Journal of Cleaner Production 108 (2015) 978e986

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Environmental impacts of phosphoric acid production using

di-hemihydrate process: a Belgian case study
Sandra Belboom a, *, Carl Szo
€ cs b, Ange
lique Le
onard a
a
Department of Chemical Engineering, PEP's, University of Li
ege, 3 All
ee de la Chimie, 4000 Li
ege, Belgium
b
Prayon SA, 144 Rue Joseph Wauters, 4480 Engis, Belgium

a r t i c l e i n f o a b s t r a c t

Article history: This paper undertakes an environmental evaluation of phosphoric acid production, using industrial data
Received 17 September 2014 from Prayon SA in Belgium. Phosphoric acid is produced using the wet di-hemihydrate process also
Received in revised form called Central Prayon process. Both grades of phosphoric acid are evaluated: fertilizer and purified
29 June 2015
grades. Specificities of this plant are highlighted and improvements of the process in terms of energy and
Accepted 29 June 2015
Available online 7 July 2015
facilities integration through years are quantified as environmental benefits. The implementation on site
of two sulphuric acid production facilities and their energetic integration allow a reduction of climate
change impact of 80%. Results also show the importance of phosphogypsum valorisation which is sold for
Keywords:
Phosphoric acid
the main part in this case study. Concerning the purified grade, this specific process has been compared
Life cycle assessment (LCA) to the thermal process, using Best Available Techniques (BAT) values for the modelling. It shows a
Fertilizer grade reduced environmental impact for the wet process in the majority of categories studies.
Purified grade © 2015 Elsevier Ltd. All rights reserved.
Wet process
Di-hemihydrate

1. Introduction Commission and Joint Research Centre, 2007). Two production

processes are available: the wet and the thermal one.
Phosphoric acid is, after sulphuric acid, the most important The thermal process uses elemental phosphorus produced from
mineral acid produced in the world. It is mainly consumed during phosphate rocks but has been abandoned in the majority of Euro-
the manufacturing of phosphate fertilizers or for direct use as acid. pean countries due to the high energy requirement (European
The use as fertilizer, which represents 80% of the overall use, re- Fertilizer Manufacturers' Association, 2000). This process is still
quires a lower grade of purity than the second use (European employed in countries as China or Kazakhstan. The quality of this
Commission and Joint Research Centre, 2007). Phosphorus, tradi- acid is higher than the one required for fertilizer production as it
tionally expressed as P2O5 in the fertilizer industry, is the second allows the production of a defluorinated and purified phosphoric
nutrient consumed in the world after nitrogen. Its consumption acid. Therefore, the most common process for commercial phos-
achieved 41.8 Mt (as P2O5) in 2013 and is expected to reach phoric acid production, for 95% of the total phosphoric acid in EU, is
45.9 Mt P2O5 in 2018 (Heffer and Prud'homme, 2014). Phosphate the wet one but its main flaw is the coproduction of phosphogyp-
fertilizer is usually produced from phosphate rocks and/or com- sum, considered as one of the main hazards of wet-production of
mercial phosphoric acid (Kool et al., 2012). Worldwide phosphoric phosphoric acid (European Fertilizer Manufacturers' Association,
acid production capacity was 41.6 Mt P2O5 in 2004. In Europe, the 2000). This commercial phosphoric acid can be upgraded to a pu-
production capacity of this acid is about 3.08 Mt P2O5 (European rified grade after solvent extraction (European Commission and
Joint Research Centre, 2007).
To our knowledge, few papers related to the environmental
List of abbreviations: BAT, Best Available Technique; CTUh, Comparative Toxic impacts of commercial phosphoric acid production have been
Units for humans; DHH process, Di-hemihydrate process; EU, European Union; IEA, published and none was found about the purified acid produced
International Energy Agency; ILCD, International Life Cycle Data; ISO, International from the wet process. A paper of Kapustenko et al. (2009) focused
Standardization Organization; kt/a, kilotonnes per year; LCA, Life Cycle Assessment;
on the energy improvement and optimisation of the phosphoric
Mt, Mega tonne; PM, Particulate matter; US, United States.
* Corresponding author. Tel.: þ32 43664584; fax: þ32 43664435. acid production but without showing associated environmental
E-mail address: sbelboom@[Link] (S. Belboom). impacts. The Ecoinvent report explains how databases have been

[Link]
0959-6526/© 2015 Elsevier Ltd. All rights reserved.
 S. Belboom et al. / Journal of Cleaner Production 108 (2015) 978e986 979

modelled for both US and Morocco sites at the commercial grade impact category. The last one regroups both midpoint and endpoint
(Primas and Capello, 2004). Bojarski et al. (2008) modelled the wet approaches and is relevant to evaluate separately the environ-
phosphoric acid production process, varying the destiny of phos- mental impact of mineral and fossil fuel depletion which cannot be
phogypsum and using data from a real process plant located in performed using the first method.
Greece. Two other papers compared wet and thermal processes for This study is made in accordance with the ISO standards 14040
phosphate fertilizer production. The first one is based on the single (International Organization for Standardization (ISO), 2006a) and
superphosphate production (Silva and Kulay, 2003) and the second 14044 (International Organization for Standardization (ISO),
one compared from an environmental point of view the fused 2006b) and tends to answer these questions: “Does purified
magnesium phosphate and the triple superphosphate (Silva and grade phosphoric acid from wet process achieve better environ-
Kulay, 2005). Both plants are situated in Brazil. All previous pa- mental results than the one produced with thermal process?”,
pers are focused on wet production using hemi or dihydrate pro- “What are the environmental hotspots of commercial phosphoric
cesses. By-product phosphogypsum is then a waste which is usually acid production?” and “What are the clues of improvement to
stacked or dumped into the sea. For each tonne of phosphoric acid reduce environmental impacts of phosphoric acid (H3PO4) and
(P2O5) produced, about four to five tonnes of phosphogypsum are therefore environmental impacts of P2O5 fertilizers?”.
produced: mass ratio of phosphogypsum (PG) side product to
phosphoric acid produced, z(PG/P2O5) ¼ 4e5. Impurities contained
2.2. Scope definition
in phosphate rocks as e.g. cadmium (Cd), mercury (Hg), heavy
metals, and some radioactive elements, are partly recovered from
The functional unit of P2O5 (1 t) means that specific (divided by
the phosphogypsum. Due to its volume and the type and level of
mass) quantities are used for both fertilizer and purified phosphoric
impurities in the phosphogypsum, it constitutes an environmental
acid grades. Boundaries of the wet production process, presented in
challenge to handle (European Commission and Joint Research
Fig. 1, include eight main stages: (1) production of so-called weak
Centre, 2007). Furthermore, in Europe, disposal to the sea is
phosphoric acid, (2) concentration and production of fertilizer
forbidden and land disposal must be used. Some prevention mea-
grade phosphoric acid, (3) production of special grade intended for
sures can be conducted to avoid environmental pollution but
purification and internally called D01, (4) effluents from those three
another way of dealing with this problem is to improve the quality
first steps, (5) oxidation of previous acid, (6) extraction per solvent,
of phosphogypsum, allowing its use in construction, agriculture or
(7) defluorination step and (8) effluents due to steps (5)e(7). Pro-
industrial sectors. The valorisation of phosphogypsum is easier if its
duction of fertilizer grade acid includes steps (1), (2) and a fraction
transportation cost is low.
of (4) while production of purified acid goes from step (1) to step
A Belgian company, called Prayon SA, already valorises a high
(8).
part of its phosphogypsum (85%), mainly in the plaster industry. It
All information relative to allocation factors, data quality and
uses a wet process with di-hemihydrate recrystaliszation type
source or exclusion criteria are explained in the paragraph 2.3.
(called DHH process or Central Prayon process) with double stage
filtration (European Commission and Joint Research Centre, 2007)
which allows a sufficient purity of the phosphogypsum for further 2.3. Life cycle inventory analysis
valorisation. For fertilizer grade phosphoric acid, only the wet route
is used and the Prayon processes are applied for more than 50% of Inventory concerning wet process is based on specific data for
the worldwide production. Concerning the purified phosphoric Belgium collected in the Prayon industrial plant located in Engis
acid production, the Prayon process represents about 5% of the during the year 2012 (Prayon SA, 2012b). The nature and the
worldwide production, with a P2O5 capacity of 180 kt/a, but this quantity of each consumption and emission are specific to the plant
production is equal to 85% of the European production. and relative to primary data. To model these consumptions, com-
This paper will conduct the environmental life cycle assessment mercial Ecoinvent databases v2.2 (Swiss Centre for Life Cycle
of phosphoric acid production at both fertilizer and purified grades Inventories, 2010), were used as the goal of the paper was not to
to get a more accurate view of environmental impacts of this pro- model in details each chemical production. Inventory relative to
duction, using di-hemihydrate process which has not been thermal process is based on the Best Available Techniques
modelled yet in literature. Results of environmental impacts rela- (European Commission and Joint Research Centre, 2007) as no in-
tive to this di-hemihydrate process will be compared to the thermal dustrial data were directly available.
production process, especially for the purified grade of phosphoric
acid. This paper will also draw some clues of improvement to
2.3.1. Phosphoric acid production
reduce environmental impacts of phosphoric acid production.
[Link]. Phosphoric acid production in Prayon Engis. In Engis, the wet
2. Materials and methods process and more specifically the di-hemihydrate recrystallization
process (called DHH process or Central Prayon process) with double
2.1. Goal definition stage filtration (European Commission and Joint Research Centre,
2007) is used to produce phosphoric acid following both next
Environmental impacts of phosphoric acid production at both steps. First, the tri-calcium phosphate present in the phosphate
fertilizer and purified grades, produced in Belgian industrial plant rock is attacked by sulphuric acid to produce phosphoric acid and
of Prayon SA, are assessed using attributional LCA methodology an insoluble salt as co-product. Then, the co-product is filtered from
classified as Situation C from the ILCD handbook (European the phosphoric acid H3PO4. The previous reaction is limited by an
Commission e Joint Research Centre e Institute for Environment insoluble layer of CaSO4 but can be minimised by recirculation of
and Sustainability, 2010). They are calculated using both ILCD phosphoric acid which allows the solubilisation as mono calcium
2011 midpoint (European Commission e Joint Research Centre e phosphate which becomes calcium sulphate after precipitation
Institute for Environment and Sustainability, 2011) and ReCiPe with sulphuric acid. Equations (1)e(3) present simplified chemical
2008 (Goedkoop et al., 2009) methods. The first one is recom- reactions between rocks and sulphuric acid (European Commission
mended by the ILCD handbook and regroups the most relevant and Joint Research Centre, 2007; European Fertilizer
methods to assess the environmental impact in each studied Manufacturers' Association, 2000).
980 S. Belboom et al. / Journal of Cleaner Production 108 (2015) 978e986

Fig. 1. Scheme of defluorinated and purified phosphoric acid production: consumptions and important steps.

their geological origin. The supply of phosphate rock in Europe is

Ca3 ðPO4 Þ2 þ 3H2 SO4 /2H3 PO4 þ 3CaSO4 (1) provided mainly by Morocco and Russia. The majority of ores for
Prayon study case comes from Russia and contain about 39% of P2O5
Ca3 ðPO4 Þ2 þ 4H3 PO4 /3CaðH2 PO4 Þ2 (2) as mass fraction (European Commission and Joint Research Centre,
2007; Prayon SA, 2012b). The mining of rock requires an energy
comprised between 0.5 GJ/t and 2.8 GJ/t of rock (Kool et al., 2012).
3CaðH2 PO4 Þ2 þ 3H2 SO4 /3CaSO4 þ 6H3 PO4 (3)
In our study, as specific databases are not available for Russian
A scheme of di-hemihydrate process is presented in Fig. 2. The rocks, we use Ecoinvent databases where the required energy is
main advantages of this process are that the yield is high and 1.15 GJ/t of Moroccan rock and 1.29 GJ/t of American rock, which is
reaches an efficiency of 98% in P2O5 as well as it allows the valor- in the range published.
isation of the phosphogypsum (European Commission and Joint Inventory relative to the production of 1 t P2O5 in both fertilizer
Research Centre, 2007). and purified grades phosphoric acid are presented in Table 1
In order to produce phosphoric acid, suitable phosphate rocks (Prayon SA, 2012b). This table presents the total of specific energy
can be found all over the world with a composition varying with required by the plant for the production of the functional unit as

Fig. 2. Overview of the Di-Hemihydrate (DHH) recrystallization process with double-stage filtration based on European Commission and Joint Research Centre (2006).
 S. Belboom et al. / Journal of Cleaner Production 108 (2015) 978e986 981

well as main consumptions; specific inventory relative to each step Table 2

cannot be published due to confidential aspects. The numbers be- Used allocations between co-products of sulphuric acid production facilities, data
are given in %.
tween brackets represent the energy produced on site using natural
gas boilers or electricity from the grid; they complete the supply of Unit SO2 Steam H2SO4 Electricity
sulphuric acid facilities, as described below. For both phosphoric First facility 37 63 / /
acid grades, electricity supply by the plant itself is equal to 50%. Second facility e first step 45 45 10
Concerning steam, both sulphuric facilities achieve at least 90% of Second facility e second step / 29 71 /
Second facility e global 32 58 10
the entire demand of the production process.
Sulphuric acid is produced on site with two different facilities
both converting elemental sulphur recovered in the petroleum
industry into sulphuric acid. 31% on the overall sulphuric acid is Table 3
Energy mix for electricity in Belgium in 2012 from International Energy Agency
produced by the first facility which produces sulphur dioxide and (2015) China and Kazakhstan in 2011 from International Energy Agency (2012).
also, as a co-product, steam which is used directly on site. Sulphur Data are given in %.
dioxide is then first converted into sulphur trioxide. This compo-
Fuel Belgium China Kazakhstan
nent is absorbed in water and transformed into sulphuric acid. The
second unit which produces 69% of the total mass of sulphuric acid, Coal 6.0 79 81.1
Natural gas 28.2 1.8 9.2
in service for 5 years, uses the same principle but includes a
Hydroelectricity 1.6 14.8 9.1
cogeneration allowing the joint production of steam and electricity. Nuclear energy 53.5 1.8 0.0
This production of electricity allows the supply of around 50% of the Wind 2.6 1.5 0.0
needed electricity of the industrial plant. As both units produce Waste 2.2 0.2 0.0
Biomass 4.3 0.7 0.0
several co-products, an allocation between all these co-products
Solar PV 1.3 0.0 0.0
has been applied to divide the environmental impact of sulphur Oil 0.3 0.2 0.6
burning. This allocation is based on a physical relation between all
products which is the thermodynamic relation between sulphur
and the heat released during the combustion. For the cogeneration allocation factors for phosphogypsum has been performed and
plant, electricity is produced from steam and then, a quantity of results are presented in paragraph 3.1.3.
steam at 50 bar (gage pressure) needed for this production can be Another co-product, called fluosilicic acid, is also recovered
calculated. This amount of steam is calculated using a turbine yield during the production of fertilizer grade phosphoric acid. It is
of 80% which was calculated after thermodynamic modelling. The produced during the attack, by the sulphuric acid, of the rock which
energy included in steam at 6 bar (gage pressure) is based on the contains between 2% and 4% of fluoride (European Commission and
total enthalpy of steam from which the enthalpy of water at 25  C is Joint Research Centre, 2007; European Fertilizer Manufacturers'
subtracted. To be able to compare steam used for electricity or in Association, 2000). This acid is sold and then a part of the envi-
the plant, the reference is the steam at 50 bar (gage pressure). Then, ronmental impact due to the concentration stage must be allocated
the quantity of steam from step one at 6 bar (gage pressure) is to this co-product. An allocation based on stoichiometry relation
converted in a quantity of steam at 50 bar (gage pressure), using the has been used and fluosilicic acid is responsible of around 2% of
energy relation. Table 2 presents the calculated values for allocation these impacts. This allocation factor is in accordance with the
for each facility. Another possibility is to assume that this surplus Ecoinvent report specific to phosphoric acid production (Primas
energy (as steam or electricity) is free and the entire burden of and Capello, 2004). Furthermore, due to the small quantity of
elemental sulphur combustion is given to sulphuric acid produc- H2SiF6 produced, these mass factors also reflect the economy fac-
tion. This possibility has been assessed in a sensitivity analysis in tors and then no sensitivity analysis is required between both
paragraph 3.1.2. allocation factors. Considering H2SiF6 as a waste will not change
The remaining part of electricity needed by the industrial plant anything in the overall results for the same reasons as explained
is produced using the Belgian energy mix of fuels. The model has just before.
been performed using the IEA statistics (International Energy Effluents of the first three steps are mainly emitted in water and
Agency, 2015) and is presented in Table 3. comprise phosphorus and fluorine. Some metals as Cr, Cd or Pb are
As mentioned previously, a co-product is obtained at the first also emitted. The values taken into account are based on environ-
stage of weak acid production. 85% of this phosphogypsum is sold mental reports published by Prayon SA for 2012 (Prayon SA, 2012a).
and the remaining part is stacked. Even if there is a physical rela- To obtain a purified and defluorinated phosphoric acid, three
tion, based on stoichiometry, between weak phosphoric acid and further steps are needed. The first one consists to oxidise the pre-
phosphogypsum, the total impact has been associated to phos- vious acid using steam and electricity. The next step is the extrac-
phoric acid H3PO4 as it reflects the market reality. Furthermore, this tion per solvent, using NaOH and sulphuric acid, and also using
choice allows the comparison of the environmental impact of DHH energy, too. The last step is dedicated to the acid defluorination
process with the other ones. Sensitivity analysis using other using also energy.

Table 1
Main specific consumptions for fertilizer and purified phosphoric acid production e per tonne of P2O5.

Consumption Quantity per tonne of P2O5 Unit

Fertilizer grade (1.92 t H3PO4 71.7%) Purified grade (1.85 t H3PO4 72.5%)

Phosphate rock 2.6 3 t

H2SO4 2.5 3
Electricity 142 (72) 263 (133) kW h
Steam 2.1 (0.13) 3.9 (0.38) t
NaOH / 55.5 kg
982 S. Belboom et al. / Journal of Cleaner Production 108 (2015) 978e986

[Link]. Phosphoric acid production using thermal process. Table 4

Production of purified and defluorinated phosphoric acid can also Specific consumptions for P2O5 equivalent production using thermal process.

be achieved using the thermal process. This process consists in Consumption Average quantity per tonne of P2O5 Unit
producing elemental phosphorus from phosphate rock and then Phosphate rock 3.2 t
oxidising it into P2O5, which is hydrated to obtain phosphoric acid. Clay 0.25
The reaction due to the passage of grinded phosphate rock, mixed Coke 0.55
with a slurry consisting of water, clay, carbon and various waste Process water 40 m3
Cooling water 120
streams containing phosphorus through a furnace can be sum-
Electricity 5850 kW h
marised by Equation (4). This reaction produces elemental phos-
phorus, carbon monoxide and a liquid slag (European Commission
and Joint Research Centre, 2007; European Fertilizer
process and finally “transport” which is relative to the phosphate
Manufacturers' Association, 2000).
rock and chemicals transportation. Fig. 4 compares both production
2Ca3 ðPO4 Þ2 þ 6SiO2 þ 10C/P4 þ 10CO þ 6CaSiO3 (4) processes for purified phosphoric acid, using Prayon specific data
and BAT based thermal process data. Results relative to mineral and
The efficiency of phosphorus recovery is equal to 94%. The next fossil fuel depletion categories modelled with ReCiPe 2008 method
step of phosphoric acid production is the oxidation of elemental are added in both figures. Categories of ILCD 2011 method do not
phosphorus with the air to P2O5. This reaction is exothermic and express directly the impact of fossil fuel consumption, which is an
the heat release is used for high temperature steam generation. The important factor for interpretation especially with energetic pro-
P2O5 produced by oxidation is contacted with diluted phosphoric cesses. Absolute values of impacts for each category are presented
acid and reacts with the water content to produce phosphoric acid. in Table 5 and are commented in further paragraphs.
Reactions are described by equations (5) and (6). Concerning fertilizer grade acid, the contribution of phosphate
consumption including mining and beneficiation for fertilizer grade
P4 þ 5O2 /2P2 O5 (5) production achieves between 4% of the total impact for (h) acidi-
fication category and 65% for (o) mineral, fossil and renewable re-
P2 O5 þ 3H2 O/2H3 PO4 (6) sources depletion. In the majority of categories, it reaches around
Thermal process for phosphoric acid production in European 30% of the total impact. Transportation of phosphate and chemicals
countries is now only performed in Czech Republic and Poland impact is not negligible and achieves more than 10% except in (e)
(European Commission and Joint Research Centre, 2007). Currently, particulate matter formation, (h) acidification and (o) mineral,
this process is widely used in China and Kazakhstan, which are the fossil and renewable energy depletion. Sulphuric acid and steam
main producers of thermal process phosphoric acid. reach together 76% of the (e) particulate matter formation impact
As no specific values are available for the modelling of the and 86% for the (h) acidification impact. Emissions in water,
thermal process, average values from the Best Available Techniques composed of mainly phosphate obtain 82% of the total impact of (j)
(BAT) for the manufacture of large volume Inorganic Chemicals e freshwater eutrophication.
Ammonia, fertilizers and acids, concerning consumptions are used Production of wet process purified phosphoric acid leads to
specific environmental impacts around 1.5 times higher than the
and shown in Table 4 (European Commission and Joint Research
Centre, 2007). Due to this non-specificity of data, uncertainties fertilizer grade for the 1 t of P2O5 contained in the final product.
relative to inventory can appear but the results of environmental Production of fertilizer grade acid achieves, depending on impact
impacts obtained will be treated as a range of accessible values for category, 54e73% of the total impact of purified acid. Previous in-
thermal process and not as absolute values. Mass of needed phos- formation concerning the importance of preliminary steps for fer-
phate rocks is given by the stoichiometry of the process so a weak tilizer grade is still available for purified grade.
uncertainty is then associated to this value. Information relative to Production of purified thermal process phosphoric acid,
emissions and energy consumptions should be considered as an assumed to be produced both in China and Kazakhstan, gives
accessible range of values. environmental impacts at least 7 times higher for (a) climate
For electricity generation, energy mixes relative to China and change and (q) fossil fuel consumption, and 6 times higher for (e)
Kazakhstan have been modelled using the IEA values presented in particulate matter formation than the wet process, as shown in
Table 3 (International Energy Agency, 2012). Energy mix has been Fig. 4. Wet process leads to higher emissions in (j) freshwater
modelled with 50% for each electricity type considering a produc- eutrophication category compared to thermal process. Electricity
tion in both countries. production and consumption included in the thermal process
induce 90% of the total impact in all categories.
3. Results and discussion
3.1.1. Benefits of the second facility of sulphuric acid production
3.1. Results In 2009, production of sulphuric acid was performed using
exclusively the first production facility. The first facility was not
Fig. 3 presents a breakdown of the results for ILCD 2011 envi- able to supply the overall consumption of sulphuric acid and then
ronmental impact categories of our study. It presents the impor- the remaining part was bought on the market. Supply of electricity
tance of specific consumption or emission for the product at was obtained using exclusively the grid and the required steam
fertilizer grade using wet process in Prayon SA. The overall process using natural gas boilers. Environmental impacts of this situation
has been divided between 8 contributions: “phosphate” which have been assessed and compared with the current situation.
refers to phosphate rock mining, “H2SO4” which is relative to sul- Without the second facility, results show an increase of 10% for (j)
phuric acid production on site, “emissions in the air” specific to the freshwater eutrophication impact but around 80% for (a) climate
plant, “emissions in water” due to process effluents, “steam” which change category. The implementation of a second facility allowing
is produced on site using sulphuric acid facilities or natural gas co-generation and then energy integration allows a non-negligible
boilers, “electricity” produced on site or supplied by the grid, reduction in terms of environmental impacts in all impact
“chemicals” which refer to all chemicals consumptions of the categories.
 S. Belboom et al. / Journal of Cleaner Production 108 (2015) 978e986 983

Fig. 3. Characterization results of environmental impacts for fertilizer grade phosphoric acid: importance of flows.

Fig. 4. Comparison between wet and thermal processes for purified acid production: characterization stage of environmental impacts.
984 S. Belboom et al. / Journal of Cleaner Production 108 (2015) 978e986

Table 5
Specific environmental values for P2O5 using wet (fertilizer and purified grades) and thermal processes.

Category Quantity and symbol Unit Usual unit Fertilizer grade (1 t P2O5) Purified grade (1 t P2O5)

Wet Thermal BAT

Climate change Mass of CO2 equivalent, meq (CO2) kg kgeq CO2 626 950 7365
Human toxicity Comparative Toxic Units for humans CTUh CTUh 1.07 104 2 104 1.27 103
Particulate matter formation Mass of particulates 2.5 equivalent, meq (PM2.5) kg kgeq PM 2.5 1.78 2.63 16.2
Acidification Equivalent acidification amount, neq (Hþ) mol moleq Hþ 28.7 43.4 83
Freshwater eutrophication Mass of phosphorus equivalent, meq (P) kg kgeq P 1.1 1.5 1.04
Land use Mass of carbon deficit, meq (C) kg kg C deficit 1394 1927 10 197
Fossil depletion Mass of oil equivalent, meq (oil) kg kgeq oil 187 293 2193

3.1.2. Sensitivity analysis e allocation for sulphuric acid production Table 6

In this study, an allocation has been used between sulphuric Allocation factors for weak phosphoric acid and phosphogypsum. Data are given in
%.
acid or sulphur dioxide, steam and electricity. This analysis is based
on a physical relation given by thermodynamic values. Another Product Waste Stoichiometry Price
possibility is to allocate the overall impact to sulphuric acid, based Weak H3PO4 100 49 95.3
on the fact that it is the wanted product. Electricity and steam Phosphogypsum 0 51 4.7
jointly produced are assumed to be free of burdens and then used in
all facilities without any environmental impact. Fig. 5 presents
variation of results for the main case and the sensitivity analysis. first step (weak phosphoric acid production) is only related to the
In that case, a reduction in the total impact of the purified main product. Another possibility is to divide this impact between
phosphoric acid is obtained for impact categories considered but phosphogypsum and phosphoric acid using different allocation
value changes are comprised between 0.2% for (o) mineral, fossil factors which are presented in Table 6. Only the valorised part of
and renewable energy depletion and 10.7% for (h) acidification with phosphogypsum has been used in the calculation of these factors.
a majority of variations inferior to 5%. Using thermodynamic allo- The physical relation, recommended by ISO standards leads to
cation is then relevant in our case, as all co-products are used for an environmental impact for weak phosphoric acid step divided by
their energy content, relative to the thermodynamic values. 2 which does not reflect the reality of the market. Concerning the
economic allocation, the results obtained are quite the same as the
3.1.3. Sensitivity analysis e allocation for phosphogypsum ones used in the main text which confirms the robustness of this
In this study, the unavoidable co-product, phosphogypsum, has choice. A variation of around 5% for the weak phosphoric produc-
been considered as a waste, assuming that the overall impact of the tion step leads to a total variation lower than 5% for each impact

Fig. 5. Comparison between allocation on sulphur or not: characterization stage of environmental impacts.
 S. Belboom et al. / Journal of Cleaner Production 108 (2015) 978e986 985

category concerning purified phosphoric acid. If the physical allo- of slags and dust (European Commission and Joint Research Centre,
cation is used, the overall impact for each category is reduced by at 2007; European Fertilizer Manufacturers' Association, 2000).
least 10% for (j) eutrophication category and reaches more than 20% This study case highlights the importance of phosphate rocks
for (a) global warming, (b) ozone layer depletion and (q) fossil fuel and their transportation from Russia to Belgium in the total impact.
depletion categories. Thus, practically, phosphogypsum was Producers of phosphoric acid have generally no influence on this
considered in this work as a waste, with no allocation at all, which impact, due to the geographical position of the rocks and economic
is really the case for nearly all other phosphoric acid factories in the reasons. Type of transportation, here mainly performed by boat, is
world. also important. The lorry transport should be avoided as much as
Compared to other wet production processes in the world, possible for environmental and economic purposes. Even if di-
where the quality of phosphogypsum does not allow its use, the di- hemihydrate process for phosphoric acid production requires so-
hemihydrate process avoids the stack of phosphogypsum or its phisticated materials of construction and also a close customer for
disposal in the sea and then reduces the emissions in water due to phosphogypsum, this process avoids the disposal of phosphogyp-
leachates and also the land needed. This environmental improve- sum and its implementation in new plants could be driven by these
ment is very important, especially in countries where areas are cost benefits but also thanks to its flexibility to rock source
limited due to high population density as it is the case in Belgium. (European Commission and Joint Research Centre, 2007). Further-
more, the sulphuric acid production on site, coupled with a
3.2. Discussion cogeneration facility, has improved the process in a non-negligible
way especially in (a) climate change category. Heat recovery and its
Production of phosphoric acid using wet di-hemihydrate pro- transformation in facilities is a key point for acid phosphoric pro-
cess has as main advantage the valorisation of a high share of the cess improvement.
produced phosphogypsum. As mentioned in literature, it is gener-
ally well accepted that the destiny of phosphogypsum and its 4. Conclusions
associated leachates are the main environmental hazards in phos-
phoric acid process and should be handled with care to avoid high The life cycle assessment methodology, in accordance with the
eutrophication impact (Bojarski et al., 2008; Silva and Kulay, 2005). ISO standards, is applied to wet di-hemihydrate process also called
Even if the phosphogypsum is not as economically profitable as Central Prayon process for fertilizer and purified grades phosphoric
phosphoric acid, its valorisation avoids disposal costs. acid. The purified phosphoric acid is compared with thermal acid
Phosphate rock mining and use induce one third of the (a) and results show a reduction in all impact categories when using
climate change impact as well as in (q) fossil fuel and (p) mineral wet process instead of thermal one, excepted for (i) eutrophication.
depletion categories. Its transportation from mines to the produc- Using di-hemihydrate process for phosphoric acid production
tion plant is also an important factor. Silva and Kulay (2005) avoids the disposal of phosphogypsum and allows its use, in this
highlighted this factor in the case of H3PO4 produced in Brazil for case, in plaster industry. This permits a reduction of environmental
global warming potential, ozone layer depletion, human toxicity impacts e.g. in (i) eutrophication due to the avoidance of leachates
and freshwater aquatic ecotoxicity categories. This is explained by or sea disposal but also the reduction of the area of occupied land
the important distance between ore processing units and produc- which is an important factor especially in countries where available
tion sites with sometimes more than 700 km as it is the case in our space is limited.
study (Silva and Kulay, 2005). Concerning (j) freshwater eutrophi- Sulphuric acid production is, after the valorisation of phos-
cation, emissions of phosphate are the main contributor of this phogypsum, the main parameter in the environmental impact of
category but in the Brazilian case (Silva and Kulay, 2003, 2005), phosphoric acid production. The excess heat produced jointly
they are due to phosphogypsum being disposed in open areas and with the sulphuric acid allows an energy recovery in terms of
leading to leachates compared to our study case where emissions heat and electricity which reduces in a significant way the
only come from the production process. environmental impacts of phosphoric acid production. The
Thanks to both sulphuric acid production facilities integrated on implementation five years ago of a modern sulphuric acid pro-
the site at Prayon, the part of fossil fuel used for energy generation duction plant achieving a cogeneration process permits a
as steam or electricity is reduced. Using an allocation factor for reduction of 80% of (a) climate change impact. The energy inte-
sulphuric acid facilities and their co-products is not significantly gration coupled with the valorisation of co-products is then the
different from not using it; the results are similar from one case to best way to reduce environmental impacts of a high energy
the other which confirms the robustness of our choice. Further- consuming chemical.
more, the implementation of the second sulphuric acid facility al- As the environmental impacts of fertilizer and purified grades of
lows a reduction of grid electricity about 50%. The steam produced phosphoric acid for Belgium are now available, the next step of this
with natural gas boilers constitutes maximum 10% of the overall study will be the evaluation of the environmental impacts of
demand of the site. The total consumption of sulphuric acid is phosphate salts. This study will highlight the hotspots of this pro-
completely supplied by the plant which allows a high reduction of duction and gives clues of improvement in an environmental point
the environmental impacts of fertilizer and purified grades phos- of view.
phoric acid. The production of sulphuric acid has been cited as a As the fertilizers are one of the main important factor in the
determinant factor for GHG emissions in the manufacture of agricultural sector, which is also related to numerous products of
phosphate fertilizer (Kongshaug, 1998; Wood and Cowie, 2004). our daily life, it is important to get an accurate value of the envi-
The comparison between purified wet and thermal phosphoric ronmental impacts of their production.
acids leads to the environmental benefit for the wet process. The As wet process is used worldwide for the production of fertilizer
electricity consumption (see Tables 1 and 4) of the thermal process grade phosphoric acid, and as Prayon processes represent around
reaches the highest part of the impact in all impact categories. The 50% of the production, this study can help in modelling other
energy mix of electricity, mainly composed of coal in countries as specific industrial plants. Then, only specific data concerning
China or Kazakhstan, is responsible of this important impact. The electricity mix, sulphuric acid production or specific regulations
high energy consumption has been often evocated as the main (e.g. the sea disposal of phosphogypsum is forbidden in Europe
reason to abandon this process in Europe followed by the handling which is not the case in other continents) would be necessary to
986 S. Belboom et al. / Journal of Cleaner Production 108 (2015) 978e986

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