity and heat (most cases from own heating power plants). Usually oil gas is burned in O2 environment, thus the water is heating and the mixtures in the synthesis columns circulate. A widespread list of burdens and impacts has to be described for each stage. Table1 Stages of the LCA and upstream emissions STAGE OF THE NITRATE FERTILIZER CHAIN Construction of a new artificial fertilizer plant and activities linked to the manufacture of materials for apparatus (e.g. Al + chrome - nickel stainless steel)

EMISSIONS (* Neglected) Atmospheric and Water emissions: SO2 ,NOx, CO2 , Dust

Technologies of the nitrogen fertilizers production: -Steam Reforming of natural gas from CO2 , dust, H2 O vapor (Ammonia synthesis NH3 ) - Nitric acid synthesis HNO3 -Ammonium Nitrate synthesis (NH4 NO3 ) -neutralization -evaporation -solidification (pilling and granulation) Nitrate fertilizers in store t<32C Transport of nitrate fertilizers – train, truck, containers, ships Nitrate fertilizers usage : Ammonification Nitrification De-Nitrification Volatilization Soil alkalizing and acidifying (with and without the plants) mobilization-NH4 NO3 high Leaching and washing away (Eutrophication)

Flue-gases: CO2 , CO, NO2 , SO2; NOx Dust; NH3 , H2 S , C6 H5 OH NH3 NOx, N2 O, (NH4 + into water) NH4 NO3 in water NOx* dust, PM, NH3, NH4 NO3 as aerosol (NH2 )2CO aerosol (NH2 )2CO water NOx, CH4 , CO

NOx Volatilization (VOC) Dust, PbO, CO, CnHm, CO2 , NOx, SO2 salts NH3 , (NH4 )2HPO4 2NH3 , (NH4 )2SO4 ammonia -> nitrite -> nitrate, Mg, Phosphate, N2 O, N2 , NO2 ,NO, H2 O ammonia gas NH4 , NO3 NH4 NO3 +4O2 = 4HNO3 + 2 H2 O CO2 , H2 S*, NH3 , CH4

3. IDENTIFICATION OF THE NITROGEN FERTILIZER CHAIN BURDENS The following broad categories of ‘burdens’ have been identified: ƒ Solid and liquid wastes; Gaseous and particulate air pollutants; ƒ Occupational exposure to hazardous substances; Specific categories concerning changes in Global Nitrogen Cycle are: ƒ Euthrophication, Acidification; ƒ Damage to water use, e.g. increasing the concentration of NO2 and NO3 in the water, which can cause metabolic effects in organisms. The emission monitoring includes upstream emission of pollutants from nitrogen fertilizer production. A stand alone ammonium nitrate plant may emit to atmosphere - ammonium nitrate, ammonia

These can arise from the processes: neutralizers, evaporators, pill towers, granulators, driers and coolers. A stand alone ammonium nitrate plant may emit to drain -- ammonium nitrate, ammonia or nitric acid (which should normally be neutralized).

and the receiving waters. Such parameters may include: 1) pH; 2) Temperature; 3) Suspended solids; 4) Measurement of organic species; 5) Parameters specific to the process, for example, for process additives

These can arise from neutralizer and evaporator boiloff, equipment cleaning, and a wide range of points which are specific to a given site. An ammonium nitrate plant will always produce a surplus of water. Some other plants on the site may be able to consume all or part of this water, (after cleaning) but these routes are specific to the particular site.

The process of quantifying energy and raw materials implemented in the TRACI module concerning Inventory Analysis is summarized in the tables bellow. The inventory analysis is a technical database process of quantifying energy and raw material requirements, atmospheric emissions, waterborne emissions, solid wastes and other releases for the entire life cycle of a product, package,

The significant parameters, which should be measured, may be specific, depending on the plant

Table 3: Technical specification of raw materials for production of 1 ton NH4NO3 Raw Materials Ammonia NH3 Nitric acid HNO3 Steam Water Electricity

Fig.3.

Inventory data for the product: ammonium nitrate (NEOHIM)

process, material, or activity (USEPA 1993). The inventory data for the process “Steam reforming during the Ammonia production” is shown on fig.3. Impact assessment consists of the classification of inventory data to impact categories (e.g. NH3 releases are classified under “Eutrophication”, NOx and SO2 under acidification), global warming and of the characterisation of these data within the impact category (e.g. N2 O is characterised by its potential (factor) of 78, CO2 has a factor 49). Weighting across impact categories is still under discussion. The emissions are measured in kg per ton of product and are derived from Table 4 about the emissions per year (1998). The Ammonia production for this year is-161950t, HNO3 production -275972t, and the ammonium nitrate production (34.5%N) for the year 1998 is 336 151 tones. See also Table 2. Table 2. Technical characteristics of Neohim artificial fertilizer plant Overall fertilizers 630 000 t/y capacity Start of 1951, 1987 commercial renovated operation Thermal efficiency % Full load hours per 2880 h/y year Annual production ‘98 -336 151; t/y ‘01 -335 312; ‘02- 307 076

Quantity 0,216 – 0,217 t 0,780 – 0,785 t 0,85 – 1,0 t 20 – 40 m3 15 - 30 kWh

Fig.3. shows as an example of Life Cycle Inventory Data for the product: stabilized ammonium nitrate (for NEOHIM) and the process of compiling an inventory of relevant inputs and outputs by “TRACI” for all stages of the cycle during the production of nitrogen fertilizer. The LC stage is “Materials Manufacturing” of the process “Production of Ammonia - Steam reforming, cleaning from dust, solid particles, CO2 , H2 O vapors, …” and the chemical release during the production of Ammonia only. The life cycle of a product/process covers the following stages: Raw Materials Acquisition, Materials Manufacture, Product Fabrication, Filling /Packaging/ Distribution, Use/Reuse/Maintenance, and Recycle/Waste Management. 4. FUNCTIONAL UNIT OF KGN OF NITROGEN IN FERTILIZER The emissions in reports normally are given in kg emissions per t product. However, for better monetary valuation we have to transfer the data from “emissions per ton product” to “emissions per kgN”. We have used the functional unit of kg N of nitrogen in fertilizer. We proposed first to find the %N Percentage of total chemical nitrogen in the product. %N is calculated according to the following equations: Ammonia 1 mole NH3 = 17.032 g 1 mole N = 14.008 g %N= 100*N/NH3 =100*14.008/17.0032=82.25% Nitric Acid 1 mole HNO3 = 63.02 g 1 mole N = 14.008 g

%N= 100*N/ HNO3 =100*14.008/63.02=22.22% If the concentration of HNO3 is 60% 0.6*0.2222 If the concentration of HNO3 is 45% 0.45*0.2222

We used real “Average annual concentration of the controlled emissions” summarized in the Table 4. We made calculations of emissions about chemical plant NEOHIM (Dimitrovgrad, Bulgaria) and Agropolihim, Devnia.

Table 4: Air pollution sources from fertilizers production in “NEOHIM” – Dimitrovgrad Stack par. (H/m/d/m)

Ammonia production Sector” Nitric acid” production” 43%(Old one) Sector” Nitric acid” production” 60%(New one) Ammonia nitrate productionsector 400 (Old one) 1.Pilling 1.3 degree of evaporation

Gas temp.

Gas emissions

(o C)

(Nm3 /h)

Harmful substances

Emission s

Mass Flow

(kg/m3 )

(g/sec)

291 204 946

30.53 21.39 17.1

Annual emissio ns (ton /year) 277 194 184

40

4

115

376800

80

1.05

25

65000

NO2 CO NO2

100

2.6

220

102000

NO2

173

4.9

50.5

2437

7.8

81

11520

Dust Ammonia nitrate

31.2

0.1

1.04

170

5.9

2x76

34.5

1.2

2x12.4

55

32

142

28.4

15.9

47.5

22.9 7.7 156.1

0.51 0.5 2.3

5.2 5.1 23.5

40

0.5

160

Ammonia 44

2.9

45

2x125100

Dust Ammonia nitrate

2.Granulating Ammonia nitrate productionsector 72 (New one) Sector Formalin production

6 x. 76

22

0.8

0.15

60

40

6x75000

3780

The Admissible Emissions Levels (AELs) in Bulgaria are (Annual emissions ton /year): Dust Ammonia nitrate as aerosol – 17t Ammonia-35t Total N content in Ammonium nitrate: According to (EFMA) the N content in Ammonium nitrate is 33.5-34.5%. The N content in Ammonium nitrate in NEOHIM is ~ 34%, the N content in Ammonium nitrate in “Agropolihm” is 31%, because it is stabilized with P2 O5 to prevent its combustion. Concerning how to transfer the data from “emissions per ton product” to “emissions per kgN” we used the following equations: E[t per year/t product per year] = E[t per 1ton product] E[t/t N} = E [t per 1ton product]/(% of total N in 1t product), where E = Emission

Ammonia Dust Ammonia nitrate Ammonia Methanol HCHO CO

%N = Percentage of total chemical nitrogen in the product Example: Ammonia has 82.25% of total chemical nitrogen NO2 – 234.5 ton per year (from Table6) From Table 3 – quantity HNO3 in 1 ton NH4 NO3 is 0.78 (HNO3 production in 1999 is 275 972t) Then: NO2 = 234.5/275 972 = 0.0008497t NO2 /t HNO3 0.0008497*0.78 = 0.000662t NO2 per ton fertilizer ENO2 = 0.000662t / 0.2222 = 0.0029827 t/t N Or ENO2 = 2.9827 kg / t N = 2.9827g emission NO2 /kg N

5. STUDIES WITH BULGARIAN DATA BAT emission levels for each process of Life Cycle Stages were used for the calculations of total emissions in KGN in Table5. Real data from the two

Artificial Fertilizer Plants in Bulgaria (Neohim and Agropolihim) were used for the calculations of total emissions in KGN . All the calculations are made based on the data in Table 4 and BAT in Europe (EFMA).

Table 5 total emissions in KGN according to: BAT and two Artificial Fertilizer Plants in Bulgaria Conventional Steam Reforming (NH3 synthesis) 82.25%N

Activity Burden [g/kgN] NOx NO2 SO2 CO

Stack Fluegases

CO2 H2 S Dust CH4 NH3 (into air)

0.1185 0.314 0.0026 0.0079 0.176 256.09

Production of 44-47% Nitric Acid (HNO3 synthesis) ~22.22%N

Production Stabilized NH4 NO3

2.389 2.2837 2.98(new+old)

4.5747

(~34%N)

0.5882 0.64(new+old one)

NH3 (NH4 +into water) N2 0 VOC HNO3 HF (fluorite gases) NH4 NO3 as aerosol

0.02634

0.0004

of

Production of Urea (NH2 )2CO (~46%N)

6.959 2.4022 3.294 0.0026 0.0079 0.176 256.09

0.5434 0.0054

1.1312 0.64 0.03214

0.5434 0.001

0.7352 3.28 0.5882 0.5434 0.001

0.0061 0.7352 3.28 (new+old one) 0.5882

NH4 NO3 in water (NH2 )2CO aerosol (NH2 )2CO water PbO, NM-Hydrocarbons,

Total

Notes: Underlined emissions in KGN according to BAT Bold emissions in KGN for “Neohim” in Dimitrovgrad, Southern part of Bulgaria Italic emissions in KGN “Agropolihim” in Devnia, North-Eastern part of Bulgaria 6. INTERPRETATION Interpretation process is the evaluation of the results of the inventory analysis and impact assessment to select the preferred product, process, or activity. The interpretation step involves identifying significant issues, evaluating the completeness, sensitivity, and consistency of the data, and drawing conclusions and recommendations. The main impacts are measured as follows: EU Eutrophication kgN equiv AC Acidification moles H equiv GW Global Warming kgCO2 equiv HHCR Human Health Criteria total DALYs ( DALY =disability adjusted life years) Human Health Cancer &Noncancer: lbs C7H7 equiv.

Fig.4.

Characterization results of the calculations with TRACI (for NEOHIM)

There are two sectors in NEOHIM for Stabilized NH4 NO3 production – a new (AC72) and old one. It turns out that only during the fertilizers season (from September to May) AC72 works because it’s big capacity. Unfortunately the rest of the time the old one works for less quantity. The Average Annual Concentration of the controlled emissions exceeds BAT Emission Levels, when the old sector in NEOHIM for Stabilized NH4 NO3 production is used. The Average Annual Concentration of the controlled emissions achieves BAT Emission Levels in Europe, when the new sector in NEOHIM for Stabilized NH4 NO3 production is used. All the emissions for “Agropolihim have to be abated to BAT levels (EFM) by a range of techniques. Emissions into air can be up to 200mg.Nm-3 of particulates matters and of ammonia (2kg.t -1 of product for each) if BAT is not employed. Emissions into water can be up to 5,000mg AN N.1-1 and 2,500mg NH3 N.1-1 (6 and 3kg.t -1 of product respectively). 7. POLICIES FOR SUSTAINABLE DEVELOPMENT For fertilizer production, the basic policy option in Europe concerning taxes, tradable permits, limits on fertilizer production, to protect the environment. The policy options for Bulgaria up to now: a).Preventive Activities: Laws and Legislations, Methodology of the Regulation on the conditions and procedure for Issuing of permits for Integrated Pollution Prevention and Control for the construction of new and the operation of existing industrial installations and equipment (MOEW) b).“Regional Inspectorate of Environment and Water” in Haskovo and correspondingly “Ministry of Environment and Water of the Republic of Bulgaria” are responsible for controlling the environmental protection near “Neohim”. Monthly Sanctions for environmental damages in thousand lv. were paided from “Neohim”. For the period 1994 -98 they are about 47500 lv. Data is obtained from (Grancharov et al., 2000) and most of them are related to waste water into the river “Maritsa”. Part of them is for each month during the year, part are separate (e.g. 10000 lv. October, 1998). In the recent years there are no claims for environmental pollutions into air during the exploitation of “Neohim”. For fertilizer use, the basic policy option in Europe concerns tax, tradable permit, limits on use, to limit the amount of synthetic nitrogen fertilizer that can be used. Since the utilization rate of manure is already over 90% in most cases, any regulation to encourage even greater use of manure is unlikely to have a significant effect; we will therefore not consider it.

An interesting fact was pointed out: because the agricultural sector in several East European countries, in particular Bulgaria and the Czech Republic, is in a slump, the use of fertilizer is low at the present time. As a result the fertilizer factory in Bulgaria is running only at about half of its full capacity. Farmers are unlikely to use excessive amounts (in the sense of being near the plateau of the yield vs fertilizer input curve). This raises the question of what policy options, if any, we should consider for the case study in East Europe. Perhaps we should estimate the impact on farmers of a policy decision to internalize the external costs of N fertilizer production and the associated increase in fertilizer price.

REFERENCES EFMA. Production of Ammonium Nitrate and Calcium Ammonium Nitrate, http://www.efma.org/Publications/BAT%202 000/Bat06/section03.asp ExternE. Externalities of Energy, A Research project of the European Commission, http://externe.jrc.es/ Friedrich R, A. Rabl (2001). Quantifying the Costs of Air Pollution: the ExternE Project of the European Commision, Pollution, Atmospherique, Decembre, pp77-104 Grancharov I., et al., (2000). Final Report on Environmental impact assessment of Neochim AD, Dimitrovgrad” Inko-Apostol Marinchev-ET, Varna, (1999). Final Report on Environmental impact assessment of Agropolihim – AD, Devnia”, ISO 14040, (1997). Standard on Environmental Management: Life Cycle Assessment, DIS 14040. International Organisation for Standardisation. MOEW, Regulation on the conditions for Integrated Pollution Prevention and Control, Ministry of Environment and Water of the Republic of Bulgaria, http://moew.government. bgmanage/index_en.html NEOFERT ®- AMMONIUM NITRATE for FERTILIZING, http://www.neochim.bg/ products _en/13-01_en.html Rabl A, (2001). Pollution, Atmospherique, Decembre, pp5-14 SAN-Stabilized Ammonia Nitrate, http://www.agropolychim.bg/eng/p_sas.htm TRACI - Sustainable Technology Systems Analysis, Tool for the Reduction and Assessment of Chemical and Other Environmental Impacts; http://epa.gov/ORD/NRMRL/std/sab/iam_trac