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org/journal/ascecg Research Article

Life Cycle Environmental Impact Assessment of Sulfur-Based


Compound Fertilizers: A Case Study in China
Mengyue Liu, Yue Li, Xueliang Yuan,* Yue Xu, Liang Qiao, Qingsong Wang, and Qiao Ma
Cite This: ACS Sustainable Chem. Eng. 2022, 10, 2308−2317 Read Online

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ABSTRACT: The reduced atmospheric sulfur input has led to sulfur


deficiency in plants. Sulfur-based compound fertilizers have been widely used
in order to provide necessary sulfate. However, their environmental impacts
Downloaded via AIX-MARSEILLE UNIV on December 9, 2022 at 20:00:06 (UTC).

have been less studied. A life cycle assessment approach is applied to evaluate
the environmental impact of sulfur-based compound fertilizers from “cradle to
grave”, with a typical fertilizer produced in China as a case study and 1 ton
fertilizer as a functional unit. The results show the environmental impacts
mainly related to human carcinogenic toxicity, fossil resource scarcity,
freshwater eutrophication, freshwater ecotoxicity, terrestrial acidification, and
marine ecotoxicity. Synthetic ammonia production, conversion, and fertilizer
use processes are the key processes, which contribute 26.6, 18.7, and 23.9%,
respectively. Electricity, potassium chloride, hard coal, rock phosphate, and
emission pollutants from fertilizer use are key factors, contributing 17.6, 16.0,
14.2, 10.0, and 17.1%, respectively. Sensitivity analysis shows that electricity and
potassium chloride are the important factors to be optimized in the overall system. These results can be used to optimize the
fertilizer industry and frame policies in order to mitigate the overall environmental impacts of sulfur-based compound fertilizer
products under a life cycle framework.
KEYWORDS: sulfate, life cycle assessment, greenhouse gas emissions, fertilizer use, sustainable chemical fertilizer production

■ INTRODUCTION
With the increasing human demand for agricultural products,
from acidic atmospheric deposition from industry and the use
of fertilizers containing little or no sulfur have led to
global agriculture is facing the challenges of improving crop widespread sulfur deficiency in plants. The global agricultural
yield in a relatively reduced amount of agricultural land. sulfur deficiency in 2012 was as high as 11 Mt, including 6 Mt
Fertilizers are a basic input in agricultural production whose in Asia and 2.4 Mt in China.5 Studies showed that the addition
use can maintain soil fertility and promote crop yield. of S increased biomass and grain yield.6 The cycling of N and S
Fertilizers contribute 40−60% to global crop yield increase.1 in soil has the potential to be interactive. The deficiency of S
Fertilizers are critical to ensure food security given that food could reduce the use efficiency of N and vice versa.7 Sulfur
demand is expected to increase by 50−100% by 2050.2 China application also affects the stress resistance of a crop,8 the level
is a largely agricultural country having 9% of the world’s total of heavy metals,9 and the quality of grains.10 The most
agricultural land, and it feeds 20% of the world’s population common S sources contain either sulfate or elemental sulfur.
As an applicable approach to provide sulfate, the land use of
consuming a third of the world’s fertilizers.3 The amount of
sulfur-based compound fertilizers has received widespread
fertilizers applied in China has increased more than five times
attention.
from 8.84 million tons in 1978 to 54.04 million tons in 2019.
The fertilizer industry is a typical chemical industry with
Compound fertilizers refer to the chemical fertilizers with more
high energy consumption and pollutant emissions. The total
than one of nitrogen (N), phosphorus (P), and potassium (K)
annual energy consumption amounts (equivalent to standard
nutrients, and are widely used due to their high nutrient
coal) for the production of nitrogen, phosphorus, and
content. The proportion of compound fertilizers in total
fertilizers applied has increased annually, increasing from 27%
in 2005 to 41% in 2019.4 Compound fertilizers have become Received: August 11, 2021
the leading product of the chemical fertilizer industry in China. Revised: January 23, 2022
Sulfur-based compound fertilizers are a common compound Published: February 7, 2022
fertilizer, providing not only nitrogen, phosphorus, and
potassium but also sulfate (SO42−). Sulfur is a nutrient that
is essential for healthy growth of plants. A reduced sulfur input

© 2022 American Chemical Society https://doi.org/10.1021/acssuschemeng.1c05450


2308 ACS Sustainable Chem. Eng. 2022, 10, 2308−2317
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Figure 1. System boundary of the sulfur-based compound fertilizer.

potassium fertilizers in China are 82.41, 4.75, and 1.26 million Life cycle assessment (LCA) is an effective environmental
tons, respectively, accounting for 2.4% of total primary energy management tool that quantifies the environmental impact of a
consumption and 3.5% of industrial energy consumption in system throughout its entire life cycle from extraction,
2013.11 The fertilizer industry, which relies heavily on fossil production, use, end-of-life, and reuse. LCA has been widely
fuels, inevitably causes large greenhouse gas (GHG) emissions. used in the environmental impact assessment of fertilizer
Chemical fertilizers accounted for approximately 57% of the production in the system boundary of “cradle-to-gate”, such as
total GHG emissions from agricultural inputs in China.12 The nitrogen fertilizers,16 phosphate fertilizers,17 potash fertil-
izers,18 and compound fertilizers.19 A cradle-to-grave LCA
overuse of chemical fertilizers also poses significant environ-
for the fertilizer supply chain in Germany was investigated.20
mental risks, such as water eutrophication,13 soil degradation,14 An increasing number of researchers have focused on GHG
and damage to human health, ecosystem, and biodiversity.15 emissions in agriculture in recent years. Wang et al. evaluated
Therefore, the fertilizer industry plays an important role in the impact of various fertilizer products on GHG emissions
energy conservation and emission reduction. The environ- from “cradle-to-grave” and showed that ammonium bicar-
mental impact, energy consumption, GHG emissions, and bonate, calcium superphosphate, and potassium chloride had
sustainable development of the chemical fertilizer industry the lowest GHG emissions among N, P, and K fertilizers,
should be explored. respectively.21 Wu et al. assessed the GHG emissions of seven
2309 https://doi.org/10.1021/acssuschemeng.1c05450
ACS Sustainable Chem. Eng. 2022, 10, 2308−2317
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

fertilizers on nine crops from “cradle-to-grave” by using a life byproducts. Therefore, the hydrochloric acid is not involved in the
cycle GHG accounting approach; they found that urea, a allocation. The allocation factors of each product of the sulfur-based
compound fertilizer, and diammonium hydrogen phosphate compound fertilizer under one functional unit are shown in Table 1.
had a larger amount of GHG emissions.22 Other studies
indicate that fertilizers are the largest source of GHG emissions Table 1. Allocation Factors of Each Product of the Sulfur-
from crop production systems,23 while the GHG emissions in Based Compound Fertilizer
the use stage are determined by the nitrogen content in the market value allocation factors Af[v]
fertilizers. product name (RMB) (%)
The abovementioned studies comprehensively analyzed the sulfur-based compound 2200.00 95.98
environmental impacts of the fertilizer industry. However, fertilizer
most of the existing studies focus only on the production gypsum board 71.19 3.11
process of fertilizers or analyze only the environmental impacts methanol 20.89 0.91
of the fertilizer use stage. Moreover, studies that evaluate the hydrochloric acid 0.00 0.00
environmental impacts of the entire life cycle of fertilizers focus totals 2292.08 100
on GHG emissions only. By contrast, a considerable amount of
literature has reported that the land use of fertilizers has a large Life Cycle Inventory. The life cycle of the sulfur-based
environmental impact on water eutrophication and soil compound fertilizer consists of three major stages: transportation,
acidification. Therefore, a comprehensive environmental production, and use. The transportation stage involves the trans-
impact assessment of the whole life cycle of fertilizers should portation of raw materials and sulfur-based compound fertilizer
be conducted. The evaluation of environmental impacts of products. The raw material of hard coal is transported via a rail freight
sulfur-based compound fertilizers throughout their life cycle over a distance of 880 km. The main energy consumption of railroad
has not yet been conducted as well. transportation is composed of diesel and electricity, with consumption
In this study, a sulfur-based compound fertilizer was selected intensity rates of 0.025 L/(t·km) and 0.016 kW h/(t·km),
as the object to conduct the environmental impact assessment respectively.26 The energy consumption of road transport is from
the fuel consumption of trucks, and the value is 0.06 L/(t·km).27
of the entire life cycle including raw material extraction, Most of the raw materials except hard coal are purchased from
transportation, production, and use. The conclusion of this neighboring cities, and the road transportation distance is assumed to
study will fill the gap of LCA research in this field and provide be 50 km. Sulfur-based compound fertilizer products are transported
optimization suggestions for the sustainable development of in two stages: from producers to retailers and from retailers to
the fertilizer industry. farmers, with the average transportation distances assumed as 150 and


15 km, respectively.
In this paper, data on raw material consumption for production and
METHODS direct emissions of conventional pollutants are obtained from field
Goal and Scope. A sulfur-based compound fertilizer producer in investigation. Potassium chloride and concentrated sulfuric acid react
China was selected for a case study. The manufacturer can produce in the reaction tank to produce hydrogen chloride gas and potassium
100,000 tons of sulfur-based compound fertilizer and 30,000 tons of bisulfate solution. After the hydrogen chloride gas is absorbed by the
synthetic ammonia per year. As shown in Figure 1, the cradle-to-grave two-level falling film and two-level packed tower, 31% hydrochloric
system boundary was selected. The functional unit is the baseline to acid is produced as a byproduct. Potassium bisulfate flows into the
quantify the performance of a product system. One ton of sulfur- mixed acid tank, and the extracted phosphoric acid is added at the
based compound fertilizer was selected as the functional unit, same time to obtain the mixed acid. The mixed acid is pumped to the
including the production and use of 1 ton fertilizer. The nutrient tubular reactor, and gas ammonia is fed to the neutralization reaction
content of this sulfur-based compound fertilizer is 15−15−15 (i.e., to produce the neutralized slurry. The neutralized slurry enters the
mass percentage of nutrient composition is 15% N, 15% P2O5, and granulator and mixes with urea, ammonium sulfate, and other raw
15% K2O). materials for granulation. The final product is obtained after drying,
Multioutput processes require inventory allocation methods to cooling, and packaging. The individual production processes are
analyze the flow of material and energy and the allocation of the further divided into compound fertilizer production conversion,
corresponding environmental loads between the main products and neutralization and granulation, and waste gas treatment sections.
byproducts along the production chain.24 In the production of sulfur- Foreground data on the production of phosphoric acid and synthetic
based compound fertilizers, the phosphoric acid production process, ammonia, which are important raw materials for the production of
synthetic ammonia production, and compound fertilizer conversion compound fertilizers, are obtained from the actual production data of
section generate phosphogypsum, methanol, and hydrochloric acid as the company. Background data on the production of raw materials are
byproducts, respectively. Among them, the economic value of obtained from the Ecoinvent 3 database. The environmental impact of
phosphogypsum is less. The producer processes phosphogypsum to solid wastes from synthetic ammonia production, neutralization, and
generate gypsum boards for sale. These products are important granulation is ignored because these wastes are sold to construction
components in the supply chain and have a certain economic value. companies for reuse. In addition, the environmental impact caused by
Thus, the allocation should be considered in the production process. the infrastructure is generally not included in the inventory according
In this study, a market value-based allocation approach is applied to to the ISO 14040/14044.
assess the environmental impacts of compound fertilizer production. During the land use of fertilizers, nitrogen is mainly emitted into
This method is based on the economic value of products and the air in the form of N2O, NH3, and NOx, and leaches into water in
byproducts, and is usually the preferred method in allocation the form of NO3−.28 The loss of phosphorus into water can occur
studies.25 The principle of allocation according to market value is through runoff (phosphate), erosion to rivers (phosphorus), and
that the quality of each product is multiplied by the respective market leaching to groundwater (phosphate).29 The on-farm emission factors
price per unit of quality and divided by the sum of the quality and caused by the land use of fertilizers and related references are shown
market value of all outputs. The selling price of gypsum board of the in Table 2. Heavy metal residues caused by industrial sulfuric acid,
producer is 150 RMB/t, and the selling price of methanol is 1460 rock phosphate, and other raw materials in fertilizer production also
RMB/t. Hydrochloric acid, which is low in concentration and directly enter the soil with the use of fertilizers, thus causing
contains traces of K+ and SO42−, has a low economic value. The environmental pollution.29 Heavy metal losses are estimated by
producer commonly pays for the transportation and disposal of the input−output balances. The average contents of As, Cd, Pb, Cr, and

2310 https://doi.org/10.1021/acssuschemeng.1c05450
ACS Sustainable Chem. Eng. 2022, 10, 2308−2317
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Table 2. On-Farm Emission Factors in Fertilizer Use Background data refer to the data on the basic unit process.
Background databases for LCA have been developed and established
pollutant emissions parameter/% required data references in many countries, such as USLCI in the U.S., ELCD in Europe, and
N2O (direct emissions) 1.25 total N input 31 the Ecoinvent database in Switzerland. These databases are available
in SimaPro software.


N2O (indirect emissions 1 NH3 volatilization 32
from NH3)
N2O (indirect emissions 2.5 NO3− leaching 32 RESULTS
from NO3−) amount
NH3 7.6 total N input 33
LCIA Results. Based on the established LCI (Table S2), the
NOx 10 total N2O input 34
18 midpoint environmental impact characterization results in
NO3− 14 total N input 35 the full life cycle of the sulfur-based compound fertilizer are
P 0.2 total P input 29 quantified with the ReCiPe2016 model, as shown in Table 3.

Hg in compound fertilizers were 11.06, 0.24, 2.95, 19.7, and 0.054 Table 3. Characterization Results of the Sulfur-Based
mg/kg,30 and the specific content of heavy metals in the soil caused Compound Fertilizer
by fertilizer use was estimated.
results after
Pollutants and GHGs are released due to fuel combustion during category unit allocation
transportation, fertilizer production, and use. Emissions of pollutants
global warming kg CO2 eq 2.379 × 103
from diesel combustion during transportation and fertilizer use are
calculated according to the recommended emission coefficients.36 stratospheric ozone depletion kg CFC11 eq 2.693 × 10−2
CO2 emission is calculated with eq 1. ionizing radiation kBq Co-60 eq −8.816 × 100
ozone formation, human health kg NOx eq 4.183 × 100
44
c = e × NCV × A × O × fine particulate matter formation kg PM2.5 eq 5.205 × 100
12 (1)
ozone formation, terrestrial kg NOx eq 4.229 × 100
where c represents the carbon emission of 1 ton of sulfur-based ecosystems
compound fertilizer; e is the direct energy consumption; NCV terrestrial acidification kg SO2 eq 2.937 × 101
denotes the net calorific value; A represents the carbon content per freshwater eutrophication kg P eq 5.425 × 10−1
unit calorific value; and O is the carbon oxidation rate of the fuel. The marine eutrophication kg N eq 1.416 × 100
specific values and data sources of each parameter are shown in Table terrestrial ecotoxicity kg 1,4-DCB 2.009 × 103
S1 in the Supporting Information. A life cycle inventory (LCI) of freshwater ecotoxicity kg 1,4-DCB 2.042 × 101
sulfur-based compound fertilizers is shown in Table S2 in the
marine ecotoxicity kg 1,4-DCB 2.943 × 101
Supporting Information.
human carcinogenic toxicity kg 1,4-DCB 3.402 × 101
Life Cycle Impact Assessment (LCIA). The ReCiPe Midpoint
(H) model is used in this study to perform environmental quantitative human non-carcinogenic toxicity kg 1,4-DCB 7.876 × 102
analysis. The ReCiPe model, which integrates CML (Centrum land use m2a crop eq 6.581 × 101
Milieukunde Leiden) and the Eco-indicator model, is a widely mineral resource scarcity kg Cu eq 3.090 × 101
adopted method.37 The ReCiPe model is mainly used to solve the fossil resource scarcity kg oil eq 5.088 × 102
issues of normalization of the model and harmonize the midpoint water consumption m3 1.098 × 101
(CML) and endpoint (Eco-indicator) models into a single, consistent
approach. The ReCiPe2016 model can translate all LCA results into
18 midpoint levels. The total of 18 midpoint environmental impacts, The characterization results are normalized (eq 2) to further
such as global warming potential, ozone depletion potential, and compare the differences between the different impact
ionizing radiation potential, are quantified using midpoint character- categories. The LCA results in Figure 2 show that the entire
istic factors. life cycle of the sulfur-based compound fertilizer mainly has
The data are normalized to further analyze the contribution of each environmental impacts related to human carcinogenic toxicity,
impact category to the total environmental load; accordingly, fossil resource scarcity, freshwater eutrophication, freshwater
information on the relative importance of the LCA results can be ecotoxicity, terrestrial acidification, and marine ecotoxicity,
provided. Normalization is usually based on total emissions per capita accounting for 32.1, 20.1, 8.1, 7.9, 7.0, and 6.6%, respectively,
or total resource consumption per capita at a global or regional level.
The regionalized normalization process can provide more accurate
of the total environmental impact load. Stratospheric ozone
results, which are more consistent with local conditions. However, depletion, marine eutrophication, global warming, fine
local baselines were unavailable in most developing countries. Thus, particulate matter formation, ozone formation, and terrestrial
the normalization for this research is based on global environmental ecotoxicity also have certain environmental impacts, account-
impacts, with normalization factors referred to the data obtained using ing for 18% of the total environmental impacts. The other
the ReCiPe model. The normalization method is described as eq 2. impact categories have a less environmental impact.
CR c Identification of Key Processes. The environmental
NR c = contribution of each process is shown in Figure 3. Human
NFc,world (2) carcinogenic toxicity is the category with the highest
where NR, c, CR, NF, and world are the normalization results, environmental impact (32.1%). The main process that
category, characterization results, normalization factor, and the global contributes to this category is the synthetic ammonia
environmental potential of ecosystems caused by emission and production process, which contributes 39.7% of the environ-
extraction,38 respectively. mental impact. The conversion of compound fertilizer
LCA Modeling Platform. SimaPro 9.0 provides the ReCiPe 2016 production (18.4%), the phosphoric acid production process
model, which was selected as the modeling platform for the
environmental impact assessment in this study. The data for the (18%), and the neutralization and granulation stage (13.9%)
LCA consist of foreground data and background data. The foreground are also major contributors to human carcinogenic toxicity.
data are obtained from the producer through on-site investigation, Fossil resource scarcity, freshwater eutrophication, fresh-
which can directly reflect the amount of raw materials, energy water ecotoxicity, terrestrial acidification, and marine ecotox-
consumption, and waste emission in the production process. icity are other impact categories that account for more than 5%
2311 https://doi.org/10.1021/acssuschemeng.1c05450
ACS Sustainable Chem. Eng. 2022, 10, 2308−2317
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Figure 2. Normalized environmental impact of the sulfur-based compound fertilizer.

Figure 3. Percentage of environmental impact of each process of the sulfur-based compound fertilizer.

of the total environmental impact. The environmental impact (13.6%), and fertilizer use (22.9%) contribute more than
of terrestrial acidification comes mainly from the fertilizer use 94% of the total environmental impact. They are also the key
process, which contributes 75.2% of the environmental load. In processes in the life cycle of the sulfur-based compound
addition to terrestrial acidification, the conversion, synthetic fertilizer.
ammonia production, neutralization, and granulation processes Identification of Key Factors. The share of major factors
account for more than 10% of the remaining four impact in the environmental impacts of key processes has been
categories, with the conversion process accounting for nearly identified. As shown in Figure 4, rock phosphate, which is the
50% of the freshwater ecotoxicity and marine ecotoxicity. The raw material used in the production of phosphoric acid, is the
phosphoric acid production process also shows a large main substance that causes environmental pollution. Its
environmental contribution, with 13.8, 18.7, 7.3, and 8.3% environmental impact accounts for 78.8% of the total
for the four impact categories, respectively. environmental impact of phosphoric acid production. Hard
In general, the phosphoric acid production process (12.7%), coal and electric power account for 54.1 and 42.2% of the total
synthetic ammonia production process (26.6%), conversion influence of synthetic ammonia production, respectively.
process (18.7%), neutralization and granulation process Potassium chloride, which is the raw material for the
2312 https://doi.org/10.1021/acssuschemeng.1c05450
ACS Sustainable Chem. Eng. 2022, 10, 2308−2317
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Figure 4. Percentages of environmental impacts of key factors in (a) phosphoric acid production process, (b) synthetic ammonia production
process, (c) conversion process, (d) neutralization and granulation process, and (e) fertilizer use process.

conversion section, has an environmental impact of up to and processing of diesel greatly impact fossil resource scarcity,
85.6%, thus also being a key substance in the process. In the which contributes 41.5% of the environmental impact. The
neutralization and granulation stage, ammonium sulfate, effect of pollutant discharge during fertilizer use on terrestrial
electricity, anticaking agent, and urea are the main contributors acidification is 30.1%. Meanwhile, rock phosphate, hard coal,
to the environmental impact, with environmental impact ratios and potassium chloride contribute more than 15% of the
of 40.6, 17.6, 12.8, and 12.3%, respectively. The environmental environmental load.
impact of the fertilizer use process mainly comes from diesel Sensitivity Analysis. Figure 6 compares the degree of
and pollutant emissions to air, water, and soil, among which environmental impact of a 10% change in major input factors.
diesel contributes 20.8% of the environmental impact and The results show that electricity plays a decisive role in human
nitrogenous pollutants NH3, N2O, and NO3− account for 27.4, carcinogenic toxicity and total environmental impact load
23.4, and 12.8% of the total environmental impact of fertilizer when the input of key factors is reduced by 10%, which leads
use process, respectively. to reductions in their environmental impact by 0.998 kg 1,4-
The proportion of environmental load of different factors in DCB and 2.624 × 10−11, respectively. This finding also means
the major environmental impact categories is decomposed to that a 10% reduction in electricity would result in a decrease of
further explore the key factors (Figure 5). Electricity 2.9% in human carcinogenic toxicity and 1.7% in total
contributes the most to the environmental impact (17.6%), environmental impact. Electricity also has a large impact on
followed by pollutant emission from the fertilizer use (17.1%), fossil resource scarcity, and this effect is closely related to the
potassium chloride (16.0%), and hard coal (14.2%). The major China’s coal-based power generation structure. In addition, the
environmental impacts are concentrated in human carcino- change in the potassium chloride input has the most significant
genic toxicity for electricity, hard coal, rock phosphate, impact on freshwater ecotoxicity and marine ecotoxicity. The
ammonium sulfate, and potassium chloride. The production change in the potassium chloride input provides benefits of 4.6
2313 https://doi.org/10.1021/acssuschemeng.1c05450
ACS Sustainable Chem. Eng. 2022, 10, 2308−2317
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Figure 5. Percentage of major factors in different environmental impact categories (the left bar shows the total environmental impact load of the
sulfur-based compound fertilizer. HCT: human carcinogenic toxicity; FRS: fossil resource scarcity; TA: terrestrial acidification; FE: freshwater
eutrophication; FET: freshwater ecotoxicity; MET: marine ecotoxicity; and ROC: rest of categories).

have a 1.5% benefit on fossil resource scarcity. Changes in the


ammonium sulfate input yield a smaller environmental benefit.
Pollutant emission from the fertilizer use is also a key factor.
The excessive use of chemical fertilizers causes a greater risk to
the environment. Stratospheric ozone depletion and marine
eutrophication have the most significant environmental impact
for a 10% reduction in the land use of sulfur-based compound
fertilizers, yielding benefits of 9.9% and 9.6%, respectively.
Terrestrial acidification, fine particulate matter formation, and
global warming also have large environmental benefits,
reducing the environmental load by 7.4%, 5.2%, and 3.6%,
respectively. The results are shown in Figure 7. Therefore, the
reduced fertilizer input can effectively improve pollutant
emissions from the fertilizer use.

■ DISCUSSION
GHG Emissions from the Fertilizer Industry. The result
of the entire life cycle GHG emission of the sulfur-based
compound fertilizer is 2380 kg CO2 eq per ton of fertilizer, in
which the GHG emission of the production process is 1485 kg
CO2 eq, and the GHG emission of the fertilizer use process is
Figure 6. Sensitivity analysis results of the environmental impact of a 895 kg CO2 eq. The GHG emissions of various types of
10% change in key input factors (the size of the bubbles represents fertilizers in production, use, or the entire life cycle were
the degree of change in each environmental impact category. The analyzed after referring to other relevant studies.
larger the size of the bubble, the greater the impact on the Among the nitrogen, phosphorus, potassium, and compound
environment. The same key factors are consistent in color for fertilizers, the production and use process of potash fertilizers
environmental impacts). has the lowest GHG emissions.18,21 From the use stage, the
GHG emission of nitrogen fertilizers is the largest. Analysis of
and 4.6%, which are three times as much as those of electricity, the key factors above shows that pollutants from the fertilizer
hard coal, and rock phosphate, respectively. Therefore, the use are mainly nitrogen-containing gases, which are mainly due
optimization of power and potassium chloride is the key to to the lower nitrogen use efficiency (NUE); this phenomenon
reduce the environmental impact of sulfur-based compound results in volatilization and loss of nitrogen. A higher NUE is
fertilizers. Hard coal has a large impact on fossil resource desired to protect ground and surface waters. Studies have
scarcity, and a 10% change in its input would result in a 9.83 kg shown that S addition increased biomass and grain yield,10
oil eq reduction in fossil resource scarcity. The most significant reporting a positive interaction between N and S, which was
change in freshwater eutrophication is observed for a 10% reflected in a greater NUE.7 Hasler et al. analyzed the
change in the rock phosphate input, which produces an environmental impact of compound fertilizers with nutrient
environmental gain of 1.8%. A change in the diesel input can contents of 15−15−15.20 The GHG emissions were 1440 kg
2314 https://doi.org/10.1021/acssuschemeng.1c05450
ACS Sustainable Chem. Eng. 2022, 10, 2308−2317
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Figure 7. Sensitivity analysis of pollutant emissions from 10% change of the fertilizer use.

CO2 eq when the functional units were converted to 1 ton of High energy consumption will cause a large amount of GHG
compound fertilizer, which is lower than the GHG emissions emissions, thereby requiring producers to explore the measures
calculated in the current study. The reason for this difference is to save energy and materials. Zhang et al. reported that GHG
that the input energy in the study by Hasler et al. is mainly emissions from the fertilizer industry could be significantly
clean energy natural gas, with minimal use of coal. In addition reduced by increasing the methane recovery rate of the coal-
to nitrogen, phosphorus, and potassium elements, the mining process and the energy efficiency of the fertilizer
compound fertilizer in the current work also has sulfate production process, which resulted in a reduction in GHG
obtained through ammonium sulfate. More raw material inputs emissions of 102−357 Mt CO2 eq per year and a 2−6%
lead to greater GHG emissions. reduction in the total GHG emissions.42 In addition, the
The ammonia synthesis industry is an important part of the thermal power generation structure is an important cause of
basic chemical industry, with the global capacity of nearly 188 high GHG emissions. The construction of a clean energy-based
million tons in 2020, which is mainly for fertilizer production power structure is the way to fundamentally address GHG
(around 80%).39 Ammonia synthesis is also a typical process emissions. With the Chinese government’s proposed “Carbon
with high energy consumption and GHG emission. The main Peaking” and “Carbon Neutrality” targets, the proportion of
energy sources of ammonia production are coal, natural gas, renewable power generation capacity is expected to increase
coke, and petroleum, with an average energy consumption of from 41.9% in 2019 to 57.5% in 2025, which can lead to a
28−53 MJ/kg and a total annual emission of 451 Mt CO2.40 significant reduction of GHG emissions from sulfur-based
China is the world’s largest ammonia producer with an annual compound fertilizer production.
Optimization Suggestion. Sensitivity analysis revealed
output of 49.7 Mt, which accounts for 32% of the global
that the optimization of potassium chloride is the key to reduce
ammonia production. Unlike other countries that use natural
the environmental impact of the sulfur-based compound
gas as energy, China’s ammonia production energy is 70%
fertilizer besides power optimization. Soluble potassium salt
from coal, 10% from oil, and only 20% from natural gas. The
is an important raw material for the production of potassium
coal-based energy structure of the China’s ammonia industry chloride, but it is in short supply in China, and depends on
causes serious pollution, with much higher carbon emissions imports due to the huge demand for agricultural development.
and higher energy consumption levels than those of other However, the common methods of potassium chloride
regions of the world. In this case, the carbon emissions from production have the disadvantages of high toxicity, expensive
the production of ammonia in this enterprise account for 81% reagents, complicated processes, and high environmental
of the total emissions from the production process, which is impacts.43 The potassium chloride required to produce the
the key link of GHG emissions in fertilizer production. The sulfur-based compound fertilizer in this study accounts for
Chinese government has issued several policies and standards 15.3% of the total environmental impact load. The environ-
to strengthen energy conservation and emission reduction in mental impacts were mainly concentrated in human carcino-
the synthetic ammonia industry. In recent years, many new genic toxicity, freshwater ecotoxicity, marine ecotoxicity, fossil
energy-based ammonia production technologies have emerged resource scarcity, and terrestrial ecotoxicity, contributing 33.2,
in addition to ammonia production technologies based on 22.6, 18.9, 9.9 and 4.4% of the environmental load,
traditional fossil fuels. The hydrogen required for ammonia respectively. At present, the main production process of
synthesis can be obtained from high-temperature water potassium chloride in China is froth flotation. However, the
electrolysis, biomass gasification, and biogas reforming.41 grade of the potassium ore decreases due to improper mining
Although these new technologies can achieve zero fossil methods; moreover, the recovery rate of flotation also
energy consumption, they also have the disadvantage of low decreases obviously with the decline in temperature.44 This
economic benefits and difficulty in large-scale production. method should improve the quality of raw ore for potassium
2315 https://doi.org/10.1021/acssuschemeng.1c05450
ACS Sustainable Chem. Eng. 2022, 10, 2308−2317
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

chloride production, optimize the processes, and enhance Authors


potassium salt recovery. Producers should also explore new Mengyue Liu − School of Energy and Power Engineering,
production processes to improve the production efficiency of Shandong University, Jinan 250061, China
potassium chloride and reduce the consumption of raw Yue Li − School of Energy and Power Engineering, Shandong
materials. On the other side, potassium chloride can also be University, Jinan 250061, China
extracted from the dust ash of steel plants.45 Alternatives to Yue Xu − School of Energy and Power Engineering, Shandong
potash have attracted wide attention due to the high price of University, Jinan 250061, China
potash and the scarcity of conventional potassium sources. A Liang Qiao − School of Energy and Power Engineering,
good substitute is potassium silicate minerals, of which mica Shandong University, Jinan 250061, China
has been shown to achieve the same fertility as potassium Qingsong Wang − School of Energy and Power Engineering,
chloride.46 Shandong University, Jinan 250061, China
Rock phosphate is also a key substance that causes Qiao Ma − School of Energy and Power Engineering,
environmental impacts in fertilizer production providing the Shandong University, Jinan 250061, China
element phosphorus necessary for crop growth and providing Complete contact information is available at:
one of the three essential elements for crop growth. The https://pubs.acs.org/10.1021/acssuschemeng.1c05450
amount of phosphorus extracted from rock phosphate will peak
around 2030, and the global reserves will be exhausted within Notes
75−100 years.47 Therefore, the recovery of phosphorus
The authors declare no competing financial interest.


resources is particularly important. Humans excrete 98% of
phosphorus that ends up in sewage sludge,48 which makes it
the most valuable resource for phosphorus recovery. ACKNOWLEDGMENTS

■ CONCLUSIONS
A cradle-to-grave LCA analysis per 1 ton of sulfur-based
This research was supported by National Key R&D Plan of
China (2020YFC1910000), National Natural Science Founda-
tion (71974116), Shandong Natural Science Foundation
compound fertilizer is performed. The localized LCI in China (ZR2019MG009), Shandong Social Science Planning Research
is disclosed. Environmental impacts are classified into 18 Project (21BKRJ02), and Taishan Scholar Project
ReCiPe 2016 Midpoint impact categories. The LCA results (tsqn202103010).
showed that synthetic ammonia production, conversion, and
fertilizer use processes are the key processes. Electricity,
potassium chloride, hard coal, rock phosphate, and pollutant
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